JP7449642B2 - Colored resin composition, color filter, and image display device - Google Patents

Description

The present invention relates to a colored resin composition, a color filter, and an image display device.

Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for manufacturing color filters used in liquid crystal display devices and the like. Among them, the pigment dispersion method is the most widely adopted because it has excellent properties on average in terms of spectral properties, durability, pattern shape, precision, etc.

In color filters having pixels formed using a pigment dispersion method, miniaturization of pigments is being considered in order to achieve higher brightness and higher contrast. It is believed that by making the pigment finer, the scattering of light transmitted through the color filter by the pigment particles is reduced, thereby achieving higher brightness and higher contrast.
However, since the finely divided pigment particles tend to aggregate, there is a problem in that the dispersibility and dispersion stability deteriorate. It is known that using a dispersant is effective as a method for improving the dispersibility of finely divided pigments.

For example, Patent Document 1 describes a colored resin composition containing a block copolymer having an amine value of 80 to 150 mgKOH/g. Patent Document 2 describes a colored resin composition containing a block copolymer having an acid value of 1 to 18 mgKOH/g and a glass transition temperature of 30° C. or higher. Further, Patent Document 3 describes a colored resin composition containing a block copolymer having an amine value of 35 to 110 mgKOH/g and a glass transition temperature of 30° C. or higher.

JP2009-052010A Japanese Patent Application Publication No. 2016-122169 Japanese Patent Application Publication No. 2016-122073

In recent years, color filters are required to have sufficient electrical reliability. When electrical reliability is low, the components contained in the colored resin composition for forming the color filter enter the liquid crystal layer and move through the liquid crystal layer, reducing the voltage applied to the liquid crystal layer for a certain period of time. This prevents the image from being held and causes display defects on the image display device.
Upon investigation by the present inventors, it was found that the colored resin compositions described in Patent Documents 1 to 3 do not have sufficient electrical reliability, which is required in recent years.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a colored resin composition having good electrical reliability, a color filter having pixels formed using this colored resin composition, and an image display device having this color filter.

As a result of intensive studies, the present inventors found that the above-mentioned problem can be solved by including a specific dispersant and a specific alkali-soluble resin in the colored resin composition, leading to the present invention.
That is, the present invention has the following configurations [1] to [4].

[1] A colored resin composition containing (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, (E) a photopolymerizable monomer, and (F) a photoinitiator. hand,
The dispersant (B) includes a dispersant (b) having 50 mol% or more of repeating units represented by the following general formula (I),
A colored resin composition, wherein the binder resin (D) contains an alkali-soluble resin (d) having a repeating unit represented by the following general formula (i).

(In formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkyl group having 3 or less carbon atoms which may have a substituent.)

(In formula (i), R ^d1 represents a hydrogen atom or a methyl group.
R ^d2 represents a trivalent hydrocarbon group which may have a substituent.
R ^d3 represents a hydrogen atom or a methyl group.
R ^d4 represents a divalent hydrocarbon group which may have a substituent. )

[2] The colored resin composition according to [1], wherein the pigment (A) includes a halogenated zinc phthalocyanine pigment.
[3] A color filter having pixels created using the colored resin composition according to [1] or [2].
[4] An image display device comprising the color filter according to [3].

According to the present invention, it is possible to provide a colored resin composition with good electrical reliability, a color filter having pixels formed using this colored resin composition, and an image display device having this color filter.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL display element having a color filter of the present invention.

The constituent elements of the present invention will be explained in detail below, but these are just examples of embodiments of the present invention, and the present invention is not limited to these contents.
In addition, "(meth)acrylic", "(meth)acrylate", etc. mean "acrylic and/or methacrylic", "acrylate and/or methacrylate", etc. For example, "(meth)acrylic acid" means " acrylic acid and/or methacrylic acid. Moreover, "total solid content" shall mean all components other than the solvent component contained in the pigment dispersion liquid or the colored resin composition.

In the present invention, the term "weight average molecular weight" refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
In addition, in the present invention, the "amine value" refers to the amine value in terms of effective solid content unless otherwise specified, and is a value expressed by the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant. .
Furthermore, in the present invention, "C.I." means color index.

[1] Constituent components of colored resin composition Each constituent component of the colored resin composition of the present invention will be explained below. The colored resin composition according to the present invention comprises (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, (E) a photopolymerizable monomer, and (F) a photoinitiator. These are essential components, and if necessary, other additives other than the above components may be added.
Each component will be explained below.

[1-1] (A) Colorant The colored resin composition of the present invention contains (A) a colorant as an essential component. Colorants include pigments and dyes. As the pigment, for example, when forming pixels of a color filter, pigments of various colors such as red pigment, blue pigment, green pigment, yellow pigment, purple pigment, orange pigment, brown pigment, etc. can be used. Examples of the chemical structure include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition to these, various inorganic pigments can also be used. Specific examples of pigments that can be used are shown below using pigment numbers. "C.I." listed below means color index (C.I.).

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Among these, from the viewpoint of dispersion stability, C.I. I. Pigment Red 177, 254, or 275, more preferably C.I. I. Pigment Red 177 or 254.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, Examples include 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, and the like. Among these, from the viewpoint of dispersion stability, C.I. I. Pigment Blue 15:3 or 15:6, more preferably C.I. I. Pigment Blue 15:6.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 or 59. . Among these, from the viewpoint of dispersion stability, C.I. I. Pigment Green 36, 58 or 59, more preferably C.I. I. Pigment Green 58 or 59.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. can be mentioned. Among these, from the viewpoint of dispersion stability, C.I. I. pigment yellow 129, 138, 139, 150 or 185, more preferably C.I. I. pigment yellow 138, 150 or 185.

As the purple pigment, for example, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these, from the viewpoint of dispersion stability, C.I. I. Pigment Violet 23 or 29, more preferably C.I. I. Pigment Violet 23.

Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, etc.

Examples of inorganic pigments include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.

Among the various pigments mentioned above, from the viewpoint of chromaticity adjustment required for image display devices, C. I. Pigment Red 254, C. I. Pigment Red 177, C. I. Pigment Blue 15:6, C. I. Pigment Green 58, C. I. Pigment Green 59, C. I. Pigment Yellow 138, C. I. Pigment Yellow 150, C. I. Pigment Yellow 185 or C.I. I. Pigment Violet 23 is preferred; C.I. I. Pigment Green 58 or C. I. More preferred are halogenated zinc phthalocyanine pigments such as Pigment Green 59.

The above-mentioned various pigments can also be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used together, a blue pigment and a violet pigment can be used together, or a red pigment and a yellow pigment can be used together.
These pigments are preferably used after being dispersed so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.3 μm or less.

Further, the average primary particle size of these pigments is usually 100 nm or less, preferably 50 nm or less, more preferably 40 nm or less, particularly preferably 10 nm or more and 30 nm or less. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, it is particularly preferable that the composition contains a pigment having an average primary particle size of 10 nm or more and 30 nm or less.

When forming a light shielding material such as a black matrix of a color filter using the colored resin composition of the present invention, a black pigment can be used. The black pigment may be used alone or in combination with the above-mentioned red, green, blue, etc. pigments. Examples of black pigments that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferred from the viewpoint of light shielding rate and image characteristics.

Examples of carbon black include MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32 as products manufactured by Mitsubishi Chemical Corporation. , #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, # 1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B As products manufactured by Degussa, Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85 , Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack k4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Colo r Black S170 etc. are products manufactured by Cabot such as Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch h1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0 , REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN , RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U , RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc., respectively.

Note that it is particularly preferable to use resin-coated carbon black for producing a resin black matrix having high optical density and high surface resistivity. The resin-coated carbon black is disclosed in, for example, JP-A-9-26571, JP-A-9-71733, JP-A-9-95625, JP-A-9-238863, or JP-A-11-60989. It can be obtained by treating known carbon black by the method described in the publication.

In addition, methods for producing titanium black include a method in which a mixture of titanium dioxide and metallic titanium is heated and reduced in a reducing atmosphere (Japanese Unexamined Patent Publication No. 1983-5432), and a method obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing ultrafine titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Unexamined Patent Publication No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Unexamined Patent Publication No. 60-65069) (Japanese Patent Application Laid-Open No. 61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Application Laid-open No. 61-201610), etc. It is not limited. Examples of commercially available titanium blacks include titanium blacks 10S, 12S, 13R, 13M, and 13MC manufactured by Mitsubishi Materials.

As another example of the black pigment, a plurality of pigments such as red, green, and blue can be mixed and used as the black pigment. Colorants that can be mixed to prepare black pigments include Victoria Pure Blue (42595), Auramine O (41000), Cathylone Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70:100 (50240), Erioglaucine X (42080), No. 120/Lionor Yellow (21090), Lionor Yellow GRO (21090), Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionor Red 7B4401 (15850), Fastgen Blue TGR-L (74160), Lionor Blue SM (26150), Lionor Blue ES (Pigment Blue 15:6), Lionorgen Red GD (Pigment Red 168), Lionor Green 2YS (Pigment Green 36), etc. Furthermore, regarding other pigments that can be used in combination, C. I. Indicated by number, for example, C. I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C. I. Pigment Orange 36, 43, 51, 55, 59, 61, C. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C. I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C. I. Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C. I. Pigment Green 7, C. I. Pigment Brown 23, 25, 26, etc. can be mentioned. Note that the numbers in parentheses above mean color index (C.I.).

The particle size of these black pigments is also preferably in the same range as described above for pigments other than black.

On the other hand, as the dye, for example, a dye having a basic skeleton of xanthene, anthraquinone, or phthalocyanine and having a sulfonic acid group and/or a sulfonate group can be used. Specifically, xanthene dyes include Acid Red 52, Acid Red 87, Acid Red 91, Acid Red 92, Acid Red 94, and Acid Red 289, and anthraquinone dyes include Acid Red 80, Acid Green 25, and Acid Red. Green 27, Acid Blue 25, Acid Blue 78, Acid Blue 112, Acid Blue 182, Acid Violet 34, Acid Violet 43. Phthalocyanine dyes include Direct Blue 86, Direct Blue 87, and Acid Blue 249.

In the colored resin composition of the present invention, the content ratio of these (A) colorants is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content. More preferably 20% by mass or more, even more preferably 25% by mass or more, particularly preferably 30% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, 40% by mass or less. % or less is more preferable. By setting it to the lower limit value or more, there is a tendency for desired chromaticity and film thickness as a color filter to be obtained, and by setting it to the above upper limit value or less, the dispersion stability tends to improve.

In addition, when the colorant (A) contains a pigment, the content ratio of the pigment is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass or more based on the total solid content. It is more preferably at least 25% by mass, even more preferably at least 30% by mass, and usually at most 80% by mass, preferably at most 60% by mass, more preferably at most 50% by mass, and 40% by mass. The following are more preferred. When the amount is equal to or more than the lower limit value, the desired chromaticity and film thickness as a color filter tend to be obtained, and when it is equal to or less than the upper limit value, the dispersion stability tends to be improved.

[1-2] (B) Dispersant The colored resin composition of the present invention contains (B) a dispersant as an essential component. By including the dispersant (B), the colorant (A) can be stably dispersed.
The dispersant (B) in the colored resin composition of the present invention is a dispersant (b) having 50 mol% or more of repeating units represented by the following general formula (I) (hereinafter abbreviated as "dispersant (b)"). ).

In formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkyl group having 3 or less carbon atoms which may have a substituent.

The repeating unit represented by the general formula (I) contained in the dispersant (b) has low affinity with liquid crystal molecules due to the short carbon number of the alkyl group of R ² . Therefore, by including the dispersant (b) having 50 mol% or more of repeating units represented by the general formula (I) in the colored resin composition, it is possible to increase the affinity with the liquid crystal molecules of the colored resin composition itself. is considered to be lower. Furthermore, the steric repulsion between the dispersant (b) and the colorant is suppressed, and the adsorption of the dispersant (b) to the colorant is promoted, thereby suppressing the elution of free dispersant into the liquid crystal layer. It is thought that this will improve the voltage holding rate. Furthermore, it is thought that the short carbon number of R ² makes it highly heat resistant and less likely to be thermally decomposed by heat treatment and less likely to cause a decrease in brightness due to coloring.

( ^R2 )
In formula (I), R ² represents an alkyl group having 3 or less carbon atoms which may have a substituent.

The alkyl group may be linear or branched, but is preferably linear from the viewpoint of suppressing steric repulsion with the colorant.
Further, the number of carbon atoms in the alkyl group is not particularly limited as long as it is 3 or less, but it is preferably 2 or less, and more preferably 1. By setting it below the upper limit value, electrical reliability tends to be improved. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group, and from the viewpoint of electrical reliability, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.
The substituent that the alkyl group may have is not particularly limited, and examples thereof include a halogen atom and a hydroxyl group, but from the viewpoint of electrical reliability, it is particularly preferable that the substituent is unsubstituted.

The dispersant (b) contains the repeating unit represented by the general formula (I), but may also contain other repeating units. Among other repeating units, from the viewpoint of dispersibility, it is preferable to include a repeating unit represented by the following general formula (II).

In formula (II), R ³ represents a hydrogen atom or a methyl group. X represents a divalent linking group. R ⁴ and R ⁵ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. and R ⁴ and R ⁵ may combine with each other to form a cyclic structure.

(X)
In formula (II), X represents a divalent linking group.
Examples of the divalent linking group include a single bond, an alkylene group, an arylene group, and an alkyloxyalkyl group. Among these, alkylene groups are preferred from the viewpoint of dispersibility.

The alkylene group may be linear, branched, or cyclic, but is preferably linear from the viewpoint of dispersibility.
The number of carbon atoms in the alkylene group is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or more than the lower limit, dispersion stability tends to improve, and when the content is equal to or less than the upper limit, developability and storage stability tend to improve.
Specific examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, oxytylene group, etc. From the viewpoint of dispersibility, methylene group or ethylene group is preferable, and ethylene group group is more preferred.

(R ⁴ and R ⁵ )
In formula (II), R ⁴ and R ⁵ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ⁴ and R ⁵ may be bonded to each other to form a cyclic structure.

The alkyl group may be linear, branched, cyclic, or a combination thereof, but is preferably linear from the viewpoint of dispersibility.
The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of dispersibility, it is usually 1 or more, preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, even more preferably 3 or less, and 2 The following are particularly preferred.

Specific examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, cyclohexylmethyl group, octyl group, etc. Among these, from the viewpoint of dispersibility , preferably a methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group, more preferably a methyl group, ethyl group, propyl group, or butyl group, and a methyl group or an ethyl group. It is more preferable that

The aryl group may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group.
The number of carbon atoms in the aryl group is not particularly limited, but from the viewpoint of dispersibility, it is usually 6 or more, preferably 16 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less.
Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, etc. Among these, phenyl group, methylphenyl group, ethylphenyl group , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

An aralkyl group is a group that combines an alkylene group and an aryl group. The alkylene group may be linear, branched, cyclic, or a combination thereof. Further, the aryl group may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group.
The number of carbon atoms in the aralkyl group is not particularly limited, but from the viewpoint of dispersibility, it is usually 7 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. , is particularly preferably 8 or less.
Specific examples of aralkyl groups include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group, etc. Among these, phenylmethyl group, phenylethyl group A phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

Examples of substituents that the alkyl group, aralkyl group, or aryl group may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group.

Among these, from the viewpoint of dispersibility, storage stability, electrical reliability, and developability, it is preferable that R ⁴ and R ⁵ are each independently an alkyl group or an aralkyl group, and specifically, R ⁴ and More preferably, R ⁵ is a methyl group.

In the above formula (II), the cyclic structure formed by bonding R ⁴ and R ⁵ to each other is, for example, a 5- to 7-membered nitrogen-containing monocyclic ring or a condensed ring formed by condensing two of these. can be mentioned. The nitrogen-containing heterocycle is preferably non-aromatic, and more preferably a saturated ring. Specifically, for example, the following may be mentioned.

These cyclic structures may further have a substituent.

On the other hand, among the other repeating units, from the viewpoint of dispersion stability, it is preferable to include a repeating unit represented by the following general formula (III).

In formula (III), R ⁶ represents a hydrogen atom or a methyl group. Z represents a divalent linking group. R ⁷ to R ⁹ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent. and two or more of R ⁷ to R ⁹ may be bonded to each other to form a cyclic structure. A ^- represents a counter anion.

Further, as Z in the above formula (III), those listed as X in the above formula (II) can be preferably employed. The alkyl group which may have a substituent, the aryl group which may have a substituent, and the aralkyl group which may have a substituent in R ⁷ to R ⁹ are represented by the above formula (II). Those listed as the optionally substituted alkyl group, optionally substituted aryl group, and optionally substituted aralkyl group in R ⁴ and R ⁵ are preferably employed. can do.

( ^A- )
In formula (III), A ⁻ represents a counter anion. Examples of counter anions include Cl ^- , Br ^- , I ^- , ClO ^{4 -} , BF ^{4 -} , CH ₃ COO ^- , PF ₆ ^- and the like.

In the formula (III), the cyclic structure formed by bonding two or more of R ⁷ to R ⁹ to each other is, for example, a 5- to 7-membered nitrogen-containing monocyclic ring or a fused two or more of these. Examples include fused rings formed by: The nitrogen-containing heterocycle is preferably non-aromatic, and more preferably a saturated ring. Specifically, for example, the following may be mentioned.

In the above formula, R is any one of R ⁷ to R ⁹ . Moreover, these cyclic structures may further have a substituent.

Moreover, among other repeating units, it is preferable to include a repeating unit represented by the following general formula (IV) from the viewpoint of dispersibility and developability.

In formula (IV), R ¹⁰ represents a hydrogen atom or a methyl group. R ¹¹ represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent.

( ^R11 )
In formula (IV), R ¹¹ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. represent.

The alkyl group may be linear, branched, cyclic, or a combination thereof, but is preferably linear from the viewpoint of dispersibility.
The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of developability, it is preferably 4 or more, preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

Specific examples of alkyl groups include butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, cyclohexylmethyl group, octyl group, etc. Among these, from the viewpoint of dispersibility and developability, butyl group, pentyl group, or hexyl group, and more preferably butyl group.

The aryl group may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group.
The number of carbon atoms in the aryl group is not particularly limited, but from the viewpoint of developability, it is usually 6 or more, preferably 16 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less.
Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, etc. Among these, phenyl group, methylphenyl group, ethylphenyl group , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

An aralkyl group is a group that combines an alkylene group and an aryl group. The alkylene group may be linear, branched, cyclic, or a combination thereof. Further, the aryl group may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group.
The number of carbon atoms in the aralkyl group is not particularly limited, but from the viewpoint of developability, it is usually 7 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. , is particularly preferably 8 or less.
Specific examples of aralkyl groups include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group, etc. Among these, phenylmethyl group, phenylethyl group A phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

Examples of substituents that the alkyl group, aralkyl group, or aryl group may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group.

Among these, from the viewpoint of developability, R ¹¹ is preferably an alkyl group, more preferably a butyl group.

In the dispersant (b), the content of the repeating unit represented by the general formula (I) is 50 mol% or more, preferably 55 mol% or more, more preferably 60 mol% or more, and 65 mol% or more. is more preferably 70 mol% or more, particularly preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less. When the content is equal to or more than the lower limit, electrical reliability tends to be improved, and when the content is equal to or less than the upper limit, the dispersibility tends to be improved.

When the dispersant (b) contains a repeating unit represented by the general formula (II), its content is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and 10 mol% or more. is more preferably 15 mol% or more, particularly preferably 45 mol% or less, more preferably 40 mol% or less, even more preferably 35 mol% or less, and particularly preferably 30 mol% or less. When the content is equal to or more than the lower limit, dispersion stability tends to improve, and when the content is equal to or less than the upper limit, storage stability, electrical reliability, and developability tend to improve.

When the dispersant (b) contains a repeating unit represented by the general formula (III), its content is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and 10 mol% or more. It is more preferably 15 mol% or more, particularly preferably 100 mol% or less, more preferably 45 mol% or less, even more preferably 40 mol% or less, and particularly preferably 35 mol% or less. When the content is equal to or more than the lower limit, dispersion stability tends to be improved, and when the content is equal to or less than the upper limit, electrical reliability and developability tend to be improved.

When the dispersant (b) contains a repeating unit represented by the general formula (IV), its content is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and 8 mol% or more. is more preferably 10 mol% or more, particularly preferably 30 mol% or less, more preferably 25 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less. When the amount is equal to or more than the lower limit, dispersion stability tends to be improved, and when it is less than the upper limit, developability tends to be improved.

The dispersant (b) is not particularly limited as long as it has a repeating unit represented by the general formula (I), but from the viewpoint of further improving dispersibility, it may be a repeating unit represented by the general formula (I). The block copolymer is preferably a block copolymer containing a B block having a repeating unit and an A block having other repeating units. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. From the viewpoint of dispersibility, the A block preferably contains a repeating unit represented by the general formula (II) and/or a repeating unit represented by the general formula (III). ) is more preferably included. In addition, from the viewpoint of heat resistance, the B block contains a repeating unit represented by the above general formula (I), and a repeating unit represented by the above general formula (I) and the above general formula (IV). Preferably, the repeating unit represented is included.

Further, from the viewpoint of dispersibility, the acid value of the dispersant (b) is preferably lower, and particularly preferably 0 mgKOH/g. Here, the acid value represents the number of mg of KOH required to neutralize 1 g of solid content of the dispersant.

On the other hand, the amine value of the dispersant (b) is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, and even more preferably 80 mgKOH/g or more. It is particularly preferably at least 100 mgKOH/g, more preferably at most 170 mgKOH/g, more preferably at most 150 mgKOH/g, even more preferably at most 140 mgKOH/g, and even more preferably at most 130 mgKOH/g. Particularly preferred. When the amount is equal to or more than the lower limit, the dispersibility tends to be improved, and when the amount is less than the upper limit, the developability tends to be improved. The amine value herein refers to the amine value in terms of effective solid content, and is a value expressed by the base amount and the equivalent mass of KOH per 1 g of solid content of the dispersant.

The molecular weight of the dispersant (b) is not particularly limited, but is preferably 1,000 or more, more preferably 4,000 or more in terms of polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography). It is more preferably 6,000 or more, more preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 10,000 or less. When the amount is equal to or more than the lower limit, dispersion stability tends to be improved, and when it is equal to or less than the upper limit, deterioration in developability tends to be suppressed.

The dispersant (b) can be produced by a known method, but in the case of a block copolymer, it can be produced, for example, by living polymerization of monomers into which each of the above repeating units is introduced. . Examples of the living polymerization method include JP-A No. 9-62002, JP-A No. 2002-31713, and P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Miguchi, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R. A known method described in Hertler et al., Macromolecules, 20, 1473 (1987) and the like can be employed.

In the present invention, other dispersants can be used together with the dispersant (b). Other dispersants include, for example, Disperbyk (registered trademark) -161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2000, Disperbyk k-2001, BYK - LPN6919, BYK-LPN21116 (manufactured by BYK), Solsperse (registered trademark. The same applies hereinafter) 24000, Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), Ajisper (registered trademark. The same applies hereinafter) PB821 , Ajisper PB822, Ajisper PB823, Ajisper PB824, and Ajisper PB827 (manufactured by Ajinomoto Fine-Techno Co., Ltd.).

In the colored resin composition of the present invention, the content ratio of the dispersant (B) is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total solid content of the colored resin composition. It is more preferably 4% by mass or more, particularly preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less. When the content is equal to or more than the lower limit, the dispersibility tends to be improved, and when the content is equal to or less than the upper limit, the reliability tends to be improved.

In the colored resin composition of the present invention, the content of the dispersant (b) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more based on the total solid content of the colored resin composition. It is preferably at least 2% by mass, more preferably at least 3% by mass, preferably at most 15% by mass, more preferably at most 12% by mass, even more preferably at most 10% by mass, particularly preferably at most 8% by mass. . When the value is equal to or greater than the lower limit, heat resistance tends to improve, and when the value is equal to or less than the upper limit, reliability tends to improve.

The content of the dispersant (b) in the dispersant (B) of the colored resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. , is particularly preferably 50% by mass or more, preferably 100% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less. When the value is equal to or more than the lower limit, reliability tends to improve, and when the value is equal to or less than the upper limit, the dispersibility tends to improve.

[1-3] (C) Solvent (C) Solvent dissolves or disperses the colorant, dispersant, binder resin, photopolymerizable monomer, photoinitiator, and other components in the colored resin composition of the present invention. It has the function of adjusting the viscosity.
The solvent (C) may be any solvent as long as it can dissolve or disperse each component.

Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, Propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl - Glycol monoalkyl ethers such as 3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy methyl pentanone Ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Etherketones such as methoxymethylpentanone;
Examples include nitriles such as acetonitrile and benzonitrile.

Commercially available solvents applicable to the above include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2. Solvesso #150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names). These solvents may be used alone or in combination of two or more.

When forming pixels of a color filter by photolithography, select a solvent with a boiling point in the range of 100 to 200°C (under pressure 1013.25 [hPa] conditions; hereinafter, all boiling points are the same). is preferable. More preferably, it has a boiling point of 120 to 170°C.
Among the above-mentioned solvents, glycol alkyl ether acetates are preferred from the standpoint of having a good balance in coating properties, surface tension, etc., and relatively high solubility of the constituent components in the composition.

Furthermore, glycol alkyl ether acetates may be used alone, or may be used in combination with other solvents. Particularly preferred solvents used in combination are glycol monoalkyl ethers. Among these, propylene glycol monomethyl ether is particularly preferred from the viewpoint of solubility of the constituent components in the composition. In addition, glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, which tends to reduce the storage stability such as increasing the viscosity of the colored resin composition obtained later. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

Further, it is also preferable to use a solvent having a boiling point of 150° C. or higher. The combined use of such a high boiling point solvent makes it difficult for the colored resin composition to dry, but it has the effect of making it difficult for the mutual relationship of the pigment dispersion liquid to be destroyed due to rapid drying. The content of the high boiling point solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, particularly preferably 5% by mass to 30% by mass, based on the solvent (B). By setting the value above the lower limit, for example, there is a tendency to prevent coloring material components from precipitating and solidifying at the tip of the slit nozzle and causing foreign body defects, and by setting the value below the upper limit, the composition This tends to make it easier to avoid problems such as slow drying speed and poor tact in the vacuum drying process and pin marks during pre-baking.
Note that the solvent with a boiling point of 150°C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, there is no need to separately contain a solvent with a boiling point of 150°C or higher.
Preferred high boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate, among the various solvents mentioned above. Examples include acetate and triacetin.

When forming pixels of a color filter by an inkjet method, suitable solvents have a boiling point of usually 130°C or more and 300°C or less, preferably 150°C or more and 280°C or less. By setting it to the lower limit or more, the uniformity of the resulting coating film tends to be better, and by setting it to the upper limit or less, it tends to easily reduce the amount of residual solvent during firing.
Further, from the viewpoint of uniformity of the resulting coating film, the vapor pressure of the solvent used is usually 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less.

When manufacturing color filters using the inkjet method, the ink emitted from the nozzle is very fine, ranging from several to several tens of pL, so the solvent evaporates and the ink condenses before it lands around the nozzle opening or within the pixel bank.・Tends to dry out. In order to avoid this, it is preferable that the boiling point of the solvent is high, and specifically, it is preferable to include a solvent with a boiling point of 180° C. or higher. More preferably, the solvent contains a boiling point of 200°C or higher, particularly preferably 220°C or higher. Further, the high boiling point solvent having a boiling point of 180° C. or higher is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more of all the solvents contained in the colored resin composition. By setting it to the above lower limit or more, the effect of preventing evaporation of the solvent from the droplets tends to be sufficiently exhibited.

Preferred high boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate, among the various solvents mentioned above. Examples include acetate and triacetin.
Furthermore, in order to adjust the viscosity of the colored resin composition and the solubility of solid content, it is effective to partially contain a solvent whose boiling point is lower than 180°C. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, etc. are preferable. Among these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate and the like are particularly preferred.

On the other hand, if the solvent contains alcohol, the ejection stability in the inkjet method may deteriorate. Therefore, the alcohol content in the total solvent is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

The content of the solvent in the colored resin composition of the present invention is not particularly limited, but is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. When the amount is below the upper limit, it tends to be easier to form a coating film. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more, taking into consideration the viscosity suitable for coating.

[1-4] (D) Binder resin The colored resin composition of the present invention contains (D) a binder resin. (D) By containing the binder resin, it is possible to achieve both film curability by photopolymerization and solubility by developer.
The binder resin (D) in the colored resin composition of the present invention is an alkali-soluble resin (d) having a repeating unit represented by the following general formula (i) (hereinafter sometimes referred to as "alkali-soluble resin (d)"). ).

In formula (i), R ^d1 represents a hydrogen atom or a methyl group.
R ^d2 represents a trivalent hydrocarbon group which may have a substituent.
R ^d3 represents a hydrogen atom or a methyl group.
R ^d4 represents a divalent hydrocarbon group which may have a substituent.

Although the colored resin composition of the present invention contains the alkali-soluble resin (d), the carboxyl group in the repeating unit represented by the general formula (i) is sufficiently separated from the main chain. Because the carboxyl group is bonded to a highly fluid side chain in this way, intramolecular association due to hydrogen bonding between carboxyl groups is less likely to occur, and the ethylenic double bond is more likely to face the outside of the molecule, resulting in hardening. It is thought that this increases the voltage retention rate. Further, it is considered that the contact efficiency between the carboxyl group and the developer is high, the dissolution time is shortened, and a pattern with good linearity is easily obtained.

(R ^d2 )
In formula (i), R ^d2 represents a trivalent hydrocarbon group which may have a substituent. Examples of trivalent hydrocarbons include trivalent aliphatic hydrocarbon groups.
Examples of trivalent aliphatic hydrocarbon groups include linear ones, branched ones, cyclic ones, and combinations thereof.
The number of carbon atoms in the trivalent aliphatic hydrocarbon group is not particularly limited, but usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 15 or less, preferably 10 or less, more preferably 8 or less, 5 The following are more preferred. When the amount is equal to or more than the lower limit, the solvent affinity tends to be improved, and when the amount is less than the upper limit, the developability tends to be improved.
Specific examples of the trivalent aliphatic hydrocarbon group include the following.

Examples of substituents that the trivalent hydrocarbon group may have include a hydroxy group, a carboxy group, an amino group, a nitro group, and a sulfo group.

(R ^d4 )
In formula (i), R ^d4 represents a divalent hydrocarbon group which may have a substituent. Examples of divalent hydrocarbons include divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon ring groups.
Examples of the divalent aliphatic hydrocarbon group include linear ones, branched ones, cyclic ones, and combinations thereof.
The number of carbon atoms in the divalent aliphatic hydrocarbon group is not particularly limited, but usually 1 or more, preferably 2 or more, more preferably 3 or more, particularly preferably 4 or more, and usually 15 or less, preferably 10 or less, 8 The following is more preferable, and 5 or less is even more preferable. When the amount is equal to or more than the lower limit value, developability tends to be improved, and when it is less than the upper limit value, the linearity tends to be improved.
Specific examples of the divalent aliphatic hydrocarbon group include ethylene group, propylene group, isopropylene group, n-butylene group, tert-butylene group, and cyclohexenediyl group. Among these, cyclohexenediyl group is preferred from the viewpoint of developability.

On the other hand, the number of carbon atoms in the divalent aromatic hydrocarbon ring group is not particularly limited, but is usually 6 or more, preferably 7 or more, more preferably 8 or more, and preferably 30 or less, and 20 or less. More preferably, it is 15 or less. When the amount is equal to or more than the lower limit value, developability tends to be improved, and when it is less than the upper limit value, the linearity tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring. Examples of the aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, which have two free valences, Examples include groups such as an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

Examples of substituents that the divalent hydrocarbon group may have include a hydroxy group, a carboxy group, an amino group, a nitro group, and a sulfo group.

The alkali-soluble resin (d) has a repeating unit represented by the general formula (i), but may further contain other repeating units.
As other repeating units, repeating units represented by the following general formula (ii) are preferred from the viewpoint of curability and reliability.

In formula (ii), R ^d5 represents a hydrogen atom or a methyl group.
R ^d6 represents a trivalent hydrocarbon group which may have a substituent.
R ^d7 represents a hydrogen atom or a methyl group.

As the trivalent hydrocarbon group which may have a substituent for R ^d6 , those listed for R ^d2 can be preferably applied.

Moreover, as other repeating units, repeating units represented by the following general formula (iii) are preferable from the viewpoint of linearity.

In formula (iii), R ^d8 represents a hydrogen atom or a methyl group.
R ^d9 represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.

(R ^d9 )
In formula (iii), R ^d9 represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.
Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon ring group.

Examples of monovalent aliphatic hydrocarbon groups include linear ones, branched ones, cyclic ones, and combinations thereof.
The number of carbon atoms in the monovalent aliphatic hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, even more preferably 5 or more, particularly preferably 7 or more, and usually 20 or less, 18 or less. is preferable, 15 or less is more preferable, and 12 or less is even more preferable. When the amount is equal to or more than the lower limit, linearity tends to be improved, and when it is equal to or less than the upper limit, development solubility tends to be improved.
Specific examples of monovalent aliphatic hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, and cyclohexyl group. , benzyl group, tricyclodecanyl group, etc. Among these, tricyclodecanyl group is preferred from the viewpoint of linearity.

The number of carbon atoms in the monovalent aromatic hydrocarbon group is not particularly limited, but is usually 6 or more, preferably 7 or more, more preferably 8 or more, and preferably 30 or less, more preferably 20 or less, 15 The following are more preferred. When the amount is equal to or more than the lower limit, linearity tends to be improved, and when the amount is equal to or less than the upper limit, solubility tends to be improved.

The aromatic hydrocarbon ring in the monovalent aromatic hydrocarbon ring group may be a single ring or a fused ring. Examples of aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, each having one free valence; Examples include groups such as an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

Examples of substituents that the monovalent hydrocarbon group may have include a hydroxy group, a carboxy group, an amino group, a nitro group, and a sulfo group.

Moreover, as other repeating units, repeating units represented by the following general formula (iv) are preferable from the viewpoint of controlling dissolution time.

In formula (iv), R ^d10 represents a hydrogen atom or a methyl group.

The content ratio of the repeating unit represented by the general formula (i) contained in the alkali-soluble resin (d) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, and 30 mol% or more. is more preferably 35 mol% or more, particularly preferably 90 mol% or less, more preferably 70 mol% or less, even more preferably 50 mol% or less, and particularly preferably 45 mol% or less. When the content is equal to or more than the lower limit, the curability and solubility tend to improve, and when the content is equal to or less than the upper limit, the linearity tends to be improved.

When the alkali-soluble resin (d) contains a repeating unit represented by the general formula (ii), its content is not particularly limited, but is preferably 0.1 mol% or more, more preferably 1 mol% or more, and 5 More preferably mol% or more, even more preferably 10 mol% or more, particularly preferably 15 mol% or more, and preferably 90 mol% or less, more preferably 70 mol% or less, even more preferably 50 mol% or less, 30 Particularly preferred is mol% or less. When the amount is equal to or more than the lower limit, the curability tends to be improved, and when the amount is less than the upper limit, the linearity and solubility tend to be improved.

When the alkali-soluble resin (d) contains a repeating unit represented by the general formula (iii), its content is not particularly limited, but is preferably 0.1 mol% or more, more preferably 1 mol% or more, and 5 It is more preferably mol% or more, even more preferably 10 mol% or more, particularly preferably 20 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and 40 mol% or more. Particularly preferred is mol% or less. When the amount is equal to or more than the lower limit, linearity tends to be improved, and when the amount is equal to or less than the upper limit, solubility tends to be improved.

When the alkali-soluble resin (d) contains a partial structure represented by the general formula (iv), its content is not particularly limited, but is preferably 0.01 mol% or more, more preferably 0.1 mol% or more. , more preferably 1 mol% or more, particularly preferably 5 mol% or more, preferably 30 mol% or less, more preferably 25 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less. When the amount is equal to or more than the lower limit, linearity tends to be improved, and when the amount is equal to or less than the upper limit, solubility tends to be improved.

The method for producing the alkali-soluble resin (d) is not particularly limited, but for example, for a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, the epoxy group that the copolymer has It can be obtained by adding an unsaturated monobasic acid to at least a portion of the polybasic acid, and adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction. Specifically, the manufacturing method described in JP-A No. 2009-053652 can be adopted.

The binder resin (D) in the colored resin composition of the present invention contains the alkali-soluble resin (d), but may further contain other binder resins (d').
Other binder resins (d') can be used without particular limitation as long as they exhibit the function as a binder resin, but are described in International Publication No. 2016/158668 [1-6 -2] Linear alkali-soluble resin containing a carboxyl group in the main chain, [1-6-3] A resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the carboxyl group-containing resin, [1 -6-4] (meth)acrylic resin, [1-6-5] epoxy (meth)acrylate resin having a carboxyl group, and the like.

In the colored resin composition of the present invention, the content ratio of the binder resin (D) is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, based on the total solid content of the colored resin composition. More preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more, most preferably 25% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, More preferably, it is 30% by mass or less. When the amount is equal to or more than the lower limit, solubility tends to be improved, and when the amount is less than the upper limit, linearity tends to be improved.

In the colored resin composition of the present invention, the content ratio of the alkali-soluble resin (d) is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, based on the total solid content of the colored resin composition. , more preferably 10% by mass or more, even more preferably 12% by mass or more, particularly preferably 14% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less. , is even more preferably 25% by mass or less, particularly preferably 20% by mass or less. When the amount is equal to or more than the lower limit, solubility tends to be improved, and when the amount is less than the upper limit, linearity tends to be improved.

Further, the content ratio of the alkali-soluble resin (d) in the binder resin (D) of the colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 10% by mass or more, and 30% by mass or more. is more preferably 40% by mass or more, even more preferably 50% by mass or more, and usually 100% by mass or less. There is a tendency for linearity to be improved by setting the value to be equal to or more than the lower limit value.

[1-5] (E) Photopolymerizable monomer The colored resin composition of the present invention contains (E) a photopolymerizable monomer. By containing a photopolymerizable monomer, a strong film tends to be obtained by photopolymerization.
The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylenic compound") is preferable. The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and hardening due to the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the monomer in the present invention means a concept opposite to a so-called polymer substance, and means a concept that includes dimers, trimers, and oligomers in addition to monomers in a narrow sense.
In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds that the polyfunctional ethylenic monomer has is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably The number is 8 or less, more preferably 7 or less. Setting the value above the lower limit value tends to result in high sensitivity, and setting the value below the upper limit value tends to improve the solubility in the solvent.

Examples of ethylenic compounds include unsaturated carboxylic acids, esters of these with monohydroxy compounds, esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids, and unsaturated carboxylic acids. Esters, polyisocyanate compounds, and (meth)acryloyl-containing hydroxy compounds obtained by esterification reactions between saturated carboxylic acids, polyhydric carboxylic acids, and polyhydric hydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. Examples include ethylenic compounds having a urethane skeleton that are reacted with .

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid part of these acrylates can be replaced with methacrylic acid ester, itaconic acid ester, which is replaced with itaconic acid part, crotonic acid ester, which is replaced with crotonic acid part, or maleic acid, which is replaced with maleic acid part. Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polyvalent carboxylic acid, and a polyvalent hydroxy compound is not necessarily a single substance, but may be a mixture. Typical examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol. and glycerin condensates.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate, isophorone diisocyanate, etc. Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, 3- Examples include reactants with (meth)acryloyl group-containing hydroxy compounds such as hydroxy(1,1,1-trimethacryloyloxymethyl)propane.

Other useful ethylenic compounds for use in the present invention include, for example, acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.
Further, the ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. Polyfunctional monomers are preferred, and particularly preferred are those in which the aliphatic polyhydroxy compound in the ester is pentaerythritol and/or dipentaerythritol.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more types may be used in combination. Further, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as monomers.
The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. Setting the value above the lower limit tends to improve development and dissolution characteristics, and setting the value below the upper limit allows for better manufacturing and handling, resulting in improved photopolymerization performance, pixel surface smoothness, etc. It tends to improve curing properties. Therefore, when using two or more types of polyfunctional monomers with different acid groups, or when using polyfunctional monomers that do not have acid groups together, the acid groups as a whole of the polyfunctional monomers should be adjusted so that they fall within the above range. is preferred.

In the present invention, more preferable polyfunctional monomers having acid groups mainly include dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate succinate commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture of ingredients. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Furthermore, those described in paragraphs [0056] and [0057] of JP-A-2013-140346 can also be used.

Further, in the present invention, from the viewpoint of improving the chemical resistance of the pixel and the linearity of the edge of the pixel, it is preferable to use the polymerizable monomer described in JP-A-2013-195971. From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the development time, it is preferable to use the polymerizable monomer described in JP-A-2013-195974.

The content of the photopolymerizable monomer in the colored resin composition of the present invention is not particularly limited, but is usually 0% by mass or more, preferably 5% by mass or more, more preferably 5% by mass or more, based on the total solid content of the colored resin composition of the present invention. is 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass. % or less, particularly preferably 30% by mass or less. Further, the ratio to 100 parts by mass of the colorant (A) is usually 0 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, even more preferably 40 parts by mass. Above, it is particularly preferably 60 parts by mass or more, and usually 200 parts by mass or less, preferably 100 parts by mass or less, and more preferably 80 parts by mass or less. Setting the amount above the lower limit value tends to improve the curability, and setting the amount below the upper limit value tends to improve the solubility.

[1-6] (F) Photopolymerization initiator The colored resin composition of the present invention contains (F) a photopolymerization initiator. (F) By containing a photopolymerization initiator, film curability can be obtained by photopolymerization.
(F) The photopolymerization initiator can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and an optional additive such as a sensitizing dye. The photopolymerization initiation system is a component that has the function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate polymerization-active radicals.

Examples of photopolymerization initiators include metallocene compounds containing titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbiimidazole as described in JP-A-10-39503. derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α- Examples include aminoalkylphenone compounds and oxime ester initiators described in JP-A No. 2000-80068.

Specific examples of photopolymerization initiators that can be used in the present invention are listed below.
2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4 Halomethylated triazine derivatives such as -ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine;

2-Trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxa Diazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3, Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-( 2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5- Imidazole derivatives such as diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p -isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 1,1,1 -Acetophenone derivatives such as trichloromethyl-(p-butylphenyl)ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, Dicyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, dicyclopentadienyl-Ti-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3 , 4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dicyclopentadienyl-Ti-2,6-difluoro- Titanocene derivatives such as 3-(pyr-1-yl)-phenyl-1-yl;

2-Methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone α-Aminoalkylphenone compounds such as;
1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl]-1-(O-acetyloxime) and other oxime ester compounds.

Among these, oxime ester compounds are preferred from the viewpoint of sensitivity and surface properties.
Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, so they are highly sensitive even in small amounts and are stable against thermal reactions. Therefore, it is possible to design a highly sensitive photosensitive resin composition in a small amount. In particular, from the viewpoint of light absorption to the i-line (365 nm) of the exposure light source, oxime ester compounds having a carbazole ring which may have a substituent are preferred.

Examples of oxime ester compounds include compounds represented by the following general formula (I-1).

In the above formula (I-1), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^21b represents any substituent containing an aromatic ring or a heteroaromatic ring.
R ^22a represents an alkanoyl group which may have a substituent or an aryloyl group which may have a substituent.

The number of carbon atoms in the alkyl group in R ^21a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity to exposure, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably It is 10 or less, more preferably 5 or less. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, cyclopentylethyl group, propyl group, and the like.
Substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl or N-acetyl-N-acetoxyamino group, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ^21a include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, even more preferably 12 or less, and particularly preferably 8 or less.

Specific examples of the aromatic ring group include phenyl group, naphthyl group, pyridyl group, furyl group, etc. Among these, from the viewpoint of developability, phenyl group or naphthyl group is preferable, and phenyl group is more preferable.
Examples of substituents that the aromatic ring group may have include a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a carboxyl group, a halogen atom, and an amino group. , an amide group, an alkyl group, etc., and from the viewpoint of developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. Furthermore, examples of the substituents in the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group, and a halogen atom.
Among these, from the viewpoint of developability, R ^21a is preferably an alkyl group that may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group. .

In addition, R ^21b is an arbitrary substituent containing an aromatic ring or a heteroaromatic ring, but from the viewpoint of solubility in solvents and sensitivity to exposure, R 21b is a carbazolyl group that may have a substituent, or a carbazolyl group that may have a substituent. Preferred examples include a thioxantonyl group which may have a substituent, a diphenyl sulfide group which may have a substituent, and a group in which these groups and a carbonyl group are connected. Among these, from the viewpoint of light absorption to the i-line (365 nm) of the exposure light source, a carbazolyl group that may have a substituent or a carbazolyl group that may have a substituent and a carbonyl group are used. Groups are preferred.

Further, the number of carbon atoms in the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably It is 10 or less, more preferably 5 or less. Specific examples of the alkanoyl group include an acetyl group, an ethyl group, a propanoyl group, a butanoyl group, and the like.
Examples of substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, etc. From the viewpoint of ease of synthesis, it should be unsubstituted. is preferred.

Further, the number of carbon atoms in the aryloyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Specific examples of the aryloyl group include benzoyl group and naphthoyl group.
Examples of substituents that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, and from the viewpoint of ease of synthesis, it is preferably unsubstituted. .

Among the compounds represented by the general formula (I-1), from the viewpoint of light absorption to the i-line (365 nm) of the exposure light source, compounds represented by the following general formula (I-2) or (I-3) Examples include compounds.

In the above formula (I-2) or (I-3), R ^21a and R ^22a have the same meanings as in the above general formula (I-1).
R ^23a represents an alkyl group which may have a substituent.
R ^24a represents an alkyl group that may have a substituent, an aryloyl group that may have a substituent, a heteroaryloyl group that may have a substituent, or a nitro group.
The benzene ring constituting the carbazole ring may be further fused with an aromatic ring to form a polycyclic aromatic ring.

The number of carbon atoms in the alkyl group in ^R23a is not particularly limited, but from the viewpoint of solubility in solvents, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and Preferably it is 5 or less. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, and cyclohexyl group.
Examples of substituents that the alkyl group may have include a carbonyl group, carboxyl group, hydroxyl group, phenyl group, benzyl group, cyclohexyl group, or nitro group. It is preferable that

The number of carbon atoms in the aryloyl group in ^R23a is not particularly limited, but from the viewpoint of solubility in solvents, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, and more. It is preferably 10 or less, more preferably 9 or less. Specific examples of the aryloyl group include benzoyl group and naphthoyl group.
Examples of substituents that the aryloyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group.From the viewpoint of ease of synthesis, ethyl group It is preferable that

The number of carbon atoms in the heteroaryloyl group in R ^23a is not particularly limited, but from the viewpoint of solubility in solvents, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. , more preferably 10 or less, still more preferably 9 or less. Specific examples of the heteroaryl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group, a bromonaphthoyl group, and the like.
Examples of substituents that the heteroaryloyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group. Substitution is preferred.
Among these, R ^23a is preferably an alkyl group, more preferably an ethyl group, from the viewpoints of solubility in solvents and ease of synthesis.

The benzene ring constituting the carbazole ring may be further fused with an aromatic ring to form a polycyclic aromatic ring.

Commercial products of such oxime ester compounds include OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power Electronics Co., Ltd., and N-1919 manufactured by ADEKA. There are NCI-930, NCI-831, etc.

Specific examples of the oxime ester compound include the following compounds, but the present invention is not limited to these compounds.

These photopolymerization initiators may be used alone or in combination of two or more.

In the colored resin composition of the present invention, the content ratio of the photopolymerization initiator (F) is not particularly limited, but is preferably 0% by mass or more, and 0.3% by mass or more based on the total solid content of the colored resin composition. More preferably 0.4% by mass or more, further preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, 3% by mass or less. % or less is even more preferable, and 2 mass % or less is particularly preferable. When the amount is equal to or more than the lower limit, linearity tends to be improved, and when the amount is less than the upper limit, the solubility tends to be improved, and in particular, residues tend to be suppressed.

[1-7] Other solid contents The colored resin composition of the present invention may further contain solid contents other than the above-mentioned components, if necessary. Such components include dispersion aids, surfactants, and the like.

[1-7-1] Dispersion aid When the colored resin composition of the present invention contains a pigment, it may contain a pigment derivative or the like as a dispersion aid in order to improve the dispersibility of the pigment and improve the dispersion stability. Also good. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, and diketopyrrolot. Examples include derivatives such as pyrrole pigments and dioxazine pigments. Substituents for pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton, or alkyl groups, aryl groups, hetero Examples include those bonded via a ring group, preferably a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group, more preferably a sulfonic acid group. Furthermore, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions may be used. Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, Examples include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.

[1-7-2] Surfactant Various types of surfactants can be used, such as anionic, cationic, nonionic, and amphoteric surfactants, but they may have an adverse effect on various properties. It is preferable to use a nonionic surfactant because of its low . The content of the surfactant is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total solid content of the colored resin composition. .1% by weight or more, and usually 10% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less, and most preferably 0.3% by weight or less.

[2] Preparation of colored resin composition Next, a method for preparing the colored resin composition (hereinafter sometimes referred to as resist) according to the present invention will be explained.

When preparing a colorant containing a pigment, first, predetermined amounts of the pigment, solvent, and dispersant are weighed, and in a dispersion treatment step, the pigment containing the pigment is dispersed to prepare a pigment dispersion. In this dispersion treatment step, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. can be used. By performing this dispersion treatment, the coloring material is made into fine particles, so that the coating properties of the colored resin composition are improved, and the transmittance of pixels on the color filter substrate of the product is improved.

When dispersing pigments, as mentioned above, it is preferable to use a dispersion aid or a dispersion resin as appropriate.
When performing the dispersion treatment using a sand grinder, it is preferable to use glass beads or zirconia beads with a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set in a range of 0°C or higher, preferably room temperature or higher, and usually 100°C or lower, preferably 80°C or lower. Note that the appropriate dispersion time differs depending on the composition of the pigment dispersion liquid, the size of the sand grinder device, etc., so it is necessary to adjust the dispersion time appropriately.

A solvent, a binder resin, a photopolymerization initiator, and optionally components other than the above are mixed into the pigment dispersion obtained by the above dispersion treatment to form a uniform dispersion. In addition, in each of the dispersion treatment process and the mixing process, fine dust may be mixed in, so it is preferable to filter the obtained pigment dispersion liquid using a filter or the like.

[3] Manufacture of color filter substrate Next, the color filter according to the present invention will be explained.
The color filter according to the present invention has pixels formed using the above-mentioned colored resin composition.

[3-1] Transparent substrate (support)
The material for the transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate strength. Materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly(meth)acrylics. Examples include thermosetting resin sheets such as resins, various types of glasses, and the like. Among these, glass or heat-resistant resin is preferred from the viewpoint of heat resistance.

Transparent substrates and black matrix forming substrates are treated with corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, etc. as necessary to improve surface properties such as adhesion. may be done. The thickness of the transparent substrate is usually in the range of 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. Further, when performing a thin film formation treatment of various resins, the film thickness is usually in the range of 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less.

[3-2] Black Matrix The color filter according to the present invention can be manufactured by providing a black matrix on the above-mentioned transparent substrate and further forming usually red, green, and blue pixel images. The colored resin composition is preferably used as a coating liquid for forming green pixels (resist pattern) among red, green, and blue pixels (hereinafter sometimes abbreviated as "green resist"). Using the green resist, coating, heating drying, image exposure, A pixel image is formed by performing development and thermosetting processes.

The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a colored resin composition for black matrix. As the light-shielding metal material, metal chromium, chromium compounds such as chromium oxide and chromium nitride, nickel and tungsten alloys, etc. are used, and a plurality of layers of these may be used.
These metal light-shielding films are generally formed by a sputtering method, and after forming a desired film pattern with a positive photoresist, chromium is treated with ceric ammonium nitrate, perchloric acid, and/or nitric acid. For other materials, a black matrix is formed by removing the positive photoresist with a special remover. be able to.

In this case, first, a thin film of these metals or metal/metal oxides is formed on a transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of a colored resin composition on this thin film, the coating film is exposed and developed using a photomask having a repeating pattern such as a stripe, mosaic, or triangle to form a resist image. Thereafter, this coating film can be subjected to an etching process to form a black matrix.

When using a photosensitive colored resin composition for a black matrix, a colored resin composition containing a black colorant is used to form a black matrix. For example, one or more black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc., or red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes. A black matrix can be formed using a colored resin composition containing a mixed black coloring material in a manner similar to the method for forming red, green, and blue pixel images described below.

[3-3] Formation of Pixel The method for forming a pixel varies depending on the type of colored resin composition used, but here it will be explained using an example in which a photopolymerizable composition is used as the colored resin composition.
A colored resin composition of one color among red, green, and blue is coated on a transparent substrate provided with a black matrix, and after drying, a photomask is placed on the coated film, and image exposure is performed through this photomask. A pixel image is formed by development and, if necessary, thermal curing or photocuring. By performing this operation for each of the three colored resin compositions of red, green, and blue, a color filter image can be formed.

The colored resin composition for a color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Among these, the die coating method significantly reduces the amount of coating liquid used, has no influence from the mist that adheres when using the spin coating method, and furthermore suppresses the generation of foreign matter. It is preferable from this point of view.

If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell formation process may become difficult. On the other hand, if the thickness of the coating film is too small, it becomes difficult to increase the pigment concentration and achieve the desired level. Color development may not be possible. The thickness of the coating film after drying is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm. The range is as follows.

[3-4] Drying of coating film The coating film after coating the colored resin composition on the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried. The pre-drying conditions can be appropriately selected depending on the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected depending on the type of solvent component, the performance of the dryer used, etc., but specifically, the drying temperature is usually 40°C or higher, preferably 50°C or higher, and usually 80°C or higher. ℃ or less, preferably 70°C or less, and the drying time is usually 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or less, preferably 3 minutes or less.

The temperature conditions for reheating drying are preferably higher than the preliminary drying temperature, specifically, usually 50°C or higher, preferably 70°C or higher, and usually 200°C or lower, preferably 160°C or lower, particularly preferably 130°C or higher. The range is below ℃. Although the drying time depends on the heating temperature, it is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes. The higher the drying temperature, the better the adhesiveness to the transparent substrate, but if the drying temperature is too high, the binder resin may decompose, inducing thermal polymerization, and causing poor development. In addition, as a drying process of this coating film, a reduced pressure drying method may be used in which drying is performed in a reduced pressure chamber without increasing the temperature.

[3-5] Exposure step Image exposure is performed by overlaying a negative matrix pattern on the coating film of the colored resin composition and irradiating it with an ultraviolet or visible light source through this mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer. The light source used for the image exposure described above is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc. Laser light sources include excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. An optical filter can also be used when irradiating light with a specific wavelength.

[3-6] Development process The color filter according to the present invention is produced by subjecting the coated film using the colored resin composition according to the present invention to imagewise exposure using the above-mentioned light source. By performing development using an aqueous solution containing an alkaline compound and an alkaline compound, an image can be formed and manufactured on a substrate. This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and potassium phosphate. , sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, and other inorganic alkaline compounds, mono-, di-, or triethanolamine, mono-, di-, or trimethylamine. , mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Examples include compounds. These alkaline compounds may be a mixture of two or more.

Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkyl betaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like. The organic solvent can be used alone or in combination with an aqueous solution.
There are no particular restrictions on the conditions for development, but the development temperature is usually 10°C or higher, especially 15°C or higher, and even 20°C or higher, and usually 50°C or lower, especially 45°C or lower, and even 40°C or lower. is preferred. The developing method can be any method such as an immersion developing method, a spray developing method, a brush developing method, an ultrasonic developing method, or the like.

[3-7] Thermosetting treatment After development, the color filter is subjected to a thermosetting treatment. The heat curing conditions at this time are usually selected within the range of 100°C or higher, preferably 150°C or higher, and usually 280°C or lower, preferably 250°C or lower, and the time is 5 minutes or more and 60 minutes or less. selected within the range. Through these series of steps, the formation of a single color patterning image is completed. This process is repeated sequentially to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the above order.

[3-8] Formation of transparent electrode The color filter according to the present invention can be used as a part of components of color displays, liquid crystal display devices, etc. by forming transparent electrodes such as ITO on the image as it is. However, in order to improve surface smoothness and durability, a top coat layer of polyamide, polyimide, or the like may be provided on the image, if necessary. Further, in some applications such as a planar alignment drive system (IPS mode), a transparent electrode may not be formed.

[4] Image display device (panel)
Next, an image display device of the present invention will be explained. The image display device of the present invention has the above-mentioned color filter. Hereinafter, a liquid crystal display device and an organic EL display device will be described in detail as image display devices.

[4-1] Liquid Crystal Display Device A method for manufacturing a liquid crystal display device according to the present invention will be described. The liquid crystal display device according to the present invention is usually produced by forming an alignment film on the color filter according to the present invention, and after scattering spacers on the alignment film, bonding it to a counter substrate to form a liquid crystal cell. Liquid crystal is injected into the prepared liquid crystal cell, and wires are connected to the counter electrode to complete the process. The alignment film is preferably a resin film such as polyimide. Gravure printing and/or flexographic printing are usually used to form the alignment film, and the thickness of the alignment film is several tens of nanometers. After the alignment film is hardened by thermal baking, the surface is treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface condition that allows adjustment of the tilt of the liquid crystal.

The size of the spacer is determined according to the gap between the spacer and the opposing substrate, and a size of 2 to 8 μm is usually suitable. It is also possible to form a photo spacer (PS) of a transparent resin film on the color filter substrate by photolithography and use this instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.

The bonding gap with the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After bonding to the counter substrate, parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, the pressure is reduced in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking the inside of the chamber. . The degree of reduced pressure within the liquid crystal cell is usually in the range of 1 x 10 ^-2 Pa or more, preferably 1 x 10 ^-3 or more, and usually 1 x 10 ^-7 Pa or less, preferably 1 x 10 ^-6 Pa or less. . Further, it is preferable to heat the liquid crystal cell when the pressure is reduced, and the heating temperature is usually in the range of 30°C or higher, preferably 50°C or higher, and usually 100°C or lower, preferably 90°C or lower.

Heating and holding during reduced pressure is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in liquid crystal. A liquid crystal display device (panel) is completed by curing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected and sealing it with a UV curing resin.
The type of liquid crystal is not particularly limited, and may be any conventionally known liquid crystal such as aromatic, aliphatic, polycyclic compounds, lyotropic liquid crystal, thermotropic liquid crystal, etc. Nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, and the like are known as thermotropic liquid crystals, but any of them may be used.

[4-2] Organic EL Display Device When creating an organic EL display device having the color filter of the present invention, for example, as shown in FIG. A multicolor organic EL device is manufactured by laminating an organic light emitting body 500 on the blue color filter formed with the organic protective layer 30 and the inorganic oxide film 40 interposed therebetween.

The organic light emitter 500 can be laminated by sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter. , a method of bonding an organic light emitter 500 formed on a separate substrate onto the inorganic oxide film 40, and the like. The organic EL element 100 manufactured in this manner is applicable to both passive drive type organic EL display devices and active drive type organic EL display devices.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

<Green pigment>
C. I. Pigment Green 58 (manufactured by DIC, FASTOGEN Green A350)
<Yellow pigment>
C. I. pigment yellow 138

<Dispersant A>
A methacrylic acid-based AB block copolymer consisting of an A block having a nitrogen atom-containing functional group and a B block having a solvent-philic group. The A block has a repeating unit represented by the following formula (a1), and the B block has a repeating unit represented by the following formula (b1). The content ratios of the repeating unit represented by the following formula (a1) and the repeating unit represented by the following formula (b1) in all repeating units are 13 mol% and 87 mol%, respectively. The amine value is 70 mgKOH/g, the acid value is 0 mgKOH/g, and the weight average molecular weight Mw is 8,000.

<Dispersant B>
A methacrylic acid-based AB block copolymer consisting of an A block having a nitrogen atom-containing functional group and a B block having a solvent-philic group. The A block has a repeating unit represented by the following formula (a1), and the B block has repeating units represented by the following formulas (b1) and (b2). The content ratio of the repeating unit represented by the following formula (a1), the repeating unit represented by the following formula (b1), and the repeating unit represented by the following formula (b2) in all repeating units is 25 mol%, respectively. , 64 mol%, and 11 mol%. The amine value is 120 mgKOH/g, the acid value is 0 mgKOH/g, and the weight average molecular weight Mw is 8,000.

<Dispersant C: Byk-Chemie dispersant “BYK-LPN6919”>
A methacrylic acid-based AB block copolymer consisting of an A block having a nitrogen atom-containing functional group and a B block having a solvent-philic group. The A block has a repeating unit represented by the following formula (a1), and the B block has repeating units represented by the following formulas (b1) to (b5). The content ratios of the repeating unit represented by the following formula (a1) and the repeating units represented by (b1) to (b5) in all repeating units are 33 mol%, 26 mol%, 15 mol%, and 13 mol%, respectively. mol %, 9 mol % and 4 mol %. The amine value is 120 mgKOH/g, the acid value is 0 mgKOH/g, and the weight average molecular weight is Mw 8000.

<Resin A>
Prepare a separable flask equipped with a cooling tube as a reaction tank, charge it with 400 parts by mass of propylene glycol monomethyl ether acetate, replace it with nitrogen, and heat it in an oil bath while stirring to raise the temperature of the reaction tank to 90°C. did.

Meanwhile, in a monomer tank, 30 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, t-butylperoxy-2-ethyl 5.2 parts by mass of hexanoate and 40 parts by mass of propylene glycol monomethyl ether acetate were charged, 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged into the chain transfer agent tank, and the temperature of the reaction tank was charged. After the temperature stabilized at 90°C, dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. Each dropwise addition took 135 minutes while maintaining the temperature at 90°C, and 60 minutes after the completion of the dropwise addition, the temperature was started to rise to 110°C.

After maintaining the temperature at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (v/v) was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were placed in a reaction tank, and the mixture was heated at 110°C. The mixture was allowed to react for 9 hours.
After cooling to room temperature, a resin A having a polystyrene equivalent weight average molecular weight Mw of 8000 and an acid value of 101 mgKOH/g as measured by GPC was obtained.

<Resin B>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing the mixture with nitrogen, and the temperature was raised to 120°C. 10 parts by mass of styrene, 85 parts by mass of glycidyl methacrylate, and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and the mixture was further stirred at 120° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, and 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 52 parts by mass of methacrylic acid, and the reaction was continued at 120° C. for 6 hours. Thereafter, 60 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 120°C for 3.5 hours. Resin B thus obtained had a polystyrene equivalent weight average molecular weight Mw of about 8000 and an acid value of 80 mgKOH/g as measured by GPC.

<Photopolymerizable monomer>
Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

<Photopolymerization initiator>
Oxime ester compound having the following chemical structure (methyl 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate)

<Chain transfer agent>
Pentaerythritol tetra (3-mercaptopropionate) (manufactured by Yodo Chemical Co., Ltd.)

<Surfactant>
Megafac F-559 (manufactured by DIC)

<Preparation of green pigment dispersions A to C>
13.8 parts by mass of green pigment was used, 2.3 parts by mass of various dispersants listed in Table 1 were used as dispersants, 3.9 parts by mass of resin A was used in terms of solid content, and propylene glycol was used as a solvent. A stainless steel container was filled with 80 parts by mass of monomethyl ether acetate (including the dispersant and the solvent contained in the resin) and 225 parts by mass of zirconia beads with a diameter of 0.5 mm, and dispersed in a paint shaker for 6 hours to obtain green pigment dispersion A. -C were prepared. For the obtained green pigment dispersions A to C, the viscosity at 23.0 ± 1.0 °C was measured using an E-type viscometer "RE-80L" manufactured by Toki Sangyo Co., Ltd. before and after storage at 35 °C for 3 days. was measured. The results are shown in Table 1.

<Preparation of yellow pigment dispersion>
11.9 parts by mass of yellow pigment, 4.1 parts by mass of dispersant C in terms of solid content, 6.0 parts by mass of resin A in terms of solid content, 78 parts by mass of propylene glycol monomethyl ether acetate (dispersion) as a solvent. 225 parts by mass of zirconia beads with a diameter of 0.5 mm (including the solvent contained in the pigment and the resin) were filled in a stainless steel container and dispersed for 6 hours in a paint shaker to prepare a yellow pigment dispersion.

<Preparation of colored resin composition>
(Examples 1 and 2 and Comparative Examples 1 to 3)
Each pigment dispersion and other components were mixed in the amounts listed in Table 2 to prepare each colored resin composition. Note that the blending amount of the binder resin in Table 2 is a solid content equivalent value, and the blending amount of the solvent also includes the amount of the solvent contained in the binder resin.

<Measurement of voltage holding rate>
Electrode substrate A has an ITO film formed on the entire surface of one side of a 2.5 cm square alkali-free glass substrate (“AN-100” manufactured by Asahi Glass Co., Ltd.), and a 2 mm wide takeout is placed in the center of one side of the 2.5 cm square glass substrate. An electrode substrate B was prepared on which a 1 cm square ITO film to which electrodes were connected was formed.

The colored resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were applied onto the electrode substrate A by spin coating, and dried on a hot plate at 80° C. for 3 minutes. The coating conditions were adjusted so that the thickness of the coating film after firing was 2.5 μm.
Next, the entire surface of the coating film was exposed to light at 60 mJ/cm ² using a 2 kW high-pressure mercury lamp. Then, spray development was performed for 50 seconds at a pressure of 0.1 MPa using a 0.04% by mass potassium hydroxide aqueous solution at 23°C. Next, a water spray treatment was performed for 10 seconds at a water pressure of 0.1 MPa, and then, baking was performed at 230° C. for 30 minutes in a hot air circulation furnace.

Next, after applying an epoxy resin sealant containing silica beads with a diameter of 5 μm to the outer circumference of the electrode substrate B using a dispenser, the surface coated with the colored resin composition of the electrode substrate A is They were placed facing each other so that they were offset by 3 mm, and heated in a hot air circulation oven at 180° C. for 2 hours while being crimped.

A liquid crystal ("MLC-6846-000" manufactured by Merck Japan) was injected into the empty cell obtained as above, and the periphery was sealed with a UV curable sealant to create a liquid crystal cell for measuring voltage holding ratio. completed.

Next, the liquid crystal cell was heated at 105° C. for 2.5 hours in a hot air circulating oven. Thereafter, a pulse voltage was applied between the electrode substrates A and B under the conditions of an applied voltage of 5 V and a pulse frequency of 60 Hz and 2 Hz, and the voltage retention rate was measured. Table 3 shows the measurement results of the voltage holding ratio of each colored resin composition.

<Evaluation of color characteristics>
Each of the colored resin compositions described above was applied onto a 50 mm square, 0.7 mm thick glass substrate ("AN-100" manufactured by Asahi Glass Co., Ltd.) using a spin coater, and then dried at 80° C. for 3 minutes. Note that the rotation speed was adjusted so that the film thickness after thermosetting treatment was 2.5 μm.
Next, the entire surface was exposed using a 2 kW high-pressure mercury lamp at an exposure amount of 60 mJ/cm ² . Thereafter, spray development was carried out with a 0.04 mass % potassium hydroxide aqueous solution at 23° C. at a pressure of 0.1 MPa for 50 seconds. Next, a spray washing treatment was performed at a pressure of 0.1 MPa for 10 seconds, and then a heat curing treatment was performed at a temperature of 230° C. for 30 minutes to prepare a coated substrate.
The transmission spectrum of the coated substrate thus obtained was measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. Table 4 shows the chromaticity (x, y) and luminance (Y) calculated using the C light source.

<Evaluation of dissolution time and linearity>
Each of the colored resin compositions described above was applied by spin coating onto a glass substrate on which chromium had been vapor-deposited, and prebaked for 3 minutes on a hot plate at 80°C. Regarding coating, the rotation speed was adjusted at a temperature of 230° C. so that the film thickness after thermosetting treatment for 30 minutes was 2.5 μm.
Next, using a 2kW high-pressure mercury lamp, it was exposed to light at 60mJ/ ^cm2 through a mask having a linear opening with a width of 50μm and a length of 3mm. Spray development was performed at a pressure of 0.25 MPa. The development time was twice the dissolution time of each colored resin composition measured in advance. Note that the time during which the colored resin composition in the unexposed area was completely dissolved in the developer and the substrate was exposed was defined as the dissolution time of the colored resin composition. After development, the substrate was rinsed with sufficient water and then dried with clean air.

The five linear patterns obtained were observed at 10 times magnification using an optical microscope, the number of scratches on the edges of the patterns was counted, and the results were evaluated based on the following criteria. The results of dissolution time and linearity are shown in Table 5.
○: Number of bets is 0-5 △: Number of bets is 6-10

From Table 3, it is clear that the colored resin composition of the present invention has a high voltage holding rate of liquid crystal.
In Examples 1 and 2, by including dispersant A or dispersant B having 50 mol% or more of the repeating unit represented by the general formula (I), the affinity with liquid crystal molecules is lowered, and the pigment This suppresses steric repulsion of the dispersant and promotes adsorption of adsorption groups in the dispersant to the pigment. For this reason, it is thought that the elution of free dispersant into the liquid crystal is suppressed, and the voltage holding rate of the liquid crystal, especially the voltage holding rate under low frequency conditions, is improved. In addition, since it contains resin B having a repeating unit represented by the general formula (i), and the carboxyl groups are bonded to side chains with high fluidity, intramolecular association due to hydrogen bonding between carboxyl groups is unlikely to occur. It is thought that ethylenic double bonds tend to face the outside of the molecule, resulting in higher curability and higher voltage holding ratio.

On the other hand, since Comparative Example 1 does not contain a dispersant having 50 mol% or more of repeating units represented by the general formula (I), there is a large amount of free dispersant, which is eluted into the liquid crystal to maintain voltage. It is thought that this is because the voltage holding rate, especially under low frequency conditions, is low.

In addition, Comparative Examples 2 and 3 do not contain a resin having a repeating unit represented by the general formula (i), but contain resin A having a repeating unit derived from (meth)acrylic acid. Carboxyl groups have low fluidity because they are located near the main chain, and intramolecular association due to hydrogen bonds between carboxyl groups is likely to occur, and ethylenic double bonds tend to face inside the molecule, resulting in low curability. It is thought that the voltage holding rate became low.

Moreover, from Table 4, the colored resin composition of the present invention has high brightness.
In Examples 1 and 2, thermosetting was achieved by including dispersant A or dispersant B having 50 mol% or more of the repeating unit represented by the general formula (I) with a small number of carbon atoms in the side chain and high heat resistance. It is thought that thermal decomposition due to treatment is less likely to occur, and coloring and brightness reduction due to thermal decomposition are suppressed. On the other hand, Comparative Example 1 does not contain a dispersant having 50 mol% or more of the repeating unit represented by the general formula (I), so it has low heat resistance, thermally decomposes during heat curing treatment, and brightness decreases due to coloring. It is thought that

Furthermore, from Table 5, the colored resin compositions of Examples 1 and 2 have a short dissolution time of 30 seconds or less, whereas the colored resin compositions of Comparative Examples 2 and 3 have a dissolution time of more than 40 seconds and are not suitable for manufacturing color filters. I understand. Furthermore, it was found that Examples 1 and 2 had fewer cross-cuts in the linear pattern than Comparative Examples 2 and 3, and patterns with good linearity were obtained.
Examples 1 and 2 contain, as a binder resin, resin B having a repeating unit represented by the general formula (i), which has a structure in which a carboxyl group is added to a highly fluid side chain. It is thought that the contact efficiency with the liquid is high and the dissolution time is short. On the other hand, Comparative Example 1 contains Resin A, which is a copolymer of (meth)acrylic acid and other components, as a binder resin, so that the contact efficiency between the carboxyl group derived from (meth)acrylic acid and the developer is increased. This is thought to be due to the long dissolution time.

100 Organic EL element 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode

Claims (6)

A colored resin composition containing (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, (E) a photopolymerizable monomer, and (F) a photoinitiator, The dispersant (B) includes a dispersant (b) having 60 mol% or more of repeating units represented by the following general formula (I),
The dispersant (b) contains a repeating unit represented by the following general formula (II),
In the dispersant (b), the content of repeating units represented by the following general formula (II) is 10 mol% or more and 30 mol% or less,
The amine value of the dispersant (b) is 70 mgKOH/g or more,
A colored resin characterized in that the binder resin (D) contains an alkali-soluble resin (d) having a repeating unit represented by the following general formula (i) and a repeating unit represented by the following general formula (iv). Composition.
(In formula (I), R ¹ represents a hydrogen atom or a methyl group. ^{R 2} represents an alkyl group having 3 or less carbon atoms.)
(In formula (II), R ³ represents a hydrogen atom or a methyl group. X represents a divalent linking group. R ⁴ and R ⁵ each independently have a hydrogen atom or a substituent; represents an alkyl group, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁴ and R ⁵ may be bonded to each other to form a cyclic structure. )
(In formula (i), R ^d1 represents a hydrogen atom or a methyl group.
R ^d2 represents a trivalent hydrocarbon group which may have a substituent.
R ^d3 represents a hydrogen atom or a methyl group.
R ^d4 represents a divalent hydrocarbon group which may have a substituent. )
(In formula (iv), R ^d10 represents a hydrogen atom or a methyl group.) The colored resin composition according to claim 1 , wherein the content of the repeating unit represented by the general formula (I) in the dispersant (b) is 64 mol% or more. The colored resin composition according to claim 1 or 2 , wherein in the general formula (I), R ² represents a methyl group. The colored resin composition according to any one of claims 1 to 3 , wherein the colorant (A) contains a halogenated zinc phthalocyanine pigment. A color filter comprising pixels made using the colored resin composition according to any one of claims 1 to 4 . An image display device comprising the color filter according to claim 5 .

Images