JP2009007560A - Colored curable resin composition, color filter, liquid crystal display, and organic el display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable resin composition (ink) achieving both of surface smoothness of a pixel and a wet spreading property in a pixel bank in production of a color filter by an ink-jet technique. <P>SOLUTION: This colored curable resin composition comprises at least a coloring material (a), a binder resin (b), an organic solvent (c) and a surfactant (g), wherein a solvent (c-1) having a boiling point of 180°C or higher (as measured under the pressure of 1013.25 [hPa]) makes up 80 wt.% or more of the total amount of the organic solvent (c), and a 0.02 wt.% solution of the surfactant (g) which is prepared with the solvent (c-1) has surface tension falling within a specified range and a contact angle on a glass substrate falling within a specified range. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored curable resin composition, a color filter, a liquid crystal display device, and an organic EL display. Specifically, in the production of a color filter, a colored curable resin composition having flatness and wettability of a coating film suitable for pixel formation by an inkjet method, and a color formed using this colored curable resin composition The present invention relates to a filter, a liquid crystal display device including the color filter, and an organic EL display.

In the color filter manufacturing technology, a pixel formation method by using a coloring material (ink) in a pixel bank, that is, a substantially rectangular recessed area surrounded by a black matrix, by an inkjet method has been put into practical use.
The basic quality required for the color filter is that the flatness of the coating film serving as a pixel is good, that is, there is no color unevenness due to unevenness and bias, and there are no coating film defects such as wrinkles and cracks. . In addition, in order to stabilize the manufacturing process and improve the yield, the ink droplets that land on the inside of the liquid-repellent bank have good wetting and spreading, that is, there is no color mixing between pixels, and the pixel bank It is important that the required amount of ink can be filled therein.

However, the mechanism of drying the fine droplets landed on the substrate by the ink jet method has not yet been fully theoretically elucidated. Therefore, the process conditions and ink composition for obtaining a dry coating film with good flatness without causing the coating film defects as described above have to be adjusted empirically and through trial and error.
Similarly, the mechanism of wetting and spreading of minute droplets that have landed on the substrate by the inkjet method has not yet been fully theoretically elucidated. That is, the wetting and spreading behavior of macro droplets of about 1 μL can be described almost accurately by macro liquid properties such as contact angle and viscosity, but the wetting and spreading behavior of micro droplets of several to several tens of pL by the inkjet method. Are not necessarily correlated with them. For this reason, when the fluidity of the ink is increased, the spreadability of the wettability is often in a trade-off relationship with the flatness of the pixel.

For example, Patent Document 1 discloses a method for preventing the unevenness of the colored layer by adding a surfactant to suppress the temperature change of the surface tension of the ink. However, since the surfactant described in the document significantly reduces the surface tension of the ink itself, there is a possibility that the ejection stability by ink jetting may be impaired. Furthermore, although it is difficult to predict with general common sense, the ink described in this document has a problem of reducing the wet-spreading property of the fine droplets landed by the ink jet method.
Japanese Patent Laid-Open No. 7-216276

An object of the present invention is to solve the above-described problems in the prior art, and in particular, when forming color filter pixels by the inkjet method, the flatness of the pixels, which has often been a trade-off relationship in the past. It is another object of the present invention to provide a colored curable resin composition (ink) satisfying both wet spreading properties.
Another object of the present invention is to provide a high-quality color filter formed using such a colored curable resin composition, and a liquid crystal display device and an organic EL display provided with the color filter.

As a result of diligent investigations to solve the above problems, the present inventors have unclear the detailed mechanism of action, but are colored and cured whose surface tension is moderately low and the interfacial tension with the substrate is not too high. It was found that both the flatness and wettability of the pixel are satisfied by using the conductive resin composition. By reducing the surface tension of the colored curable resin composition, the flatness of the pixels is improved. However, if the surface tension is too low, the ejection stability of the composition from the inkjet nozzle tends to be impaired. In addition, by not increasing the interfacial tension with the base material too high, wetting and spreading properties in the pixel bank can be improved.
It has been found that the use of a specific surfactant is effective for obtaining such a colored curable resin composition. Specifically, it has been found that when a dilute solution of a surfactant prepared under certain conditions has a contact angle and surface tension within a specific range, the use of the surfactant is effective.
In order to obtain such a colored curable resin composition, it is effective to contain a fluorosurfactant composed of a polyether polymer having a specific structure having a short pendant type fluorinated alkyl group. I found. It has been found that by using such a surfactant, wetting spreadability in the pixel bank and surface flatness of the resulting pixel can be improved without significantly reducing the surface tension of the composition. Reached.
Furthermore, it has been clarified that the effect of the present invention becomes even more remarkable when a dispersant containing a block copolymer having a specific structure is used in combination.
That is, the gist of the present invention is as follows.
[1] In a colored curable resin composition containing at least (a) a color material, (b) a binder resin, (c) an organic solvent, and (g) a surfactant,
(C) 80% by weight or more of the organic solvent is occupied by a solvent (c-1) having a boiling point of 180 ° C. or higher (a boiling point under a pressure of 101.25 [hPa]),
A colored curable resin characterized in that a 0.02% by weight solution of (g) surfactant prepared using the solvent (c-1) satisfies the following conditions (1) and (2): Composition.
(1) The contact angle with respect to the glass substrate is 10 ° or less. (2) The surface tension σ satisfies (σ ₀ −2) ≦ σ <σ ₀ with respect to the surface tension σ _{0 of} the solvent (c-1).
[2] The colored curable resin composition according to [1], wherein the surfactant (g) contains a compound represented by the following general formula (10).

(Wherein R ₁ represents an alkylene group having 2 to 6 carbon atoms, R ₂ represents an alkylene group having 2 to 3 carbon atoms, R ₃ represents a hydroxyl group or a hydrogen atom, and G represents 1 to 4 carbon atoms) Represents a fluorinated alkyl group, v, w and u each independently represent an integer of 0 to 2, x and t each independently represents 1 or 2, s represents an integer of 0 to 10, n represents 2 Represents an integer of ~ 100.
In addition, a plurality of molecules per molecule

May be the same or different groups. )
[3] The colored curable resin composition according to [2], wherein the compound represented by the general formula (10) is a compound represented by the following general formula (0).

(In the above formula, the substituent G represents a fluorinated alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 100.)
[4] In the above general formula (10) or general formula (0), the substituent G is a perfluoroalkyl group having 1 to 3 carbon atoms, and n is an integer of 5 to 30, The colored curable resin composition according to [3].
[5] The colored curable resin composition according to any one of [1] to [4], wherein the condition (2) is the following condition (3).
(3) The surface tension σ is 28 mN / m or more and less than 30 mN / m.
[6] The colored curable resin composition according to any one of [1] to [5], wherein in the condition (1), a contact angle with respect to the glass substrate is less than 5 °.
[7] In a colored curable resin composition containing at least (a) a color material, (b) a binder resin, (c) an organic solvent, and (g) a surfactant,
(C) 80% by weight or more of the organic solvent is occupied by a solvent (c-1) having a boiling point of 180 ° C. or higher (a boiling point under a pressure of 101.25 [hPa]),
(G) A colored curable resin composition, wherein the surfactant contains a compound represented by the following general formula (10).

(Wherein R ₁ represents an alkylene group having 2 to 6 carbon atoms, R ₂ represents an alkylene group having 2 to 3 carbon atoms, R ₃ represents a hydroxyl group or a hydrogen atom, and G represents 1 to 4 carbon atoms) Represents a fluorinated alkyl group, v, w and u each independently represent an integer of 0 to 2, x and t each independently represents 1 or 2, s represents an integer of 0 to 10, n represents 2 Represents an integer of ~ 100.
In addition, a plurality of molecules per molecule

May be the same or different groups. )
[8] The colored curable resin composition according to [7], wherein the compound represented by the general formula (10) is a compound represented by the following general formula (0).

(In the above formula, the substituent G represents a fluorinated alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 100.)
[9] In the above general formula (10) or general formula (0), the substituent G is a perfluoroalkyl group having 1 to 3 carbon atoms, and n is an integer of 5 to 30, The colored curable resin composition according to [8].
[10] The colored curable resin composition according to any one of [1] to [9], wherein the content of the surfactant (g) is 0.005 to 5% by weight based on the total solid content. .
[11] The colored curable resin composition according to any one of [1] to [10], wherein the colorant contains a pigment.
[12] The colored curable resin composition according to [11], further including (e) a dispersant. [13] An AB block copolymer and / or a B-A-B block in which the dispersant (e) comprises an A block having an amino group in the side chain and a B block having no amino group in the side chain. The colored curable resin composition according to the above [12], which contains a copolymer and has an amine value of 10 mgK0H / g (in terms of effective solid content) or more.
[14] Solvent (c-1) having a boiling point of 180 ° C. or higher (boiling point under pressure of 101.25 [hPa]) is diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether The colored curable resin composition according to any one of [1] to [13], which is at least one selected from acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin. object.
[15] Color curing according to the above [14], wherein the solvent (c-1) having a boiling point of 180 ° C. or higher (boiling point under a pressure of 101.25 [hPa]) is diethylene glycol mono-n-butyl ether acetate. Resin composition.
[16] (c) The colored curable resin composition according to any one of [1] to [15], wherein the alcohol content is 20% by weight or less based on the total amount of the organic solvent.
[17] The colored curable resin composition according to any one of [1] to [16], wherein a contact angle with respect to the glass substrate is less than 5 °.
[18] A colored curable resin composition for inkjet color filters, comprising the colored curable resin composition according to any one of [1] to [17].
[19] A color filter formed using the colored curable resin composition according to any one of [1] to [18].
[20] A liquid crystal display device comprising the color filter according to [19].
[21] An organic EL display comprising the color filter according to [19].

  According to the present invention, when forming a pixel of a color filter in an inkjet method, a colored curable resin composition having both excellent pixel flatness and wet spreadability can be provided, so that the color filter can be provided with high quality and high yield. The liquid crystal display device can be manufactured at low cost in large quantities.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention does not exceed the gist thereof. It is not limited to the contents of.

[1] Colored curable resin composition
The colored curable resin composition of the present invention contains at least (a) a color material, (b) a binder resin, (c) an organic solvent, and (g) a surfactant, and (c) 80% by weight or more of the organic solvent. The solvent (c-1) having a boiling point of 180 ° C. or higher (boiling point under pressure of 101.25 [hPa]), and (g) a surfactant prepared using the solvent (c-1) A 0.02 wt% solution satisfies the following conditions (1) and (2).
(1) The contact angle with respect to the glass substrate is 10 ° or less. (2) The surface tension σ satisfies (σ ₀ −2) ≦ σ <σ ₀ with respect to the surface tension σ _{0 of} the solvent (c-1).
The colored curable resin composition of the present invention contains at least (a) a coloring material, (b) a binder resin, (c) an organic solvent, and (g) a surfactant, and (c) 80% by weight of the organic solvent. The solvent (c-1) having a boiling point of 180 ° C. or higher (boiling point under a pressure of 101.25 [hPa]) occupies the above, and (g) the surfactant is represented by the following general formula (10). It is characterized by containing a compound.

(Wherein R ₁ represents an alkylene group having 2 to 6 carbon atoms, R ₂ represents an alkylene group having 2 to 3 carbon atoms, R ₃ represents a hydroxyl group or a hydrogen atom, and G represents 1 to 4 carbon atoms) Represents a fluorinated alkyl group, v, w and u each independently represent an integer of 0 to 2, x and t each independently represents 1 or 2, s represents an integer of 0 to 10, n represents 2 Represents an integer of ~ 100.
In addition, a plurality of molecules per molecule

, They may be the same or different groups. )
The components of the colored curable resin composition of the present invention will be described below. “(Meth) acryl”, “(meth) acrylate” and the like are “acryl and / or methacryl”, “acrylate and / or methacrylate”. Etc., for example, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”. In addition, “(co) polymer” means “single polymer (homopolymer) and / or copolymer (copolymer)”.
“Total solid content” refers to all components in the curable resin composition of the present invention other than the solvent components described later.
The weight average molecular weight (Mw) of the resin ((co) polymer) is a value in terms of polystyrene measured by GPC (gel permeation chromatography).
The “amine value” represents an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the weight of KOH equivalent to the amount of base per 1 g of the solid content of the dispersant. The measuring method will be described later.
In the following, the colored curable resin composition may be simply referred to as “ink”.

[1-1] (g) Surfactant
In the present invention, (g) surfactant was prepared by using the above-mentioned solvent (c-1), and a 0.02% by weight solution of (g) surfactant was subjected to the following conditions (1) and (2). It satisfies.
(1) The contact angle with respect to the glass substrate is 10 ° or less. (2) The surface tension σ satisfies (σ ₀ −2) ≦ σ <σ ₀ with respect to the surface tension σ _{0 of} the solvent (c-1).
By using the surfactant (g) that satisfies the above conditions (1) and (2), it becomes possible to control the interfacial tension and surface tension of the colored curable resin composition with the base material within an appropriate range. As a result, it is possible to improve both the wet spreadability of the colored curable resin composition in the pixel bank and the surface flatness of the obtained pixel.
Conventionally, a surfactant used in a composition for forming a pixel for a color filter improves the coatability of the composition by reducing the surface tension of the composition containing the surfactant, or the coating film obtained. It worked to improve surface smoothness. On the other hand, most of them have the function of increasing the interfacial tension with the base material. An increase in the interfacial tension of the composition with the substrate causes a decrease in wet spreadability in the pixel bank of the composition.
The colored curable resin composition of the present invention is “(g) a surfactant 0.02 wt% solution prepared using a solvent (c-1)” (hereinafter, “(g) surfactant solution”). The surfactant having a contact angle of 10 ° or less with respect to the glass substrate is significantly improved in the wettability in the pixel bank. (G) The contact angle of the surfactant solution with respect to the glass substrate is more preferably less than 5 °.
The surface tension σ of the surfactant solution (g) is (σ ₀ −2) ≦ σ <σ ₀ with respect to the surface tension σ ₀ of the solvent (c-1). When σ is (σ ₀ −2) or less, the fine droplets ejected from the inkjet nozzle are not formed well, and the ejection stability becomes insufficient. It is obvious that (g) the surface tension σ of the surfactant solution is lower than the surface tension σ ₀ of the solvent (c-1) as the solvent.
Especially, the case where surface tension (sigma) is 28 mN / m or more and less than 30 mN / m is more preferable.
The (g) surfactant in the colored curable resin composition of the present invention is preferably a compound represented by the following general formula (10).

In the formula, R ₁ represents an alkylene group having 2 to 6 carbon atoms, R ₂ represents an alkylene group having 2 to 3 carbon atoms, R ₃ represents a hydroxyl group or a hydrogen atom, and G represents a fluoride having 1 to 4 carbon atoms. Represents an alkyl group. v, w and u each independently represent an integer of 0 to 2, x and t each independently represents 1 or 2, and s represents an integer of 0 to 10. n represents an integer of 2 to 100.
In addition, a plurality of molecules per molecule

, They may be the same or different groups.
In the general formula (10), R ₁ is an alkylene group having 2 to 6 carbon atoms. When there are too many carbon atoms, the hydrophilicity of this compound may be reduced. R ₁ is preferably an alkylene group having 2 to 4 carbon atoms.
In the general formula (10), R ₃ represents a hydroxyl group or a hydrogen atom. When the value of s described later is 0, R ₃ is preferably a hydrogen atom, and when s is an integer of 1 to 10, R ₃ is preferably a hydroxyl group.
In the general formula (10), v, w and u each independently represent an integer of 0 to 2, x and t are each independently 1 or 2, and s represents an integer of 0 to 10. t and u are both 2 or less, but if these values are 3 or more, steric hindrance may occur, and the desired performance may not be obtained.
In the said General formula (10), n represents the integer of 2-100, Preferably the integer of 5-30 is represented. When n exceeds 100, the molecular weight becomes too large and the solubility may be impaired. On the other hand, when n is less than 2, the molecular weight becomes too small and the stability in the solution may be impaired.
Among the compounds represented by the general formula (10), a compound represented by the following general formula (0) is particularly preferable.

(In the above formula (0), the substituent G represents a fluorinated alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 100.)
In the compound represented by the general formula (0), the substituent G represents a fluorinated alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms. When the number of carbon atoms is 5 or more, the substituent portion becomes too bulky, and the orientation to the interface may be impaired.
Of these, a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms is preferred. Further, the number of fluorine-substituted carbon atoms is preferably 1 to 3, and more preferably 1 or 2. When four or more carbon atoms are fluorine-substituted, they may show harmful effects accumulated in the human body.
As such a substituent G, specifically, —CF ₃ , —CF ₂ CF ₃ , —CF ₂ C ₂ F ₅
Among them, —CF ₃ or —CF ₂ CF ₃ is particularly preferable.
N in the general formula (0) represents an integer of 2 to 100, preferably an integer of 5 to 30. When n exceeds 100, the molecular weight becomes too large and the solubility may be impaired. On the other hand, when n is less than 2, the molecular weight becomes too small and the stability in the solution may be impaired.
Of the compounds represented by the general formula (0), the most preferable compounds are, for example, the following compounds.

Moreover, the compound represented by the general formula (0) is commercially available, for example, “PF-636”, “PF-656”, “PF-6320”, “PF-6520” (all trade names of OMNOVA). .) Etc. can be used.
From the viewpoint of spreading in the pixel bank, the colored curable resin composition preferably has a small contact angle with the transparent substrate of the color filter described later, for example, the colored curable resin composition of the present invention. In this case, the contact angle with respect to the glass substrate (clean glass) is preferably less than 5 °. In terms of easily achieving such a contact angle, for example, (ii), (iii) and (iv) are particularly preferable among the above four compounds.
The compound represented by general formula (0) may be used individually by 1 type, or may use 2 or more types together.
The content of the surfactant (g) in the colored curable resin composition of the present invention is generally 0.005 to 5% by weight, preferably 0.02 to 1% by weight, more preferably 0.8%, based on the total solid content. 05 to 0.5% by weight. (G) If the surfactant content is too high, it may be deposited or the surface tension may be excessively lowered. If it is too low, the pixel flatness may be poor.
(G) The surfactant may contain a surfactant other than the above as long as the effects of the present invention are not impaired. In this case, it is preferable to use it in the form of replacing a part of the content of the compound represented by the general formula (0). Specific examples of the surfactant that can be used in combination will be described later.

[1-2] (a) Color material
(A) A coloring material means what colors the coloring curable resin composition of this invention. (A) As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Specific examples of pigments that can be used are shown below by pigment numbers. Note that “CI” described below means a color index (CI).

  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, 17 , 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. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 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, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 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. Of these, C.I. I. Pigment Green 7, 36, 58.

  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, 17 174, 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. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

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. Among these, C.I. I. And CI pigment oranges 38 and 71.

Examples of purple pigments include 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. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.
A plurality of the above-described various pigments can be used in combination. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

The average particle size of these pigments is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less.
The average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering DLS. For particle size measurement, a sufficiently diluted colored curable resin composition (usually diluted and prepared to have a pigment concentration of about 0.005 to 0.2% by weight. However, if there is a concentration recommended by the measuring instrument, According to its concentration) and measured at 25 ° C.
Examples of the dye that can be used as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
Among these, it is preferable to use a pigment for the colorant (a) mainly in that light resistance and / or weather resistance and fastness of the coating film finally obtained are excellent. Further, in terms of color tone adjustment, pigments and dyes may be used in combination as necessary.

In the colored curable resin composition of the present invention, the proportion of the color material (a) relative to the total solid content is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and particularly preferably 40%. It is 90% by weight or less, preferably 80% by weight or less, more preferably 60% by weight or less.

  (A) When the content ratio of the color material is too small, the coloring power is lowered, the film thickness becomes too thick with respect to the color density, and adversely affects the gap control during the liquid crystal cell formation. On the other hand, when the content ratio of (a) the color material is too large, for example, the dispersion stability of the pigment is deteriorated, and there is a risk that problems such as re-aggregation and thickening occur.

[1-3] (b) Binder resin
The colored curable resin composition of the present invention comprises (b) a binder resin as an essential component. (B) Examples of the binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, and JP-A-2000-56118. Known polymer compounds described in JP-A Nos. 2003-233179 and the like can be used, and (b) a particularly preferable binder resin will be described below.

(B-1): “Unsaturated monobasic acid in at least part of the epoxy group of the copolymer with respect to the copolymer of epoxy group-containing (meth) acrylate and other radical polymerizable monomer Or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction "
As one of particularly preferred resins, “with respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, at least a part of the epoxy group of the copolymer is unsaturated. A resin obtained by adding a basic acid or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction (hereinafter referred to as “(b-1) resin”). Can be mentioned.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  As the “other radical polymerizable monomer” copolymerized with the epoxy group-containing (meth) acrylate, mono (meth) acrylate having a structure represented by the following general formula (1) is preferable.

In the above formula (1), R ^{1 to} R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ and R ⁸ each independently represent a hydrogen atom or carbon number. 1 to 3 alkyl groups, and R ⁷ and R ⁸ may be linked to each other to form a ring.
In the formula (1), the ring formed by connecting R ⁷ and R ⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and has 5 to 6 carbon atoms. Is preferred.
Especially, as a structure represented by General formula (1), the structure represented by following formula (1a), (1b), or (1c) is preferable.
By introducing these structures into the binder resin, when the colored curable resin composition of the present invention is used in a color filter or a liquid crystal display element, the heat resistance of the colored curable resin composition is improved, It is possible to increase the strength of the pixel formed using the colored curable resin composition.
In addition, the mono (meth) acrylate which has a structure represented by General formula (1) may be used individually by 1 type, and may use 2 or more types together.

  As the mono (meth) acrylate having the structure represented by the general formula (1), various known ones can be used as long as the structure has the structure, and those represented by the following general formula (2) are particularly preferable. .

In the formula (2), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents the structure of the general formula (1).
In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (1) is: Among repeating units derived from “other radical polymerizable monomers”, those containing 5 to 90 mol% are preferable, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable. preferable.

  The “other radical polymerizable monomer” other than the mono (meth) acrylate having the structure represented by the general formula (1) is not particularly limited. Specifically, for example, styrene, vinyl aromatics such as α-, o-, m-, or p-position alkyl, nitro, cyano, amide, or ester derivatives of styrene; butadiene, 2,3- Dienes such as dimethylbutadiene, isoprene, chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid -N-butyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meth) acrylic Hexyl acid, (meth) acrylic acid-2-ethylhexyl, lauryl (meth) acrylate, (meth) acrylic acid Decyl, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, (meta ) Propargyl acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, ( (Meth) acrylic acid furyl, (meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl, ( (Meth) acrylic acid-1 , 1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenyl (meth) acrylate Such as methyl, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. (Meth) acrylic acid esters; (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (Meth) acrylates such as (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenylamide, etc. (Meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl compounds such as N-vinylpyrrolidone, vinylpyridine, vinyl acetate; Unsaturated dicarboxylic acid diesters such as diethyl acid, diethyl maleate, diethyl fumarate and diethyl itaconate; monoesters such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide Maleimides; N- (meth) acryloylphthalimide and the like.

Among these “other radical polymerizable monomers”, in order to impart excellent heat resistance and strength to the colored curable resin composition, it was selected from styrene, benzyl (meth) acrylate, and monomaleimide. It is effective to use at least one kind. In particular, in the repeating unit derived from “another radical polymerizable monomer”, the content of the repeating unit derived from at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 70 mol. % Is preferable, and 3 to 50 mol% is more preferable.
The epoxy group-containing (meth) acrylate and the “other radical polymerizable monomer”
A well-known solution polymerization method is applied to the copolymerization reaction. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.

  Specific examples of the solvent include ethyl acetate; isopropyl acetate; ethylene glycol monoalkyl ether acetates such as cellosolve acetate and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate. Propylene glycol monoalkyl ether acetates; acetate esters such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, and butyl carbitol; triethylene glycol Dialkyl ethers; propylene glycol dialkyl Ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane Petroleum petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more. The amount of these solvents used is usually 30 to 1000 parts by weight, preferably 50 to 800 parts by weight, with respect to 100 parts by weight of the resulting copolymer. When the amount of the solvent used is outside this range, it becomes difficult to control the molecular weight of the copolymer.

  The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can do. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy-2-ethyl. Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxide Oxydicarbonate, diisopropyl -Oxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1- Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like can be mentioned. Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide. Among these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 weight part with respect to a total of 100 weight part of the monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.

  The copolymerization reaction may be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or by adding the monomer to which the radical polymerization initiator has been added. Alternatively, the reaction may be performed dropwise in a solvent that has been heated and stirred. Further, the monomer may be added dropwise while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the “other radical polymerizable monomer”, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, And those containing 10 to 95 mol% of repeating units derived from other radical polymerizable monomers, more preferably those containing 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and the former. Those containing 30 to 70 mol% and the latter 70 to 30 mol% are particularly preferred.
When there are too few epoxy-group-containing (meth) acrylates, the addition amount of the polymeric component mentioned later and a polybasic acid anhydride may become inadequate, on the other hand, there are too many epoxy-group containing (meth) acrylates, When there are too few other radically polymerizable monomers, heat resistance and intensity | strength may become inadequate.

Subsequently, an unsaturated monobasic acid (polymerizable component) and, if necessary, a polybasic acid on the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radical polymerizable monomer React with anhydride.
As the unsaturated monobasic acid to be added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These 1 type may be used independently and may use 2 or more types together.
By adding such components, polymerizability can be imparted to the binder resin used in the present invention.

  These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of the unsaturated monobasic acid is too small, the temporal stability of the colored curable resin composition may be lowered. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and succinic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.
By adding such a component, it is possible to expect improvement in wettability in the pixel bank of the colored curable resin composition of the present invention.

  These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%. Adjustment of the addition ratio in this range is considered effective for controlling the wettability of the composition. However, if the addition ratio is too small, the above-described effect cannot be expected so much. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

When the colored curable resin composition of the present invention is a photocurable composition as described later,
In order to improve the photosensitivity, after adding the above-mentioned polybasic acid anhydride, a glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to a part of the generated carboxyl group. Good. Moreover, in order to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group to some produced | generated carboxyl groups. Both of these may be added.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. As commercial products, for example, trade names “Denacol EX-111”, “Denacol EX-121”, “Denacol EX-141”, “Denacol EX-145”, “Denacol EX-146”, “Denacol EX-146” manufactured by Nagase Chemical Industries, Ltd. Denacol EX-171 "," Denacol EX-192 "and the like.
The structure of such a resin is described in, for example, JP-A-8-297366 and JP-A-2001-89533, and is already known.

  3000-100000 are preferable and, as for the weight average molecular weight (Mw) of polystyrene conversion measured by GPC of the above-mentioned (b-1) resin, 5000-50000 are especially preferable. When the weight average molecular weight is less than 3000, heat resistance and film strength may be inferior. When it exceeds 100000, the viscosity of the resin increases, and the discharge properties from the nozzle of a composition using the resin tend to decrease. is there. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

(B-2): Carboxyl group-containing linear resin
The carboxyl group-containing linear resin (hereinafter referred to as “(b-2) resin”) is not particularly limited as long as it has a carboxyl group, and usually a polymerizable monomer containing a carboxyl group is used. Obtained by polymerization.
Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Adipic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2 -(Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyl Oxybutyl succinic acid, 2- (meta Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; Monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone; succinic acid, maleic acid, phthalic acid, or anhydrides thereof to hydroxyalkyl (meth) acrylate The monomer etc. which added the thing are mentioned. A plurality of these may be used.
Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.

Moreover, (b-2) resin may copolymerize other polymerizable monomer which does not have a carboxyl group to said carboxyl group-containing polymerizable monomer.
Other polymerizable monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate , Benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy (Meth) acrylic esters such as ethyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; vinyl aromatics such as styrene and its derivatives Vinyl compounds such as N-vinylpyrrolidone; N-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide; polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl Examples thereof include macromonomers such as (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, and polycaprolactone macromonomer. These may be used in combination.

Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, They are butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide.
(B-2) The resin may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like. Is mentioned. By copolymerizing these with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.

(B-2) Specific examples of the resin include (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and cyclohexyl (meth). Polymeric monomers not containing hydroxyl groups such as acrylate and cyclohexylmaleimide, and hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate Copolymer; (meth) acrylic acid and (meth) acrylic acid ester such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. Copolymer; (meth) acrylic Copolymers of acid and styrene; a copolymer of (meth) acrylic acid and styrene and α- methylstyrene; a copolymer of (meth) acrylic acid and cyclohexyl maleimide.
From the viewpoint of excellent pigment dispersibility, a copolymer resin containing benzyl (meth) acrylate is particularly preferable.

The acid value of (b-2) resin in this invention is 30-500 KOHmg / g normally, Preferably it is 40-350 KOHmg / g, More preferably, it is 50-300 KOHmg / g.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-20000 normally, Preferably it is 3000-50000, More preferably, it is 4000-30000. If the weight average molecular weight is too small, the stability of the colored curable resin composition tends to be inferior. If it is too large, the viscosity of the resin increases, and the ejection properties from the nozzle of the composition using this tend to decrease. There is.

(B-3): (b-2) Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin
A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the (b-2) resin (hereinafter referred to as “(b-3) resin”) is also particularly preferable.
The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.
For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- Acyclic epoxy group-containing unsaturated compounds such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but from the viewpoints of heat resistance and dispersibility of the pigment described later, alicyclic epoxy group-containing unsaturated compounds are used. preferable.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. Further, the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group, and suitable alicyclic epoxy group-containing unsaturated compounds are represented by the following general formulas (3a) to (3m). And the compounds represented.

In formulas (3a) to (3m), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group, R ¹³ represents a divalent hydrocarbon group, and n is an integer of 1 to 10, is there.
In general formulas (3a) to (3m), the alkylene group represented by R ¹² preferably has 1 to 10 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and a methylene group, an ethylene group, and a propylene group are preferable. As the hydrocarbon group R ^13, preferably has 1 to 10 carbon atoms, alkylene group, a phenylene group, and the like.

These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Among these, a compound represented by the general formula (3c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
A known method can be used to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the (b-2) resin. For example, a carboxyl group-containing linear resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyl Quaternary ammonium salts such as triethylammonium chloride; in the presence of a catalyst such as pyridine and triphenylphosphine, the reaction is carried out in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours. Group-containing unsaturated compounds can be introduced.

(B-3) The acid value of the resin is usually 10 to 200 KOH mg / g, preferably 20 to 150 KOH mg / g, more preferably 30 to 150 KOH mg / g.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-100000 normally, Preferably it is 4000-50000, More preferably, it is 5000-30000.

(B-4): (Meth) acrylic resin
(B-4) (Meth) acrylic resin (hereinafter referred to as “(b-4) resin”) is a polymer obtained by polymerizing acrylic acid and / or acrylic acid ester as monomer components. Say. Preferable (b-4) resin includes, for example, (b-4-1): a polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate, and (b-4-) 2): A polymer obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (4) and / or (5) can be mentioned.

In formula (4), R ^1a and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (5), R ^1b represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X is represented by the following formula (6). A group or an adamantyl group which may be substituted;

In Formula (6), R ^2b , R ^3b , and R ^4b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, and L ¹ and L ² represent a divalent linking group. In addition, L < ^{3 >} in Formula (5) may combine with R ^{< 3b>} or R ^<4b> to form a ring. Further, L ¹ , L ² and two or more of L ³ in the formula (5) may be bonded to each other to form a ring.

(B-4-1): a polymer obtained by polymerizing monomer components containing (meth) acrylic acid and benzyl (meth) acrylate
A polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate (hereinafter referred to as “(b-4-1) resin”) has a high affinity with a pigment. Are preferably used.
The ratio of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component is not particularly limited, but (meth) acrylic acid in the total monomer component is usually 10 to 90% by weight, preferably 15%. -80% by weight, more preferably 20-70% by weight. Moreover, benzyl (meth) acrylate is 5 to 90 weight% normally in all the monomer components, Preferably it is 15 to 80 weight%, More preferably, it is 20 to 70 weight%. If the amount of (meth) acrylic acid is too large or too small, dispersion tends to be difficult.

(B-4-2): a polymer obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (4) and / or (5) (hereinafter referred to as “(b-4-2) resin”. .)
First, the compound of General formula (4) is demonstrated.
In the ether dimer represented by the general formula (4), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1a and R ^2a is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-
Alicyclic groups such as 2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ^1a
And R ^2a may be the same or different substituents.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like. Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be used alone or in combination of two or more.

  The ratio of the ether dimer in the monomer component in obtaining the (b-4-2) resin is not particularly limited, but is usually 2 to 60% by weight, preferably 5 to 5% in all monomer components. It is 55% by weight, more preferably 5 to 50% by weight. If the amount of the ether dimer is too large, it may become difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, transparency, heat resistance, etc. There is a possibility that the performance of the coating film becomes insufficient.

Then, the compound of General formula (5) is demonstrated.
In General Formula (5), R ^1b preferably represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
In the general formula (6), the organic groups represented by R ^2b , R ^3b and R ^4b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, or an acyl group. Carboxyl group or acyloxy group, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkenyl group having 3 to 18 carbon atoms. Group, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, or an acyloxy group having 1 to 15 carbon atoms, and more preferably. Is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms.

Preferred substituents among R ^2b , R ^3b and R ^4b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
In general formula (5) and general formula (6), L ¹ and L ² are each independently a divalent linking group, and L ³ is not particularly limited as long as it is a divalent linking group or a direct bond, At least either L ¹ or L ² is preferably a linking group having 1 or more carbon atoms. L ¹ , L ² and L ³ are each independently a direct bond, alkylene having 1 to 15 carbon atoms, —O—
, -S-, -C (= O)-, alkenylene having 1 to 15 carbon atoms, phenylene, or a combination thereof is preferable.
As a preferable combination of L ¹ , L ² , and L ³ , L ³ is a direct bond, alkylene having 1 to 5 carbon atoms, or a ring formed by combining with R ^3b or R ^4b, and L ¹ and L ² Are each independently an alkylene group having 1 to 5 carbon atoms.
Moreover, as a preferable thing of General formula (6), the compound shown by following General formula (7) can be mentioned.

In the formula (7), R ^2b , R ^3b , R ^4b , L ¹ and L ² have the same meaning as in the formula (6), and R ^5b and R ^6b each independently represent a hydrogen atom, a hydroxyl group or a halogen atom. Represents an amino group or an organic group.
In the general formula (7), the organic groups represented by R ^5b and R ^6b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, or An acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, and 1 carbon atom. -15 alkoxy group, C1-C15 alkylthio group, C1-C15 acyl group, C1-carboxyl group, or C1-C15 acyloxy group, more preferably C1-C15. Or an alkyl group having 10 to 10 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms.
Particularly preferred substituents among R ^5b and R ^6b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
In addition, the alkyl group of R ^1b , the organic groups of R ^2b , R ^3b and R ^4b , the divalent linking group of L ¹ , L ² and L ³ , and the adamantyl group of X are each independently a substituent. Specific examples thereof include the following substituents.

Halogen atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group A linear or branched alkyl group having 1 to 18 carbon atoms such as n-heptyl group, n-octyl group and t-octyl group; carbon number such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and adamantyl group A cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyl A linear or branched alkoxy group having 1 to 18 carbon atoms such as a xyl group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octyloxy group; methylthio group, Ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, a linear or branched alkylthio group having 1 to 18 carbon atoms such as t-octylthio group; an aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; carbon such as benzyl group and phenethyl group Aralkyl group having 7 to 18 carbon atoms; straight chain or branched chain having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group, hexenyloxy group Alkenyloxy group; represented by -OCOR ^18; carboxyl group; an acyl group represented by -COR ^17; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group An acyloxy group represented by —NR ¹⁹ R ²⁰ ; an acylamino group represented by —NHCOR ²¹ ; a carbamate group represented by —NHCOOR ²² ; a carbamoyl group represented by —CONR ²³ R ²⁴ ; Carboxylic acid ester group represented by ²⁵ ; sulfamoyl group represented by —SO ₃ NR ²⁶ R ²⁷ ; sulfonic acid ester group represented by —SO ₃ R ²⁸ ; 2-thienyl group, 2-pyridyl group, furyl group , Oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide A saturated or unsaturated heterocyclic group such as a side group; a trialkylsilyl group such as a trimethylsilyl group;

R ^{17 to} R ²⁸ are each a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or An aralkyl group which may have a substituent is represented.
Moreover, the positional relationship of the said substituent is not specifically limited, When it has a some substituent, it may be same or different.
Specific examples of the compound represented by the general formula (5) include the following (M-1) to (M-22).

  In the monomer component constituting the (b-4-2) resin according to the present invention, the ratio of the general formula (5) is not particularly limited, but usually 0.5 to 60% by weight in the total monomer components. The amount is preferably 1 to 55% by weight, more preferably 5 to 50% by weight. If the amount is too large, the dispersion stability may decrease when used as a dispersant.

  The (b-4) acrylic resin in the present invention preferably has an acid group, including the (b-4-1) resin and the (b-4-2) resin. By having an acid group, the resulting colored curable resin composition can be cured by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter abbreviated as acid-epoxy curing). It can be set as a curable resin composition. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more.

  (B-4) In order to introduce an acid group into the resin, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter “monomer for introducing an acid group”) May be used as a monomer component. In addition, when using "monomer which can provide an acid group after superposition | polymerization" as a monomer component, the process for providing an acid group as mentioned later is required after superposition | polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Among these, (meth) acrylic acid is especially preferable.
Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta And monomers having an isocyanate group such as acrylate.
These monomers for introducing an acid group may be only one type or two or more types.

(B-4) When the monomer component for obtaining the resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited. It is -70 weight%, Preferably it is 10-60 weight%.
Moreover, (b-4) resin may have a radically polymerizable double bond.

(B-4) In order to introduce a radical polymerizable double bond into a resin, for example, “a monomer capable of providing a radical polymerizable double bond after polymerization” (hereinafter referred to as “single monomer for introducing a radical polymerizable double bond”). After polymerization as a monomer component, a treatment for imparting a radical polymerizable double bond as described later may be performed.
Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomers: Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

(B-4) When the monomer component for obtaining the resin also includes the monomer for introducing the radical polymerizable double bond, the content ratio is not particularly limited, but usually the total amount It is 5-70 weight% in a body component, Preferably it is 10-60 weight%.
When the (b-4) resin of the present invention is a polymer having the compound of the general formula (4) as an essential monomer component described in the section of (b-4-2) resin, an epoxy group It is preferable to have.
In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one kind or two or more kinds.
(B-4) When the monomer component for obtaining the resin also includes the monomer for introducing the epoxy group, the content ratio is not particularly limited, but usually 5% of all the monomer components. It is -70 weight%, Preferably it is 10-60 weight%.

(B-4) The monomer component for obtaining the resin may contain other copolymerizable monomers, if necessary, in addition to the essential monomer component.
Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene; Substituted butadiene compounds; ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like.
Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.
Further, in particular, when a part or all of the resin (b-4) is used as a dispersant as described later, it is preferable to use benzyl (meth) acrylate, and the content thereof is usually all monomer components. The content is 1 to 70% by weight, preferably 5 to 60% by weight.

  (B-4) When the monomer component in obtaining the resin also includes the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by weight or less, and 85% by weight or less. More preferred.

Next, (b-4) resin production method (polymerization method) will be described.
There is no particular limitation on the method for polymerizing the monomer component, and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. , Depending on the molecular weight of the target polymer. The polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C. Regarding the polymerization concentration, the polymerization concentration is preferably 5 to 50%, more preferably 10 to 40%.

  Moreover, what is necessary is just to use the solvent used by normal radical polymerization reaction when using a solvent at the time of superposition | polymerization. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform; Dimethyl sulfoxide and the like Is mentioned. These solvents may be used alone or in combination of two or more.

When the monomer component is polymerized, a polymerization initiator may be used as necessary. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amyl. Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane Carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) and the like. These polymerization initiators may be used alone or in combination of two or more.
The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is not gelled. It is usually 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer components, in that thousands to tens of thousands of polymers can be obtained.

  Moreover, you may add a chain transfer agent for molecular weight adjustment. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and α-methylstyrene dimer. Preferred are n-dodecyl mercaptan and mercaptoacetic acid, which can be reduced and easily obtained. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but without gelation It is usually 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer components, in that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained.

In addition, when the compound of the general formula (4) is used as an essential monomer component, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously in the polymerization reaction. The conversion rate is not necessarily 100 mol%.
When the acrylic resin is obtained, when the acid group is introduced by using the monomer capable of imparting the acid group described above as the monomer component, it is necessary to perform a treatment for imparting the acid group after polymerization. . The treatment varies depending on the type of monomer used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride An acid anhydride such as a product may be added. When a monomer having an epoxy group such as glycidyl (meth) acrylate is used, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or first ( An acid such as meth) acrylic acid may be added, and an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like may be added to the resulting hydroxyl group. When a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

When obtaining the resin (b-4), when the radical polymerizable double bond is introduced by using the monomer capable of imparting the radical polymerizable double bond described above as the monomer component, radical polymerization is performed after the polymerization. It is necessary to perform a treatment for imparting a sex double bond.
The treatment varies depending on the type of monomer used. For example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( A compound having an epoxy group and a radically polymerizable double bond such as (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate is added. Just do it. When a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether is used, ) A compound having an acid group such as acrylic acid and a radical polymerizable double bond may be added.

Although the weight average molecular weight of (b-4) resin of this invention is not restrict | limited in particular, Preferably the weight average molecular weight of polystyrene conversion measured by GPC is 2000-200000, More preferably, it is 4000-100000. When the weight average molecular weight exceeds 200,000, the viscosity becomes high, and the discharge property from the nozzle of the composition containing this may decrease, whereas when it is less than 2000, the film strength tends to be insufficient. .
When said (b-4) resin has an acid group, a preferable acid value is 30-500 mgKOH / g, More preferably, it is 50-400 mgKOH / g.

  Among the resin components (b-4), a polymer having the compound represented by the general formula (4) as an essential monomer component is a compound known per se, for example, JP-A-2004-300203. And the compounds described in JP-A-2004-300204.

(B-5): Epoxy acrylate resin having a carboxyl group (hereinafter referred to as “(b-5) resin”)
The (b-5) epoxy acrylate resin in the present invention is obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to the epoxy resin. It is synthesized by reacting a basic acid anhydride. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc., manufactured by Japan Epoxy Resin Co., Ltd.), Epoxy resin obtained by reaction of alcoholic hydroxyl group and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, manufactured by Japan Epoxy Resin Co., Ltd.) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc."), epoxy resins obtained by reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (for example, Nippon Kayaku) “NE” -7406 "(epoxy equivalent 350, softening point 66 ° C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example," YX-4000 "manufactured by Japan Epoxy Resin), phenol novolac type epoxy resin (for example, Nippon Kayaku) "EPPN-201" manufactured by Yakuhin Co., "EP-152", "EP-154" manufactured by Japan Epoxy Resin, "DEN-438" manufactured by Dow Chemical Co.), (o-, m-, p-) Cresol novolac type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), Trisphenol methane type epoxy resin (for example, “EPPN-501” manufactured by Nippon Kayaku Co., Ltd., “ PN-502 ”,“ EPPN-503 ”), fluorene epoxy resin (for example, cardo epoxy resin“ ESF-300 ”manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (“ Celoxide 2021P manufactured by Daicel Chemical Industries, Ltd. ”) ”,“ Celoxide EHPE ”), dicyclopentadiene type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example,“ XD-1000 ”manufactured by Nippon Kayaku Co., Ltd.,“ EXA-7200 "," NC-3000 "," NC-7300 "manufactured by Nippon Kayaku Co., Ltd.), and an epoxy resin represented by the following structural formula (see JP-A-4-355450) are preferably used. Can do.

These may be used alone or in combination of two or more.
Another example of the epoxy resin is a copolymerization type epoxy resin. Examples of the copolymerization type epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “first component of copolymerization type epoxy resin”) and the like. Monofunctional ethylenically unsaturated group-containing compound (hereinafter referred to as “second component of copolymerization type epoxy resin”), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- Hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono (meth) acrylate, the following general formula ( Is it a compound represented by 8) One or more co-polymer obtained by reacting selected and the like.

In formula (8), R ⁶¹ represents hydrogen or an ethyl group, R ⁶² represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10.
Examples of the compound of the general formula (8) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate; methoxydiethylene glycol mono ( Examples thereof include alkoxy polyethylene glycol (meth) acrylates such as meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

As for the molecular weight of the said copolymerization type epoxy resin, about 1000-200000 is preferable. The amount of the first component of the copolymerization type epoxy resin used is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably 70% by weight based on the second component of the copolymerization type epoxy resin. % By weight or less, particularly preferably 50% by weight or less.
As such a copolymerization type epoxy resin, specifically, “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, “CP-50S”, “CP-50M”, “CP-20MA” and the like are exemplified.

  The molecular weight of the raw material epoxy resin is usually in the range of 200 to 200,000, preferably 300 to 100,000, as the weight average molecular weight in terms of polystyrene measured by GPC. If the weight average molecular weight is less than the above range, there may be a problem in film forming properties. Conversely, if the resin exceeds the above range, gelation tends to occur during the addition reaction of α, β-unsaturated monocarboxylic acid. In some cases, manufacturing may be difficult.

Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is highly reactive. Therefore, it is preferable.
Examples of α, β-unsaturated monocarboxylic acid esters having a carboxyl group in the ester moiety include acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylate-2-succinoyloxyethyl, methacrylate-2-malenoyloxyethyl, methacrylate-2-phthaloyloxyethyl, methacrylate-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred. These may be used alone or in combination of two or more.

  The addition reaction of the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety and the epoxy resin can be carried out using a known method, for example, esterification It can implement by making it react at the temperature of 50-150 degreeC in catalyst presence. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

  The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated carboxylic acid ester having a carboxyl group in the ester moiety is 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the raw material epoxy resin. A range is preferable, and a range of 0.7 to 1.1 equivalents is more preferable. When the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated carboxylic acid ester having a carboxyl group in the ester portion is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid anhydride The reaction is also insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β-unsaturated monocarboxylic acid or α, β-unsaturated carboxylic acid ester having a carboxyl group in the ester moiety remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  Polybasic acid anhydrides to be further added to an epoxy resin in which an α, β-unsaturated carboxylic acid or an α, β-unsaturated carboxylic acid ester having a carboxyl group is added to the ester moiety include maleic anhydride and succinic anhydride Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, anhydrous methylhexahydrophthalic acid, endomethylenetetrahydrophthalic anhydride Acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc., preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexa Hydrophthalic acid, pyromellitic anhydride, none Trimellitic acid, biphenyltetracarboxylic acid dianhydride and the like, particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic acid dianhydride. These may be used alone or in combination of two or more.

A known method can also be used for the addition reaction of polybasic acid anhydride, which is similar to the addition reaction of α, β-unsaturated carboxylic acid or α, β-unsaturated carboxylic acid ester having a carboxyl group in the ester moiety. It can implement by making it continue reaction on conditions.
The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mgKOH / g, more preferably in the range of 20 to 140 mgKOH / g. In addition, from the viewpoint of storage stability of the composition, a lower acid value is preferable.

As other epoxy acrylate resins having a carboxyl group, for example, naphthalene-containing resins described in JP-A-6-49174; JP-A-2003-89716, JP-A-2003-165830, JP-A-2005-325331, JP-A-2001. Examples of the fluorene-containing resins described in JP-A Nos. -354735 and JP-A Nos. 2005-126684, 2005-55814, and 2004-295084.
Moreover, the commercially available epoxy acrylate resin which has a carboxyl group can also be used, and "ACA-200M" by Daicel Corporation etc. can be mentioned as a commercial item, for example.

As the binder resin, for example, an acrylic resin described in JP-A-2005-154708 can also be used.
Among the various resins described above, as the (b) binder resin in the present invention, (b-1): “for a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, Resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the copolymer, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction Is particularly preferred. Further, the molecular weight is particularly preferably about 5000 to 20000 as a polystyrene-reduced weight average molecular weight measured by GPC.

As will be described later, the colored curable resin composition of the present invention may be photocurable, thermosetting, or cured by both actions.
In the case of curing using a thermosetting action, the binder resin is (b-1): “the copolymer of epoxy group-containing (meth) acrylate and other radical polymerizable monomer. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the polymer, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, and The following (b-6) resins having an epoxy group are most preferable.
In addition, when forming a pixel for a color filter by the ink jet method, it does not require a photopolymerization initiator that may reduce luminance, and from the point that productivity can be increased by omitting the photocuring process, It is preferable to use a thermosetting colored curable resin composition.

(B-6): Resin having an epoxy group
The resin (b-6) having an epoxy group (hereinafter referred to as “(b-6) resin”) according to the present invention is not particularly limited in its structure as long as it has an epoxy group in the resin.
Among them, alicyclic polyether compounds having an epoxy group in the side chain, polyglycidyl ether compounds, polyglycidyl ester compounds, polyglycidyl amine compounds, and (meth) acrylates having an epoxy group are used alone or in combination. Examples thereof include a polymer obtained by polymerization as described above, or a copolymer of (meth) acrylate having an epoxy group and another monomer.
(B-6) Specific examples of the resin are shown below, but are not limited thereto.

(B-6-1): Alicyclic polyether compound having an epoxy group in the side chain
Examples of the alicyclic polyether compound having an epoxy group in the side chain include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, Examples include polycyclohexyl ether having an epoxy group in the side chain. Examples of such commercially available compounds include EHPE3150 (manufactured by Daicel Chemical Industries).

(B-6-2): Polyglycidyl ether compound
Examples of the polyglycidyl ether compound include polyethylene glycol diglycidyl ether type epoxy, bis (4-hydroxyphenyl) diglycidyl ether type epoxy, and bis (3,5-dimethyl-4-hydroxyphenyl) diglycidyl ether type. Epoxy, diglycidyl ether type epoxy of bisphenol F, diglycidyl ether type epoxy of bisphenol A, diglycidyl ether type epoxy of tetramethylbisphenol A, diglycidyl ether type epoxy of ethylene oxide-added bisphenol A, dihydroxy fluorene type epoxy, di Hydroxyalkyleneoxylfluorene type epoxy, bisphenol A / aldehyde novolac type epoxy, phenol novolac type epoxy, crezo Lunovolak type epoxy and polyglycidyl ether resins include bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, polymerized epoxy resin of phenol and naphthalene. And phenol resin type epoxy resin.
These (poly) glycidyl ether compounds may be those obtained by reacting a remaining hydroxyl group with an acid anhydride, a divalent acid compound or the like to introduce a carboxyl group.

(B-6-3): polyglycidyl ester compound
Examples of the polyglycidyl ester compound include a diglycidyl ester type epoxy of hexahydrophthalic acid, a diglycidyl ester type epoxy of phthalic acid, and the like.

(B-6-4): polyglycidylamine compound
Examples of the polyglycidylamine compound include diglycidylamine type epoxy of bis (4-aminophenyl) methane, triglycidylamine type epoxy of isocyanuric acid, and the like.

(B-6-5): A polymer obtained by polymerizing one or more (meth) acrylates having an epoxy group.
As an example of the (b-6) resin of the present invention, a polymer obtained by polymerizing one kind or two or more kinds of (meth) acrylates having an epoxy group such as the above compound (hereinafter referred to as “(b-6-5)”. ) Resin ”).
(B-6-5) Examples of the (meth) acrylate having an epoxy group, which is a raw material for the resin, include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α- n-butyl glycidyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic Examples include acid-6,7-epoxyheptyl. Particularly preferred is glycidyl (meth) acrylate.
(B-6-6): Copolymer of (meth) acrylate having an epoxy group and another monomer As another example of the (b-6) resin of the present invention, (b-6-5) Examples thereof also include copolymers of “(meth) acrylate having an epoxy group” mentioned in the above section and other monomers. Hereinafter, the copolymer is referred to as “(b-6-6) resin”. Content of another monomer is 10-70 mol% normally among all the monomers which comprise (b-6-6) resin, Preferably it is 15-60 mol%.
Examples of other monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid-2-ethylhexyl, and (meth) acrylic. Esters of (meth) acrylic acid such as phenyl acid, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and styrene And vinyl aromatic compounds such as α-methylstyrene, p-methylstyrene, and vinylnaphthalene.
As the (meth) acrylate having an epoxy group, glycidyl (meth) acrylate is particularly preferable. Particularly preferred examples of the other monomer include dicyclopentanyl (meth) acrylate and α-methylstyrene.

In addition, the epoxy group used in the resin (b-6) in the present invention is usually a 1,2-epoxy group, but 1,3-epoxy is used for the purpose of improving stability over time or imparting flexibility. A group (oxetane) or a 4,3-epoxycyclohexyl group can also be used.
In addition, in the (b-6) resin, those that do not contain an aromatic ring or those that contain no phenyl group or a phenyl group having a substituent at the p (para) position are preferred because discoloration due to heat treatment can be suppressed. . Examples of such an epoxy compound include a bisphenol A type epoxy resin, an epoxy resin having a fluorene skeleton which may have a substituent, and a copolymer of glycidyl (meth) acrylate.

The content of the (b-6) resin is usually 0.5 mol% or more, preferably 1.0 mol% or more, and usually 70 mol% or less, preferably 65, based on the entire resin (b-1). It is less than mol%. (B-6) If the amount of the resin is too small, the chemical resistance tends to be insufficient. If the amount is too large, the storage stability may be insufficient.
(B-6) The weight average molecular weight (Mw) of the resin is usually 300 or more, preferably 500 or more, and usually 100,000 or less, preferably 50,000 or less. If the molecular weight is too small, the heat resistance and the film strength tend to be inferior. If it is too large, the solubility may be insufficient, or the liquid properties as a coating solution may be non-Newtonian. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2.0 or more and 5.0 or less.

(B-6) The ratio of the resin is preferably 0.5% by weight or more, more preferably 1% by weight or more, and usually 50% by weight or less, in the total solid content in the colored curable resin composition of the present invention. Preferably it is 40 weight% or less, More preferably, it is 35 weight% or less. (B-6) If the ratio of the resin is too small, the effect of improving the chemical resistance cannot be expected so much, and if it is too large, the storage stability tends to be insufficient.
The various binder resins described above may be used alone or in combination of two or more.
In the colored curable resin composition of the present invention, the content of the (b) binder resin is usually 1% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably in the total solid content. Is 60% by weight or less. (B) When content of binder resin is less than this range, a film | membrane will become weak and the adhesiveness to a board | substrate may fall. On the other hand, if it exceeds this range, the film hardness may be insufficient or the coloring power may be insufficient.

[1-4] (c) Organic solvent
The colored curable resin composition of the present invention contains (c) an organic solvent as an essential component. (C) The organic solvent has a function of adjusting the viscosity by dissolving or dispersing the respective components.
Such (c) organic solvent is not particularly limited as long as it can dissolve or disperse each component constituting the colored curable resin composition, but (c) 80% by weight or more of the organic solvent has a boiling point of 180 ° C. The solvent (c-1) which occupies the above (boiling point under pressure of 101.25 [hPa]) occupies.
(C) Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl- 3-methoxybutanol, triethylene glycol monomer Ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as 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 Roh ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, glycol alkyl ether acetates such as ethylene glycol diacetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

Like 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, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, butanediol, triethylene glycol, methoxymethylpentanol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;

Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, 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, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as propyl, butyl 3-methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.

Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 solvent, Apco thinner, and Soal 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) and the like.
These solvents may be used alone or in combination of two or more.

In the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several to several tens of pL. Therefore, before landing on the periphery of the nozzle opening or in the pixel bank, the solvent evaporates and the ink is concentrated and dried. There is a tendency to harden.
In order to avoid this, the colored curable resin composition of the present invention comprises (c) 80% by weight or more of the organic solvent having a boiling point of 180 ° C. or higher (boiling point under pressure of 101.25 [hPa]). It is essential that (c-1) occupies. When the ratio of the solvent (c-1) is less than 80% by weight, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited. The boiling point of the solvent (c-1) is preferably 200 ° C. or higher, particularly preferably 220 ° C. or higher.
The solvent (c-1) is preferably 80% by weight or more, and more preferably 90% by weight or more in the (c) organic solvent.
Examples of the solvent (c-1) include 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 among the various solvents described above. -Hexanol diacetate, triacetin and the like. Of these, diethylene glycol mono-n-butyl ether acetate is particularly preferable.

In order to adjust the viscosity of the ink and the solubility of the solid content, it is also effective to partially contain a solvent having a boiling point 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, and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferable.
On the other hand, when (c) the organic solvent contains alcohol, the ejection stability in the ink jet method may be lowered. Therefore, the alcohol is preferably 20% by weight or less in the total solvent, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.
(C) The vapor pressure of the organic solvent is usually 10 mmHg or less, more preferably 5 mmHg or less, and further preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.

The proportion of the organic solvent (c) in the colored curable resin composition of the present invention is not particularly limited, but is usually 50% by weight or more, preferably 60% by weight or more, and usually 99% by weight or less, preferably 95% by weight or less. (C) If there is too much organic solvent, the solid content becomes relatively low and it becomes unsuitable for forming a coating film, or the viscosity of the ink becomes too high. Problems such as hindering may occur, and when the composition is applied to an ink jet method, ejection stability may be lowered.

[1-5] (e) Dispersant
The colored curable resin composition of the present invention preferably further contains (e) a dispersant. (E) The type of the dispersant is not particularly limited as long as the effects of the present invention are not impaired, but (e-1): a graft copolymer containing a nitrogen atom, (e-2): containing a nitrogen atom. Acrylic block copolymer (e-3): It is preferable to contain one or more dispersants selected from urethane resin dispersants.

In the above (e-1) to (e-3), the nitrogen atom contained therein has an affinity for the pigment surface, and the portion other than the nitrogen atom increases the affinity for the medium. It is estimated that it contributes to the improvement of sex.
The performance of the dispersant is greatly influenced by its adsorption behavior on the solid surface. Regarding the relationship between the molecular architecture and the adsorption behavior, it is known that when the same unit is used, the adsorption behavior is excellent in the order of random copolymerization <graft copolymer <block copolymer. (For example, Jones and Richards, “Polymers at Surfaces and Interfaces” p281).

Although the detailed mechanism is unknown, the following can be inferred.
That is, in the case of a normal random copolymer, the monomer constituting the copolymer has a high probability of being stably arranged in the copolymer sterically and / or electrically during the formation of the polymer. . Since the portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, it may be an obstacle when adsorbed on the pigment. In contrast, for resins with a controlled molecular arrangement such as graft copolymers or block copolymers, the part that prevents the adsorption of the dispersant should be placed at a position away from the adsorption part of the pigment and the dispersant. Can do. That is, an optimum portion for adsorption can be arranged in the adsorption portion between the pigment and the dispersant, and a portion suitable for it can be arranged in the portion requiring solvent affinity. In particular, for the dispersion of a colorant containing a pigment having a small crystallite size, it is presumed that this molecular arrangement affects good dispersibility.

(E-1): Graft copolymer containing nitrogen atom
A graft copolymer containing a nitrogen atom (hereinafter sometimes referred to as “(e-1) copolymer”) is preferable in that (g) the pigment can be dispersed extremely efficiently. The reason is not clear, but it has a structure that can positively eliminate the part (molecule) that obstructs the adsorption of the pigment and the dispersant around the adsorption part to the pigment. It is guessed. As the graft copolymer containing a nitrogen atom, those having a repeating unit containing a nitrogen atom in the main chain are preferred. Especially, it is preferable to have a repeating unit represented by Formula (I) or / and a repeating unit represented by Formula (II).

In the formula (I), R ⁵¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any one of the following formulas (III) to (V).
In the formula (I), R ⁵¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably an ethylene group. It is. A represents a hydrogen atom or any one of the following formulas (III) to (V), preferably formula (III).

Wherein ^{(II), R 51} and A have the same meanings as ^{R 51} and A in formula (I).

In formula (III), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, hexylene and the like is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In formula (IV), Y ₁ represents a divalent linking group, and in particular, 1 to C carbon atoms such as ethylene and propylene.
4 alkylene groups or C1-C4 alkyleneoxy groups, such as ethyleneoxy and propyleneoxy, are preferable. W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, or butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable. Y ₂ represents a hydrogen atom or —CO—R ⁵² (R ⁵² represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among which carbon number 2 such as ethyl, propyl, butyl, pentyl, etc. To 5 alkyl groups are preferred. q represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the formula (V), W ₃ is an alkyl group having 1 to 50 carbon atoms or 1 to 5 carbon atoms having a hydroxyl group.
Represents a hydroxyalkyl group having ˜50, among which a C10-20 alkyl group such as stearyl and a C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as monohydroxystearyl are preferable.
The content of the repeating unit represented by the formula (I) or (II) in the graft copolymer of the present invention is preferably as high as possible, usually 50 mol% or more, and preferably 70 mol% or more. The repeating unit represented by formula (I) and the repeating unit represented by formula (II) may both be present, and the content ratio is not particularly limited, but the repeating unit represented by formula (I) It is preferable to contain a large amount of. The total number of repeating units represented by formula (I) or formula (II) is usually 1 to 100, preferably 10 to 70, more preferably 20 to 50 in one molecule.

Moreover, repeating units other than formula (I) and formula (II) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. The graft copolymer of the present invention, the terminal -NH ₂ and ^-R 51 -NH ₂ ^{(R 51} is the ^{R 51} as defined) ones are preferred.
In addition, if the above-mentioned conditions are satisfied, the main chain may be linear or branched.
(E-1) The amine value of the copolymer is usually 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g, and more preferably 15 to 40 mgKOH / g or less. If the amine value is too high or too low, the dispersion stability may decrease and the viscosity may become unstable. Moreover, when too high, the electrical property after forming a liquid crystal panel may fall.
The amine value of the dispersant is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HCLO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve is taken as the titration end point, and the amine value is determined by the following formula.
Amine value [mgKOH / g] = (561 × V) / (W × S)
(W represents the amount of the dispersant sample weighed [g], V represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)

As for the weight average molecular weight of polystyrene conversion measured by GPC of the said (e-1) copolymer, 3000-50000 are preferable and 5000-20000 are especially preferable. When the weight average molecular weight is less than 3000, (a) aggregation of the coloring material cannot be prevented, and the viscosity or gelation may occur.
If it exceeds 50000, the viscosity itself becomes high, and (c) the solubility in an organic solvent may be insufficient. Further, due to the steric hindrance of the dispersant molecule itself, (a) adsorption to the coloring material may be inhibited, and the dispersibility may be lowered.

As a method for synthesizing the dispersing agent, a known method can be employed. For example, a method described in JP-B-63-30057 can be used.
In the present invention, a commercially available graft copolymer having the same structure as described above can also be applied.

(E-2): Acrylic block copolymer having a nitrogen atom
An acrylic block copolymer having a nitrogen atom (hereinafter sometimes referred to as “(e-2) copolymer”) is preferable in that (a) the coloring material can be dispersed extremely efficiently. The reason is not clear, but it is presumed that (a) there are few structures that obstruct the adsorption to the coloring material because the molecular arrangement is controlled.
(E-2) As a copolymer, A- which consists of A block which has a quaternary ammonium base and / or amino group in a side chain, and B block which does not have a quaternary ammonium base and / or amino group. B block copolymers and / or B-A-B block copolymers are preferred.

(E-2) The A block constituting the copolymer has a quaternary ammonium base and / or an amino group.
The quaternary ammonium base is preferably —N ⁺ R ³¹ R ³² R ³³ · Z ⁻ (where R ³¹ , R ³² and R ³³ are each independently a hydrogen atom, or an optionally substituted cyclic or chain) Or two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure, and Z ⁻ represents a counter anion). With the quaternary ammonium base represented. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

As the cyclic structure formed by combining two or more of R ³¹ , R ³² and R ³³ with each other in —N ⁺ R ³¹ R ³² R ³³ · Z ^— , for example, a 5- to 7-membered nitrogen-containing heterocyclic ring Examples thereof include a single ring or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

In the above formula, R represents any group of R ³¹ , R ³² , and R ³³ .
These cyclic structures may further have a substituent.
As ^{R 31,} R ^{32, R 33} in ^{-N + R 31 R 32 R 33} , has more preferably each independently an optionally substituted alkyl group having 1 to 3 carbon atoms, a substituent It may be a phenyl group which may be substituted, or a benzyl group which may have a substituent.

  As the A block having a quaternary ammonium base, those containing a partial structure represented by the following general formula (VI) are preferable.

In the general formula (VI), R ³¹ , R ³² , and R ³³ each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R ³¹ , R ³² , and R ³³ may be bonded to each other to form a cyclic structure. R ³⁴ represents a hydrogen atom or a methyl group. X ¹ represents a divalent linking group, and Z ⁻ represents a counter anion.
In the general formula (VI), the hydrocarbon groups of R ³¹ , R ³² , and R ³³ are each independently a substituent having an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms. Groups are preferred. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, or a benzyl group is preferable.
Examples of the divalent linking group X ¹ in the general formula (VI) include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ³⁵ —, —COO—R ³⁶ — (provided that R ³⁵ and R ³⁶ each independently represent a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms ^{(-R 37 -O-R 38 -} : R 37 and ^{R 38} is an alkylene independently Group))) and the like, and —COO—R ³⁶ — is preferable.

Examples of the counter anion Z ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .
As the A block, those having an amino group are particularly preferred. The amino group is preferably —NR ⁴¹ R ⁴² (provided that R ⁴¹ and R ⁴² each independently has a cyclic or chain-like alkyl group which may have a substituent, or a substituent. It represents a good allyl group or an aralkyl group which may have a substituent.), More preferably, an amino group represented by the following formula is mentioned.

^{However, R 41} and ^{R 42,} the above ^{R 41} and ^{R 42} as ^{defined, R 43} is an alkylene group having 1 or more carbon ^{atoms, R 44} represents a hydrogen atom or a methyl group. )
Among them, R ⁴¹ and R ⁴² are preferably a methyl group, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a hydrogen atom. Examples of such a compound include a substituent represented by the following formula.

Two or more kinds of partial structures containing the specific quaternary ammonium base and / or amino group as described above may be contained in one A block. In that case, two or more quaternary ammonium bases and / or amino group-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization.
Further, a partial structure containing neither the quaternary ammonium base nor the amino group may be contained in the A block. Examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. The content of the partial structure containing neither the quaternary ammonium base nor the amino group in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the amino group-free partial structure is not contained in the A block.

On the other hand, as the B block constituting the (e-2) copolymer, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (meth) acrylic acid Propyl, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate (Meth) acrylate monomers such as glycidyl ethyl acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; vinyl acetate monomers; glycidyl ethers such as allyl glycidyl ether and crotonic acid glycidyl ether Monomer Like polymer structure obtained by copolymerizing comonomers is.
The B block is particularly preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (VII).

(In general formula (VII), R ³⁹ represents a hydrogen atom or a methyl group. R ⁴⁰ may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents an allyl group or an aralkyl group which may have a substituent.)
Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more kinds of monomers is present in the B block, each partial structure may be contained in the B block in any form of random copolymerization or block copolymerization. When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 99% by weight, more preferably 0 to 85% by weight.

The (e-2) copolymer in the present invention is an AB block or a B-A-B block copolymer composed of such an A block and a B block. It is prepared by a polymerization method.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

  In synthesizing such an acrylic block copolymer, JP-A-60-89452, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 ( 1984), BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), K. Hatada, K. Ute, et al, Polym. J.18, 1037 (1986), Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987), K. Matyaszewski et al, Chem. Rev. 2001, 101, 2921-2990, etc. can be employed.

  The amine value (effective solid content conversion) in 1 g of the (e-2) copolymer according to the present invention is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 50 mgKOH / g or more, Particularly preferably, it is 80 mgKOH / g or more, and usually 300 mgKOH / g or less.

Moreover, although the acid value of (e-2) copolymer is based also on the presence and kind of acidic group which becomes the origin of this acid value, generally the lower one is preferable and it is usually 100 mgKOH / g or less, The molecular weight is The weight average molecular weight (Mw) in terms of polystyrene measured by GPC is usually in the range of 1000 or more and 100,000 or less. When the molecular weight of the block copolymer is too small, the dispersion stability is lowered. When the molecular weight is too large, due to the steric hindrance of the dispersant molecule itself, (a) the adsorption to the coloring material is inhibited and the dispersibility tends to be lowered. .
In the present invention, a commercially available acrylic block copolymer having the same structure as described above can also be applied.

(E-3): Urethane resin dispersant
The urethane resin dispersant (hereinafter sometimes referred to as “(e-3) dispersant”) is a polyisocyanate compound, a compound having one or two hydroxyl groups in the same molecule, and active in the same molecule. A urethane resin obtained by reacting hydrogen with a compound having a tertiary amino group is particularly preferred.

  Examples of the polyisocyanate compound include aroma such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω ' -Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane; xylylene diisocyanate, α, α, α ', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate; lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate And triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane) and tris (isocyanatephenyl) thiophosphate; and their trimers, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate, which can be used alone or in combination. Good.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, or one terminal hydroxyl group of these compounds is an alkyl group having 1 to 25 carbon atoms and alkoxy. Or a mixture of two or more of these.
Examples of the polyether glycol include polyether diol, polyether ester diol, or a mixture of two or more of these. As the polyether diol, those obtained by homopolymerizing or copolymerizing alkylene oxide, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, Or the mixture of 2 or more types of those is mentioned. Examples of the polyether ester diol include those obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or an anhydride thereof, or by reacting polyester glycol with an alkylene oxide. And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Examples of the polyester glycol include dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and phthalic acid, or anhydrides thereof, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene. Glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neo Pentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentane Diol, 1,6-hexanediol, 2-methyl-2 4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene Aliphatic glycols such as glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene Obtained by polycondensation with a diol such as N-alkyldialkanolamine such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, or the like; The diols The polylactone diol or polylactone monool obtained by using a monohydric alcohol having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone, or mixture of two or more thereof. Most preferred as the polyester glycol is a polycaprolactone glycol or polycaprolactone starting from an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. is there.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like.
Of these compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred. In addition, the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

  In the compound having an active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom includes a hydroxyl group, an amino group, a thiol group, etc. Among these, a hydrogen atom in the functional group is mentioned, and an amino group, particularly a primary amino group hydrogen atom is preferable. As the tertiary amino group, for example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, or the like, and the dialkylamino group are linked to form a heterocyclic structure. More specifically, an imidazole ring or a triazole ring can be mentioned. Among them, a dimethylamino group and an imidazole ring are preferable because of excellent dispersion stability.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  As the tertiary amino group is a nitrogen-containing heterocycle, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include nitrogen-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring; nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. It is done. Further, specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H. -1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino Examples include -1,4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4- Triazole and the like are preferable.

  The preferred use ratio of these (e-3) dispersant raw materials is usually 10 to 200 parts by weight, preferably 20 parts by weight of the compound having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. -190 parts by weight, more preferably 30-180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2-25 parts by weight, preferably 0.3-24 parts by weight. .

The (e-3) dispersant is produced according to a known method for producing a urethane resin. Solvents used in the production are usually ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone; esters such as ethyl acetate, butyl acetate and cellosolve; benzene, toluene, xylene and hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol and tert-butanol; halogenated hydrocarbons such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide, N- Aprotic polar solvents such as methyl pyrrolidone and dimethyl sulfoxide are used. Moreover, as a catalyst at the time of manufacture, a normal urethanization reaction catalyst is used. For example, tin system such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannous octoate; iron system such as iron acetylacetonate and ferric chloride; tertiary amine system such as triethylamine and triethylenediamine It is done.
In addition, the amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g by the amine value of the (e-3) dispersant resin after the reaction, More preferably, it is the range of 5-80 mgKOH / g, More preferably, it is the range of 10-60 mgKOH / g. When the amine value is out of the above range, the dispersion ability tends to be lowered. In addition, when an isocyanate group remains in the (e-3) dispersant molecule by the above reaction, the aging stability of the (e-3) dispersant is further increased by reacting an alcohol or an amino compound with the isocyanate group. Is preferable because of high.

  The weight average molecular weight in terms of polystyrene measured by GPC of these urethane resin dispersants is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. Range. When the molecular weight is 1,000 or less, the dispersibility and dispersion stability tend to be inferior. When the molecular weight is 200,000 or more, the solubility is lowered and the dispersibility is inferior.

(E-4): Other dispersant
The (e) dispersant used in the colored curable resin composition of the present invention may contain other dispersants in addition to the dispersants (e-1) to (e-3) described above.
(E-4) Other dispersants include, for example, polyallylamine-based dispersants, dispersants composed of amino group-containing monomers and macromonomers, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, Examples thereof include polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

  Specific examples of such a dispersant include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (manufactured by Shinetsu) Chemical products), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and other series names can be mentioned.

In the colored curable resin composition of the present invention, the content ratio of (e) the dispersant is usually 95% by weight or less, preferably 65% by weight or less, more preferably 50% by weight or less based on (a) the colorant. Moreover, it is 5 weight% or more normally, Preferably it is 7 weight% or more, Most preferably, it is 10 weight% or more. (E) If the content ratio of the dispersant is too small, (a) adsorption to the coloring material is insufficient, aggregation cannot be prevented, and viscosity or gelation may occur. As a result, dispersion stability deteriorates, and problems such as reaggregation and thickening may occur. On the other hand, if the amount is too large, the ratio of the coloring material (a) is relatively reduced, so that the coloring power is lowered. For this reason, the film thickness becomes too thick with respect to the color density, and when used in a color filter, a cell gap control defect may occur in the liquid crystal cell forming step.
In the colored curable resin composition of the present invention, among the various dispersants described above, particularly when (e-2): an acrylic block copolymer is included, the effect is remarkably exhibited.
Specifically, an A-B block copolymer and / or a B-A-B block copolymer consisting of an A block having an amino group in the side chain and a B block having no amino group in the side chain are included. And the dispersing agent whose amine value of this block copolymer is 10 mgK0H / g (effective solid content conversion) or more is mentioned. The amine value (in terms of effective solid content) of the dispersant is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 50 mgKOH / g or more, particularly preferably 80 mgKOH / g or more. Usually 300 mgKOH / g or less.
In addition, the colored curable resin composition of the present invention uses a part of the above-mentioned (b) binder resin together with the above (e) dispersant in the dispersion treatment step to be described later, and both serve as a dispersant. You may let them. In this way, a resin that performs the same function as the dispersant may be referred to as a “dispersion resin”.

[1-6] (f) Monomer
The colored curable resin composition of the present invention preferably contains (f) a monomer. (F) The monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).
When the colored curable resin composition of the present invention is irradiated with actinic rays, the ethylenic compound undergoes addition polymerization by the action of a photopolymerization initiation system described later or by the action of a thermal polymerization initiator described later by heating. It is a compound having an ethylenic double bond that cures. In addition, the monomer in this invention means the concept opposite to what is called a polymeric substance, and also contains a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.

  Examples of the ethylenic compound include unsaturated carboxylic acid such as (meth) acrylic acid, ester of monohydroxy compound and unsaturated carboxylic acid, ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid, aromatic polyhydroxy Esters obtained by esterification reaction of an ester of a compound with an unsaturated carboxylic acid, an unsaturated carboxylic acid and a polyvalent carboxylic acid and a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound, poly Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting an isocyanate compound and a (meth) acryloyl group-containing hydroxy compound.

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meta) ) Acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, triglycerol di (meth) acrylate Isopropyloxy of diglycerol di (meth) acrylate, etc. (meth) acrylic acid ester. Moreover, itaconic acid ester in which the (meth) acrylic acid portion of these acrylates is replaced with itaconic acid portion, crotonic acid ester in which crotonic acid portion is replaced, or maleic acid ester in which maleic acid portion is replaced.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate and the like. The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  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; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

Other examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylenebis (meth) acrylamide; allyl esters such as diallyl phthalate;
And vinyl group-containing compounds such as divinyl phthalate.
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferred, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. These monomers may be used alone, but since it is difficult to obtain a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.

  A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer are within the above range. It is preferable to adjust so that it may enter.

In the present invention, more preferred polyfunctional monomers having an acid group are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate, which are commercially available as “TO1382” manufactured by Toagosei Co., Ltd. It is a mixture mainly composed of ester. A combination of this polyfunctional monomer and another polyfunctional monomer can also be used.
When the colored curable resin composition of the present invention is used for producing an ink jet color filter, the monomer (f) is preferably a linear monomer or a monomer having a relatively small molecular weight, for example, ethoxylated trimethylol. Propane tri (meth) acrylate, triglycerol di (meth) acrylate, isopropyloxylated diglycerol di (meth) acrylate and the like are preferable. Such compounds are commercially available as “70PA”, “80MFA” (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.), “A-TMPT-3EO” (trade names, manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

  In the colored curable resin composition of the present invention, the content ratio of these (f) monomers is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. In addition, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. Further, the content ratio to (a) the color material is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less. It is preferably 100% by weight or less, more preferably 80% by weight or less.

[1-7] (h) Photopolymerization initiation system and / or thermal polymerization initiator
The curable resin composition of the present invention contains (h) a photopolymerization initiation system and / or a thermal polymerization initiator (hereinafter sometimes referred to as “(h) component”) for the purpose of curing the coating film. However, the curing method may be other than the method using the initiator.
In particular, when the curable resin composition of the present invention includes (b) a resin having an ethylenic C = C double bond as a binder resin component, or (f) when an ethylenic compound is included as a monomer component. Is a photopolymerization initiation system having a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical and / or a thermal polymerization start to generate a polymerization active radical by heat. It is preferable to add an agent to the curable resin composition.
In the present invention, the (h) component as the photopolymerization initiation system is a photopolymerization initiator (hereinafter arbitrarily referred to as (h1) component) to an accelerator (hereinafter arbitrarily referred to as (h2) component), It means a mixture in which an additive such as a sensitizing dye (hereinafter arbitrarily referred to as component (h3)) is used in combination.

[1-7-1] Photopolymerization initiation system
The colored curable resin composition of the present invention may contain a photopolymerization initiation system as the component (h). The photopolymerization initiation system as the component (h) is usually a mixture of (h1) a photopolymerization initiator, and (h2) a polymerization accelerator and (h3) an additive such as a sensitizing dye, which are added as necessary. And is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiation system (h1) include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; JP-A-10-300922 Biimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s-triazine Derivatives, radical activators such as N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Examples include oxime ester derivatives described in JP 2000-80068 A and the like.

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1 monoyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny- 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-difluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

Biimidazole derivatives include 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-diphenylimidazole dimer and the like.
Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

Examples of the α-aminoalkylphenone derivatives include 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-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like It is.
The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime) and the like.

  Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (pmethoxyphene Nil) acridine derivatives such as acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; anthrone derivatives such as benzanthrone and the like.

Examples of the (h2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; or mercapto compounds such as aliphatic polyfunctional mercapto compounds.
Each of these (h1) photopolymerization initiator and (h2) polymerization accelerator may be used alone or in combination of two or more.

  In the colored curable resin composition of the present invention, the total content of these (h1) photopolymerization initiator and (h2) polymerization accelerator is usually 0.1% by weight or more, preferably 0.8% in the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less. If this content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.

Further, (h3) sensitizing dye is used for the purpose of increasing the sensitivity as required. (H3) As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; Coumarin dyes having a heterocyclic ring described in Kaihei 3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes described in JP-A-3-239703, JP-A-5-289335, etc. Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP-A 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP No. -107761, JP-A-5-210240, it may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p- Ethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (P-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine P-dialkylaminophenyl group-containing compounds such as Of these, 4,4'-dialkylaminobenzophenone is most preferred. A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

  In the colored curable resin composition of the present invention, the content of the sensitizing dye (h3) is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% in the total solid content. It is in the range of not less than wt%, usually not more than 20 wt%, preferably not more than 15 wt%, more preferably not more than 10 wt%.

[1-7-2] Thermal polymerization initiator
Specific examples of the thermal polymerization initiator as the component (h) used in the present invention include azo compounds, organic peroxides and hydrogen peroxide. Of these, azo compounds are preferably used.
As the azo compound, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2 2,2'-azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2'-azobis [N-butyl-2-methylpropionamide], 2,2'-azobis (N-cyclohexyl) -2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionate), 2,2'-azobis (2, 4,4-trimethylpen Among these, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like are preferable.

Examples of the organic peroxide include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like. Specifically, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di (2-ethoxyethyl) peroxy Dicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t -Butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide , Di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 2, 5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2- Ethylhexanoate, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy)- 3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di- ( t-Butylperoxy) cyclohexyl) propane, t-hex Silperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5- Di- (3-methylbenzoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-di-methyl-2 , 5-Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl4,4-di- ( t-Butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide) Oxy) f Sun, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3 , 3-Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyltrimethylsilyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, di (3-methylbenzoyl) peroxide And benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide, and mixtures thereof.
Among the above-mentioned (h1) photopolymerization initiators, there are those that also function as thermal polymerization initiators, such as α-aminoalkylphenone compounds. Therefore, as the thermal polymerization initiator, a compound selected from (h1) examples given as examples of the photopolymerization initiator may be used.

These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
When the ratio of the thermal polymerization initiator is too small, the film is not sufficiently cured, and the durability as a color filter is insufficient. If the amount is too large, the degree of thermal shrinkage will increase, and cracking and cracking will occur after thermosetting. In addition, the storage stability is lowered. Therefore, it is preferable to make it into the range of 0-30 weight% in the total solid of the colored curable resin composition of this invention, especially 0-20 weight%.

[1-8] Other surfactants
As described above, the colored curable resin composition of the present invention contains other surfactants in addition to the compounds described in the section (g) Surfactant as long as the effects of the invention are not impaired. Also good.
As other surfactants, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but various properties such as voltage holding ratio and compatibility with (c) organic solvents are available. It is preferable to use a nonionic surfactant because it is less likely to adversely affect the surface.
Examples of anionic surfactants include alkyl sulfate ester surfactants such as “Emar 10” manufactured by Kao Corporation, and alkylnaphthalene sulfonate surfactants such as “Perex NB-L” manufactured by Kao Corporation. And special polymer surfactants such as “Homogenol L-18” and “Homogenol L-100” manufactured by Kao Corporation. Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

Examples of the cationic surfactant include alkylamine salt surfactants such as “Acetamine 24” manufactured by Kao Corporation, and quaternary ammonium salt interfaces such as “Cotamine 24P” and “Coatamine 86W” manufactured by Kao Corporation. Examples include activators. Of these, quaternary ammonium salt surfactants are preferred, and stearyltrimethylammonium salt surfactants are more preferred.
Nonionic surfactants include, for example, “SH8400” manufactured by Tore Silicone; silicone surfactants such as “KP341” manufactured by Silicone; “FC430” manufactured by Sumitomo 3M; Dainippon Ink and Chemicals, Inc. "F470" manufactured by KK; fluorine-based surfactants such as "DFX-18" manufactured by Neos; polyoxyethylene-based surfactants such as "Emulgen 104P" and "Emulgen A60" manufactured by Kao Corporation, etc. . Of these, silicone surfactants are preferable, and so-called polyether-modified or aralkyl-modified silicone surfactants having a structure in which a side chain of a polyether group or an aralkyl group is added to polydimethylsiloxane are more preferable.

Two or more surfactants may be used in combination, for example, silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer. And combinations of surfactants. Of these, a combination of silicone surfactant / fluorine surfactant is preferable.
Examples of the silicone surfactant / fluorine surfactant combination include a polyether-modified silicone surfactant / oligomer-type fluorine surfactant combination. Specifically, for example, “TSF4460” manufactured by GE Toshiba Silicone / “DFX-18” manufactured by Neos, “BYK-300” manufactured by BYK Chemie / “S-393” manufactured by Seimi Chemical Co., “KP340 manufactured by Shin-Etsu Silicone Co., Ltd.” "F-478" manufactured by Dainippon Ink & Chemicals, "SH7PA" manufactured by Tore Silicone, "DS-401" manufactured by Daikin, "L-77" manufactured by Nihon Unicar, and "FC4430" manufactured by Sumitomo 3M The combination of is mentioned.

[1-9] Other components
In addition to the above components, the colored curable resin composition of the present invention includes a dispersion aid, an organic carboxylic acid or / and an organic carboxylic acid anhydride, a plasticizer, a dye, a thermal polymerization inhibitor, a storage stabilizer, and a surface protection. Agents, adhesion improvers, development improvers, and the like.
The dispersion aid is used for improving the dispersibility of the pigment in the colorant (a), improving the dispersion stability, and the like. For example, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, Examples thereof include pigment derivatives such as isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine.

Examples of the substituent of these pigment derivatives include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. These substituents may be directly bonded to the pigment skeleton, or may be bonded via an alkyl group, an aryl group, a heterocyclic group or the like. Of the substituents, a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group are preferable, and a sulfonic acid group is more preferable.
A plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions.

  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 anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, diketo Examples include sulfonic acid derivatives of pyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments. Among these, sulfonic acid derivatives of Pigment Yellow 138, sulfonic acid derivatives of Pigment Yellow 139, sulfonic acid derivatives of Pigment Red 254, sulfonic acid derivatives of Pigment Red 255, sulfonic acid derivatives of Pigment Red 264, and sulfonic acid of Pigment Red 272 are preferable. A sulfonic acid derivative of Pigment Red 209, a sulfonic acid derivative of Pigment Violet 23, and a sulfonic acid derivative of Pigment Yellow 138, and a sulfonic acid derivative of Pigment Red 254.

  In the colored curable resin composition of the present invention, the content ratio of these dispersion aids is usually 0.1% by weight or more, and usually 300% by weight or less, preferably 200% with respect to the color material component. % By weight or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less. If the added amount is small, the effect is not exhibited. Conversely, if the added amount is too large, the dispersibility and dispersion stability tend to be deteriorated.

When the colored curable resin composition of the present invention is used in a color filter as described later, in order to further reduce the residual undissolved matter of the colored curable resin composition while maintaining high pattern adhesion, An organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride may be contained. These are preferably contained when (e-3) the urethane resin dispersant is included as the above-mentioned (e) dispersant.
Specific examples of the organic carboxylic acid include aliphatic carboxylic acids and aromatic carboxylic acids.
Aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, (meth) acrylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid And dicarboxylic acids such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid; and tricarboxylic acids such as tricarbaric acid and aconitic acid. Examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and a carboxylic acid in which a carboxyl group is bonded to the phenyl group through a carbon bond.

Among these, those having a molecular weight of 600 or less are preferable, and those having a molecular weight of 50 to 500 are particularly preferable. Specifically, maleic acid, malonic acid, succinic acid, and itaconic acid are preferable.
Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specifically, acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, Aliphatic carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride Things. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.
Among these, those having a molecular weight of 600 or less are preferable, and those having a molecular weight of 50 to 500 are particularly preferable. Specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred.

In the colored curable resin composition of the present invention, the content of these organic carboxylic acids or / and organic carboxylic anhydrides is usually 0.01% by weight or more, preferably 0.03% by weight or more, based on the total solid content. More preferably, it is 0.05% by weight or more, and is usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less.
The colored curable resin composition of the present invention may contain a plasticizer. Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, and tricresyl. Examples include phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The content of these plasticizers is preferably in the range of 10% by weight or less based on the total solid content.

  The colored curable resin composition of the present invention may contain a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6- Examples include t-butyl-p-cresol, β-naphthol and the like. The content of these thermal polymerization inhibitors is preferably in the range of 3% by weight or less based on the total solid content.

[2] Method for Preparing Colored Curable Resin Composition Next, a method for preparing the colored curable resin composition of the present invention will be described.
In addition, the colored curable resin composition of the present invention may be prepared by preparing a pigment dispersion in advance and mixing other components thereto, or may mix all the components together. Below, the case where it prepares according to the former method is demonstrated to an example, However, It is not limited to this. .
First, (a) a color material, (c) an organic solvent, and (a) when the color material contains a pigment, (e) a dispersant, which is an optional component, are weighed in predetermined amounts, and in the dispersion treatment step, (a) color The pigment in the material is dispersed to obtain a pigment dispersion. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By carrying out this dispersion treatment, the pigment is made into fine particles, so that the application characteristics of the colored curable resin composition are improved, and the light transmittance of the pixels of the color filter produced using this is improved.

  When dispersing the pigment, it is preferable to use (b) a part of the binder resin and a dispersion aid as appropriate. Moreover, when performing a dispersion process using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the pigment dispersion, the size of the sand grinder apparatus, and the like.

In addition to the pigment dispersion obtained by the above dispersion treatment, (g) a surfactant and (b) a binder resin, (c) an organic solvent, and optionally an optional component (f) monomer. (H) A colored curable resin composition is obtained by mixing a photopolymerization initiation system and / or a thermal polymerization initiator and other components to obtain a uniform dispersion solution. In addition, since fine dust may be mixed in each of the dispersion treatment step and the mixing step, the obtained pigment dispersion is preferably filtered with a filter or the like.

[3] Application of colored curable resin composition
The colored curable resin composition of the present invention is usually in a state where all components are dissolved or dispersed in a solvent. This is supplied onto the substrate to form the color filter and the constituent members of the liquid crystal display device.
Hereinafter, a method for producing a color filter using the colored curable resin composition of the present invention and a liquid crystal display device (panel) using the same will be described.

[3-1] Color filter
The manufacturing method of the color filter by the inkjet method using the colored curable resin composition of this invention is demonstrated.
In the inkjet method, a partition pattern (black matrix) is first provided on a substrate, and pixel forming ink is directly applied in the pattern to produce a color filter. Since ink droplets can be drawn at a desired position, high productivity and cost reduction of the color filter can be achieved.

The black matrix (BM) of the color filter by the ink jet method not only functions as a light shielding function that is conventionally required, but also functions as a partition wall for preventing RGB inks that are driven into the pixels from being mixed, so that the conventional photo Compared to the case of a color filter by lithography, the film thickness is thick (usually a film thickness of 1.5 μm or more, preferably about 1.8 to 2.5 μm, more preferably about 2.0 to 2.3 μm. There is a feature. Further, in order to prevent color mixing of RGB ink, liquid repellent treatment is often applied to the upper surface of the black matrix.
Therefore, it was formed using a photosensitive material including a black color material from a conventionally used chromium compound such as chromium, chromium oxide and chromium nitride, and a black matrix made of a light-shielding metal material such as nickel and tungsten alloy. A resin black matrix (BM) is preferred.

In the color filter of the present invention, the resin black matrix (BM) may be formed by a general photolithography method. The obtained resin BM is made hydrophilic on the surface of the transparent substrate and lyophobic on the BM pattern by chemical treatment or physical treatment, respectively.
Next, in a substantially rectangular recessed area surrounded by the resin BM pattern, the colored curable resin composition of the present invention is used to draw with an inkjet apparatus, and the composition is dried, photocured, and / or heat cured. A color filter is obtained by completely curing and forming pixels. As the colored curable resin composition for pixel formation, three colors of R (red), G (green), and B (blue) are often used, but are not limited thereto.

  The material of the transparent substrate used in the color filter of the present invention is not particularly limited. For example, a polyester such as polyethylene terephthalate; a polyolefin such as polypropylene and polyethylene; a thermoplastic such as polycarbonate, polymethyl methacrylate, and polysulfone. Examples thereof include a plastic sheet; a thermosetting plastic sheet such as an epoxy resin, a polyester resin, and a poly (meth) acrylic resin; or various glass plates. In particular, a glass plate and a heat-resistant plastic plate are preferably used from the viewpoint of heat resistance.

  For drying the coating film of the colored curable resin composition, heat drying such as a hot plate, IR (infrared) oven, convection oven or the like can be used. Preferred drying conditions are 40 to 150 ° C., and the drying time is 10 seconds to The range is 60 minutes. Further, reduced pressure (vacuum) drying can be used, and preferable drying conditions are 0.1 to 1 Torr, and drying time is in the range of 10 seconds to 60 minutes. Furthermore, both can be used together and can also be performed sequentially or simultaneously.

  When the colored curable resin composition of the present invention is cured by photocuring, examples of the light source used for exposure include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and a medium pressure mercury lamp. And lamp light sources such as low-pressure mercury lamps and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, and the like. In the case where only the wavelength of specific irradiation light is used, an optical filter can also be used.

[3-2] Liquid crystal display device
Next, the liquid crystal display device (panel) of the present invention will be described.
The liquid crystal display device of the present invention is manufactured, for example, as follows using the above-described color filter of the present invention.
First, an alignment film is formed on the color filter, a spacer is disposed on the alignment film, and then a liquid crystal cell is formed by bonding to the counter substrate. Next, liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode to complete.

The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method or a flexographic printing method is usually employed, and the thickness of the alignment film is usually 10 to 100 nm. After the alignment film is cured by thermal baking, it is surface-treated by ultraviolet (UV) irradiation or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.
A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film is formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an 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, then the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. To do. The degree of vacuum in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, Preferably it is 50-90 degreeC. The warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. In the liquid crystal cell into which the liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

The type of the liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of a lyotropic liquid crystal, a thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of these may be used.
[3-3] Organic EL Display When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. A part thereof is formed using the colored curable resin composition of the present invention), and a resin black matrix (not shown) provided between adjacent pixels 20 is formed. The organic EL element can be manufactured by stacking the organic light emitter 500 through the organic protective layer 30 and the inorganic oxide film 40 on the color filter.
As a method for laminating the organic light emitter 500, 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 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, published on August 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 thus manufactured, etc. Thus, an organic EL display can be produced.
The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
(Synthesis Example 1: (e-2) Equivalent to an acrylic block copolymer containing a nitrogen atom)
Acrylic AB block copolymer having a tertiary amino group according to Example 1 of JP-A-1-229014 except that the amino group (dimethylamino group) in the copolymer was not quaternized. A coalescence was synthesized. The weight average molecular weight Mw of the obtained copolymer was 9000, the amine value was 121 mgKOH / g, and the acid value was 0 mgKOH / g.
The amine value was expressed by the following method in terms of the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent, and was measured by the following method.
In a 100 mL beaker, 0.5 to 1.5 g in the dispersant obtained by the above synthesis was precisely weighed and dissolved in 50 mL of acetic acid. This solution was neutralized with a 0.1 mol / L HCLO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. With the inflection point of the titration pH curve as the end point of titration, the amine value was determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)

(Synthesis Example 2: (b) Synthesis of binder resin)
Prepare a separable flask with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while stirring to raise the temperature of the reaction tank to 90 ° C. did.
Meanwhile, 10 parts by weight of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 15 parts by weight of methacrylic acid, 20 parts by weight of methyl methacrylate, 55 parts by weight of benzyl methacrylate, t- 2.6 parts by weight of butyl peroxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate were charged, 5.2 parts by weight of n-dodecyl mercaptan and 27 parts of propylene glycol monomethyl ether acetate were added to the chain transfer agent tank. A weight part was charged, and after the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. While maintaining the temperature at 90 ° C., each dropping was performed over 135 minutes, and after 60 minutes from the completion of dropping, the temperature was raised to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a 30 wt% polymer solution having a weight average molecular weight of 9200 and an acid value of 107 mg KOH / g.

Example 1
(A) 8.6 g of Pigment Green 36 and 8.6 g of Pigment Yellow 150 as a colorant (pigment), 5.8 g of the compound obtained in Synthesis Example 1 as a dispersant, (b)
5.8 g of the resin obtained in Synthesis Example 2 as a binder resin, (c) 115.2 g of diethylene glycol mono-n-butyl ether acetate (DEGBEA) as an organic solvent, and after stirring and homogenizing, the particle diameter was 0.5 mm. 300 g of the above zirconia beads were added and dispersed by shaking for 5 hours with a paint conditioner to prepare a pigment dispersion.
Separately, (b) 10.5 g of an epoxy resin EHPE3150 manufactured by Daicel Chemical Co., Ltd. as a binder resin, (g) 1.4 g of Irgacure 907 manufactured by Ciba Geigy Co., Ltd. 0.02 g of the compound represented by the structural formula (iii) (“PF-6320” manufactured by OMNOVA) and (c) 16.2 g of diethylene glycol mono-n-butyl ether acetate (DEGBEA) as an organic solvent were mixed to be clear. A base was made.
In addition, according to the measuring method mentioned later, surface tension (sigma) and contact angle (theta) with respect to a glass substrate were measured about the 0.02 weight% DEGBEA solution of the compound represented by following structural formula (iii). The results are shown in Table-1. The surface tension σ ₀ of DEGBEA measured by the same method is 30
mN / m.

While stirring 22.0 g of the pigment dispersion, 28.0 g of the clear base was dropped and mixed, and then filtered through a 5 μm membrane filter to obtain a uniform colored curable resin composition.
The surface tension of the colored curable resin composition was measured with a fully automatic surface tension meter “CBVP-Z” manufactured by Kyowa Interface Science Co., Ltd. and found to be 29.8 mN / m.
About the obtained colored curable resin composition, wetting spreadability and pixel flatness were evaluated by the method mentioned later. The evaluation results are shown in Table-1.

<Measurement of surface tension σ>
It was measured with a fully automatic surface tension meter “CBVP-Z” manufactured by Kyowa Interface Science Co., Ltd.
<Measurement of contact angle θ>
After cleaning the glass substrate for liquid crystal panels (“AN100” manufactured by Asahi Glass Co., Ltd.) with a cleaning agent (“Sunwash TL-100” manufactured by Lion Co., Ltd.), UV cleaning is performed at 1000 mJ, and light cleaning is performed. A clean glass substrate having an angle of 0 °, that is, a completely wet spread is prepared. Next, the static contact angle θ of the sample solution with respect to the glass substrate was measured at 23 ° C. by using a commercially available contact angle measuring device (“CA-DT” manufactured by Kyowa Interface Science Co., Ltd.).

(Example 2)
Coloring and curing were carried out in the same manner as in Example 1 except that (g) the surfactant to be added to the clear base was changed to a compound represented by the following structural formula (iv) (PF-6520 manufactured by OMNOVA). A functional resin composition was obtained. In the same manner as in Example 1, the surface tension σ and the contact angle θ with respect to the glass substrate of the 0.02 wt% DEGBEA solution of the compound represented by the following structural formula (iv) were measured. The results are shown in Table-1.
The surface tension of this colored curable resin composition was 28.0 mN / m. In addition, Table 1 shows the evaluation results of wet spreadability and pixel flatness.

(Example 3)
(G) Coloring curability in exactly the same procedure as in Example 1 except that (g) the surfactant to be added to the clear base was changed to the compound represented by the following structural formula (ii) (OMNOVA PF-656). A resin composition was obtained. For the 0.02 wt% DEGBEA solution of the compound represented by the following structural formula (ii), the surface tension σ and the contact angle θ with respect to the glass substrate were measured in the same manner as in Example 1. The results are shown in Table-1.
The surface tension of this colored curable resin composition was 29.8 mN / m. In addition, Table 1 shows the evaluation results of wet spreadability and pixel flatness.

(Comparative Example 1)
A colored curable resin composition was obtained in the same procedure as in Example 1 except that the surfactant was not added to the clear base. Moreover, the surface tension of this colored curable resin composition was 30.0 mN / m. In addition, Table 1 shows the evaluation results of wet spreadability and pixel flatness.
(Comparative Example 2)
Add to the clear base (g) Color and cure in exactly the same way as in Example 1 except that the surfactant is Surflon “S-393” (nonionic; fluorine surfactant) manufactured by Seimi Chemical Co., Ltd. A functional resin composition was obtained. For the 0.02 wt% DEGBEA solution of “S-393”, the surface tension σ and the contact angle θ with respect to the glass substrate were measured in the same manner as in Example 1. The results are shown in Table-1.
The colored curable resin composition had a surface tension of 24.0 mN / m. In addition, Table 1 shows the evaluation results of wet spreadability and pixel flatness.
(Comparative Example 3)
(G) The same procedure as in Example 1 except that the surfactant is “F-475” (non-ionic; silicone-containing fluorine-based surfactant) manufactured by Dainippon Ink and Chemicals, Inc. A colored curable resin composition was obtained. For the 0.02 wt% DEGBEA solution of “F-475”, as in Example 1, the surface tension σ and the contact angle θ with respect to the glass substrate were measured. The results are shown in Table-1.
Moreover, the surface tension of this colored curable resin composition was 27.0 mN / m. In addition, Table 1 shows the evaluation results of wet spreadability and pixel flatness.

(Evaluation method for wet spread and pixel flatness)
Asahi Glass Co., Ltd. alkali-free glass substrate “AN635” 10 cm square is coated with a photosensitive resin composition containing a black color material so as to have a film thickness of 0.7 mm, and a line width of 20 μm and opening width by photolithography. A black matrix pattern of 220 μm × 700 μm and a thickness of 2.0 μm was formed.
After this substrate was subjected to a liquid repellent treatment by a fluorine-based gas plasma treatment, the central portion of each pixel bank formed by a black matrix pattern was obtained by the inkjet method in each example and comparative example. About 200 pl of the colored curable resin composition was applied. This was allowed to stand for 3 minutes in a windless environment at a temperature of 23 ° C. and a relative humidity of 55%, and then the area ratio (%) of the wet-spread portion of the colored curable resin composition to the area inside the pixel bank was measured.
Similarly, about 2000 pl of the colored curable resin composition obtained in each Example and Comparative Example was applied in a pixel bank and allowed to stand for 5 minutes in a windless environment at a temperature of 23 ° C. and a relative humidity of 55%. Subsequently, the coated substrate was dried by a decompression process to form pixels. The surface shape of the obtained pixel was measured with a three-dimensional laser microscope, and the area ratio (%) of the flat portion to the pixel area was evaluated by image measurement of a micrograph.

Evaluation of the colored curable resin compositions of Examples and Comparative Examples shown in Table 1 was performed as follows.
Wet spread was evaluated as x when the area ratio of wet spread was less than 40%, Δ when 40% or more and less than 60%, and ○ when 60% or more.
Pixel flatness was evaluated as x when the area ratio of the flat portion to the pixel area was less than 60%, Δ when it was 60% or more and less than 80%, and ○ when it was 80% or more.
The surface tension was rated as x for those less than 25 mN / m, Δ for those of 25 mN / m or more and less than 28 mN / m, and ◯ for those of 28 mN / m or more and 31 mN / m or less.
From the evaluation results shown in Table 1, the colored curable resin composition of the present invention has a wet spread and pixel without causing an excessive decrease in surface tension due to the addition of the compound represented by the general formula (0). It was found that a colored curable resin composition having good flatness can be obtained.

  According to the present invention, there is provided a colored curable resin composition (ink) exhibiting excellent performance in both surface smoothness of pixels and wettability in a pixel bank in color filter production by an inkjet method. be able to. Further, by using such an ink, a high-quality color filter can be manufactured with a high yield, and a large-scale and inexpensive supply of a liquid crystal display device can be realized.

It is a photograph which shows the wet spread property in the pixel bank of the colored curable resin composition prepared in the Example and comparative example of this invention. It is a photograph which shows the surface flatness of the pixel formed using the colored curable resin composition prepared in the Example and comparative example of this invention. It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the color filter of this invention.

Explanation of symbols

10 Transparent support substrate
20 pixels
30 Organic protective layer
40 Inorganic oxide film
50 transparent anode
51 Hole injection layer
52 Hole transport layer
53 Light emitting layer
54 Electron injection layer
55 Cathode
100 Organic EL device
500 Organic light emitter

Claims (21)

In a colored curable resin composition containing at least (a) a color material, (b) a binder resin, (c) an organic solvent, and (g) a surfactant,
(C) 80% by weight or more of the organic solvent is occupied by a solvent (c-1) having a boiling point of 180 ° C. or higher (a boiling point under a pressure of 101.25 [hPa]),
A colored curable resin characterized in that a 0.02% by weight solution of (g) surfactant prepared using the solvent (c-1) satisfies the following conditions (1) and (2): Composition.
(1) The contact angle with respect to the glass substrate is 10 ° or less. (2) The surface tension σ satisfies (σ ₀ −2) ≦ σ <σ ₀ with respect to the surface tension σ _{0 of} the solvent (c-1). (G) The coloring curable resin composition of Claim 1 in which surfactant contains the compound represented by following General formula (10).

(Wherein R ₁ represents an alkylene group having 2 to 6 carbon atoms, R ₂ represents an alkylene group having 2 to 3 carbon atoms, R ₃ represents a hydroxyl group or a hydrogen atom, and G represents 1 to 4 carbon atoms) Represents a fluorinated alkyl group, v, w and u each independently represent an integer of 0 to 2, x and t each independently represents 1 or 2, s represents an integer of 0 to 10, n represents 2 Represents an integer of ~ 100.
In addition, a plurality of molecules per molecule

May be the same or different groups. ) The colored curable resin composition according to claim 2, wherein the compound represented by the general formula (10) is a compound represented by the following general formula (0).

(In the above formula, the substituent G represents a fluorinated alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 100.)   In the said General formula (10) or General formula (0), the substituent G is a C1-C3 perfluoroalkyl group, and n is an integer of 5-30, It is an integer of 5-30. Colored curable resin composition. The colored curable resin composition according to any one of claims 1 to 4, wherein the condition (2) is the following condition (3).
(3) The surface tension σ is 28 mN / m or more and less than 30 mN / m.   The colored curable resin composition according to any one of claims 1 to 5, wherein, in the condition (1), a contact angle with respect to the glass substrate is less than 5 °. In a colored curable resin composition containing at least (a) a color material, (b) a binder resin, (c) an organic solvent, and (g) a surfactant,
(C) 80% by weight or more of the organic solvent is occupied by a solvent (c-1) having a boiling point of 180 ° C. or higher (a boiling point under a pressure of 101.25 [hPa]),
(G) A colored curable resin composition, wherein the surfactant contains a compound represented by the following general formula (10).

(Wherein R ₁ represents an alkylene group having 2 to 6 carbon atoms, R ₂ represents an alkylene group having 2 to 3 carbon atoms, R ₃ represents a hydroxyl group or a hydrogen atom, and G represents 1 to 4 carbon atoms) Represents a fluorinated alkyl group, v, w and u each independently represent an integer of 0 to 2, x and t each independently represents 1 or 2, s represents an integer of 0 to 10, n represents 2 Represents an integer of ~ 100.
In addition, a plurality of molecules per molecule

May be the same or different groups. ) The colored curable resin composition according to claim 7, wherein the compound represented by the general formula (10) is a compound represented by the following general formula (0).

(In the above formula, the substituent G represents a fluorinated alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 100.)   In the said General formula (10) or General formula (0), the substituent G is a C1-C3 perfluoroalkyl group, and n is an integer of 5-30, It is an integer of 5-7. Colored curable resin composition.   (G) Colored curable resin composition as described in any one of Claims 1 thru | or 9 whose content of surfactant is 0.005 to 5 weight% with respect to the total solid.   The colored curable resin composition according to claim 1, wherein (a) the color material contains a pigment.   The colored curable resin composition according to claim 11, further comprising (e) a dispersant.   (E) AB block copolymer and / or BAB block copolymer in which the dispersant is an A block having an amino group in the side chain and a B block having no amino group in the side chain. The colored curable resin composition according to claim 12, wherein the block copolymer has an amine value of 10 mgK0H / g (effective solid content conversion) or more.   The solvent (c-1) having a boiling point of 180 ° C. or higher (boiling point under pressure of 101.25 [hPa]) is diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 1 The colored curable resin composition according to claim 1, which is at least one selected from 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin.   The colored curable resin composition according to claim 14, wherein the solvent (c-1) having a boiling point of 180 ° C. or higher (boiling point under a pressure of 1013.15 [hPa]) is diethylene glycol mono-n-butyl ether acetate. .   (C) The colored curable resin composition according to any one of claims 1 to 15, wherein the content of the alcohol with respect to the total amount of the organic solvent is 20% by weight or less.   The colored curable resin composition according to any one of claims 1 to 16, wherein a contact angle with respect to the glass substrate is less than 5 °.   A colored curable resin composition for an inkjet color filter, comprising the colored curable resin composition according to any one of claims 1 to 17.   The color filter formed using the colored curable resin composition as described in any one of Claims 1 thru | or 18.   A liquid crystal display device comprising the color filter according to claim 19.   An organic EL display comprising the color filter according to claim 19.

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