JP2008102505A - Curable resin composition for color filter, color filter, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition for a color filter having high dark room contrast and excellent chemical resistance. The present invention also provides a color filter and a liquid crystal display device having a good darkroom contrast. [Solution] (A) A color material, and (B) a curable colored resin composition for a color filter containing a resin composition, B) A curable colored resin composition for color filters, in which the resin composition contains (a) a monomer, (b) a binder resin, and (c) a solvent and has specific properties, and a color filter using the same And liquid crystal display device.
[Selection figure] None

Description

  The present invention relates to a curable resin composition for a color filter, a color filter, and a liquid crystal display device. Specifically, the present invention relates to a curable resin composition for a color filter with little change in dark room contrast, a color filter formed using the same, and a liquid crystal display device.

Conventionally, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and an ink jet method are known as methods for producing a color filter used in a liquid crystal display device. From the viewpoint of spectral characteristics, durability, pattern shape and accuracy, a pigment dispersion method having excellent characteristics on average is most widely adopted. In addition, with respect to the curable resin composition (hereinafter sometimes referred to as “resist”) used for the color filter, the color filter pixel formability, the degree of cure, the durability, the adhesion to the substrate, and the composition. Various studies such as selection of a binder resin have been performed for the purpose of improving stability and the like (Patent Document 1, etc.).
In recent years, liquid crystal display devices have been used as televisions, and the contrast of liquid crystal display devices (hereinafter sometimes referred to as “contrast a” as appropriate) has become a very important characteristic. Factors affecting the contrast a include liquid crystal materials, polarizing plates, color filter contrasts (hereinafter sometimes referred to as “contrast b” as appropriate), and the like.

The pigment used for the color filter resist is usually an optically anisotropic particle. Therefore, light that has passed through the polarizing plate from the backlight is optically anisotropically scattered by the pigment particles, and the polarization state changes. Moreover, since the binder resin used for the resist for color filters may have birefringence, it may affect the optical characteristics of a color filter (nonpatent literature 1). The optical anisotropy of the color filter due to the above-described factors and others is the so-called color filter contrast (contrast b), which is one of the important characteristics of the color filter. The contrast b was not so important in the era when the use of personal computer monitors was mainstream. However, in recent years, with the development to applications that require high-quality images such as television applications, it has become a remarkable feature. This is mainly because if the contrast b is not good, a small amount of light leaks during black display (that is, the dark room contrast is not good), and black with good image quality cannot be reproduced.
JP 2005-154708 A Fumio Ide, “Transparent Resin That Has Been Here”, 2001, Industrial Research Committee

An object of the present invention is to solve the above-mentioned problems in the prior art, and to provide a curable resin composition for a color filter that has particularly high darkroom contrast and excellent chemical resistance.
Another object of the present invention is to provide a color filter and a liquid crystal display device having good dark room contrast using such a curable resin composition for a color filter.

As a result of diligent research to solve the above-mentioned problems, the present inventors may sometimes refer to components excluding color materials in the curable resin composition for color filters (hereinafter referred to as “transparent components” as appropriate). It has been found that a curable resin composition for a color filter having a high darkroom contrast can be obtained by setting () a specific physical property.
That is, the present inventors paid attention to the birefringence of the binder resin component that is the main component of the transparent component. In general, the birefringence of a transparent resin includes intrinsic birefringence due to the chemical structure of the material, orientation birefringence generated during molding, and stress birefringence (Non-Patent Document 1). In systems that polymerize by heat or light, intrinsic birefringence and stress birefringence are the main factors of birefringence.

In the present invention, it is necessary to sufficiently cure the coating film in order to increase the durability. In this case, it is assumed that stress birefringence occurs to some extent. Therefore, it is necessary to lower the birefringence in a sufficiently cured state.
As a simple method for examining the birefringence of the binder resin component, the present inventors set the contrast ratio of a transparent coating film having a thickness of 1 μm and a thickness of 2 μm as a transparent component of a curable resin composition for a color filter. A method for evaluation was found, and when a curable resin composition for a color filter in which this value falls within a specific range was used, it was found that high contrast was obtained as a color filter.

Further, the inventors have found that by adding a resin having an epoxy group, the chemical resistance of the color filter curable resin composition can be further improved while maintaining the contrast b at a high value, and the present invention has been achieved. .
That is, the gist of the present invention is as follows.
[1] A curable resin composition for a color filter containing (A) a color material and (B) a resin composition, wherein (B) the resin composition comprises (a) a monomer, (b) a binder resin, And (c) a curable resin composition for a color filter containing a solvent and having the following characteristics (hereinafter sometimes referred to as “the curable resin composition for a color filter of the first invention”).

(B) The resin composition is applied on a glass substrate, and after pre-baking at 110 ° C. for 3 minutes, the film thickness (1 ± 0.2) μm and the film thickness (2) obtained by post-baking at 240 ° C. for 30 minutes In the light-transmitting coating film of ± 0.2) μm, each darkroom luminance contrast CTR ₁ and CTR ₂ is expressed by the following formula.
0.97 ≦ CTR ₁ / CTR ₂ ≦ 1.04
[2] A curable resin composition for a color filter containing (A) a color material and (B) a resin composition, wherein (B) the resin composition comprises (a) a monomer, (b) a binder resin, And (c) a curable resin composition for a color filter containing a solvent and having the following characteristics (hereinafter sometimes referred to as “the curable resin composition for a color filter of the second invention”).

(B) A resin composition is applied onto a glass substrate, irradiated with ultraviolet light having a wavelength of 365 nm at 100 mJ / m ² , and then subjected to a shower development process at 23 ° C. and a water pressure of 0.25 MPa, followed by post-processing at 240 ° C. for 30 minutes. In the light-transmitting coating films having a film thickness (1 ± 0.2) μm and a film thickness (2 ± 0.2) μm obtained by baking, the respective darkroom luminance contrasts CTR ₁ and CTR ₂ are expressed by the following equations. The
0.97 ≦ CTR ₁ / CTR ₂ ≦ 1.04
[3] The resin composition (B) is composed of at least the following monomer components (b-1A) and (b-1B) as the binder resin (b), and the component (b-1A) is 20 mol% or more. The curable resin composition for a color filter according to the above [1] or [2], comprising a binder resin to be contained.

(B-1A) Mono (meth) acrylate having an aromatic ring
(B-1B) Mono (meth) acrylate having a structure represented by the following general formula (1)

(In the formula ^(1), R 1 to R ⁶ each independently represent a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms, ^{R 7} and ^{R 8} are each independently a hydrogen atom or a carbon atoms Represents an alkyl group of ˜3, or may be linked to form a ring.)
[4] The curable resin composition for a color filter according to any one of [1] to [3], further including a resin having an epoxy group.

[5] The curable resin composition for a color filter according to any one of [1] to [4], further including a photopolymerization initiation system and / or a thermal polymerization initiation system.
[6] The color according to any one of [1] to [5], wherein (a) the monomer in the resin composition (B) contains an addition-polymerizable compound having at least one ethylenic double bond. Curable resin composition for filters.

[7] A color filter formed using the curable resin composition for a color filter according to any one of [1] to [6].
[8] A liquid crystal display device formed using the color filter according to [7].

  According to the present invention, it is possible to provide a curable resin composition for a color filter that has particularly high darkroom contrast and excellent chemical resistance. Moreover, the color filter and liquid crystal display device with favorable dark room contrast can be provided using the said curable resin composition for color filters.

Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is limited to these contents as long as the gist thereof is not exceeded. Is not to be done.
[1] Curable resin composition for color filter The curable resin composition for a color filter of the first aspect of the present invention contains (A) a color material and (B) a resin composition, and (B) a resin composition. Contains (a) a monomer, (b) a binder resin, and (c) a solvent, and has the following characteristics.

(B) The resin composition is applied on a glass substrate, and after pre-baking at 110 ° C. for 3 minutes, the film thickness (1 ± 0.2) μm and the film thickness (2) obtained by post-baking at 240 ° C. for 30 minutes In the light-transmitting coating film of ± 0.2) μm, each darkroom luminance contrast CTR ₁ and CTR ₂ is expressed by the following formula.
0.97 ≦ CTR ₁ / CTR ₂ ≦ 1.04
In the curable resin composition for a color filter of the second invention, the (B) resin composition has the following characteristics.

(B) A resin composition is applied onto a glass substrate, irradiated with ultraviolet light having a wavelength of 365 nm at 100 mJ / m ² , and then subjected to a shower development process at 23 ° C. and a water pressure of 0.25 MPa, followed by post-processing at 240 ° C. for 30 minutes. In the light-transmitting coating films having a film thickness (1 ± 0.2) μm and a film thickness (2 ± 0.2) μm obtained by baking, the respective darkroom luminance contrasts CTR ₁ and CTR ₂ are expressed by the following equations. The
0.97 ≦ CTR ₁ / CTR ₂ ≦ 1.04
Moreover, the curable resin composition for a color filter of the present invention may further contain other components as required.

Hereafter, the structural requirements of the curable coloring composition for color filters of this invention are explained in full detail.
[1-1] (A) Coloring Material (A) The coloring material refers to a coloring material for the curable resin composition of the present invention. 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. In addition, “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, 1
4, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.
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. Of 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.

The above-mentioned various pigments can be used in combination. For example, in order to adjust the 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.

Examples of dyes that can be used as the colorant 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) 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 curable resin composition of the present invention, the ratio of the (A) color material to the total solid content in the curable resin composition is set according to the target film thickness, but is usually 20% by weight or more, Preferably, it is 30% by weight or more, more preferably 40% by weight or more, and usually 95% by weight or less.

  (A) If the content ratio of the color material is too small, the coloring power becomes low, the film thickness becomes too thick with respect to the color density, and there is a case where the gap control at the time of forming a liquid crystal cell is adversely affected. On the other hand, if the content ratio of the color material (A) is too large, the dispersion stability deteriorates and there is a risk of problems such as re-aggregation and thickening. When the component (A) is in the above range, a color filter having a high color density and a thin film thickness can be produced.

[1-2] (B) Resin Composition In the curable resin composition of the present invention, the (B) resin composition is the curable resin composition of the present invention except for the above-mentioned (A) color material. The so-called “transparent component”. (B) The resin composition contains (a) a monomer, (b) a binder resin, and (c) a solvent, and may contain other components if necessary.

[1-2-1] Dark Room Luminance Contrast The (B) resin composition in the curable resin composition of the present invention must have predetermined characteristics in the dark room luminance contrast. That is, in the curable resin composition for a color filter of the first aspect of the present invention, the (B) resin composition has the following characteristics.
The resin composition is applied onto a glass substrate, and after prebaking at 110 ° C. for 3 minutes, the film thickness (1 ± 0.2) μm and the film thickness (2 ± 0. 2) In a light-transmitting coating film of μm, darkroom brightness contrasts CTR ₁ and CTR ₂ are expressed by the following formulae.
0.97 ≦ CTR ₁ / CTR ₂ ≦ 1.04
Moreover, as for the curable coloring resin composition for color filters of 2nd this invention, the said (B) resin composition has the following characteristics.

The resin composition is coated on a glass substrate, irradiated with ultraviolet light having a wavelength of 365 nm at 100 mJ / m ² , and then obtained by post-baking at 240 ° C. for 30 minutes after a shower development process at 23 ° C. and a water pressure of 0.25 MPa. In the translucent coating film having a film thickness (1 ± 0.2) μm and a film thickness (2 ± 0.2) μm, the dark room luminance contrasts CTR ₁ and CTR ₂ are expressed by the following equations.
0.97 ≦ CTR ₁ / CTR ₂ ≦ 1.04
Specifically, the translucent coating film is produced, for example, as follows.

After dripping the curable resin composition of this invention in the center of a glass substrate, it spin-coat-coats by rotating this glass plate at 100-2000 rpm. When the curable resin composition has heat curing as a main curing mechanism, it is vacuum-dried, pre-baked at 110 ° C. for 3 minutes, and then post-baked at 240 ° C. for 30 minutes.
When the curable resin composition has photocuring as the main curing mechanism, it is irradiated with ultraviolet light at 100 mJ / m ² (amount of light energy at 365 nm) instead of prebaking, and then at 23 ° C., carbonic acid as a developer. After a shower development process using a sodium aqueous solution and a water pressure of 0.25 MPa, post-baking is performed at 240 ° C. for 30 minutes.

The coating amount of the curable resin composition was such that the film thickness of the translucent coating film to be formed (hereinafter sometimes referred to as “dry film thickness”) was (1 ± 0.2) μm and (2 Adjust as appropriate so that ± 0.2) μm.
When the dark room luminance contrasts of the translucent coating films having the thicknesses of (1 ± 0.2) μm and (2 ± 0.2) μm formed in this way are CTR ₁ and CTR ₂ , respectively, CTR ₁ / CTR ₂ of the curable composition is preferably 0.98 or more, preferably 1.03 or less, more preferably 1.02 or less. Note that the darkroom brightness contrast referred to here is based on the following measurement method.

Create a sample in which a translucent coating film formed on a glass substrate is sandwiched between two polarizing plates without leaving a gap, and a color luminance meter ("BM-5A" manufactured by Topcon Corporation) is installed in the dark room. Used to measure the amount of white light incident on the surface opposite to the color luminance meter through the sample. Light quantity A (cd / m ² ) when two polarizing plates in a sample are arranged orthogonally (crossed Nicols),
The ratio B / A of the light quantity B (cd / m ² ) when arranged in parallel is defined as the dark room luminance contrast.

As a specific means for obtaining a curable resin composition capable of producing a cured product in which the dark room luminance contrast ratio CTR ₁ / CTR _{2 of the} translucent coating film obtained under the specific conditions as described above falls within the above range, Examples thereof include a method of preparing a composition by selecting a monomer to be blended, a binder resin, a polymerization initiator, and the like.
[1-2-2] (B) Constituent Component of Resin Composition (B) The resin composition contains (a) a monomer, (b) a binder resin, and (c) a solvent. It may contain. Hereinafter, each component will be described in detail. In the following, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ". In addition, “(co) polymer” means “single polymer (homopolymer) and / or copolymer (copolymer)”.

In the following, “total solid content” refers to all components in the curable resin composition of the present invention other than the solvent components described later.
Moreover, below, the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin ((co) polymer) are the values of polystyrene conversion measured by GPC (gel permeation chromatography).

[1-3] (a) Monomer (a) The monomer is not particularly limited as long as it is a low molecular weight compound that can be polymerized. However, an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylene”). Preferred compound "). The ethylenic compound is an ethylenic compound that undergoes addition polymerization and cures by the action of a photopolymerization initiation system and / or thermal polymerization initiation system described below when the colored resin composition of the present invention is irradiated with actinic rays. It is a compound having a heavy bond. In addition, the monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept also containing a dimer, a trimer, and an oligomer other than the monomer (monomer) in a narrow sense.

  Examples of the ethylenic compounds include unsaturated carboxylic acids, esters thereof with monohydroxy compounds, esters of aliphatic polyvalent hydroxy compounds and unsaturated carboxylic acids, aromatic polyvalent hydroxy compounds and unsaturated carboxylic acids, and the like. Esters obtained by esterification with unsaturated carboxylic acids and polyvalent carboxylic acids, and polyhydric hydroxy compounds such as the above aliphatic polyvalent hydroxy compounds and aromatic polyvalent hydroxy compounds, polyvalent isocyanates Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting a compound with a (meth) acryloyl-containing hydroxy compound.

  Esters of aliphatic polyvalent hydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dimethylol tricyclodecane di (meth) a Relate, 2-hydroxy-3-acryloyloxypropyl methacrylate, (meth) acrylic acid adduct of ethylene glycol diglycidyl ether, (meth) acrylic acid adduct of glycerin diglycidyl ether, hydrogenated bisphenol A ethylene oxide adduct Di (meth) acrylate, hydrogenated bisphenol A propylene oxide adduct di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri Examples include (meth) acrylic acid esters such as (meth) acrylate and glycerol (meth) acrylate. Furthermore, the (meth) acrylic acid portion of these (meth) acrylates may be an itaconic acid ester substituted for an itaconic acid portion, a crotonic acid ester substituted for a crotonic acid portion, or a maleic acid ester substituted for a maleic acid portion. It is done.

  Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include di (meth) acrylate of bisphenol A ethylene oxide adduct, di (meth) acrylate of bisphenol A propylene oxide adduct, and bisphenol A diglycidyl ether. (Meth) acrylic acid adduct, bisphenol A ethylene oxide adduct diglycidyl ether (meth) acrylic acid adduct, bisphenol A propylene oxide adduct diglycidyl ether (meth) acrylic acid adduct, hydroquinone di (meth) acrylate Hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.

  The esters obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound are not necessarily a single substance, and may be a mixture. Typical examples are condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyvalent isocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, and fats such as cyclohexane diisocyanate and isophorone diisocyanate. Aromatic diisocyanates such as cyclic diisocyanates, tolylene diisocyanate, diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- Hydroxy compounds containing (meth) acryloyl groups such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane Reaction products of the like.

Examples of the ethylenic compounds other than those described above include acrylamides such as ethylene bisacrylamide, allyl esters such as diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate.
Among the ethylenic compounds, compounds having a (meth) acryloyl group are preferable from the viewpoint of film durability and transparency, and among them, a compound having an acryloyl group is particularly preferable. Of these, (meth) acrylates of aliphatic polyvalent hydroxy compounds are preferable, and acrylates are more preferable in that they are less colored.

Tetrafunctional monomers such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate have high curability, excellent chemical resistance and heat resistance, and sensitivity as photolithography. In addition to being high, it is also particularly preferable from the viewpoint of improving birefringence.
Moreover, you may use a diacrylate from a compatible viewpoint with binder resin. Among them, ethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 2-butyl-2-ethyl-1,3-propane Diol diacrylate, hydroxypivalate neopentyl glycol diacrylate, and dimethylol tricyclodecane diacrylate are preferable, and ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,6-hexanediol diacrylate are particularly preferable.

  The blending ratio of these monomers (a) is usually 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 80% in the total solid content of the curable resin composition of the present invention. % 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. Particularly preferred is 20% by weight or less. Moreover, the ratio with respect to (A) coloring material is 5 weight% or more normally, Preferably it is 10 weight% or more, and is 200 weight% or less normally, Preferably it is 150 weight% or less, More preferably, it is 100 weight% or less.

Although the monomer (a) can be used alone, two or more kinds of monomers may be used in combination as necessary.
[1-4] (b) Binder resin (b) The binder resin is blended as a binder of the curable resin composition of the present invention. As the binder resin (b) according to the curable resin composition of the present invention, a binder composed of a specific monomer component (b-1) described later from the viewpoint of suppressing the above-described fluctuation in dark room luminance contrast. It is preferable to contain a resin. Moreover, it is more preferable to contain (b-2) resin which has an epoxy group from a chemical-resistant viewpoint. Further, depending on the required performance such as the target pixel formability, degree of cure, durability, adhesion to the substrate and stability of the composition, (b-3) may contain other resins. .

[1-4-1] (b-1) Binder resin composed of specific monomer components (b-1) As a binder resin composed of specific monomer components according to the present invention,
For example, a binder resin composed of at least the following monomer components (b-1A) and (b-1B) and containing 20 mol% or more of the component (A) can be mentioned.
(B-1A) Mono (meth) acrylate having an aromatic ring (b-1B) Mono (meth) acrylate having a structure represented by the following general formula (1)

(In formula (1), R ^{1 to} R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, etc., and R ⁷ and R ⁸ are each independently a hydrogen atom, or a methyl group, an ethyl group, or represents an alkyl group having 1 to 3 carbon atoms such as a propyl group, or linked to by connecting good .R ⁷ and R ⁸ may form a ring The ring formed is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Hereinafter, the monomer component constituting the (b-1) resin will be described.

[1-4-1-1] (b-1A) Mono (meth) acrylate having an aromatic ring (b-1A) As mono (meth) acrylate having an aromatic ring, for example, phenyl (meth) acrylate, naphthyl ( (Meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, EO-modified cresol acrylate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxypropyl phthalate, ethoxylated phenyl acrylate, neopentyl glycol benzoate Acrylate, nonylphenoxypolyethylene glycol acrylate (carbon number of ethylene group (hereinafter referred to as “n”); 1), nonylphenoxypolyethylene glycol acrylate (n; 2), nonylphenoxypolyethylene glycol acrylate (n; 4), nonylphenoxy Polyethylene glycol acrylate (n; 8) Nonyl phenoxy polyethylene glycol acrylate (n; 16-17), Nonyl phenoxy polypropylene glycol acrylate, paracumyl phenoxy ethylene glycol acrylate, ECH modified phenoxy acrylate, phenoxy diethylene glycol acrylate, phenoxy ethyl acrylate, phenoxy hexaethylene Glycol acrylate, phenoxytetraethylene glycol Relate, tribromophenyl acrylate, EO-modified tribromophenyl acrylate, nonylphenoxypoly (ethylene glycol-propylene glycol) methacrylate, nonylphenoxypolyethylene glycol methacrylate, nonylphenoxypolypropylene glycol methacrylate, EO, PO-modified phthalic acid methacrylate, EO-modified phthalic acid Examples thereof include methacrylate and tribromophenyl methacrylate, and benzyl (meth) acrylate is particularly preferable. These (b-1A) components may be used individually by 1 type, and 2 or more types may be mixed and used for them. The aromatic ring may have a substituent other than a hydrogen atom, and examples of the substituent include a halogen atom and an alkyl group having 1 to 10 carbon atoms.

The content of the component (b-1A) is usually 20 mol% or more, preferably 25 mol% or more, and usually 80 mol% or less, preferably 70 mol% or less, based on the entire resin (b-1). is there. When the amount of the (b-1A) component is too small, the dark room contrast is lowered, and when it is too much, the thermal stability is lowered.
[1-4-1-2] (b-1B) Mono (meth) acrylate having a specific structure As this (b-1B) component, that is, as another radical polymerizable compound that can be copolymerized with (b-1A) component Is preferably one or more of mono (meth) acrylates having a structure represented by the following general formula (1).

In formula (1), R ^{1 to} R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and R ⁷ and R ⁸ are each independently , A hydrogen atom, or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or may be linked to form a ring. The ring formed by connecting R ⁷ and R ⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

  In the said General formula (1), the mono (meth) acrylate which has a structure represented by following Structural formula (2), (3), or (4) is preferable. By introducing these structures into the resin, it is possible to increase heat resistance and strength. Of course, these mono (meth) acrylates may be used alone or in combination of two or more.

  As the mono (meth) acrylate having the structure represented by the general formula (1), various known ones can be used, and those represented by the following general formula (5) are particularly preferable.

(In the formula (5), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents the general formula (1)).
The content of the component (b-1B) is usually 5 mol% or more, preferably 8 mol% or more, and usually 90 mol% or less, preferably 80 mol% or less, based on the entire resin (b-1). is there. If the amount of the component (b-1B) is too small, the dark room contrast is lowered. If the amount is too large, the viscosity of the liquid is increased, resulting in production inconvenience, and the thermal stability of the ink is impaired.

[1-4-1-3] (C) Other monomer components (C) Other monomer components include (C1) epoxy group-containing (meth) acrylate and / or (C2) epoxy group-containing (meta ) Monomers other than acrylates can be mentioned.
Examples of (C1) epoxy group-containing (meth) acrylates include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl. Although (meth) acrylate glycidyl ether etc. can be illustrated, glycidyl (meth) acrylate is especially preferable.

Moreover, the following are mentioned as other monomer components other than (C2) epoxy group containing (meth) acrylate.
Styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene;
Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene;
(Meth) acrylic acid, 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 acid hexyl, (meta ) 2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, (meth) acrylic acid Dicyclohexyl, isobornyl (meth) acrylate, (meth) acrylic acid adam Chill, allyl (meth) acrylate, propargyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydro (meth) acrylate Furyl, pyranyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, (meth) (Perfluoro-iso-propyl 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) acrylic acid N, (Meth) acrylic amides such as N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide;
Vinyl compounds such as (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate;
Unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate;
Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide;
N- (meth) acryloylphthalimide.

These (C) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The content of the component (C1) is usually 0.5 mol% or more, preferably 1 mol% or more, and usually 90 mol% or less, preferably 80 mol% or less, based on the total amount of the resin (b-1). is there. If the amount of the component (C1) is too small, the chemical resistance is lowered, and if it is too much, the thermal stability is lowered or the darkroom contrast is lowered.

The content of the component (C2) is usually 90 mol% or less, preferably 80 mol% or less, based on the entire (b-1) resin. (C2) When there are too many components, dark room contrast will fall.
[1-4-1-4] Characteristics and Production Examples of Binder Resin (b-1) (b-1) The binder resin composed of the specific monomer component according to the present invention has an acid value of usually 10 Above, preferably 20 or more, usually 300 or less, preferably 250 or less. If the acid value is too low or too high, the dispersion stability deteriorates.

  The weight average molecular weight (Mw) is usually 300 or more, preferably 5000 or more, and usually 100,000 or less, preferably 50000. If the molecular weight is too small, the heat resistance and the film strength are inferior. 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.

  As long as the binder resin composed of the specific monomer component (b-1) according to the present invention is composed of the specific monomer component, its production method is not particularly limited. ) Component, (B) component and (C) component, and (D) unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group contained in the resulting copolymer, A curable resin obtained by adding (E) a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl group produced when the component is added) is preferred.

  (D) component added to the epoxy group contained in the copolymer with (A) component, (B) component, and (C) component includes unsaturated monobasic acid. (D) As a component, a well-known thing can be used and the unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned, As an example, acrylic acid, methacrylic acid, crotonic acid, o-, Examples thereof include monocarboxylic acids such as m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano substitution. Of these, acrylic acid and / or methacrylic acid are preferred. These (D) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The component (D) is added to 10 to 100 mol% of the epoxy group contained in the copolymer obtained by the copolymerization reaction with the components (A), (B) and (C), preferably It is added to 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of the component (D) is too small, there are concerns about adverse effects due to residual epoxy groups such as stability over time.
As a method of adding the component (D) to the copolymer of the component (A), the component (B) and the component (C), a known method can be adopted.

  The (E) polybasic acid anhydride added to the hydroxyl group produced when the component (D) is added to the copolymer of the component (A), the component (B) and the component (C) Dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride Examples thereof include polybasic acid anhydrides such as acid, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. (E) A component may be used individually by 1 type and may be used in mixture of 2 or more types. By adding such components, the (b-1) binder resin according to the present invention can be made alkali-soluble.

The component (E) is added to 10 to 100 mol% of the hydroxyl group produced when the component (D) is added, preferably 20 to 90 mol%, more preferably 30 to 80 mol%. . When the addition ratio is too large, the remaining film ratio at the time of development may decrease, and when it is too small, the solubility becomes insufficient.
As a method of adding the component (E) to the hydroxyl group produced when the component (D) is added to the copolymer of the component (A), the component (B) and the component (C), a known method is used. Can be adopted.

  In the present invention, in order to further improve the photosensitivity, after adding the polybasic acid anhydride of the component (E), a part of the generated carboxyl group has glycidyl (meth) acrylate or a polymerizable unsaturated group. In order to add glycidyl ether compounds or to improve developability, after adding polybasic acid anhydride of component (E), add glycidyl ether compounds that do not have a polymerizable unsaturated group to a part of the generated carboxyl groups It is also possible to add both of them. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (manufactured by Nagase Chemical Industries, Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol) EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like.

Specifically, including methods other than the above manufacturing method, for example, in JP-A-8-297366, JP-A-2001-89533, JP-A-2004-300203, and JP-A-2004-300204, etc. It can be produced by the known methods described.
[1-4-2] (b-2) Resin Having Epoxy Group (b) The binder resin constituting the curable resin composition of the present invention is, as described above, from the viewpoint of improving chemical resistance (b- 2) It preferably contains a resin having an epoxy group.

  The (b-2) resin having an epoxy group according to the present invention is not particularly limited in its structure as long as it has an epoxy group in the resin, but among them, an alicyclic ring having an epoxy group in the side chain is preferred. Polyether compound, polyglycidyl ether compound, polyglycidyl ester compound, polyglycidylamine compound Polymer obtained by combining (meth) acrylate having epoxy group alone or in combination of two or more, or having epoxy group (meta ) Polymers obtained by polymerizing acrylate with other monomers in an amount of usually 10 to 70 mol%, preferably 15 to 60 mol%, based on all monomers.

Specific examples of the resin containing an epoxy group include the following compounds.
[1-4-2-1] Alicyclic polyether compound having an epoxy group in the side chain As the alicyclic polyether compound having an epoxy group in the side chain, for example, 2,2-bis (hydroxymethyl) -1 -Polycyclohexyl ether having an epoxy group in the side chain, such as 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of butanol. Examples of such commercially available compounds include EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.).

[1-4-2-2] Polyglycidyl ether compound Examples of the polyglycidyl ether compound include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), and bis (3,5 Diglycidyl ether type epoxy of -dimethyl-4-hydroxyphenyl), 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 Glycidyl ether type epoxy, dihydroxyoxyfluorene type epoxy, dihydroxyalkyleneoxylfluorene type epoxy, bisphenol A / aldehyde novolak type epoxy Bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, Examples thereof include phenol resin type epoxy resins such as a polymerization epoxy resin of phenol and naphthalene.

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.
[1-4-2-3] 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.

[1-4-2-4] Polyglycidylamine compound Examples of the polyglycidylamine compound include diglycidylamine type epoxy of bis (4-aminophenyl) methane and triglycidylamine type epoxy of isocyanuric acid, respectively. It is done.
[1-4-2-5] Other monomers As other examples, for example, 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 acid-6 , 7-epoxyheptyl and other (meth) acrylates having a single (meth) acrylate or a combination of two or more, or other comonomer in a (meth) acrylate structural unit having an epoxy group Usually, a polymer containing 10 to 70 mol%, preferably 15 to 60 mol% is used. Among these, as the copolymer, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, (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. A preferred (meth) acrylate having an epoxy group is glycidyl (meth) acrylate. Preferred copolymers include dicyclopentanyl (meth) acrylate and α-styrene.

In addition, the epoxy group used in the resin having (b-2) an epoxy group used in the present invention is usually a 1,2 epoxy group, but for the purpose of improving stability over time or imparting flexibility. 1,3 epoxy group (oxetane) and 4,3-epoxycyclohexyl group can also be used.
In addition, in the resin containing an epoxy group according to the present invention, those which do not contain an aromatic ring, or those which contain an unsubstituted or phenyl group having a substituent at the p (para) position, suppress discoloration due to heat treatment. Therefore, it is preferable. 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.

(B-2) The content of the resin having an epoxy group is usually 0.5 mol% or more, preferably 1.0 mol% or more, and usually 70 mol% or less, based on the entire resin (b-1). , Preferably it is 65 mol% or less. If the amount of the component (b-2) is too small, the chemical resistance is insufficient, and if it is too large, the storage stability is insufficient.
In addition, (b-2) the resin having an epoxy group may be copolymerized with the above-mentioned epoxy group-containing (meth) acrylate and another polymerizable monomer. Examples thereof include the polymerizable monomers described in chapters [1-4-1-1] to [1-4-1-3].

In addition, since (b-2) resin which has an epoxy group concerning this invention needs to have an epoxy group in resin, as described in [1-4-1-4], (D), ( The resin obtained by the process of adding the component E) and reacting with the epoxy group is not preferred.
(B-2) The weight average molecular weight (Mw) of the resin having an epoxy group is usually 300 or more, preferably 5,000 or more, and usually 100,000 or less, preferably 50,000 or less. If the molecular weight is too small, the heat resistance and film strength are inferior, and if it is too large, the solubility in the developer is insufficient, and the liquid properties as a coating solution become 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.

  In the above [1-4-2] chapter, the proportion of the resin having (b-2) epoxy group is usually 0% by weight or more, preferably 0 in the total solid content in the curable resin composition of the present invention. 0.5% by weight or more, more preferably 1% by weight or more, usually 50% by weight or less, preferably 40% by weight or less, more preferably 35% by weight or less. When the proportion of the component (b-2) is too small, the chemical resistance is insufficient, and when it is too large, the storage stability is insufficient.

[1-4-3] (b-3) Other resins (b) The binder resin constituting the curable resin composition of the present invention is, as described above, the target pixel formability, curing degree, and durability. (B-3) Other resins may be appropriately selected and used in accordance with required performance such as the property, adhesion to the substrate, and stability of the composition.
Specific examples of such (b-3) other resins include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, Homopolymers such as vinylidene chloride and maleimide, or copolymers containing these monomers, polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetyl cellulose, novolac resin, resole resin, polyvinyl Examples thereof include phenol and polyvinyl butyral. In the present invention, “acrylic resin” means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic ester having a carboxyl group.

  Among the other resins (b-3) listed above, an acrylic resin is preferable, and an acrylic resin containing a monomer having a carboxyl group or a phenolic hydroxyl group in the side chain or main chain is particularly preferable. . When an acrylic resin having these functional groups is used, the obtained color filter has good adhesion to the substrate. Among them, preferred are acrylic resins having a carboxyl group, such as acrylic acid (co) polymers, styrene-maleic anhydride resins, and novolak epoxy acrylate anhydride-modified resins. Among them, a (co) polymer containing (meth) acrylic acid or a (co) polymer containing a (meth) acrylic acid ester having a carboxyl group is particularly preferable. Those using these acrylic resins are excellent in adhesion to the substrate, transparency, etc., and can produce copolymers having different performance in combination with various monomers, and the production method is controlled. It is easy.

[1-4-3-1] Acrylic Resin (b-3) The acrylic resin as the other resin is, for example, a (co) polymer mainly composed of the following monomers.
As monomers, (meth) acrylic acid, succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- (meth) acryloyloxy) Ethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- (meth) acryloyloxypropyl) ester , Adipic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxypropyl) ester, phthalic acid (2- (meth) acryloyloxypropyl) ester, maleic acid (2- (meth) acryloyloxypropyl) ester, succinic acid (2- (meth) acryloyloxy) Butyl) ester, adipic acid (2- (meth) acryloyloxybutyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxybutyl) ester, phthalic acid (2- (meth) acryloyloxybutyl) ester , Maleic acid (2- (meth) acryloyloxybutyl) ester, hydroxyalkyl (meth) acrylate, (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid (anhydride) 1 type, or 2 or more types, such as a compound to which is added.

  Monomers that can be copolymerized with the above monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, cinnamic acid, maleic acid, fumaric acid, maleic anhydride, itacone. Unsaturated group-containing carboxylic acids such as acids, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl Esters of (meth) acrylic acid such as (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, and (meth) acrylic acid Caprolactone, β-propio Compounds containing lactones such as kuton, γ-butyrolactone, δ-valerolactone, acrylonitriles such as acrylonitrile and methacrylonitrile, (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloyl Acrylamides such as morpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethylacrylamide, vinyl acids such as vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate and vinyl pivalate 1 type, or 2 or more types, etc. are mentioned.

In addition, as “other resin” preferable for improving the strength of the coating film on the substrate, at least one of the following (b11) monomer group and at least one of the following (b12) monomer group: An acrylic resin obtained by copolymerization with one kind is mentioned.
(b11) Monomers include styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, and hydroxyphenyl (meth) acrylic. And monomers having a phenyl group such as sulfoamide.

  (b12) As the monomer group, (meth) acrylic acid or succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- (Meth) having a carboxyl group such as (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester Examples include acrylic acid esters.

The acrylic resin comprising these copolymers contains (b11) monomer group in an amount of 10 to 98 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and (b12) monomer group. 2 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%.
(B-3) The acrylic resin as the other resin preferably has an ethylenic double bond in the side chain. (B-3) When an acrylic resin having an ethylenic double bond in the side chain is used as the other resin, the curability of the curable resin composition of the present invention is improved. The adhesion with the coating film can be further improved.

(B-3) Examples of methods for introducing ethylenic double bonds into the side chains of other resins include the methods described in JP-B-50-34443, JP-B-50-34444, and the like. .
(B-3) Specific examples of other resins include JP-A-7-207211, JP-A-8-297366, JP-A-8-259876, JP-A-10-300922, and JP-A-11-. 140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2001-89533, JP-A-2003-233179, JP-A-2004-224894, JP-A-2004-300203 Known polymer compounds described in JP-A-2004-300204 and the like can be mentioned.

In the above [1-4-3] chapter, the proportion of (b-3) other resin is usually 0% by weight or more and usually 80% by weight or less in the total solid content in the curable resin composition of the present invention. , Preferably 50% by weight or less, more preferably 30% by weight or less. When the ratio of other resins is too large, the contrast is lowered.
The proportion of the resin (b) is usually 5% by weight or more, preferably 10% by weight or more, and usually 85% by weight or less, preferably 50% by weight in the total solid content in the curable resin composition of the present invention. It is as follows.

(B) If the proportion of the resin is too high, the coating film will have insufficient hardness or the viscosity of the curable resin composition will be too high. When it is not obtained or when alkali development is performed, there may be a problem that sufficient developability cannot be secured.
[1-5] (c) Solvent (c) The solvent functions in the curable resin composition of the present invention to dissolve or disperse each component and adjust the viscosity.

  Examples of usable solvent components include alcohols, phenols, glycols, glycol ethers, ethers, esters, ketones, acetates, aromatic hydrocarbons, halogenated hydrocarbons, nitriles, and amides. Alcohols, glycols, glycol ethers, ethers, esters, ketones, and acetates are preferable, and glycol ethers and ether acetates are particularly preferable.

  Specifically, ethanol, propanol, butanol, propylene glycol, butanediol, diethylene glycol, triethylene glycol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, Propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, carbitol, 3-ethoxy Ethyl propionate, propylene glycol Nomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, diisopropyl ether, mineral spirit, n-pentane, amyl ether Le, ethyl caprylate, n- hexane, diethyl ether, isoprene, ethyl isobutyl ether, n- octane, diisobutylene, Apuko thinner, butyl ether, diisobutyl ketone, methyl cyclohexene, methyl nonyl ketone, propyl ether, dodecane, Sokal Solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl Chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl Acetate, amyl formate, bicyclohexyl, dipentene, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, methyl ethyl Ketone, ethyl cellosolve acetate, cyclohexanone, ethyl acetate and the like.

  Among these solvents, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, and cyclohexanone are preferable.

Although the said (c) solvent may be used individually by 1 type, you may use 2 or more types of solvents together as needed.
(C) The boiling point of the solvent (the boiling point under the pressure of 1013.15 [hPa]. The same applies hereinafter) is usually 100 ° C. or higher and 300 ° C. or lower. If the boiling point is too low, the uniformity of the resulting coating film will be poor. Also, if the boiling point is too high, the effect of suppressing the drying property of the curable resin composition is high, but there are many residual solvents in the coating film even after heat baking, causing problems in quality, vacuum drying, etc. In some cases, the drying time in the oven becomes longer, causing problems such as an increase in tact time.

Moreover, (c) The vapor pressure of a solvent can use the thing below 10 mmHg normally from a viewpoint of the uniformity of the coating film obtained.
The proportion of the solvent (c) in the entire 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 the amount of the solvent is too large, the solid content is too small to be suitable for forming a coating film. If the amount is too small, the viscosity becomes too high and the stability of the composition is hindered. Or unsuitable for application.

[1-6] (d) Photopolymerization initiation system and / or thermal polymerization initiation system The curable resin composition of the present invention is used for the purpose of curing the coating film. It is preferable to include a system, but the curing method may be other than the above method using an initiator.
In particular, when the curable resin composition of the present invention contains an ethylenic compound as the component (a), it absorbs light directly or undergoes photosensitization to cause a decomposition reaction or a hydrogen abstraction reaction, resulting in a polymerization active radical. It is preferable to add a photopolymerization initiation system having a function of generating a polymerization and / or a thermal polymerization initiation system that generates a polymerization active radical by heat to the curable resin composition. In the present invention, the component (d) as the photopolymerization initiation system is a photopolymerization initiator (hereinafter arbitrarily referred to as component (d1)) to an accelerator (hereinafter arbitrarily referred to as component (d2)), It means a mixture in which an additive such as a sensitizing dye (hereinafter arbitrarily referred to as component (d3)) is used in combination.

[1-6-1] Photopolymerization Initiating System The photopolymerization initiating system generally means a compound that exhibits sensitivity to ultraviolet light to visible light, and it is preferable to use an exposure light source corresponding to the compound for image exposure. As the photopolymerization initiation system, a compound that exhibits sensitivity to ultraviolet light to visible light, particularly a compound that exhibits spectral sensitivity at a wavelength of 450 nm or less, particularly 400 nm or less, is preferable.

Examples of the photopolymerization initiator constituting the photopolymerization initiation system (d1) include, for example, JP-A-59-152.
No. 396, JP-A 61-151197, metallocene compounds including titanocene compounds, hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-phenylglycine, etc. described in JP-A-10-39503 N-aryl-α-amino acids, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone compounds, JP-A 2000-80068, Examples thereof include oxime ester initiators described in JP-A-2006-36750.

Specific examples of the polymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2
-(4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Halomethylated triazine derivatives such as ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-
Trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)] Halomethylated oxadiazole derivatives such as -1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;
2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- ( 2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5 -Imidazole derivatives such as diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1
-Anthraquinone derivatives such as chloroanthraquinone;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl -Acetophenone derivatives such as (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazines such as 9,10-dimethylbenzphenazine Derivatives;
Anthrone derivatives such as benzanthrone;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl -1 monoyl, di-cyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentagenyl-Ti-2,6-dipuruolophen-1-yl, di-cyclopentagenyl-Ti-2,4-difluorophenyl-1-yl, Di-methylcyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentagenyl-Ti-bis-2,6-di-fluoropheny -1-yl, di-cyclopentagenyl-Ti-2,6-di-fluoro-3- (pi 1-yl) - titanocene derivatives such as 1-yl;
2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as
N-acetoxy-N- {4-acetoxyimino-4- [9-ethyl-6- (O-toluoyl) -9H-carbazol-3-yl] butan-2-yl} acetamide, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1 Oxime ester compounds such as-(O-acetyloxime).

  As the oxime ester compound, other compounds shown below can be preferably used.

  Examples of the component (d2) (accelerator) constituting the component (d) include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds. The component (d1) and the component (d2) may be a mixture of two or more.

  Specific examples of the component (d) (photopolymerization initiator system) are described, for example, on pages 16 to 26 of “Fine Chemical” (March 1, 1991, vol. 20, No. 4). In addition to dialkyl acetophenone series, benzoin, thioxanthone derivatives, etc., as described in JP-A No. 58-403023, JP-B No. 45-37377, etc., Combinations of titanocene and xanthene dye, addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or urethane group described in JP-A-4-221958 and JP-A-4-219756 , Etc.

If the proportion of the component (d) is extremely low, the sensitivity to exposure light may be reduced. Conversely, if the proportion is extremely high, the stability of the composition may be impaired. The total solid content in the composition is preferably selected in the range of 0.1 to 30% by weight. Among these, 0.5 to 20% by weight is preferable, and 0.7 to 10% by weight is more preferable.
If necessary, the component (d) may contain a component (d3) (sensitizing dye) corresponding to the wavelength of the light source for curing the coating film for the purpose of improving the sensitivity. Examples of these components (d3) are xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703, JP-A-5-289335, and the like. Coumarin dyes having a heterocyclic ring, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335 and the like, and pyromethene dyes described in JP-A-6-19240 In addition, JP 47-2528, JP 54-155292, JP 45-37377, JP 48-84183, JP 52-112681, JP 58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-5. -168088 discloses, can be mentioned JP-A 5-107761, JP-A No. 5-210240, JP-dye having a dialkylamino benzene skeleton are described in, JP-A-4-288818 discloses the like.

  Among these (d3) components, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having both an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-bis (dimethylamino) benzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3, Benzophenone compounds such as 3′-diaminobenzophenone and 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) Nzothiazole, 2- (p-diethylaminophenyl) 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 P-dialkylaminophenyl group-containing compounds such as -diethylaminophenyl) pyrimidine. Of these, 4,4'-dialkylaminobenzophenone is most preferred. (D3) A sensitizing dye may also be used alone or in combination of two or more.

  If the proportion of the component (d3) is too large, the proportion relative to the components (a) and (b) becomes relatively large, and the film strength becomes insufficient due to a decrease in the amount of polymerization components. If the amount is too small, sufficient sensitivity may not be obtained. Therefore, it is preferable to select in the range of 0 to 20% by weight in the total solid content in the curable resin composition of the present invention. More preferably, it is 0.2-15 weight%, More preferably, it is 0.5-10 weight%.

[1-6-2] Thermal Polymerization Initiation System Specific examples of the thermal polymerization initiation system (thermal polymerization initiator) 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'-azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2'-azobis [N-butyl-2-methylpropion Amido], 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionamide) Pionate), 2,2'-azobis (2,4,4-trimethylpentene), and the like. 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 a mixture of benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide.

In addition, some of the compounds mentioned in the section of [1-6-1] photopolymerization initiation system also function as a thermal polymerization initiator. Therefore, as the thermal polymerization initiator, for example, (d1) a compound selected from the compounds listed as examples of the photopolymerization initiator may be used.
If the proportion 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 reduced. Therefore, it is preferable to select in the range of 0 to 30% by weight, particularly 0 to 20% by weight, based on the total solid content of the curable resin composition of the present invention.

[1-7] (e) Other components In the curable resin composition of the present invention, as described above, (e) other components can be further blended as necessary. , Dispersion aids, thermal polymerization inhibitors, plasticizers, surfactants, storage stabilizers, surface protective agents, smoothing agents, coating aids, adhesion improvers, coatability improvers, silane coupling agents, development improvers, etc. Can be added.

[1-7-1] Dispersant In the curable resin composition of the present invention, a dispersant can be used mainly for the purpose of finely dispersing (A) the color material and stably dispersing it. Examples of the dispersant that can be used include a polymer having a quaternary ammonium base, a polymer obtained by polymerizing a monomer essentially containing a compound represented by the following general formula (11), a urethane-based dispersant, and a polyalkylimine. Examples thereof include a dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

(In formula (11), R ²¹ and R ²² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
Among the dispersants, a polymer having a quaternary ammonium base and a monomer component essentially comprising the compound represented by the general formula (11) are polymerized from the viewpoint of storage stability of the curable resin composition. It is preferable to use a polymer, a polyalkylimine-based dispersant, and a urethane-based dispersant, and a monomer component having a quaternary ammonium base-containing polymer and the compound represented by the general formula (11) as an essential component. It is more preferable to use a polymer obtained by polymerization. Hereinafter, preferable dispersants will be described.

[1-7-1-1] Polymer having quaternary ammonium base The polymer having a quaternary ammonium base as described above is not particularly limited, but may be a block polymer or graft polymer having a controlled structure. In view of dispersion stability of the composition, AB block polymer and / or B-A comprising an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base, among others. -B block polymers are preferred.

The following is an AB block copolymer and / or a B-A-B block copolymer consisting of an A block having a quaternary ammonium base in the side chain and a B block not having a quaternary ammonium base. The dispersant characterized by this will be described.
The A block constituting the AB block copolymer and / or the BAB block copolymer has a quaternary ammonium base and optionally an amino group.

The quaternary ammonium base is preferably —N ⁺ R ^1a R ^2a R ^3a · Y ⁻ (where R ^1a , R ^2a and R ^3a are each independently a hydrogen atom, or an optionally substituted cyclic or chain) Or two or more of R ^1a , R ^2a and R ^3a may be bonded to each other to form a cyclic structure, and Y ⁻ represents a counter anion). It has 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.

In -N ⁺ R ^1a R ^2a R ^3a , as a cyclic structure formed by combining two or more of R ^1a , R ^2a and R ^3a with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the following are mentioned, for example.

(In the above formula, R represents any group of R ^{1a to} R ^3a .)
These cyclic structures may further have a substituent.
As R ^1a to R ^3a in the ^{-N + R 1a R 2a R 3a} , and more preferably may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a benzyl group which may have a phenyl group or a substituent.

  As the A block, those containing a partial structure represented by the following general formula (7) are particularly preferable.

(In the above general formula (7), R ^1a , R ^2a and R ^3a each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ^1a , R ^2a And two or more of R ^3a may be bonded to each other to form a cyclic structure, R ^4a represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents Represents a counter anion.)
In the general formula (7), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ^5a —, —COO—R ^6a — (provided that R ^5a and R ^6a is independently a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ^7a —O—R ^8a —: R ^7a and R ^8a are each independently alkylene; Group) and the like, and -COO-R ^6a -is preferred.

Further, Y ⁻ of the counter anion includes Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ CO.
O ^-, PF ₆ ^-, and the like.
The amino group is preferably —NR ^1b R ^2b (wherein R ^1b and R ^2b are each independently a cyclic or chain alkyl group which may have a substituent, or a substituent. The partial structure represented by General Formula (7) is more preferably represented by the following General Formula (8), which represents a good allyl group or an aralkyl group which may have a substituent. What is done.

(In the above formula, R ^1b and R ^2b have the same meanings as R ^1b and R ^2b , R ^3b represents an alkylene group having 1 or more carbon atoms, and R ^4b represents a hydrogen atom or a methyl group.)
Among them, R ^1b and R ^2b are preferably methyl groups, R ^3b is preferably a methylene group and an ethylene group, and R ^4b is preferably a methyl group.
As the partial structure represented by the general formula (8), a partial structure represented by the following structural formula (9) is preferably exemplified (Me is a methyl group).

  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. Moreover, the partial structure which does not contain this quaternary ammonium base and / or amino group may be contained in A block, As an example of this partial structure, it is derived from the below-mentioned (meth) acrylic acid ester monomer. Examples include partial structures. The content of such a quaternary ammonium base and / or a partial structure not containing an 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 block copolymer of the dispersant, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) methacrylate , (Meth) acrylic acid isopropyl, (meth) acrylic acid butyl, (meth) acrylic acid octyl, (meth) acrylic acid 2-ethylhexyl, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, (Meth) acrylate monomers such as glycidyl ethyl acrylate and N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, N -Methylolacrylamide, N (Meth) acrylamide monomers such as N-dimethylacrylamide and N, N-dimethylaminoethylacrylamide; polymers obtained by copolymerizing comonomers such as vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N-methacryloylmorpholine Structure is mentioned.

  The B block is preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (10).

(In the general formula (10), R ^9a represents a hydrogen atom or a methyl group. R ^10a may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents a good 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 monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be. 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.

Whether the dispersant is an A-B block copolymer or a B-A-B block copolymer, the A block / B block ratio constituting the copolymer is 1/99 to 80 / 20, in particular 5/95 to 60/40 (weight ratio) is preferred, and outside this range, it may not be possible to combine good heat resistance and dispersibility.
In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer according to the present invention is preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.

Such a block copolymer usually contains an amino group produced in the production process, but its amine value is preferably about 1 to 100 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of a basic amino group with an acid.
Further, the acid value of the block copolymer depends on the presence and type of the acid group from which the acid value is based, but generally it is preferably lower, usually 100 mg-KOH / g or less, preferably 50 mg-KOH / g. g or less, more preferably 10 mg-KOH / g or less.

The weight average molecular weight (Mw) of the block copolymer 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, and when it is too large, the developability and the resolution tend to be lowered.
In addition to the block copolymer, the dispersant in the present invention may contain a phosphate ester compound.

[1-7-1-2] Polymer formed by polymerizing monomer component having specific compound as essential Polymer formed by polymerizing monomer component having specific compound as essential is represented by the following general formula ( 11) A polymer obtained by polymerizing a monomer component essentially comprising the compound represented by (11).

(In formula (11), R ²¹ and R ²² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
In the general formula (11) showing an ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ²¹ and R ²² 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 , Alicyclic groups such as t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl An alkyl group substituted with an aryl group 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 ²¹ and R ²² may be the same type of substituent or different substituents.

  Specific examples of the ether dimer represented by the general formula (11) include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene). )] Bis-2-propenoate, di (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 (methyl) )] Bis-2-propenoate, 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- Lopenoate, di (t-butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2 -Propenoate, di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, And diadamantyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, and the like. It is done. 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 only one kind or two or more kinds.

The polymer obtained by polymerizing the monomer component essentially comprising the compound represented by the general formula (11) is a compound known per se, such as JP-A-2004-300203 and JP-A-2004-300204. And the compounds described in the publication No ..
[1-7-1-3] Urethane-based dispersant As urethane-based dispersants, <i> polyisocyanate compounds, <ii> compounds having one or two hydroxyl groups in the same molecule, <iii> same molecules A dispersion resin obtained by reacting an active hydrogen with a compound having a tertiary amino group is preferable.

<I> Polyisocyanate compound Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, Aromatic diisocyanates such as tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) , Ω, ω'-diisocyanate dimethylcyclohexane, alicyclic diisocyanates, xylylene diisocyanate, α an aliphatic diisocyanate having an aromatic ring such as α, α ′, α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, triisocyanate such as tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyols thereof Examples include adducts. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

  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.

<Ii> Compounds having one or two hydroxyl groups in the same molecule As compounds having one or two hydroxyl groups in the same molecule, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and these compounds And a mixture of two or more of these having one end hydroxyl group alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned. Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly 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.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (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, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. .

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

<Iii> Compound having active hydrogen and tertiary amino group in the same molecule Directly bonded to active hydrogen of a compound having active hydrogen and tertiary amino group in the same molecule, that is, oxygen atom, nitrogen atom or sulfur atom Examples of the hydrogen atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Among them, an amino group, particularly a primary amino group is preferred. The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  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.

  In addition, the tertiary amino group is a nitrogen-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-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. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole 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. . Further, specific examples of the compound having a triazole ring and an 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-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.

  A preferable blending ratio of the urethane-based dispersant raw material is 10 to 200 parts by weight of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. Is 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight. .

The weight average molecular weight (Mw) of such a urethane-based dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor, and at the same time, it becomes difficult to control the reaction.
The production of such a urethane-based dispersant is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl One or more of aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

In the production, a usual urethanization reaction catalyst is used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned.
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 mg-KOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value by neutralizing and titrating a basic group with an acid. If the amine value is lower than the above range, the dispersing ability tends to be lowered, and if it exceeds the above range, the developability tends to be lowered.

In addition, when an isocyanate group remains in the dispersion resin obtained by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability with time of the product becomes high.
Specific examples of commercially available dispersants listed in [1-7-1] include, for example, trade names such as “EFKA” series manufactured by EFKA Chemicals Beebuy (EFKA), “Disperbyk160” manufactured by BYK Chemie, “ “Disperbyk” series such as “Disperbyk161”, “Disperbyk162”, “Disperbyk163”, “Disperbyk164”, “Disperbyk166”, “Disperbyk167”, etc., “Disparon” manufactured by Enomoto Kasei Co., Ltd., “SOLSPERSE20000” manufactured by Abyssia Corporation "SOLSPERSE24000", "SOLSPERSE27000", "SOLSPERSE28000", "SOLSPERSE34750", "SOLSPERSE36000" and other "SOLSPERSE" series, Shin-Etsu Chemical Co., Ltd. "KP" series, Kyoeisha Chemical Co., Ltd. "Polyflow", Ajinomoto ( "Ajisper" manufactured by Co., Ltd. can be mentioned.

In the present invention, the above-described dispersant may be used alone, but two or more kinds may be used in combination.
The amount of the dispersant used is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, based on the colorant (A) in terms of storage stability of the composition, etc. It is 100 weight% or less, Preferably it is 80 weight% or less, More preferably, it is 60 weight% or less.

[1-7-2] Dispersion aid Examples of the dispersion aid include pigment derivatives. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine And derivatives such as pigments. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, 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 azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, and diketopyrrolopyrrole pigment sulfonic acid. Derivatives, sulfonic acid derivatives of dioxazine pigments and the like. These may be used alone or in combination of two or more.

The blending amount of the pigment derivative is usually 0.1 to 20% by weight, preferably 0.5 to 15% by weight or less, more preferably 1 to 10% by weight, based on the total solid content of the curable resin composition of the present invention. is there. If the addition amount of the pigment derivative is small, the dispersion stability is deteriorated, and problems such as reaggregation and thickening occur. On the other hand, if the amount is too large, the contribution to dispersion stability is saturated, and on the contrary, the color purity may be lowered.
[1-7-3] Thermal polymerization inhibitor Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol, and the like. Or 2 or more types are mentioned. The blending amount of the thermal polymerization inhibitor is preferably selected in the range of usually 0 to 3% by weight with respect to the total solid content of the curable resin composition of the present invention.

[1-7-4] Plasticizer Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 1 type (s) or 2 or more types. The blending amount of the plasticizer is preferably selected in the range of usually 0 to 10% by weight with respect to the total solid content of the curable resin composition of the present invention.

[1-7-5] Surfactant As the surfactant, various types such as anionic, cationic, nonionic, and amphoteric surfactants may be used alone or in admixture of two or more. However, it is preferable to use a nonionic surfactant because it is less likely to adversely affect various properties.
Silicone-based and fluorine-based surfactants can be preferably used.

Specific examples of commercially available silicone-based and fluorosurfactants include BYK-302, BYK-306, BYK-307, BYK-310, BYK-322, BYK-323, and BYK-325. BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK-373, BYK-375, BYK-356, BYK-359, BYK-361, BYK-051, BYK-052, BYK -053, BYK-055, BYK-057, BYK-065, BYK-066, BYK-067, BYK-070, BYK-077, BYK-080, BYK-088, BYK-141 (above BYK-Chemie products) Silicone surfactants such as Surflon S-381, Surflon S- 83, Surflon S-393, Surflon
SC-101, Surflon SC-105, Surflon KH-40, Surflon SA-100 (above Seimi Chemical product), Megafuck F470, Megafuck F471, Megafuck F472SF, Megafuck F474, Megafuck F475, Megafuck F477, Fluorosurfactants such as Megafuck F478, Megafuck F479, Megafuck F483, Megafuck F484 (above Dainippon Ink Co., Ltd.), Fluorard FC-430, Fluorado FC-431 (above Sumitomo 3M Co.) are used. it can.

  The compounding amount of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0% with respect to the total solid content of the curable resin composition of the present invention. 0.5 wt%, most preferably 0.03-0.3 wt%. If the amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film formed cannot be expressed. If the amount is too large, the smoothness and uniformity of the coating film cannot be expressed, and other characteristics deteriorate. There is a case.

[1-7-6] Silane coupling agent The curable resin composition of the present invention can also contain a silane coupling agent for the purpose of improving the affinity of the interface between the colorant and the binder resin. . The blending amount of the silane coupling agent is preferably selected in the range of usually 0.1 to 10% by weight with respect to the total solid content of the curable resin composition of the present invention.

[1-7-7] Others The curable resin composition of the present invention includes, in addition, an epoxy curing agent, a storage stabilizer, a surface protective agent, a smoothing agent, a coating aid, an adhesion improving agent, a coating property improving agent, and development. An improver or the like can be added as necessary. The amount of these components added is usually preferably 20% by weight or less based on the total solid content of the curable resin composition of the present invention.

[1-8] Method for Preparing Curable Resin Composition Next, a method for preparing the curable resin composition of the present invention will be described.
First, (A) a coloring material, (c) a solvent, and if necessary, a predetermined amount of a dispersant are weighed, and in the dispersion treatment step, (A) the coloring material is dispersed in the solvent (C) and a liquid resin composition is obtained. (Ink-like material). 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. Since the colorant (A) is finely divided by this dispersion treatment, the coating characteristics of the curable resin composition are improved, and a color filter with improved transmittance and contrast of transmitted light is obtained.

(C) When (A) the coloring material is dispersed in the solvent, (b) a dispersing agent such as a binder resin or a surfactant, a dispersion aid, or the like may be used in combination as appropriate. For example, when the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.05 to several millimeters.
The temperature during the dispersion treatment is usually set in the range of 0 to 100 ° C, preferably 10 to 80 ° C. The dispersion time varies depending on the composition of the ink-like material, the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted as appropriate.

  Uniform curing by mixing (a) monomer, (b) binder resin, and if necessary, a predetermined amount of (d) component, (e) component, etc. into the ink-like material obtained by the dispersion treatment step. A liquid of the functional resin composition. In each of the dispersion treatment step and the mixing step, fine dust may be mixed, and thus the obtained ink-like material or curable resin composition is preferably filtered with a filter or the like.

[2] Color filter Next, the color filter of the present invention will be described.
The color filter of the present invention is characterized by having pixels formed of the above-described curable resin composition for a color filter.
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, silane coupling agents, and thin film formation treatment of various resins such as urethane resins May be performed. The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

  The color filter of the present invention can be manufactured by providing a black matrix on a transparent substrate and forming pixel images of red, green and blue colors. Therefore, the above-mentioned curable resin composition of the present invention is used as a coating solution for at least one color filter among black, red, green, and blue. For black resist, on the transparent glass substrate glass surface, for red, green and blue, on the resin black matrix forming surface formed on the transparent substrate, or metal black formed using a chromium compound or other light shielding metal material A pixel pattern is formed on the matrix formation surface by a coating method such as a spinner method, a die coating method, or an ink jet method, and a curing process using light or heat is performed to form a pixel image of each color. An overcoat may be formed on the obtained color filter for the purpose of preventing elution of impurities from the liquid crystal and improving flatness.

The black matrix is formed on a transparent substrate using a light shielding metal thin film or a black matrix pigment dispersion. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloys, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, etching is performed by mixing ceric ammonium nitrate and perchloric acid for chromium. Other materials are etched using an etchant according to the material, and finally a positive photoresist is stripped with a dedicated stripper to form a black matrix.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the curable resin composition on the thin film, the coating film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  When using a black matrix pigment dispersion, a curable resin composition containing a black colorant is used to form a black matrix. For example, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or red, green, blue or the like appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed using a curable resin composition containing a black color material by mixing in the same manner as in the following method for forming red, green, and blue pixel images.

  On a transparent substrate provided with a black matrix, a curable resin composition for electronic displays containing red, green, and blue coloring materials is applied by a spinner method, a die coating method, an ink jet method, etc., dried, and if necessary Then, a pixel image is formed by heat curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three color curable resin compositions for red, green, and blue.

  The curable resin composition for a color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, an ink jet method, or the like. Among these, the die coating method and the ink jet method can greatly reduce the amount of coating solution used, and the ink jet method particularly has a great advantage in terms of manufacturing cost, such as omitting the development step.

Application conditions by a spinner method, a die coating method, an ink jet method or the like may be appropriately selected depending on the composition, viscosity, surface tension, and the like of the curable resin composition.
The coating film after the curable resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried. The predrying conditions (temperature and time) can be appropriately adjusted according to the type of the component (b), the performance of the dryer used, and the like.

The reheating drying temperature condition is preferably higher than the preliminary drying temperature. The drying time is preferably 10 seconds to 10 minutes, and more preferably 15 seconds to 5 minutes, depending on the heating temperature. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, thermal polymerization may be induced to cause development failure.
The thickness of the coating film of the curable resin composition for a color filter after drying is in the range of 0.5 to 3 μm, preferably 1 to 2.5 μm.

In the drying process of the coating film, a vacuum drying method may be used in which drying is performed in a vacuum chamber without increasing the temperature.
The coating film by the color filter curable resin composition of the present invention can be cured by stimulation with heat and / or light.
Image exposure can be performed as necessary. Under the present circumstances, in order to prevent the fall of the sensitivity of the photopolymerizable layer by oxygen as needed, you may expose, after forming oxygen barrier layers, such as a polyvinyl alcohol layer, on the coating film of curable resin composition.

  The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp. Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. When irradiating and using light of a specific wavelength, an optical filter can be used.

Moreover, after performing image exposure with the above-mentioned light source as necessary, an image is formed on a substrate by development using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound as a developer. can do. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. And alkali compounds. These alkaline compounds may be used individually by 1 type, and may use 2 or more types together.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids. These surfactants may be used alone or in combination of two or more.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution. An organic solvent may be used individually by 1 type, and may use 2 or more types together. Moreover, you may use as aqueous solution.

There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any method such as a development method and an ultrasonic development method may be used.
In addition to the manufacturing method described above, the color filter of the present invention can be manufactured by a method of applying the curable resin composition of the present invention to a substrate and forming a pixel image by an etching method. As other production methods, the curable resin composition of the present invention is used as a colored ink, and a pixel image is directly formed on a transparent substrate by a printing machine, or the curable resin composition of the present invention is electrodeposited. Examples thereof include a method of depositing a colored film on an ITO electrode that is used as a solution and immersed in the electrodeposition solution to form a substrate. Furthermore, the film coated with the curable resin composition of the present invention is attached to a transparent substrate and peeled off, and image exposure and development are performed to form a pixel image, or the curable resin composition of the present invention is used as a colored ink. And a method of forming a pixel image with an ink jet printer. As a method for producing the color filter, a method suitable for the color filter curable resin composition is employed depending on the composition of the color filter curable resin composition.

  The color filter after development is subjected to heat curing. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above. Further, as in the case of forming a pixel image with an ink jet printer, a plurality of types of colors may be patterned simultaneously.

  The color filter according to the present invention forms a transparent electrode such as ITO on the pixel image as it is, and is used as a part of components such as a color display and a liquid crystal display device. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[3] Liquid Crystal Display Device Next, a method for producing the liquid crystal display device (liquid crystal panel) of the present invention will be described as an example.
In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter of the present invention, spacers are dispersed on the alignment film, and then bonded to a counter substrate to form a liquid crystal cell. It is manufactured by injecting liquid crystal into the cell and connecting it to the counter electrode. Moreover, you may form the overcoat layer on the color filter of this invention as needed.

As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is usually several tens of nm. The alignment film is cured by thermal baking, and then surface-treated by irradiation with ultraviolet rays or a rubbing cloth to process the surface state so that 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 can be formed on the color filter substrate by photolithography, 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 being bonded 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 ultraviolet (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 decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure 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, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device (liquid crystal panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds are used, and any of lyotropic liquid crystals, thermotropic liquid crystals, and the like may be used. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

EXAMPLES Next, 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.
[1-1] Synthesis Example 1: Synthesis of Polymer Dispersant A 50 parts by weight of polyethyleneimine having a molecular weight of about 5000 and 40 parts by weight of polycaprolactone with n = 5 are mixed with 300 parts by weight of propylene glycol monomethyl ether acetate, and 150 The mixture was stirred at 0 ° C. for 3 hours under a nitrogen atmosphere. The weight average molecular weight (Mw) of the obtained polymer dispersant A was about 9000.

[1-2] Synthesis Example 2: Synthesis of Polymer Dispersant B A separable flask equipped with a cooling tube was prepared as a reaction tank, charged with 400 parts by weight of propylene glycol monomethyl ether acetate, purged with nitrogen, and then stirred. It heated with the oil bath and raised the temperature of the reaction tank to 90 degreeC.
On the other hand, 40 parts by weight of dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, 32 parts by weight of methacrylic acid, 48 parts by weight of methyl methacrylate, 80 parts by weight of benzyl methacrylate, t- 3 parts by weight of butyl peroxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate are charged, 6 parts by weight of n-dodecyl mercaptan and 24 parts by weight of propylene glycol monomethyl ether acetate are charged in a chain transfer agent tank, After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer vessel and the chain transfer agent vessel to initiate polymerization.

While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a polymer dispersant B having a weight average molecular weight (Mw) of 17000 and an acid value of 104 mg-KOH / g.
[2] Preparation and Evaluation of (B) Resin Composition In order to evaluate the (B) resin composition (transparent component) in the curable resin composition for a color filter of the present invention, the following Reference Examples 1 to 4 and Comparative Reference Example 1 was prepared.

[2-1] Preparation of Reference Examples 1 to 4 and Reference Comparative Example 1 With the component formulation described in Table 1 below, each component was mixed and stirred using a mixer to prepare a resin composition (B).

Binder resin I: Random copolymer represented by the following formula (acid value 80 mg-KOH / g, weight average molecular weight (Mw) 14,000)

Binder resin II: Random copolymer represented by the following formula (acid value 100 mg-KOH / g, weight average molecular weight (Mw) 17,300)

(In the above structural formula, k = 0.07, l = 0.65, and m = 0.28 are shown.)
Binder resin III: Synthetic resin III: Random copolymer represented by the following formula (acid value 30
mg-KOH / g, weight average molecular weight (Mw) 8,200)

(In the above structural formula, k = 0.3, l = 0.1, and m = 0.6 are shown.)
Solvent: Diethylene glycol monobutyl ether acetate (DEGBEA)
Polymerization initiator: Ciba Geigy's acetophenone photopolymerization initiator “Irgacure 907” Surfactant: Silicone surfactant (BIC Chemie's “BYK-300” series)
Next, a translucent coating film was formed using each of the prepared resin compositions (B).

  First, the resin composition (B) obtained in Reference Examples 1 to 4 and Comparative Reference Example 1 was applied onto a glass substrate (“AN100” manufactured by Asahi Glass Co., Ltd.) by a spin coating method, and at 110 ° C. with a hot plate. After pre-baking for 3 minutes, it was post-baked at 240 ° C. for 30 minutes in a Yamato Scientific dryer. The coating film thickness at the time of spin coating was adjusted to obtain two types of translucent coating films having a film thickness of 1 μm and a film thickness of 2 μm.

[2-2] Measurement of Dark Room Luminance Contrast of Reference Examples 1 to 4 and Reference Comparative Example 1 For the translucent coating films obtained in Reference Examples 1 to 4 and Comparative Reference Example 1, dark room luminance contrast was as follows. And the contrast ratio CTR ₁ / CTR ₂ was calculated. The results are shown in Table 2 below.
[2-2-1] Method for Measuring Dark Room Luminance Contrast A translucent coating film formed on a glass substrate is placed in close contact between two polarizing plates without any gap, and a color luminance meter (Topcon Corporation) Using “BM-5A”), the amount of white light incident from the surface opposite to the color luminance meter is measured. The ratio B / A of the light amount A (cd / m ² ) when the upper and lower polarizing plates are arranged orthogonally (crossed Nicols) and the light amount B (cd / m ² ) when they are arranged in parallel is defined as the dark room luminance contrast. .

From the above, the resin compositions of Reference Examples 1 to 3 using the binder resins I and II have a contrast ratio within the range of the following formula (Table 2, “Evaluation” ○), and the resin composition of Comparative Reference Example 1 is It was confirmed that the contrast ratio exceeded the range of the following formula (Table 2, “Evaluation” ×).
0.97 ≦ CTR ₁ / CTR ₂ ≦ 1.04
Next, a curable resin composition for a color filter was prepared based on the above Reference Examples and Reference Comparative Examples.

[3] Preparation of curable resin composition In the composition of ingredients shown in Table 3 below, each component was mixed and stirred using a mixer to prepare a mill base, which was then mixed with a sand grinder to obtain a particle size of 0. A pigment dispersion composition (ink) was prepared by performing a dispersion treatment at room temperature for 5 hours using 5 mm zirconia beads.
Next, to the obtained pigment dispersion composition, other components were added so as to have the composition described in Table 4 below, and filtered through a 5 μm membrane filter. Examples 1 to 5 and Comparative Example 1 2 curable resin composition was prepared. In addition, the pigment concentration of each curable resin composition was prepared to be 45% by weight in the total solid content.

Green pigment: C.I. I. Pigment Green 36
Yellow pigment: C.I. I. Pigment Yellow 150
Dispersant A: Polymer Dispersant A of Synthesis Example 1
Dispersant B: Polymer Dispersant B of Synthesis Example 2
Dispersant C: “Disperbyk 2000” manufactured by Big Chemie. An AB block copolymer having a block structural unit derived from a methacrylic acid ester (B block) and a block structural unit derived from a monomer having a quaternary ammonium base having the following structure in the side chain derived from methacrylic acid (A block) It is a commercial product. The weight average molecular weight (Mw) is about 3,500, and the amount of the quaternary ammonium base is 1.75 mmol per 1 g of the dispersant, the amine value is 4 mg-KOH / g, and the acid value is 0 mg-KOH / g.

Solvent A: Diethylene glycol monobutyl ether acetate (DEGBEA)
Solvent B: Propylene glycol monomethyl ether (PGME)

Synthetic resin IV: Random copolymer represented by the same formula as synthetic resin III (acid value 24 mg-KOH / g, weight average molecular weight (Mw) 7,600)
Synthetic resin V: random copolymer represented by the following formula (acid value 0 mg-KOH / g, weight average molecular weight (Mw) 6,100)

[4] Evaluation of curable resin composition [4-1] Production of translucent coating film The curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were prepared by spin coating. It is applied on a glass substrate (“AN100” manufactured by Asahi Glass Co., Ltd.), pre-baked at 110 ° C. for 3 minutes with a hot plate, and then post-baked at 240 ° C. for 30 minutes in a Yamato Scientific Co., Ltd. A light-sensitive coating film was obtained.

[4-2] Dark Room Luminance Contrast Ratio For Examples 1 to 5 and Comparative Examples 1 and 2, dark room luminance contrast was measured as follows. The results are shown in Table 5 below.
[4-2-1] Measuring Method of Dark Room Luminance Contrast A translucent coating film formed on a glass substrate is placed in close contact between two polarizing plates without leaving a gap, and a color luminance meter (Topcon Corporation) The amount of white light incident from the opposite side of the color luminance meter is measured using “BM-5A” manufactured by “BM-5A.” When the upper and lower polarizing plates are arranged orthogonally (crossed Nicols), the amount of light A (cd / m ² ) and the ratio B / A of the light quantity B (cd / m ² ) when arranged in parallel are defined as the dark room luminance contrast.

[4-3] Chemical resistance evaluation Chemical resistance evaluation was performed as follows for Examples 1 to 5 and Comparative Examples 1 and 2. The results are shown in Table 5 below.
Chemical resistance evaluation method: A post-baked glass substrate with a light-transmitting coating film is immersed in N-methylpyrrolidone at room temperature, left to stand for 30 minutes, then lifted, and N-methylpyrrolidone in running water with pure water and dry air After washing, the color change and the state of the coating film were observed visually or with a microscope and evaluated according to the following evaluation criteria.
Evaluation: Evaluation criteria A: There was no change in the state of the coating film.

○: Peeling or dissolution of the coating film was observed in a very small part.
Δ: Peeling or dissolution of the coating film was observed in a partial region.
X: Peeling and dissolution of the coating film were observed in most areas.

From the above, it was confirmed that the curable resin compositions of Examples 1 to 5 had high contrast. In addition, it was confirmed that the curable resin compositions of Examples 1, 2, and 4 to which (b-2) the binder resin was added also had good chemical resistance.

  According to the present invention, it is possible to provide a curable resin composition for a color filter that has particularly high darkroom contrast and excellent chemical resistance. Moreover, the color filter and liquid crystal display device with favorable dark room contrast can be provided using the said curable resin composition for color filters. Therefore, the industrial applicability of the present invention is extremely high in each field related to the color filter curable resin composition, the color filter, and the liquid crystal display device.

Claims (8)

A curable resin composition for a color filter comprising (A) a color material and (B) a resin composition, wherein (B) the resin composition comprises (a) a monomer, (b) a binder resin, and (c) ) A curable resin composition for a color filter containing a solvent and having the following characteristics.
(B) The resin composition is applied on a glass substrate, and after pre-baking at 110 ° C. for 3 minutes, the film thickness (1 ± 0.2) μm and the film thickness (2) obtained by post-baking at 240 ° C. for 30 minutes In the light-transmitting coating film of ± 0.2) μm, each darkroom luminance contrast CTR ₁ and CTR ₂ is expressed by the following formula.
0.97 ≦ CTR ₁ / CTR ₂ ≦ 1.04 A curable resin composition for a color filter comprising (A) a color material and (B) a resin composition, wherein (B) the resin composition comprises (a) a monomer, (b) a binder resin, and (c) ) A curable resin composition for a color filter containing a solvent and having the following characteristics.
(B) A resin composition is applied onto a glass substrate, irradiated with ultraviolet light having a wavelength of 365 nm at 100 mJ / m ² , and then subjected to a shower development process at 23 ° C. and a water pressure of 0.25 MPa, followed by post-processing at 240 ° C. for 30 minutes. In the light-transmitting coating films having a film thickness (1 ± 0.2) μm and a film thickness (2 ± 0.2) μm obtained by baking, the respective darkroom luminance contrasts CTR ₁ and CTR ₂ are expressed by the following equations. The
0.97 ≦ CTR ₁ / CTR ₂ ≦ 1.04 (B) The binder in which the resin composition is composed of at least the following monomer components (b-1A) and (b-1B) as the binder resin (b) and contains 20 mol% or more of the component (b-1A) The curable resin composition for a color filter according to claim 1 or 2, comprising a resin.
(B-1A) Mono (meth) acrylate having an aromatic ring
(B-1B) Mono (meth) acrylate having a structure represented by the following general formula (1)

(In the formula ^(1), R 1 to R ⁶ each independently represent a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms, ^{R 7} and ^{R 8} are each independently a hydrogen atom or a carbon atoms Represents an alkyl group of ˜3, or may be linked to form a ring.)   Furthermore, the curable resin composition for color filters as described in any one of Claim 1 thru | or 3 containing resin which has an epoxy group.   The curable resin composition for a color filter according to any one of claims 1 to 4, further comprising a photopolymerization initiation system and / or a thermal polymerization initiation system.   (B) Curability for a color filter according to any one of claims 1 to 5, wherein (a) the monomer in the resin composition contains an addition-polymerizable compound having at least one ethylenic double bond. Resin composition.   The color filter formed using the curable resin composition for color filters of any one of Claim 1 thru | or 6.   A liquid crystal display device formed using the color filter according to claim 7.