JP2018022024A - Photosensitive colored resin composition, color filter, method for producing the same, liquid crystal display device, and light-emitting display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored resin composition capable of forming a colored layer excellent in solvent resistance, a color filter formed using the photosensitive colored resin composition, and a liquid crystal display device and a light-emitting display device having the color filter.SOLUTION: The photosensitive colored resin composition contains (A) a coloring material, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent. The polyfunctional monomer (D) contains a phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group.SELECTED DRAWING: None

Description

  Embodiments of the present disclosure relate to a photosensitive colored resin composition, a color filter and a method for manufacturing the same, a liquid crystal display device, and a light emitting display device.

Many thin image display devices represented by displays and the like, so-called flat panel displays, have been put on the market, characterized by being thinner than a cathode ray tube type display and taking up little space in the depth direction. The market price has become affordable year by year with the evolution of production technology, the demand has further expanded, and the production volume has been increasing year by year. In particular, color LCD TVs have almost reached the mainstream of TV. In addition, a light-emitting display device such as an organic light-emitting display device such as an organic EL display that is highly visible due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and light emitting display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, the amount of light is controlled by electrically driving the liquid crystal, and color expression is performed by the light passing through a color filter. Therefore, a color filter must be present in the color representation of a liquid crystal television and plays a major role in determining the performance of the display. In the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed as in the liquid crystal display device.

  Here, the color filter is generally located on a transparent substrate, a transparent layer on the transparent substrate, and a colored layer composed of colored patterns of the three primary colors of red, green, and blue, and the transparent substrate so as to partition each colored pattern. And a light shielding portion located.

  In general, a liquid crystal display device is manufactured by individually manufacturing a color filter and a counter substrate having a TFT (Thin-Film-Transistor) array substrate and bonding them with a liquid crystal layer interposed therebetween. At this time, an alignment film such as polyimide for aligning the liquid crystal is formed on the colored layer of the color filter. For this reason, the colored layer is required to have resistance to a highly polar solvent such as N-methylpyrrolidone (NMP) used as a solvent when forming the alignment film.

  Further, as a recent trend, there is a demand for power saving of an image display device, and in order to improve the utilization efficiency of a backlight, a high brightness of a color filter is particularly demanded. As one means for achieving high brightness, a photosensitive colored resin composition using a dye has been studied. Dyes generally have higher transmittance than pigments and can produce high-luminance color filters, but colored resin compositions using dyes have the problem of poor solvent resistance of cured coatings. In addition, the dye has poor heat resistance and light resistance, and has a problem that chromaticity is easily changed during high-temperature heating in the color filter manufacturing process.

As a technique for improving various resistances of dyes, a technique for salting a dye is known (for example, Patent Document 1). However, even when the salt is formed, there is a problem in the solvent resistance of the cured coating film.
In the patent document 2, the present applicant discloses a color filter using a specific color material containing a divalent or higher cation in which a plurality of dye skeletons are cross-linked by a cross-linking group and a divalent or higher anion. . According to the salt-forming colorant of the dye, it is disclosed that a molecular aggregate is formed by containing a divalent or higher cation and a divalent or higher anion, and the solvent resistance is improved.
However, further improvement is required for the solvent resistance of the cured coating film of the colored resin composition.

  In Patent Document 3, a lake pigment, which is a salt forming color material of a dye, is dispersed using a polymer containing a structural unit in which at least a part of a nitrogen site and an acidic organic phosphorus compound form a salt as a dispersant. Is disclosed. However, even if such a dispersant is used, the solvent resistance of the cured coating film is insufficient, and further improvement is required.

  Patent Document 4 discloses a colored resin composition containing a phosphoric acid (meth) acrylate compound for the purpose of improving resolution during development and background staining. Patent Document 5 discloses a green photosensitive resin composition excellent in developability and resolution by containing a polyfunctional monomer having an acidic group. Patent Document 6 includes a phosphoric acid ester having an ethylenically unsaturated group, which is excellent in developability and also has an effect of suppressing yellowing of an alkali-soluble resin having a nitrogen-containing monomer unit such as an N-substituted maleimide. It is shown that there is. Patent Document 7 discloses a photosensitive resin composition that contains a phosphate ester having an ethylenically unsaturated group, has high definition, good adhesion, and no development residue. However, in the techniques of Patent Documents 4 to 7, the solvent resistance of the colored layer is insufficient, and further improvement of the solvent resistance has been demanded.

  On the other hand, Patent Document 8 discloses a coloring composition for a color filter containing a monomer having a specific isocyanurate skeleton, and describes that heat resistance and a remaining film ratio are improved.

JP 2001-81348 A International Publication No. 2012/144521 JP 2013-250446 A JP-A-9-227635 JP 2009-244321 A JP 2013-148602 A JP 2010-237449 A JP2013-164586A

  An embodiment of the present disclosure has been made in view of the above problems, and is formed using a photosensitive colored resin composition capable of forming a colored layer having excellent solvent resistance, and the photosensitive colored resin composition. An object is to provide a color filter, and a liquid crystal display device and a light-emitting display device each having the color filter.

One embodiment of the present disclosure includes (A) a color material, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent. And containing
Provided is a photosensitive colored resin composition in which the (D) polyfunctional monomer contains a phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group.

  In one embodiment of the present disclosure, a photosensitive colored resin composition in which an acid value of a phosphorus atom-containing monomer contained in the photosensitive colored resin composition is less than 190 mgKOH / g is provided.

  In one embodiment of the present disclosure, there is provided a photosensitive colored resin composition in which the color material (A) includes a salt-forming color material of a dye.

  In one embodiment of the present disclosure, the salt coloring material of the dye includes a photosensitive coloring resin including a salt forming color material of at least one dye selected from a triarylmethane basic dye and a xanthene basic dye A composition is provided.

  In one embodiment of the present disclosure, there is provided a photosensitive colored resin composition in which the salt forming color material of the dye includes a salt forming color material of a dye and a polyacid.

  In one embodiment of the present disclosure, there is provided a photosensitive colored resin composition in which the dye salt-forming color material includes a color material represented by the following general formula (I).

(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. aliphatic hydrocarbon radical having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, O in the carbon chain, S, may be contained N is .B ^c-'s c-valent poly R ^{i to} R ^v each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R good .Ar ¹ be ^iv and ^{R v} are bonded to form a ring structure represents a divalent aromatic group which may have a substituent. plural ^R i to R ^v and Ar ¹ each They may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

  One embodiment of the present disclosure is a color filter including at least a transparent substrate and a colored layer on the transparent substrate, the color filter having a colored layer that is a cured product of the photosensitive colored resin composition described above. provide.

One embodiment of the present disclosure is a method of manufacturing a color filter including at least a transparent substrate and a colored layer on the transparent substrate,
Provided is a method for producing a color filter, comprising a step of forming at least one of the colored layers by curing the photosensitive colored resin composition described above.

  One embodiment of the present disclosure provides a liquid crystal display device including the color filter described above, a counter substrate, and a liquid crystal layer positioned between the color filter and the counter substrate.

  One embodiment of the present disclosure provides a light-emitting display device that includes the color filter described above and a light emitter.

  One embodiment of the present disclosure provides a phosphorus atom-containing polyfunctional monomer represented by the following general formula (II) or the following general formula (III).

(In General Formula (II), W ¹ , W ² and W ³ are each independently a direct bond or —O— bond, and when there are a plurality of W ¹ , W ² and W ³ , they may be the same as each other. R ¹ is a hydrocarbon group or a group obtained by bonding a hydrocarbon group with at least one of an ether bond and an ester bond, and when there are a plurality of R ^{1 s} , they are the same. Z ¹ is a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group or a group represented by the following general formula (IV), and at least ^one of all Z ¹ One is a group represented by the following general formula (IV), and when there are a plurality of Z ^{1 s} , they may be the same or different, and R ² is a hydrocarbon group or a hydrocarbon. The group has few ether bonds and ester bonds. A group attached by Kutomo one is a (meth) acryloyl group, (meth) acrylamide groups, either no group of the group represented by a vinyl group and the following general formula (IV), R ² is When there are a plurality of them, they may be the same or different from each other, each of the hydrocarbon groups may have a substituent, f is 1, 2 or 3, and g is 0 or 1 And f + g is 1, 2 or 3. When g and 3-f-g are each 0, no bond exists.

(In General Formula (III), W ⁴ , W ⁵ , W ⁶ , W ⁷ , W ⁸ and W ⁹ are each independently a direct bond or an —O— bond, and W ⁴ , W ⁵ , W ⁶ , W ⁷ , when there are a plurality of W ⁸ and W ⁹ , they may be the same or different, and R ³ and R ⁴ each independently represents a hydrocarbon group or a hydrocarbon group with an ether bond and It is a group bonded by at least one ester bond, and when there are a plurality of R ³ and R ⁴ , they may be the same or different, and Z ² and Z ³ are each independently (meta ) An acryloyl group, a (meth) acrylamide group, a vinyl group and a group represented by the following general formula (IV), and at least one of all Z ² and Z ³ is represented by the following general formula (IV ) with a group represented, ^{Z 2} and Z There may be cases where more than one each identical, each good .R ⁵ and R ⁶ may be different independently, a hydrocarbon group, or at least one hydrocarbon group having an ether bond and an ester bond A bonded group, which is a group having neither a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, or a group represented by the following general formula (IV), and there are a plurality of R ⁵ and R ⁶ The hydrocarbon groups may each have a substituent, h and h ′ are each independently 0, 1 or 2, and may be the same or different. i and i ′ are each independently 0 or 1, h + h ′ is 1, 2, 3 or 4, i + i ′ is 0 or 1, and h + i and h ′ + i ′ are each independently 1 or 2, h, h ′, i, i ′, 2-h When i and 2-h'-i 'is 0, respectively, not bonded to each exist.)

(In the general formula (IV), R ⁷ and R ⁸ are each independently a hydrocarbon group or a group in which a hydrocarbon group is bonded by at least one of an ether bond and an ester bond, and Z ⁴ and Z ⁵ are Each independently is —O— (C═O) —CR ⁹ ═CH ₂ and —NR ¹⁰ — (C═O) —CR ¹¹ ═CH ₂ , wherein R ⁹ and R ¹¹ are each Independently, it is a hydrogen atom or a methyl group, and R ¹⁰ is a hydrogen atom, a methyl group or an ethyl group, and each of the hydrocarbon groups may have a substituent.

  Embodiments of the present disclosure include a photosensitive colored resin composition capable of forming a colored layer having excellent solvent resistance, a color filter formed using the photosensitive colored resin composition, and a liquid crystal display including the color filter. An apparatus and a light-emitting display device can be provided.

It is a schematic sectional drawing which shows an example of the color filter of this indication. It is a schematic sectional drawing which shows an example of the liquid crystal display device of this indication. It is a schematic sectional drawing which shows an example of the light emission display apparatus of this indication.

Hereinafter, the photosensitive colored resin composition, the color filter, the liquid crystal display device, and the light emitting display device according to the present disclosure will be described in order.
In addition, in this specification, (meth) acryl represents each of acrylic and methacryl, (meth) acrylate represents each of acrylate and methacrylate, and (meth) acryloyl represents each of acryloyl and methacryloyl. .
In the present specification, light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.

1. Photosensitive Colored Resin Composition The photosensitive colored resin composition of the present disclosure includes (A) a coloring material, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, and (E). A photoinitiator and (F) a solvent,
The (D) polyfunctional monomer contains a phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group.

Conventionally, when a composition containing a highly polar solvent such as N-methylpyrrolidone (NMP) is applied to form an alignment film on the colored layer, the colored layer peels off from the substrate or the colored layer swells. Or the chromaticity of the colored layer may change or the colored layer may be dissolved, and it has been desired to improve the solvent resistance.
On the other hand, the photosensitive colored resin composition of the present disclosure can improve solvent resistance by containing a phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group, and particularly N-methyl. Resistance to pyrrolidone (NMP) (NMP resistance) can be improved.
The reason why the photosensitive colored resin composition of the present disclosure can improve the solvent resistance is that the phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group has a large specific gravity because it contains a phosphorus atom, and is cured. It is presumed that the cross-linking reaction is carried out at a higher density in the film and the molecule becomes rigid because it contains an isocyanurate group, and the solubility in a solvent such as NMP is lowered, so that the penetration of the solvent is suppressed. . In addition, it is considered that the isocyanurate group has a large molecular weight and is a hydrophobic group, which contributes to the improvement of NMP resistance.

  The photosensitive colored resin composition of the present disclosure includes (A) a color material, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, F) It contains a solvent, and may contain other components as necessary. Hereinafter, each component will be described in order.

[(A) Color material]
The color material (A) used in the photosensitive colored resin composition of the present disclosure is not particularly limited as long as it can produce a desired color. As the colorant (A), for example, organic pigments, dyes, salt-forming colorants of dyes, and the like can be used alone or in admixture of two or more.
The salt forming color material of the dye may be a color material in which the dye forms a salt with a counter ion. Also included are organic pigments called lake pigments in which a water-soluble dye is precipitated with a rake agent (precipitating agent) to make it insoluble. Since the salt-forming colorant of the dye is derived from the dye, the transmittance is higher than that of a normal pigment, but there are generally many materials having low heat resistance.
In the following description, when color index names are described, when only color index names having different numbers are listed, only the numbers may be listed.

As the organic pigment, conventionally known organic pigments can be used, and are not particularly limited. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279; I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175 176,177,179,180,181,182,185,187,188,193,194,199,213,214; C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73; C. I. Pigment Green 7, 10, 36, 37, 58; I. The Cl substituents of Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. 80; C.I. I. Pigment violet 1, 19, 23, 27, 32, 37, 42; C.I. I. Pigment brown 25, 28; C.I. I. And CI pigment black 1 and 7.
In addition, a high-brightness pigment such as a zinc halide phthalocyanine pigment or a diketopyrrolopyrrole pigment has a high transmittance, but has a weak coloring power and has a problem of thinning a colored layer. By using a halogenated zinc phthalocyanine pigment or a diketopyrrolopyrrole pigment as the coloring material (A) in the colored resin composition, a high-luminance colored layer can be formed with a thinner film.

A conventionally known dye can be used as the dye and is not particularly limited, and examples thereof include an acid dye, a basic dye, and a direct dye.
Specific examples of the acid dye include C.I. I. Acid Violet 15, 16, 17, 19, 21, 21, 24, 25, 38, 49, 72, C.I. I. Acid Blue 1, 3, 5, 7, 9, 19, 22, 83, 90, 93, 100, 103, 104, 109, C.I. I. Acid green 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 50, and the like triarylmethane acid dyes; I. Acid Red 50, 51, 52, 87, 91, 92, 93, 94, 98, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Acid Blue 19, C.I. I. Acid Orange 11, C.I. I. And xanthene acid dyes such as Acid Yellow 73 and 74 and Sulforhodamine 101. Among the xanthene acid dyes, C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 289, C.I. I. Acid Violet 9, C.I. I. Acid Violet 30, C.I. I. A rhodamine acid dye such as Acid Blue 19 is preferred.

In addition, C.I. I. Acid Red 80, 81, 82, 83, C.I. I. Acid Violet 34, 36, 39, 41, 42, 43, 47, 48, 51, 63, 109, 126, C.I. I. Acid Blue 23, 25, 27, 35, 40, 41, 43, 45, 46, 47, 49, 51, 52, 53, 55, 56, 62, 68, 69, 78, 80, 81, 96, 111, 124, 127, 127: 1, 129, 138, 140, 145, 150, 175, 183, 215, 225, 230, 251, 258, 260, 264, 271, 277, 281, 290, 324, 344, 350, C. I. Anthraquinone acid dyes such as Acid Green 25, 27, 28, 36, 37, 38, 40, 41, 42, 44, 54, 95; I. Indigo acid dyes such as Acid Blue 74; C.I. I. Acid Blue 249, C.I. I. Phthalocyanine acid dyes such as Direct Blue 86 and 87; I. Acid Yellow 38, 42, 44, 56, 68, 79, 86, 87, 105, 117, 183, 219, 228, C.I. I. Acid Orange 4, 24, 25, 33, 45, 49, 55, 56, 63, 79, 95, 116, 128, 156, 165, C.I. I. Acid Red 47, 56, 65, 66, 70, 71, 73, 85, 86, 89, 97, 99, 104, 111, 112, 114, 115, 117, 119, 126, 128, 134, 142, 144, 145, 148, 150, 151, 154, 158, 163, 164, 170, 173, 323, 350, 351, 374, 444, C.I. I. Acid Violet 131, C.I. I. Acid Blue 26, 29, 36, 44, 85, 87, 92, 113, 114, 116, 118, 120, 128, 352, C.I. I. Acid Green 19, 20, 34, C.I. I. Direct yellow 4, 12, 13, 15, 24, 25, 31, 33, 34, 41, 42, 44, 50, 51, 52, 67, 69, 70, 72, 73, 74, 83, 86, 117, 118, 120, 130, 132, 134, 138, 142, 162, 167, C.I. I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 24, 25, 26, 29, 30, 31, 32, 33, 49, 69, 72, 74, 83, 85, 90, 92, 96, 101, 102, 104, 108, 118, C.I. I. Direct Red 2, 4, 6, 7, 8, 10, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 28, 29, 31, 33, 34, 36, 37, 39, 42, 43, 44, 46, 49, 50, 52, 53, 54, 55, 56, 57, 59, 60, 61, 62, 63, 67, 68, 72, 73, 74, 75, 77, 79, 81, 83, 85, 88, 89, 90, 98, 99, 101, 108, 110, 117, 120, 121, 122, 127, 130, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 173, 174, 176, 180, 181, 185, 186, 189, 191, 220, 224, 227, 239, 243, 250, 253, 257, 259, 260, 264, . I. Direct violet 1, 4, 5, 6, 7, 9, 11, 12, 13, 14, 16, 17, 21, 22, 25, 26, 27, 28, 31, 32, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 47, 48, 49, 51, 53, 57, 62, 63, 64, 66, 72, 77, 78, 79, 80, 81, 83, 85, 87, 88, 89, 102, 103, C.I. I. Direct Blue 1, 2, 3, 4, 6, 8, 9, 10, 11, 12, 14, 15, 16, 19, 21, 22, 23, 25, 26, 27, 29, 30, 31, 35, 36, 37, 38, 39, 42, 43, 45, 48, 49, 50, 51, 53, 54, 55, 58, 60, 63, 64, 65, 67, 76, 80, 84, 90, 93, 94, 95, 96, 98, 111, 116, 122, 123, 124, 128, 129, 130, 131, 132, 136, 138, 140, 145, 149, 150, 151, 152, 158, 164, 166, 167, 168, 175, 176, 177, 183, 184, 185, 191, 201, 214, 215, 218, 226, 230, 231, 273, 278, 290, 295, 297, 306, C I. Direct Green 1, 3, 6, 7, 8, 9, 10, 11, 12, 13, 19, 20, 21, 22, 34, 38, 39, 42, 49, 55, 57, 58, 60, 85, etc. Disazo acid dyes of
C. I. Acid Yellow 54, 59, 98, 99, 100, 106, 118, 120, 121, 151, 156, 220, 233, 241, 259, 260, 262, C.I. I. Acid Orange 61, 72, 74, 97, 125, 142, 148, 164, C.I. I. Acid Red 179, 180, 183, 184, 186, 187, 198, 201, 214, 251, 308, 357, 359, 362, 315, 316, 443, 405, 407, C.I. I. Acid Violet 56, 58, 61, 90, 91, 92, C.I. I. Acid Blue 42, 70, 154, 155, 158, 161, 169, 193, 198, 284, 317, 335, 349, C.I. I. Acid Green 12, 35, 43, 45, 73, 125, C.I. I. Monoazo acid dyes such as direct violet 46 and 56; and the like.

  The basic dye is an ionic dye having a cation moiety as a chromophore, such as diazine dyes, oxazine dyes, thiazine dyes, azo dyes, anthraquinone dyes, xanthene dyes, triarylmethane dyes. And dyes, phthalocyanine dyes, auramine dyes, acridine dyes, methine dyes, and the like. Specific examples include those with the following color index (CI) names.

C. I. Basic Red 2, 5, 6, 10, C.I. I. Basic Blue 13, 14, 16, C.I. I. Basic violet 5, 6, 8, 12, C.I. I. Diazine dyes such as basic yellow 14;
C. I. Oxazine dyes such as Basic Blue 3, 6, 10, 12, 74;
C. I. Basic Blue 9, 17, 24, 25, C.I. I. Thiazine dyes such as Basic Green 5;
C. I. Basic Red 18, 22, 23, 24, 29, 30, 31, 32, 34, 38, 39, 46, 51, 53, 54, 55, 62, 64, 76, 94, 111, 118, C.I. I. Basic Blue 41, 53, 54, 55, 64, 65, 66, 67, 162, C.I. I. Basic violet 18, 36, C.I. I. Basic Yellow 15, 19, 24, 25, 28, 29, 38, 39, 49, 51, 57, 62, 73, C.I. I. Azo dyes such as Basic Orange 1, 2, 24, 25, 29, 30, 33, 54, 69;
C. I. Anthraquinone dyes such as Basic Blue 22, 44, 47, 72;
C. I. Basic Red 1, 1: 1, 3, 4, 8, 11, C.I. I. Xanthene dyes such as basic violet 10, 11, 11: 1;
C. I. Basic Red 9, C.I. I. Basic Blue 1, 2, 5, 7, 8, 11, 15, 18, 20, 23, 26, 35, 81, C.I. I. Basic violet 1, 2, 3, 4, 14, 23, C.I. I. Triarylmethane dyes such as Basic Green 1 and 4;
C. I. Phthalocyanine dyes such as Basic Blue 140;
C. I. Auramine dyes such as basic yellow 2, 3, 37;
C. I. Basic Yellow 5, 6, 7, 9, C.I. I. Acridine dyes such as Basic Orange 4, 5, 14, 15, 16, 17, 18, 19, 23;
C. I. Basic Red 12, 13, 14, 15, 27, 28, 37, 52, 90, C.I. I. Basic Yellow 11, 13, 20, 21, 52, 53, C.I. I. Basic orange 21, 22, C.I. I. Methine dyes such as Basic Violet 7, 15, 16, 20, 21, 22 etc.
In the present disclosure, as the triarylmethane basic dye, a dye having a cation of a coloring material represented by the general formula (I) described later is also preferable.
These dyes can be used alone or in combination of two or more.

  In the salt coloring material of the dye, the counter ion varies depending on the kind of the dye, the counter ion of the acidic dye is a cation, and the counter ion of the basic dye is an anion. Therefore, the counter ion is appropriately selected and used according to the dye. That is, when the acid dye is insolubilized, a compound that generates a counter cation of the dye is used as a rake agent. When the basic dye is insolubilized, a counter anion of the dye is generated as a rake agent. A compound is used.

As counter cations of acid dyes, in addition to ammonium cations, metal cations such as phosphonium cations, sulfonium cations, calcium ions, barium ions, strontium ions, manganese ions, aluminum ions, cesium ions, lanthanum ions, neodymium ions, cerium ions, Examples thereof include inorganic polymers such as polyaluminum chloride and zirconium oxychloride.
Examples of the compound that generates ammonium ions include primary amine compounds, secondary amine compounds, tertiary amine compounds, and the like. Among them, secondary amine compounds are preferred because of their excellent heat resistance and light resistance. Alternatively, it is preferable to use a tertiary amine compound.

On the other hand, the counter anion of the basic dye may be an organic anion or an inorganic anion. Examples of the organic anion include organic compounds having an anionic group as a substituent. Examples of the anionic group include —SO ₂ N ^— SO ₂ CH ₃ , —SO ₂ N ^— COCH ₃ , —SO ₂ N ^— SO ₂ CF ₃ , —SO ₂ N ^— COCF ₃ , —CF ₂ SO _{2. ^{N - SO 2 CH 3, -CF}} 2 SO 2 N - COCH 3, -CF 2 SO 2 N - SO 2 CF 3, -CF 2 SO 2 N - COCF 3 or imidate group such as, -SO ₃ ^-, —CF ₂ SO ₃ ⁻ , —PO ₃ ²⁻ , —COO ⁻ , —CF ₂ PO ₃ ²⁻ , —CF ₂ COO ^{— and the} like can be mentioned. Among these, from the viewpoint of heat resistance and light resistance, an imido acid group, —SO ₃ ^— and —CF ₂ SO ₃ ^— are preferable, and —SO ₃ ^— (sulfonate group) is more preferable.
On the other hand, examples of the inorganic anion include an oxo acid anion (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ²⁻ ), molybdate ion (MoO ₄ ²⁻ ), and the like) Mention may be made of inorganic anions such as polyacid anions condensed with oxo acids and mixtures thereof.
The polyacid may be an isopolyacid anion (M _m O _n ) ^c- or a heteropoly acid anion (X _l M _m O _n ) ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. Examples of the poly atom M include Mo, W, V, Ti, and Nb. Examples of the hetero atom X include Si, P, As, S, Fe, and Co. Moreover, a counter cation such as Na ⁺ or H ⁺ may be partially included.
Among these, a heteropolyacid anion is preferable from the viewpoint of high brightness and excellent heat resistance and light resistance.
Among these, an anion of an inorganic acid containing at least one of tungsten (W) and molybdenum (Mo) is preferable from the viewpoint of high brightness and excellent heat resistance and light resistance.

Examples of the polyacid containing at least one of tungsten (W) and molybdenum (Mo) include, for example, tungstate ion [W ₁₀ O ₃₂ ] ⁴⁻ and molybdate ion [Mo ₆ O ₁₉ ] ²⁻ which are isopolyacids. Or phosphotungstic acid ions [PW ₁₂ O ₄₀ ] ³⁻ , [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , silicotungstic acid ions [SiW ₁₂ O ₄₀ ] ⁴⁻ , phosphomolybdate ions [PMo] ₁₂ O ₄₀ ] ³⁻ , silicomolybdate ion [SiMo ₁₂ O ₄₀ ] ⁴⁻ , phosphotungsto molybdate ion [PW _12-x Mo _x O ₄₀ ] ³⁻ (x is an integer of 1 to 11), [P ₂ W _18-y Mo _y O ₆₂ ] ^6- (y is an integer of 1 to 17), a catalyst molybdate ion [Si W _12-x Mo _x O ₄₀ ] ⁴⁻ (x is an integer of 1 to 11). The polyacid containing at least one of tungsten (W) and molybdenum (Mo) is preferably a heteropolyacid among the above from the viewpoint of heat resistance and the availability of raw materials, and more preferably phosphorus (P It is more preferable that it is a heteropolyacid containing).
Furthermore, it is heat resistant to be any one of phosphotungsto molybdate ion [PW ₁₀ Mo ₂ O ₄₀ ] ³⁻ , [PW ₁₁ Mo ₁ O ₄₀ ] ³⁻ , and phosphotungstate ion [PW ₁₂ O ₄₀ ] ³⁻ . It is further preferable from the viewpoint of sex.

Examples of rake agents that generate inorganic anions include alkali salts and alkali metal salts of the above inorganic anions.
The counter ions in the salt forming colorant of the dye can be used alone or in combination of two or more.
Further, the counter ion in the salt forming color material of the dye preferably contains at least divalent ions from the viewpoint of improving various resistances.

  In the present disclosure, the salt-forming color material of the dye has a solubility of the color material at 23 ° C. of 0.1 (mg / 10 g solvent) or less with respect to the solvent contained in the composition from the viewpoint of improving various resistances. Further, the solubility of the coloring material at 23 ° C. is preferably 0.01 (mg / 10 g solvent) or less.

The solubility of the coloring material can be easily determined by the following evaluation method.
10 g of the solvent to be evaluated is put into a 20 mL sample tube bottle, and further 0.1 g of the coloring material is put in, covered, shaken well for 20 seconds, and then left to stand in a 23 ° C. water bath for 10 minutes. 5 g of this supernatant liquid is filtered to remove insoluble matters. The absorbance spectrum of a solution obtained by further diluting the obtained filtrate 1000 times is measured with a UV-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation) using a 1 cm cell, and the absorbance at the maximum absorption wavelength is obtained. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solubility of the coloring material can be evaluated to be 0.1 (mg / 10 g solvent) or less.

The color material (A) used in the present disclosure preferably includes a salt-forming color material of a dye. In the case where the (A) color material contains a salt forming color material of a dye, fading of the salt forming color material of the dye due to high-temperature heating performed at the time of forming the coloring layer can be suppressed, so that high-intensity coloring The layer can be formed with a thinner film.
In the photosensitive coloring resin composition of the present disclosure, in the color filter manufacturing process, by using a combination of a phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group in a coloring material containing a salt-forming coloring material of a dye. Even under high temperature heating of 200 ° C. or higher, fading of the salt forming color material of the dye is suppressed, and a colored layer having higher luminance than that of the colored resin composition containing the conventional salt forming color material of the dye can be realized.

The reason why the above effect is exhibited by the combination of the salt forming colorant of the dye and the specific phosphorus atom-containing polyfunctional monomer is presumed as follows.
Under high-temperature heating, active oxygen increases, while vibration due to heat is transmitted to the dye molecules and the molecular motion of the dye molecules becomes intense. It is presumed that the dye molecules moving in such a violent molecular motion are easily oxidized by the surrounding active oxygen, and discolored when the dye molecules decompose.
On the other hand, the specific phosphorus atom-containing polyfunctional monomer has an antioxidant function such as stabilizing hydroperoxide generated from active oxygen, the phosphorus atom is heavier than the carbon atom, and the vibration frequency due to heat is low. Since it is small, it is presumed that the coloring material has a function of making it difficult to transmit vibration due to heat. In addition, since the specific phosphorus atom-containing polyfunctional monomer has a large specific gravity, the density of phosphorus atoms around the coloring material is increased, and further, vibration due to heat is hardly transmitted to the coloring material, and oxidation is suppressed. Estimated.
Normally, active oxygen increases under high-temperature heating, but in the present disclosure, as described above, the effect of reducing hydroperoxide and the like in the coating film by the specific phosphorus atom-containing polyfunctional monomer, and the coloring material As a result of a synergistic effect with the effect of suppressing vibration due to heat, it contributes to the suppression of fading of the salt-stained colorant of the dye even under post-baking by heating at a high temperature of 200 ° C. or higher after the coating film is formed, and the brightness is very high It is estimated that a high colored layer is obtained.

  The dye salt-forming colorant used in the present disclosure is selected from triarylmethane basic dyes and xanthene basic dyes from the viewpoints of high coloring power and high permeability, heat resistance and light resistance. It is preferable to include a salt-forming color material of at least one dye, and a color material represented by the following general formula (I) is more preferable.

(The symbols in general formula (I) are as described above.)

The cation part of the color material represented by the general formula (I) may be the same as the cation part of the color material represented by the general formula (I) described in International Publication No. 2012/144521.
A in the general formula (I) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) has no π bond, and the organic group is saturated at least at the terminal directly bonded to N. An aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group is represented, and O (oxygen atom), S (sulfur atom), and N (nitrogen atom) are present in the carbon chain. It may be included. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as the color tone and transmittance of the cationic coloring portion are not affected by the linking group A and other coloring portions, Similar colors can be retained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a π bond. The carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
The aromatic group having an aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Especially, it is preferable that A contains a cyclic | annular aliphatic hydrocarbon group or an aromatic group from the point of the robustness of frame | skeleton.
Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness. The bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane, dicyclopentadiene and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferable. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is preferable.
From the viewpoint of easy availability of raw materials, A is preferably divalent to tetravalent, preferably divalent to trivalent, and more preferably divalent. For example, when A is a divalent organic group, an aromatic group in which two alkylene groups having 1 to 20 carbon atoms such as a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a xylylene group are substituted. Family groups and the like.

The alkyl group in R ^{i to} R ^v is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms may be mentioned. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and the carbon number is 1 to 5 The following linear or branched alkyl groups are more preferable from the viewpoint of ease of production and raw material procurement. Among them, it is particularly preferred alkyl groups in R ⁱ to R ^v is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group, and examples of the substituted alkyl group include a benzyl group.
The aryl group in R ^{i to} R ^v is not particularly limited. For example, a phenyl group, a naphthyl group, etc. are mentioned. Examples of the substituent that the aryl group may have include an alkyl group and a halogen atom.

R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v are combined to form a ring structure. R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v form a ring structure through a nitrogen atom Say. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

Among them, from the viewpoint of chemical stability, R ^{i to} R ^v are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v. Are preferably bonded to form a pyrrolidine ring, piperidine ring, or morpholine ring.

R ^{i to} R ^v can each independently have the above structure, and among these, R ⁱ is preferably a hydrogen atom from the viewpoint of color purity, and from the viewpoint of ease of production and raw material procurement, R ⁱⁱ to R ^v More preferably, R ^v are all the same.

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group may be a heterocyclic group in addition to an aromatic hydrocarbon group composed of a carbocyclic ring. As an aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to a benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; biphenyl, terphenyl, Examples thereof include chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have O, S, and N in the chain skeleton such as diphenyl ether. On the other hand, the heterocyclic ring in the heterocyclic group includes 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; And condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like. These aromatic groups may have a substituent.

  Examples of the substituent that the aromatic group may have include an alkyl group having 1 to 5 carbon atoms and a halogen atom.

Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group composed of a condensed polycyclic carbocycle having 10 to 14 carbon atoms. Among these, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.

A plurality of R ^{i to} R ^v and Ar ¹ in one molecule may be the same or different. In the case where a plurality of R ^{i to} R ^v and Ar ¹ are the same, the color development site exhibits the same color development, so that the same color as the single color development site can be reproduced, which is preferable from the viewpoint of color purity. On the other hand, when at least one of R ^{i to} R ^v and Ar ¹ is a different substituent, a color obtained by mixing a plurality of types of monomers can be reproduced and adjusted to a desired color. it can.

The anion (B ^c− ) of the colorant represented by the general formula (I) is a diacid or higher polyacid anion.
The polyacid anion may be appropriately selected from the polyacid anions as described above.
Among these, from the viewpoint of high brightness and excellent heat resistance and light resistance, it is preferably a polyacid anion containing at least one of tungsten (W) and molybdenum (Mo), including at least tungsten and containing molybdenum. It is more preferable that it is a good polyacid anion from the viewpoint of heat resistance.

In the polyacid anion containing at least tungsten (W), the content ratio of tungsten and molybdenum is not particularly limited, but the molar ratio of tungsten to molybdenum is in the range of 100: 0 to 85:15, particularly in terms of excellent heat resistance. Is preferably within the range of 100: 0 to 90:10.
As the polyacid anion (B ^c− ), the above-mentioned polyacid anions can be used alone or in combination of two or more, and when used in combination of two or more, tungsten and molybdenum in the entire polyacid anion The molar ratio is preferably within the above range.

The colorant represented by the general formula (I) may be a double salt containing other cations and anions as long as the effects of the present disclosure are not impaired. Specific examples of such cations include other basic dyes, organic compounds containing functional groups capable of forming salts with anions such as amino groups, pyridine groups, and imidazole groups, sodium ions, potassium ions, and magnesium ions. Metal ions such as calcium ion, copper ion and iron ion. Specific examples of anions include acid dyes, halide ions such as fluoride ions, chloride ions and bromide ions, and anions of inorganic acids. Examples of the anion of the inorganic acid include anions of oxo acids such as phosphate ions, sulfate ions, chromate ions, tungstate ions (WO ₄ ²⁻ ), and molybdate ions (MoO ₄ ²⁻ ).
In addition, as a coloring material represented by general formula (I), it can prepare with reference to international publication 2012/144520 pamphlet, for example.

When the color material (A) includes a salt-forming color material of a dye, another color material may be further contained for the purpose of controlling the color tone. Examples of other colorants include the organic pigments and the dyes.
The content of the other colorant in the case where the (A) colorant contains a salt-forming colorant of a dye is from the point of obtaining a high-luminance colored layer even after high-temperature heating in the color filter manufacturing process. ) The total amount of the coloring material is preferably less than 50% by mass, more preferably 30% by mass or less, and still more preferably 10% by mass or less.

The average dispersed particle size of the color material (A) is not particularly limited as long as it can produce a desired color when it is used as a colored layer of a color filter, but has excellent dispersibility and improves contrast and brightness. And from the point which is excellent in heat resistance and light resistance, it is preferable that they are 10 nm or more and 200 nm or less, and it is more preferable that they are 20 nm or more and 100 nm or less. When the average dispersed particle size of the color material (A) is in the above range, the contrast of the liquid crystal display device and the light emitting display device manufactured using the photosensitive colored resin composition of the present disclosure is improved, and high quality is achieved. Can be.
The average dispersed particle size of the color material (A) is a dispersed particle size of color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is. For the measurement of the particle size with a laser light scattering particle size distribution meter, a solvent used in the photosensitive colored resin composition is prepared in advance before preparing the photosensitive colored resin composition or the photosensitive colored resin composition. The colorant dispersion is appropriately diluted to a concentration measurable with a laser light scattering particle size distribution meter (for example, 1000 times), and then a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA- manufactured by Microtrack Bell). EX150) and can be measured at 23 ° C. by a dynamic light scattering method. The average dispersed particle size here is a volume average particle size.

  The total content of the color material (A) with respect to the total solid content of the photosensitive colored resin composition of the present disclosure is such that the photosensitive colored resin composition has a predetermined film thickness (usually 1.0 μm or more and 5.0 μm or less). It is preferably 10% by mass or more, more preferably 20% by mass or more from the viewpoint that the colored layer when applied has a sufficient color density. Further, from the viewpoint of obtaining a colored layer having excellent dispersibility and dispersion stability and sufficient hardness and adhesion to the substrate, the above-mentioned (with respect to the total solid content of the photosensitive colored resin composition of the present disclosure ( A) The total content of the coloring material is preferably 65% by mass or less, more preferably 50% by mass or less. In the present specification, the solid content refers to everything other than the solvent, and includes liquid polyfunctional monomers and the like.

[(B) Dispersant]
In the photosensitive colored resin composition of the present disclosure, it is preferable that (A) the color material is used by being dispersed in a solvent by (B) a dispersant. (B) The dispersant can be appropriately selected from those conventionally used as dispersants. As specific examples of the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed. These (B) dispersants may be used alone or in combination of two or more.

  Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes Long chain polyaminoamide phosphates; polyethylenimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxyls) Polyester, polyamide or ester-amide co-condensation with groups The reaction product obtained by reacting one or more compound selected from among the three compounds of (polyester amide)), and the like.

  Examples of such commercially available dispersants include Disperbyk-2000, 2001, BYK-LPN6919, 21116, 21324 (above, manufactured by Big Chemie Japan), Azisper PB821, 881 (manufactured by Ajinomoto Fine Techno) and the like. it can. Among these, BYK-LPN6919 and 21116 are preferable from the viewpoint of heat resistance, electrical reliability, and dispersibility.

As the polymer dispersant, among them, a polymer having at least a structural unit represented by the following general formula (V) from the viewpoint that the (A) colorant can be suitably dispersed and the dispersion stability is good, And it is preferable that it is 1 or more types selected from the group which consists of a urethane type dispersing agent which consists of a compound which has a 1 or more urethane bond (-NH-COO-) in 1 molecule.
Hereinafter, the preferable dispersant will be described in detail.

<Polymer having at least a structural unit represented by the following general formula (V)>
In the photosensitive colored resin composition of the present disclosure, as the (B) dispersant, a polymer having at least a structural unit represented by the following general formula (V) can be suitably used.

(In the general formula (V), R ²¹ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, Q is a group represented by the following general formula (Va), or a substituted group. Represents a nitrogen-containing heterocyclic group which may have a group and can form a salt.)

(In the general formula (Va), R ²² and R ²³ each independently represents a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R ²² and R ²³ may be the same or different from each other. May be.)

In general formula (V), A is a direct bond or a bivalent coupling group. The direct bond means that Q is directly bonded to the carbon atom in the general formula (V) without a linking group.
Examples of the divalent linking group in A include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (-R ' -OR "-: R 'and R" each independently represents an alkylene group) and combinations thereof.
Among them, from the viewpoint of dispersibility, A in the general formula (V) is preferably a direct bond, a -CONH- group, or a divalent linking group containing a -COO- group.

  Moreover, the structural unit represented by the above general formula (V) of these dispersants can be particularly suitably used by forming a salt with the following salt forming agent at an arbitrary ratio.

As the polymer having the structural unit represented by the general formula (V), among others, WO2011 / 108495, JP2013-054200A, JP2010-237608A, JP2011-75661A. The block copolymer and graft copolymer having the structure described in 1. can improve the dispersibility and dispersion stability of the coloring material and the heat resistance of the resin composition, and can form a colored layer with high brightness and high contrast. To preferred.
Moreover, BYK-LPN6919 etc. are mentioned as a commercial item of the polymer which has a structural unit represented by general formula (V).

(Salt forming agent)
In the photosensitive colored resin composition of the present disclosure, a preferable dispersant is a salt formed by at least a part of the nitrogen portion of the structural unit represented by the general formula (V) (hereinafter sometimes referred to as salt modification). )).
As the salt forming agent, acidic organic phosphorus compounds, organic sulfonic acid compounds, quaternizing agents and the like described in WO2011 / 108495 and JP2013-054200A can be suitably used. In particular, when the salt forming agent is an acidic organic phosphorus compound, a colored layer with higher brightness can be formed even after a high temperature heating step in the color filter manufacturing step.

<Urethane-based dispersant>
The urethane-based dispersant suitably used as the dispersant is a dispersant composed of a compound having one or more urethane bonds (—NH—COO—) in one molecule.
By using a urethane-based dispersant, good dispersion can be achieved with a small amount. By making the amount of the dispersant small, it is possible to relatively increase the amount of the curing component and the like, and as a result, it is possible to form a colored layer having excellent heat resistance.

  In the present disclosure, the urethane dispersant includes, among others, (1) polyisocyanates having two or more isocyanate groups in one molecule, (2) polyesters having a hydroxyl group at one end or both ends, and one end or It is preferably a reaction product with one or more selected from poly (meth) acrylates having hydroxyl groups at both ends, and (1) polyisocyanates having two or more isocyanate groups in one molecule; (2) at least one selected from polyesters having a hydroxyl group at one or both ends, and poly (meth) acrylates having a hydroxyl group at one or both ends, and (3) active hydrogen in the same molecule And a reaction product of a compound having a basic group or an acidic group.

  Examples of commercially available urethane dispersants include Disperbyk-161, 162, 163, 164, 167, 168, 170, 171, 174, 182, 183, 184, 185, BYK-9077 (above, manufactured by Big Chemie Japan), Azisper PB711 (manufactured by Ajinomoto Fine Techno), EFKA-46, 47, 48 (manufactured by EFKA CHEMICALS) and the like can be mentioned. Among these, Disperbyk-161, 162, 166, 170, and 174 are preferable from the viewpoint of heat resistance, electrical reliability, and dispersibility.

  In the photosensitive colored resin composition of the present disclosure, the content of the (B) dispersant is not particularly limited as long as (A) the colorant can be uniformly dispersed. ) From the viewpoint of excellent dispersibility and dispersion stability of the color material, and excellent storage stability, it is preferably 3% by mass or more, preferably 5% by mass or more, based on the total solid content of the colored resin composition. It is more preferable. In addition, the content of the (B) dispersant is preferably 50% by mass or less, and 40% by mass or less, based on the total solid content of the colored resin composition, from the viewpoint of good developability. Is more preferable, and it is still more preferable that it is 30 mass% or less.

[(C) Alkali-soluble resin]
The alkali-soluble resin in the present disclosure has an acidic group, acts as a binder resin, and is appropriately selected and used as long as it is soluble in a developer used when forming a pattern, particularly preferably in an alkali developer. be able to.
A preferable alkali-soluble resin in the present disclosure is preferably a resin having a carboxyl group as an acidic group, specifically, an acrylic copolymer having a carboxyl group, an epoxy (meth) acrylate resin having a carboxyl group, or the like. Can be mentioned. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Further, these acrylic copolymers and epoxy (meth) acrylate resins may be used in combination of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the photosensitive colored resin composition.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the photosensitive colored resin composition, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

Specific examples of the acrylic copolymer having a carboxyl group include those described in International Publication No. 2012/144521, specifically, for example, methyl (meth) acrylate, ethyl ( Examples thereof include a copolymer composed of a monomer having no carboxyl group, such as (meth) acrylate, and one or more selected from (meth) acrylic acid and anhydrides thereof. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is 5% by mass or more from the viewpoint that the resulting coating film has good solubility in an alkaline developer and facilitates pattern formation. It is preferable that it is 10 mass% or more. In addition, the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is from the point of suppressing dropping of the formed pattern from the substrate and film roughness of the pattern surface during development with an alkaline developer. 50% by mass or less, and more preferably 40% by mass or less.

  The preferred weight average molecular weight of the carboxyl group-containing copolymer is preferably 1,000 or more, more preferably 3,000 or more, and development with an alkali developer from the viewpoint of suppressing a decrease in the binder function after curing. From the point of facilitating pattern formation sometimes, it is preferably 200,000 or less, more preferably 50,000 or less. In addition, a mass average molecular weight is calculated | required as a standard polystyrene conversion value by gel permeation chromatography (GPC).

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones. Specific examples include those described in International Publication No. 2012/144521. Each of the epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride may be used alone or in combination of two or more.

  The alkali-soluble resin used in the photosensitive colored resin composition may be used singly or in combination of two or more, and the content thereof is from the point of obtaining sufficient alkali developability. The amount of the coloring material is preferably 10 parts by mass or more, more preferably 25 parts by mass or more with respect to 100 parts by mass of the coloring material contained in the photosensitive coloring resin composition. From the viewpoint of obtaining a coloring concentration, the content of the alkali-soluble resin is preferably 500 parts by mass or less, more preferably 300 parts by mass with respect to 100 parts by mass of the color material contained in the photosensitive colored resin composition. It is below mass parts.

[(D) Polyfunctional monomer]
The polyfunctional monomer used in the photosensitive colored resin composition is not particularly limited as long as it can be polymerized by a photoinitiator described later, and a compound having two or more ethylenically unsaturated double bonds is usually used.
The polyfunctional monomer used in the photosensitive colored resin composition of the present disclosure contains a phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group.

<Phosphorus atom-containing polyfunctional monomer>
In the present disclosure, the phosphorus atom-containing polyfunctional monomer may be a compound containing a phosphorus atom and containing two or more polymerizable functional groups in one molecule.

Examples of the polymerizable functional group that the phosphorus atom-containing polyfunctional monomer has include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, and an allyl group. In the present disclosure, the (meth) acrylamide group is a group represented by the general formula CH ₂ ═CRCONR′—, in which R is a hydrogen atom or a methyl group, and R ′ is a hydrogen atom or an alkyl group. It is a group. R is preferably a hydrogen atom because it has high sensitivity in radical photopolymerization and improves the NMP resistance of the cured film. In addition, R ′ is preferably a hydrogen atom from the viewpoint that NMP resistance can be improved by forming a hydrogen bond and more strongly crosslinking.
As the polymerizable functional group, at least one of (meth) acryloyl group and (meth) acrylamide group has high sensitivity in radical photopolymerization and improves NMP resistance of a cured coating film and pattern adhesion at the time of alkali development. 1 type is preferable and it is preferable that a (meth) acryloyl group is included at least from a soluble viewpoint with respect to the (F) solvent mentioned later.

The phosphorus atom-containing polyfunctional monomer is obtained by, for example, reacting a halogenated phosphorus compound such as phosphorus oxychloride with a compound containing a polymerizable functional group and a hydroxyl group, or phosphoric acid, phosphonic acid, polyphosphoric acid, organic phosphorus. By a method of reacting at least one acidic group selected from an acid, an organic phosphonic acid and an organic polyphosphoric acid with a functional group that reacts with the acid of a compound containing a functional group that reacts with an acid and a polymerizable functional group, Can be obtained.
The phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group, contained in the photosensitive colored resin composition of the present disclosure, is further added as an isocyanate as a compound containing the polymerizable functional group and a hydroxyl group in the above-described method. It can be obtained by using a compound containing a nurate group or by using a compound further containing an isocyanurate group as the compound containing a functional group that reacts with an acid and a polymerizable functional group.

  Examples of the phosphorus halide compound include phosphorus oxychloride, phosphorus oxybromide, methyl dichlorophosphate, ethyl dichlorophosphate, phenyl dichlorophosphate, diphosphoryl chloride, methylphosphonic acid dichloride, ethylphosphonic acid dichloride, phenylphosphonic acid dichloride, Examples thereof include, but are not limited to, p-methoxyphenylphosphonic dichloride.

Examples of the compound containing a polymerizable functional group, a hydroxyl group and an isocyanurate group include compounds containing one hydroxyl group, one isocyanurate group and at least one polymerizable functional group in one molecule. A compound containing one hydroxyl group, one isocyanurate group and two polymerizable functional groups is preferably used. Examples of the compound containing a polymerizable functional group, a hydroxyl group and an isocyanurate group include bis ((meth) acryloyloxyethyl) hydroxyethyl isocyanurate and bis ((meth) acryloyloxypropyl) hydroxypropyl isocyanurate. However, it is not limited to these.
As the compound containing a polymerizable functional group, a hydroxyl group, and an isocyanurate group, a commercially available product may be used, but it can be appropriately synthesized using a conventionally known synthesis method.
Compounds that do not contain an isocyanurate group and contain a polymerizable functional group and a hydroxyl group include hydroxyethyl (meth) acrylamide, hydroxymethyl (meth) acrylamide, hydroxypropyl (meth) acrylamide, hydroxybutyl (meth) acrylamide, ( (Meth) acrylamide having an alcoholic hydroxyl group such as 2,2-dimethoxy-1-hydroxyethyl)-(meth) acrylamide; (meth) acrylamide having a phenolic hydroxyl group such as hydroxyphenyl (meth) acrylamide;
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, methyl 2- (hydroxymethyl) acrylate, 2-hydroxy-3- Phenoxypropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) arylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. (Meth) acrylate having an alcoholic hydroxyl group; (meth) acrylate having a phenolic hydroxyl group such as 4-hydroxyphenyl (meth) acrylate;
2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, cyclohexane dimethanol monovinyl ether, vinyl compounds having an alcoholic hydroxyl group such as propenyl alcohol, vinyl alcohol; phenolic hydroxyl groups such as vinylphenol and isopropenylphenol Vinyl compounds; and the like.

As the organic phosphoric acid, a material having a structure in which a part of three hydrogen atoms of phosphoric acid (O═P (OH) ₃ ) is replaced with an organic group is used. Examples of such organic phosphoric acid include, but are not limited to, methyl phosphoric acid, ethyl phosphoric acid, propyl phosphoric acid, butyl phosphoric acid, pentyl phosphoric acid, hexyl phosphoric acid, octyl phosphoric acid, and lauryl phosphoric acid.
The organic phosphonic acid is a series of compounds represented by the general formula R—P (═O) (OH) ₂ (wherein R is an organic group in which an atom bonded to P is a carbon atom). A group. Examples of the organic phosphonic acid include methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, vinylphosphonic acid, and phenylphosphonic acid. Is not to be done.
The organic group is a general term for functional groups containing at least one carbon atom.

  Examples of the polyphosphoric acid include, but are not limited to, pyrophosphoric acid and tripolyphosphoric acid.

  As the organic polyphosphoric acid, a compound having a structure in which a part of hydrogen atoms of the polyphosphoric acid is replaced with an organic group is used. Here, the organic group represents a general term for functional groups containing at least one carbon atom. As an organic group which the said organic polyphosphoric acid has, a C1-C20 alkyl group etc. are mentioned, for example. Specific examples of such organic polyphosphoric acid include alkyl pyrophosphates such as 2-ethylhexyl pyrophosphate, dibutyl pyrophosphate, dihexyl pyrophosphate, dioctyl pyrophosphate, diisooctyl pyrophosphate; 2-ethylhexyl tripolyphosphate, etc. Alkyl triphosphates such as alkyl tripolyphosphates;

In a compound containing a functional group that reacts with an acid and a polymerizable functional group, examples of the functional group that reacts with an acid include a hydroxyl group, an epoxy group, and an oxetanyl group.
As a compound containing a functional group that reacts with an acid, a polymerizable functional group, and an isocyanurate group, one functional group that reacts with an acid, one isocyanurate group, and at least one polymerizable functional group per molecule. A compound containing 1 functional group that reacts with an acid, 1 isocyanurate group, and 2 polymerizable functional groups is preferably used in one molecule. Examples of the compound containing a functional group that reacts with an acid, a polymerizable functional group, and an isocyanurate group include bis ((meth) acryloyloxyethyl) hydroxyethyl isocyanurate and bis ((meth) acryloyloxypropyl) hydroxypropyl. Although isocyanurate, diallyl monoglycidyl isocyanurate, etc. are mentioned, It is not limited to these.
Examples of the compound that does not contain an isocyanurate group and contains a functional group that reacts with an acid and a polymerizable functional group include (meth) acrylates, (meth) acrylamides, and vinyl compounds having an alcoholic hydroxyl group as described above. , And 3,4-epoxycyclohexylalkyl (meth) acrylate such as glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate, N- [4- (2,3-epoxypropan-1-yloxy) ) -3,5-dimethylbenzyl] (meth) acrylamide, 1,2-epoxy-4-vinylcyclohexane, 3-ethyl-3-oxetanylmethyl (meth) acrylate, vinyl oxetanyl ether, etc. Is not to be done.

  Examples of the phosphorus atom-containing polyfunctional monomer include a reaction product of a halogenated phosphorus compound and a compound containing an alcoholic hydroxyl group and a polymerizable functional group; phosphonic acid or the organic phosphonic acid, and at least one of an epoxy group and an oxetanyl group. A reaction product with a compound containing a seed and a polymerizable functional group is preferably used.

Moreover, as said phosphorus atom containing polyfunctional monomer, it is preferable that the acidic group contained in 1 molecule is 1 or less.
The phosphorus atom-containing polyfunctional monomer used in the present disclosure preferably includes a phosphorus atom-containing polyfunctional monomer having no acidic group from the viewpoint of solvent resistance.
In the phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group used in the present disclosure, the isocyanurate group has a large molecular weight and is a hydrophobic group, and therefore has good NMP resistance even if it contains an acidic group. It is easy to become.
As the phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group used in the present disclosure, an acidic group contained in one molecule is preferably 1.2 or less on average, and 1.0 or less on average. It is more preferable that
As the phosphorus atom-containing polyfunctional monomer that does not contain an isocyanurate group used in the present disclosure, it is preferable that the average number of acidic groups contained in one molecule is less than one, and that the average is 0.9 or less. More preferably, the average is 0.8 or less.
Here, examples of the acidic group in the polyfunctional monomer include a P—OH group, a carboxy group, a sulfonic acid group, and a phenolic hydroxyl group contained in phosphoric acid, phosphonic acid, and phosphinic acid.
The average number of acidic groups contained in one molecule of the phosphorus atom-containing polyfunctional monomer used in the present disclosure can be analyzed using LC-MS, GC-MS, or the like.

A phosphorus atom-containing polyfunctional monomer having no acidic group is usually obtained by reacting a halogenated phosphorus compound with a compound containing a polymerizable functional group and a hydroxyl group, or phosphoric acid, polyphosphoric acid, phosphonic acid, or organic phosphoric acid. In addition, at least one acidic group selected from organic phosphonic acid and organic polyphosphoric acid, and a functional group that reacts with the acid of a compound containing a functional group that reacts with an acid and a polymerizable functional group, the acidic group remains. Can be obtained by reacting with all of the acidic groups.
The polyfunctional monomer containing a phosphorus atom and an isocyanurate group and containing no phosphorus group, which is contained in the photosensitive colored resin composition of the present disclosure, has the above-mentioned polymerizable functional group in the above-described method. By using a compound further containing an isocyanurate group as a compound containing a group and a hydroxyl group, or further containing an isocyanurate group as a compound containing a functional group capable of reacting with an acid and a polymerizable functional group It can be obtained by using a compound.

  The phosphorus atom-containing polyfunctional monomer having no acidic group is a reaction product of a halogenated phosphorus compound and a compound containing an alcoholic hydroxyl group and a polymerizable functional group, and has no acidic group; A reaction product of an acid or the organic phosphonic acid, a compound containing at least one of an epoxy group and an oxetanyl group and a polymerizable functional group, and a compound having no acidic group is preferably used.

  Moreover, as a phosphorus atom containing polyfunctional monomer containing the phosphorus atom and isocyanurate group used in this disclosure, a phosphorus atom containing polyfunctional monomer represented by the following general formula (II) or the following general formula (III) is used. preferable.

(In General Formula (II), W ¹ , W ² and W ³ are each independently a direct bond or —O— bond, and when there are a plurality of W ¹ , W ² and W ³ , they may be the same as each other. R ¹ is a hydrocarbon group or a group obtained by bonding a hydrocarbon group with at least one of an ether bond and an ester bond, and when there are a plurality of R ^{1 s} , they are the same. Z ¹ is a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group or a group represented by the following general formula (IV), and at least ^one of all Z ¹ One is a group represented by the following general formula (IV), and when there are a plurality of Z ^{1 s} , they may be the same or different, and R ² is a hydrocarbon group or a hydrocarbon. The group has few ether bonds and ester bonds. A group attached by Kutomo one is a (meth) acryloyl group, (meth) acrylamide groups, either no group of the group represented by a vinyl group and the following general formula (IV), R ² is When there are a plurality of them, they may be the same or different from each other, each of the hydrocarbon groups may have a substituent, f is 1, 2 or 3, and g is 0 or 1 And f + g is 1, 2 or 3. When g and 3-f-g are each 0, no bond exists.

(In General Formula (III), W ⁴ , W ⁵ , W ⁶ , W ⁷ , W ⁸ and W ⁹ are each independently a direct bond or an —O— bond, and W ⁴ , W ⁵ , W ⁶ , W ⁷ , when there are a plurality of W ⁸ and W ⁹ , they may be the same or different, and R ³ and R ⁴ each independently represents a hydrocarbon group or a hydrocarbon group with an ether bond and It is a group bonded by at least one ester bond, and when there are a plurality of R ³ and R ⁴ , they may be the same or different, and Z ² and Z ³ are each independently (meta ) An acryloyl group, a (meth) acrylamide group, a vinyl group and a group represented by the following general formula (IV), and at least one of all Z ² and Z ³ is represented by the following general formula (IV ) with a group represented, ^{Z 2} and Z There may be cases where more than one each identical, each good .R ⁵ and R ⁶ may be different independently, a hydrocarbon group, or at least one hydrocarbon group having an ether bond and an ester bond A bonded group, which is a group having neither a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, or a group represented by the following general formula (IV), and there are a plurality of R ⁵ and R ⁶ The hydrocarbon groups may each have a substituent, h and h ′ are each independently 0, 1 or 2, and may be the same or different. i and i ′ are each independently 0 or 1, h + h ′ is 1, 2, 3 or 4, i + i ′ is 0 or 1, and h + i and h ′ + i ′ are each independently 1 or 2, h, h ′, i, i ′, 2-h When i and 2-h'-i 'is 0, respectively, not bonded to each exist.)

(In the general formula (IV), R ⁷ and R ⁸ are each independently a hydrocarbon group or a group in which a hydrocarbon group is bonded by at least one of an ether bond and an ester bond, and Z ⁴ and Z ⁵ are Each independently is —O— (C═O) —CR ⁹ ═CH ₂ and —NR ¹⁰ — (C═O) —CR ¹¹ ═CH ₂ , wherein R ⁹ and R ¹¹ are each Independently, it is a hydrogen atom or a methyl group, and R ¹⁰ is a hydrogen atom, a methyl group or an ethyl group, and each of the hydrocarbon groups may have a substituent.

W ² in the general formula (II) and W ⁵ and W ⁷ in the general formula (III) are Z ¹ in the general formula (II) and Z in the general formula (III) to which each is bonded. ^{When 2} and Z ³ are groups represented by the general formula (IV), a direct bond is preferable.

The hydrocarbon group in R ¹ in the general formula (II), R ³ and R ⁴ in the general formula (III), and R ⁷ and R ⁸ in the general formula (IV) is a divalent hydrocarbon. Examples of the group include an alkylene group, an alkenylene group, an arylene group, and a combination thereof. The alkylene group and alkenylene group may be linear, branched or cyclic, and may be linear or a combination of branched and cyclic.
For example, methylene group, ethylene group, vinylene group, propenylene group, various propylene groups, propenylene groups, various butylene groups, cyclohexylene group, bornylene group, isobornylene group, dicyclopentanylene group, adamantylene group, and methylenecyclohexylene Examples include a combination of a linear or branched alkylene group such as a methylene group and a cyclic alkylene group.
Examples of the arylene group include a phenylene group, a biphenylene group, and a naphthylene group, and may further have a substituent for the aromatic ring described later. The number of carbon atoms of the arylene group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less.
Further, R ^{1 in} the general formula (II), R ³ and R ^{4 in the} general formula (III), and R ⁷ and R ⁸ in the general formula (IV) are converted into at least an ether bond and an ester bond. The group bonded by one is -R'-O-R "-, -R '-(C = O) -O-R"-, or -R'-O- (C = O) -R ". -(Wherein R ′ and R ″ are each independently a divalent hydrocarbon group or a group in which a divalent hydrocarbon group is bonded by at least one of an ether bond and an ester bond). It is a group. For example, as in the case of including a polyoxyalkylene group, one group may have two or more ether bonds and ester bonds. The divalent hydrocarbon group for R ′ and R ″ may be the same as described above.
The number of carbon atoms of the hydrocarbon group in R ^{1 in} the general formula (II), R ³ and R ^{4 in the} general formula (III), and R ⁷ and R ⁸ in the general formula (IV) is as follows. Except for the number of carbon atoms, it is preferably 1 or more and 15 or less, more preferably 2 or more and 12 or less, and still more preferably 2 or more and 8 or less.

Z ¹ in the general formula (II) and Z ² and Z ³ in the general formula (III) have high sensitivity in photo radical polymerization, and improve NMP resistance of the cured film and pattern adhesion at the time of alkali development. In view of the above, it is preferable to be at least one selected from a (meth) acryloyl group, a (meth) acrylamide group, and a group represented by the general formula (IV). In the (meth) acryloyl group and the general formula (IV), More preferably, it is at least one of the groups represented. Among them, the phosphorus atom-containing polyfunctional monomer represented by the general formula (II) from the viewpoint that the molecular rigidity increases, the solubility of the cured film in a solvent such as NMP decreases, and the heat resistance is improved, It is preferable to have two or more Z ¹ which is a group represented by the general formula (IV), and the phosphorus atom-containing polyfunctional monomer represented by the general formula (III) is represented by the general formula (IV). It is preferable to have two or more Z ² or Z ³ as a group to be used.
In addition, the compatibility with other components in the cured film is improved, and since the uniform film is formed, the solvent resistance and heat resistance are improved, so that the phosphorus atom represented by the general formula (II) The containing polyfunctional monomer preferably has Z ¹ which is a (meth) acryloyl group, and the phosphorus atom-containing polyfunctional monomer represented by the general formula (III) is Z ² or Z which is a (meth) acryloyl group. ³ is preferable.
From the viewpoint of solubility in the solvent (F) described later, the phosphorus atom-containing polyfunctional monomer represented by the general formula (II) and the phosphorus atom-containing polyfunctional monomer represented by the general formula (III) are: It is preferable to have at least one (meth) acryloyl group, and the (meth) acryloyl group may be included in the group represented by the general formula (IV).

Examples of the hydrocarbon group in R ² in the general formula (II) and R ⁵ and R ⁶ in the general formula (III) include, for example, an alkyl group having 1 to 18 carbon atoms, and 2 to 18 carbon atoms. Examples include an alkenyl group, an aralkyl group, and an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples thereof include a cyclopentyl group, a cyclohexyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that a double bond is present at the terminal of the alkenyl group.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group, and may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less.
Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, Furthermore, you may have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less.
Examples of the substituent for the aromatic ring such as an aryl group and an aralkyl group include alkenyl groups and halogen atoms in addition to linear and branched alkyl groups having 1 to 4 carbon atoms.
The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

In R ² in the general formula (II) and R ⁵ and R ⁶ in the general formula (III), a group in which a hydrocarbon group is bonded with at least one of an ether bond and an ester bond is —R′—O—. R ″ ′, —R ′ — (C═O) —O—R ″ ′, or —R′—O— (C═O) —R ″ ′ (where R ′ and R ″ ′ are each independently And a group represented by a hydrocarbon group or a group in which a hydrocarbon group is bonded by at least one of an ether bond and an ester bond). For example, like a polyalkyleneoxy group, one group may have a total of two or more of at least one of an ether bond and an ester bond. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an aralkyl group, and an aryl group. Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, an arylene group, and combinations thereof. The group of is mentioned. These groups may be the same as described above.

R ⁹ and R ¹¹ in Z ⁴ and Z ⁵ in the general formula (IV) are hydrogen atoms, and the sensitivity in photoradical polymerization is high, and the NMP resistance of the cured film and the pattern adhesion during alkali development are high. It is preferable from the viewpoint of improvement.

R ¹⁰ in Z ⁴ and Z ⁵ in the general formula (IV) is preferably a hydrogen atom from the viewpoint of having hydrogen bonding properties.

  In the general formula (II), general formula (III), and general formula (IV), examples of the substituent that the hydrocarbon group may have include a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and the like. Can be mentioned.

  In view of improving the solvent resistance, in the general formula (II), f is preferably 2 or 3, and g and 3-f-g are each preferably 0 independently. In the general formula (III), h and h ′ are preferably 1 or 2, h + h ′ is preferably 3 or 4, and i, i ′, 2-hi and 2-h It is preferable that '-i' is independently 0.

  The phosphorus atom-containing polyfunctional monomer represented by the general formula (III) is preferably a phosphorus atom-containing polyfunctional monomer represented by the following general formula (III-a).

(The symbols in general formula (III-a) are the same as those in general formula (III).)

  Examples of the phosphorus atom-containing polyfunctional monomer represented by the general formula (II) include a compound represented by the following general formula (II-1), and a phosphorus atom represented by the general formula (III). As a containing polyfunctional monomer, the compound represented by the following general formula (III-1) is mentioned, for example.

(In General Formula (II-1), j is an integer of 2 or more and 6 or less, and a plurality of j may be the same or different. R ¹² is a hydrogen atom or a methyl group. The plurality of R ¹² may be the same or different from each other, p is 1, 2 or 3, q is 0 or 1, and p + q is 1, 2 or 3. (When q and 3-pq are each 0, no bond exists.)

(In General Formula (III-1), k is each independently an integer of 2 or more and 6 or less, and a plurality of k may be the same or different. R ¹³ is a hydrogen atom. Or a plurality of R ^{13 s} may be the same or different, and s and s ′ are each independently 0, 1 or 2, and t and t ′ are each Independently 0 or 1, s + s ′ is 1, 2, 3 or 4, t + t ′ is 0 or 1, s + t and s ′ + t ′ are each independently 1 or 2, s, (When s ′, t, t ′, 2-st, and 2-s′-t ′ are each 0, no bond exists.)

R ¹² in the general formula (II-1) and R ¹³ in the general formula (III-1) are each a hydrogen atom, which is highly sensitive to radical photopolymerization, and has a NMP resistance of a cured film and an alkali development time. This is preferable from the viewpoint of improving the pattern adhesion.

  J in the general formula (II-1) and k in the general formula (III-1) are each independently 2 or more and 3 or less to increase the phosphorus atom content in the cured film, and This is preferable from the viewpoint of ensuring the rigidity of the molecule derived from the nurate skeleton.

  In the general formula (II-1), q is preferably 0 from the viewpoint of improving solvent resistance. In the general formula (III-1), t and t ′ are preferably 0.

In the present disclosure, the (D) polyfunctional monomer contains a phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group in an amount of 20% by mass or more in the total amount of the (D) polyfunctional monomer. It is preferable from a solvent viewpoint, it is more preferable to contain 30 mass% or more, and it is still more preferable to contain 50 mass% or more.
In the present disclosure, the total content of the phosphorus atom-containing polyfunctional monomer in the total amount of the (D) polyfunctional monomer is preferably 20% by mass or more from the viewpoint of further improving the solvent resistance. 50% by mass or more is more preferable.
In addition, the total of the phosphorus atom-containing polyfunctional monomer referred to here is a phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group, and a phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group. And different phosphorus atom-containing polyfunctional monomers.

Moreover, the (D) polyfunctional monomer used for the photosensitive coloring resin composition of this indication may use the other polyfunctional monomer which does not contain a phosphorus atom in the range which does not impair the effect of this indication.
Such other polyfunctional monomer not containing a phosphorus atom may be appropriately selected from conventionally known monomers. Specific examples include those described in International Publication No. 2012/144521.

  As the other polyfunctional monomer not containing the phosphorus atom, one kind may be used alone, or two or more kinds may be used in combination. In addition, when the colored resin composition of the present disclosure requires excellent photocurability (high sensitivity), the polyfunctional monomer has three (trifunctional) or more polymerizable double bonds. Preferred are poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid of dipentaerythritol penta (meth) acrylate Modified product, dipentaerythritol hexa Meth) acrylate are preferable.

The acid value of the phosphorus atom-containing monomer contained in the photosensitive colored resin composition of the present disclosure is preferably less than 190 mgKOH / g, more preferably 100 mgKOH / g or less, and 80 mgKOH / g or less. More preferably, it is more preferably 60 mgKOH / g or less. The phosphorus atom-containing monomer here includes not only a polyfunctional monomer having two or more polymerizable functional groups but also a monomer having one polymerizable functional group.
The acid value represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the phosphorus atom-containing monomer, and is measured by the method described in JIS K 0070. Value.
In the present disclosure, if the acid value of the phosphorus atom-containing monomer contained in the photosensitive colored resin composition is too high, it forms a salt with a commonly used basic photoinitiator and aggregates in the photosensitive colored resin composition. There is a possibility that foreign matter is generated or a salt is formed with the basic pigment dispersant in the colorant dispersion liquid to deteriorate the dispersibility of the colorant and reduce the contrast. In addition, if the total acid value of the phosphorus atom-containing monomer is too high, the solubility in an alkaline developer becomes too high, making it difficult for the pattern to remain at the time of development, or the crosslink density is lowered, resulting in a marked deterioration in solvent resistance. There is a fear.

  The content of the (D) polyfunctional monomer used in the photosensitive colored resin composition is not particularly limited. However, the alkali-soluble resin 100 is used from the viewpoint of sufficiently proceeding photocuring and suppressing elution of an exposed portion. Preferably it is 5 mass parts or more with respect to a mass part, More preferably, it is 20 mass parts or more. The content of the polyfunctional monomer (D) is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, with respect to 100 parts by mass of the alkali-soluble resin, from the viewpoint of improving alkali developability. It is.

  In the photosensitive colored resin composition of the present disclosure, the total content of the (D) polyfunctional monomer is preferably 5% by mass or more and 70% by mass or less in the total solid content of the photosensitive colored resin composition. More preferably, it is 10 mass% or more and 50 mass% or less.

[(E) Photoinitiator]
There is no restriction | limiting in particular as a photoinitiator used in the photosensitive coloring resin composition of this indication, It can use combining 1 type (s) or 2 or more types from the conventionally well-known various photoinitiators. Specific examples include those described in International Publication No. 2012/144521.

  The content of the photoinitiator used in the photosensitive colored resin composition is preferably based on 100 parts by mass of the polyfunctional monomer from the viewpoint of sufficiently causing a polymerization reaction and sufficient hardness of the colored layer. Is 0.01 parts by mass or more, more preferably 5 parts by mass or more. Moreover, from the point which makes content of coloring materials etc. in solid content of a colored resin composition sufficient, and obtains sufficient coloring density, content of a photoinitiator is 100 mass parts of said polyfunctional monomers. , Preferably it is 100 mass parts or less, More preferably, it is 60 mass parts or less.

[(F) Solvent]
In the present disclosure, the solvent (F) does not react with each component in the photosensitive colored resin composition, and can be appropriately selected from solvents that can dissolve or disperse them. Specifically, organic solvents such as alcohols, ether alcohols, esters, ketones, ether alcohol acetates, ethers, aprotic amides, lactones, unsaturated hydrocarbons, saturated hydrocarbons are used. Among them, it is preferable to use an ester solvent from the viewpoint of solubility during dispersion and coating suitability.

Preferred ester solvents include, for example, methyl methoxypropionate, ethyl ethoxypropionate, methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl Acetate, ethoxyethyl acetate, ethyl cellosolve acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,6-hexanediol diacetate, diethylene glycol monoethyl ether acetate, Examples include diethylene glycol monobutyl ether acetate.
Among them, it is preferable to use propylene glycol monomethyl ether acetate (PGMEA) from the viewpoint of low risk to the human body and low volatility near room temperature but good heat drying properties. In this case, there is a merit that no special cleaning process is required even when switching to the photosensitive colored resin composition using the conventional PGMEA.
These solvents may be used alone or in combination of two or more.

[Optional components]
The photosensitive colored resin composition of the present disclosure may include various additives as necessary within a range that does not impair the effects of the photosensitive colored resin composition of the present disclosure described above.

(Antioxidant)
The photosensitive colored resin composition preferably further contains an antioxidant from the viewpoints of heat resistance and light resistance. The antioxidant may be appropriately selected from conventionally known antioxidants. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. From the viewpoint, it is preferable to use a hindered phenol-based antioxidant.
The hindered phenol antioxidant contains at least one phenol structure, and has a structure in which a substituent having 4 or more carbon atoms is substituted on at least one of the 2-position and 6-position of the hydroxyl group of the phenol structure. Means an antioxidant. Moreover, the latent antioxidant in which the hindered phenol was made latent as described in Unexamined-Japanese-Patent No. 2015-132791 may be sufficient.

  When using antioxidant, the compounding quantity will not be specifically limited if the effect of the photosensitive coloring resin composition of this indication is not impaired. As a compounding quantity of antioxidant, it is preferable that it is 0.1 mass% or more with respect to the solid content whole quantity in a colored resin composition from the point which is excellent in heat resistance, and it is 0.5 mass% or more. From the point that the photosensitive colored resin composition can be made highly sensitive, it is preferably 5.0% by mass or less, based on the total solid content in the colored resin composition, and is preferably 4.0% by mass. % Or less is more preferable.

(Other additives)
As additives, in addition to the above antioxidants, for example, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, etc. Is mentioned.
Specific examples of the surfactant and the plasticizer include those described in International Publication No. 2012/144521 pamphlet.

<Combination ratio of each component in the photosensitive colored resin composition>
In the photosensitive colored resin composition of the present disclosure, the total amount of (C) an alkali-soluble resin, (D) a polyfunctional monomer, and (E) a photoinitiator serving as a binder component with respect to the total solid content of the colored resin composition. Is preferably 10% by mass or more, more preferably 30% by mass or more from the viewpoint that a colored layer having sufficient hardness and adhesion to the substrate can be obtained. From the viewpoint of suppressing generation of fine wrinkles due to heat shrinkage, it is preferably 90% by mass or less, more preferably 80% by mass or less.

  (F) The content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. From the point of being excellent in applicability with respect to the total amount of the colored resin composition containing the solvent, it is usually preferably in the range of 55% by mass or more and 95% by mass or less, particularly 65% by mass. More preferably, it is in the range of 88% by mass or less.

<Method for producing photosensitive colored resin composition>
The method for producing a photosensitive colored resin composition of the present disclosure includes (A) a color material, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, and (E) a photoinitiator. And (F) a solvent and various additive components used as required, and any method can be used as long as the coloring material can be uniformly dispersed in the solvent by the dispersant, and is not particularly limited. It can be prepared by using and mixing.
Examples of the method for preparing the photosensitive colored resin composition include (1) a colorant dispersion containing a colorant, a dispersant, and a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. (2) Two or more kinds of coloring materials are separately dispersed in a solvent together with a dispersing agent, or other coloring materials contain a dispersing agent. Color material dispersion prepared by dissolving in a solvent without using it, and optionally a color material solution, a binder component containing an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and various additions used as desired (3) A method in which a coloring material, a dispersing agent, a binder component, and various additive components used as desired are simultaneously added and mixed in a solvent; (4) in a solvent; dispersion When a binder component, were added and various additive components optionally used, were mixed, a method of mixing by adding a colorant; and the like.
Among these methods, the method (1) or (2) of preparing the color material dispersion in advance is preferable from the viewpoint of effectively preventing the color material from being aggregated and uniformly dispersing.

  The method for producing a color material dispersion includes (A) a color material, (B) a dispersant, (F) a solvent, and various additive components used as desired, and (A) the color material is a dispersant. As long as it is a method that can be uniformly dispersed in a solvent, it can be prepared by mixing using a known mixing means.

  As a method for preparing the dispersion, (B) the dispersant is mixed and stirred in the solvent (F) to prepare a dispersant solution, and then the (A) coloring material and other materials as necessary are added to the dispersant solution. A dispersion can be prepared by mixing the components and dispersing them using a known stirrer or disperser. Moreover, when using 2 or more types of color materials, it is good also as a color material dispersion liquid of this indication by preparing a color material dispersion liquid separately about each color material, and mixing these.

  Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 mm or more and 2.00 mm or less, more preferably 0.05 mm or more and 1.0 mm or less.

  Specifically, preliminary dispersion is performed with 2 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a membrane filter of 0.5 μm or more and 5.0 μm or less after dispersion.

2. Color filter The color filter according to the present disclosure is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, and is a cured product of the photosensitive colored resin composition according to the present disclosure. Has a colored layer.
Further, the method for producing a color filter of the present disclosure is a method for producing a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate,
It includes a step of forming at least one of the colored layers by curing the photosensitive colored resin composition according to the present disclosure.

  Such a color filter according to the present disclosure will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view illustrating an example of the color filter of the present disclosure. According to FIG. 1, the color filter 10 of the present disclosure includes a transparent substrate 1, a light shielding unit 2, and a colored layer 3.

(Colored layer)
At least one of the colored layers used in the color filter of the present disclosure is a cured product of the photosensitive colored resin composition according to the present disclosure.
The colored layer is usually formed in an opening of a light shielding part on a transparent substrate, which will be described later, and is usually composed of three or more colored patterns.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the photosensitive colored resin composition, but is usually preferably in the range of 1 μm to 5 μm.

The colored layer can be formed by the following method.
First, the photosensitive colored resin composition is applied onto a transparent substrate, which will be described later, using an application means such as spray coating, dip coating, bar coating, roll coating, spin coating, slit coating, or die coating. Then, a wet coating film is formed.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized. A photosensitive coating film is used. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

(Shading part)
The light shielding part in the color filter of the present disclosure is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light shielding part include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a laminate of two Cr films, and a CrO _x film (x is an arbitrary number) with a reduced reflectance. , CrN _y film (y is an arbitrary number) and three layers of Cr film may be laminated.
When the light shielding part is a material in which a black color material is dispersed or dissolved in a binder resin, the light shielding part can be formed by any method that can pattern the light shielding part, and is not particularly limited. For example, a photolithography method, a printing method, an ink jet method and the like using the colored resin composition for the light shielding part can be exemplified.

  The thickness of the light-shielding part is set to about 0.2 μm to 0.4 μm in the case of a metal thin film, and 0.5 μm to 2 μm in the case where a black color material is dispersed or dissolved in a binder resin. Set by degree.

(Transparent substrate)
The transparent substrate in the color filter of the present disclosure is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, alkali-free glass, or synthetic quartz plate, or a flexible or flexible resin such as a transparent resin film, an optical resin plate, or flexible glass. A transparent flexible material is mentioned.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this indication, the thing of about 50 micrometers or more and 1 mm or less can be used, for example.
The color filter of the present disclosure includes, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning a liquid crystal material, a columnar spacer, and the like in addition to the transparent substrate, the light shielding portion, and the colored layer. It may be what was done. The color filter of the present disclosure is not limited to the configuration exemplified above, and a known configuration generally used for a color filter can be appropriately selected and used.

3. Liquid Crystal Display Device A liquid crystal display device according to the present disclosure includes the color filter according to the present disclosure described above, a counter substrate, and a liquid crystal layer positioned between the color filter and the counter substrate.
Such a liquid crystal display device of the present disclosure will be described with reference to the drawings. FIG. 2 is a schematic diagram illustrating an example of the liquid crystal display device of the present disclosure. As illustrated in FIG. 2, the liquid crystal display device 40 of the present disclosure includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer 15 positioned between the color filter 10 and the counter substrate 20. And have. In FIG. 2, the alignment film 13a and the alignment substrate 13b are positioned on the color filter 3 side and the counter substrate 20 side of the color filter 10, and the liquid crystal layer 15 is positioned between the two alignment films 13a and 13b. Shows about. Further, in FIG. 2, the liquid crystal display device 40 is disposed on the polarizing plate 25 a located outside the color filter 10, the polarizing plate 25 b located outside the counter substrate 20, and the counter substrate 20 side of the liquid crystal display device 40. The example which has the backlight 30 located in the outer side rather than the polarizing plate 25b located is shown.
Note that the liquid crystal display device of the present disclosure is not limited to the configuration illustrated in FIG. 2, and may be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present disclosure is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present disclosure, any of these methods can be suitably used.
Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present disclosure.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present disclosure.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. In addition, the liquid crystal layer can be formed by overlapping the color filter and the counter substrate under reduced pressure and bonding them with a sealant. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

Moreover, as a backlight used for the liquid crystal display device of this indication, it can select and use suitably according to the use of a liquid crystal display device. As the backlight, for example, a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp), a backlight unit using a white LED or a white organic EL as a light source can be provided.
As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, UV LED, red light emitting phosphor, and green light emitting fluorescence And a white LED that obtains white light by color mixing by combining a body and a blue light emitting phosphor. As the phosphor, quantum dots may be used.

4). Light Emitting Display Device A light emitting display device according to the present disclosure includes the color filter according to the present disclosure described above and a light emitter. Examples of the light emitting display device according to the present disclosure include an organic light emitting display device having an organic light emitter as the light emitter. The light emitter is not limited to an organic light emitter, and an inorganic light emitter can also be used as appropriate.
Such a light emitting display device of the present disclosure will be described with reference to the drawings. FIG. 3 is a schematic diagram illustrating an example of the light-emitting display device of the present disclosure. As illustrated in FIG. 3, the light emitting display device 100 of the present disclosure includes the color filter 10 and a light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the light emitter 80.

As a method of laminating the light emitter 80, for example, a method of sequentially forming the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 on the upper surface of the color filter. For example, a method of attaching the light emitter 80 formed on another substrate onto the inorganic oxide film 60 may be used. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the light emitter 80, known structures can be appropriately used. The light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the light-emitting display device according to the present disclosure is not limited to the light-emitting display device having the configuration illustrated in FIG. 3, and can generally be configured as a light-emitting display device using a color filter. .

Hereinafter, the present disclosure will be specifically described with reference to examples. These descriptions do not limit the present disclosure.
³¹ P-NMR measurement was performed under the following conditions.
Device name: AVANCE 3 HD made by BRUKER
Resolution: 400MHz
Nuclide: ³¹ P
Solvent: DMSO-d6
Concentration: 0.2g / 1ml
Temperature: Room temperature (25 ° C)
Chemical shift standard: phosphoric acid 0 ppm and specified window function: exponential

(Synthesis example 1: Synthesis of phosphorus atom-containing polyfunctional monomer A)
A reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 75 parts by mass of ethyl acetate and 3.83 parts by mass of phosphoryl chloride. After cooling the liquid temperature to about 5 ° C. using a bath, 30.47 parts by mass (93% active ingredient) bis (acryloyloxyethyl) hydroxyethyl isocyanurate (isocyanuric acid EO-modified diacrylate, manufactured by Toagosei Co., Ltd., Aronix M215) ), A solution obtained by diluting 8.35 parts by mass of triethylamine with 35 parts by mass of ethyl acetate was continuously added dropwise over 15 minutes while adjusting the liquid temperature so as not to exceed 30 ° C. After completion of dropping, the ice bath was removed and the mixture was stirred at room temperature for 17 hours. Thereafter, 2.9 parts by mass of hydroxyethyl acrylate (HEA) was added and stirred for 4 hours. Thereafter, 50 parts by mass of pure water was added and the mixture was further stirred for 4 hours, and then the taken out reaction solution was washed twice with pure water and once with saturated saline. The organic layer was dehydrated with magnesium sulfate, filtered, 0.015 parts by mass of p-methoxyphenol was added, and the solvent was distilled off to obtain 21.5 g of phosphorus atom-containing polyfunctional monomer A (yield 60%). )Obtained. The acid value of the obtained compound was 50 mgKOH / g. When the phosphorus atom-containing polyfunctional monomer A was confirmed by ³¹ P-NMR and ¹ H-NMR measurements, the molar ratio of the group to which Aronix M215 was added, the group to which HEA was added, and the P—OH group was about 67: 7. : 26, and the mixture of each compound represented by the following chemical formula (1) was the main component and contained a trace amount of phosphoric acid monoester.

(In the chemical formula (1), p and q are the same as those in the general formula (II-1), respectively, and the same applies to the case where no bond exists).

(Synthesis Example 2: Synthesis of phosphorus atom-containing polyfunctional monomer B)
70 parts by mass of ethyl acetate and 6.29 parts by mass of diphosphoryl chloride were added, and the mixture was cooled to about 5 ° C. using an ice bath while stirring in a nitrogen atmosphere, and then bis (acryloyloxyethyl) hydroxyethyl isocyanate. A solution obtained by diluting 40.63 parts by mass (93% active ingredient) of nurate (isocyanuric acid EO-modified diacrylate, manufactured by Toagosei Co., Ltd., 93%) and 30 parts by mass of ethyl acetate with 30 parts by mass of ethyl acetate has a liquid temperature of 30. It was continuously added dropwise over 15 minutes while adjusting so as not to exceed ° C. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 18 hours. Thereafter, 1.16 parts by mass of hydroxyethyl acrylate (HEA) was added and stirred for 4 hours. Thereafter, 50 parts by mass of pure water was added and the mixture was further stirred for 4 hours, and then the taken out reaction solution was washed twice with pure water and once with saturated saline. The organic layer was dehydrated with magnesium sulfate, filtered, 0.015 parts by mass of p-methoxyphenol was added, and then the solvent was distilled off to obtain 29.2 g of phosphorus-functional polyfunctional monomer B (yield 74%). )Obtained. The acid value of the obtained compound was 50 mgKOH / g. When the phosphorus atom-containing polyfunctional monomer B was confirmed by ³¹ P-NMR and ¹ H-NMR measurement, the molar ratio of the group to which Aronix M215 was added, the group to which HEA was added, and the P—OH group was about 69: 4. The mixture of each compound represented by the following chemical formula (2) was the main component and contained a small amount of pyrophosphoric acid diester and pyrophosphoric acid monoester.

(In the chemical formula (2), s, s ′, t, and t ′ are the same as those in the general formula (III-1), respectively, and the case where no bond is present is the same as that in the general formula (III-1). .)

(Synthesis Example 3: Synthesis of Blue Color Material α)
(1) Synthesis of Intermediate 1 Referring to the method for producing Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, 15.9 g of intermediate 1 represented by the following chemical formula (3) was obtained. Rate 70%).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), divalent, elemental analysis value: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (7
(8.06%, 7.75%, 7.69%)

(2) Synthesis of Blue Color Material α 5.00 g (4.58 mmol) of the intermediate 1 was added to 300 ml of water and dissolved at 90 ° C. to obtain an intermediate 1 solution. Next, 10.44 g (3.05 mmol) of phosphotungstic acid · n hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O (n = 30) (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) was placed in 100 ml of water, and 90 ° C. To prepare an aqueous phosphotungstic acid solution. The aqueous phosphotungstic acid solution prepared in the intermediate 1 solution was mixed at 90 ° C., and the formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g of a blue color material α of a metal lake color material of a triarylmethane basic dye represented by the following chemical formula (4).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 510 (+), divalent, elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%) (5.17%, 4.11%)

(Synthesis Example 4: Synthesis of Binder Resin A)
A reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 120 parts by mass of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) as a solvent, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. After heating, 32 parts by mass of methyl methacrylate, 22 parts by mass of cyclohexyl methacrylate, 24 parts by mass of methacrylic acid, 2.0 parts by mass of azobisisobutyronitrile (abbreviated as AIBN) as an initiator and n-dodecyl as a chain transfer agent A mixture containing 4.5 parts by mass of mercaptan was continuously added dropwise over 1.5 hours.
Thereafter, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropping.
Next, while blowing air, 22 parts by mass of glycidyl methacrylate was added, the temperature was raised to 110 ° C., 0.2 parts by mass of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours. 45 mass% solid content) was obtained.
The obtained binder resin A had a mass average molecular weight (Mw) of 8850, a number average molecular weight (Mn) of 4200, a molecular weight distribution (Mw / Mn) of 2.11 and an acid value of 78 mgKOH / g.

(Synthesis Example 5: Preparation of salt type block polymer dispersant A solution)
35.64 parts by mass of PGMEA 60.74 parts by mass and a block copolymer containing a tertiary amino group (trade name: BYK-LPN6919, manufactured by Big Chemie) (amine value 120 mgKOH / g, solid content 60% by weight) (Effective solid content 21.38 parts by mass) were dissolved, 3.62 parts by mass of PPA (0.5 molar equivalent to the tertiary amino group of the block copolymer) was added, and the mixture was stirred at 40 ° C. for 30 minutes. Thus, a salt type block polymer dispersant A solution (solid content 25%) was prepared.

(Production Example 1: Production of Colorant Dispersion A)
13.30 parts by mass of the blue color material α of Synthesis Example 3 as a coloring material, 18.20 parts by mass of the dispersant A solution of Synthesis Example 5 (solid content of 4.55 parts by mass), binder resin A of Synthesis Example 4 00 parts by mass (solid content 5.85 parts by mass) and PGMEA 55.80 parts by mass were mixed and pre-dispersed with 2 mm zirconia beads for 1 hour using a paint shaker (manufactured by Asada Tekko), and further 0.1 mm zirconia beads as the main dispersion. For 4 hours to obtain a colorant dispersion A.

Example 1
(1) Preparation of binder composition A 44.36 parts by mass of PGMEA, 28.44 parts by mass of binder resin A (solid content 45% by mass) of Synthesis Example 4, 5-6 functional acrylate monomer (trade name: Aronix M402, Toagosei Co., Ltd.) 4.8 parts by mass, phosphorus atom-containing polyfunctional monomer A of Synthesis Example 1 (containing isocyanurate group, phosphorus atom number 1, acid value 50 mgKOH / g), 14.4 parts by mass, 2-methyl-1 [4- (Methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF) 6.00 parts by mass, 2,4 diethylthioxanthone (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.) ) Binder composition A (solid content 40% by mass) was prepared by mixing 2.00 parts by mass.

(2) Preparation of photosensitive colored resin composition 33.57 parts by mass of colorant dispersion A obtained in Production Example 1, 25.23 parts by mass of binder composition A obtained in (1) above, PGMEA 40.65 1 part by weight, 0.05 parts by weight of surfactant R08MH (manufactured by DIC) and 0.5 parts by weight of silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) were added and mixed, and pressure filtration was performed. A colored resin composition was obtained.

(Example 2)
In Example 1, instead of the binder composition A, instead of the phosphorus atom-containing polyfunctional monomer A in the binder composition A, the phosphorus atom-containing polyfunctional monomer B of Synthesis Example 2 (isocyanurate group-containing, phosphorus atom number 2) The photosensitive colored resin composition of Example 2 was obtained in the same manner as in Example 1 except that the binder composition B containing an acid value of 50 mgKOH / g) was used.

(Comparative Example 1)
In Example 1, instead of the binder composition A, a binder containing a 5-6 functional acrylate monomer (trade name: Aronix M402, manufactured by Toagosei Co., Ltd.) instead of the phosphorus atom-containing polyfunctional monomer A in the binder composition A A photosensitive colored resin composition of Comparative Example 1 was obtained in the same manner as Example 1 except that Composition C was used.

(Comparative Example 2)
In Example 1, instead of the binder composition A, instead of the phosphorus atom-containing polyfunctional monomer A in the binder composition A, a polyfunctional monomer that does not contain a phosphorus atom and contains an isocyanurate group (trade name: Aronix M315) A photosensitive colored resin composition of Comparative Example 2 was obtained in the same manner as in Example 1 except that binder composition D containing Toagosei Co., Ltd., having an acid value of 1 mgKOH / g or less) was used.

  In addition, the polyfunctional monomer (trade name: Aronix M315, manufactured by Toagosei Co., Ltd., acid value of 1 mgKOH / g or less) used in Comparative Example 2 has a structure in which the main component is represented by the following chemical formula (5), and a phosphorus atom And has an isocyanurate group.

(Comparative Example 3)
In Example 1, instead of the binder composition A, instead of the phosphorus atom-containing polyfunctional monomer A in the binder composition A, light ester P-2M (trade name: light ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd., acid value) A photosensitive colored resin composition of Comparative Example 3 was obtained in the same manner as in Example 1 except that the binder composition E containing 280 mgKOH / g) was used.

In addition, light ester P-2M (trade name: light ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd., acid value 280 mgKOH / g) used in Comparative Example 3 has a structure in which the main component is represented by the following chemical formula (6). Yes, it does not have an isocyanurate group, but has an acidic group (P-OH). ^When confirmed by ³¹ P-NMR measurement, phosphoric acid diester and phosphoric acid monoester were the main components, and orthophosphoric acid and a small amount of phosphoric acid triester were also detected.

[Evaluation]
<Optical characteristic evaluation>
The photosensitive colored resin composition obtained in each Example and each Comparative Example was applied on a glass substrate having a thickness of 0.7 mm (manufactured by Nippon Electric Glass, “OA-10G”) using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (blue colored layer) was obtained by irradiating ultraviolet rays of 40 mJ / cm ² using an ultrahigh pressure mercury lamp. The chromaticity after curing is set to y = 0.0820, and the chromaticity (x, y), luminance (Y), L, a, b (L ₀ , a ₀ , b ₀ ) of the obtained colored substrate Was measured using "Microspectrophotometer OSP-SP200" manufactured by Olympus. The substrate on which the colored film is formed is post-baked for 60 minutes in a clean oven at 230 ° C., and the chromaticity (x, y), luminance (Y), and L, a, b (L ₁ ) of the obtained colored film. , A ₁ , b ₁ ) were measured.
As the heat resistance evaluation, the color difference (ΔEab) was calculated from the following formula.
ΔEab = {(L ₁ −L ₀ ) ² + (a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² } ^1/2
Table 1 shows the chromaticity (x, y) and luminance (Y) of the colored film after post-baking, and the color difference (ΔEab) before and after post-baking.

<NMP resistance evaluation>
A substrate having a colored layer of the colored resin composition obtained by the above-described optical performance and heat resistance evaluation cross-cut by a cutter at 1 mm intervals is placed on an 80 ° C. hot plate, and NMP is placed on the cross-cut surface. It left still for 20 minutes and confirmed the presence or absence of peeling of a cured film visually.
<Evaluation criteria>
A: No peeling of the cross cut surface.
B: The crosscut surface peeled off.
C: The cross cut surface was dissolved.

(Summary of results)
In Example 1 and Example 2 using the photosensitive colored resin composition of the present disclosure, (D) the polyfunctional monomer contains a phosphorus atom-containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group. Thus, it was revealed that a colored layer having excellent solvent resistance can be formed. Moreover, in Example 1 and Example 2, since it contained the said specific phosphorus atom containing polyfunctional monomer, it is a colored layer by the high temperature heating in a color filter manufacturing process, using the salt-forming coloring material of a dye. It has been clarified that it is possible to form a colored layer with high brightness and excellent solvent resistance.

On the other hand, in Comparative Example 1 using only a polyfunctional monomer containing neither a phosphorus atom nor an isocyanurate group, in the NMP resistance evaluation, NMP was placed on the crosscut surface and the cured film was peeled off 7 minutes later. Moreover, the brightness | luminance after high temperature heating in a color filter manufacturing process was low, and the color difference became large. Moreover, the film thickness of the colored layer was increased to obtain the same chromaticity as that of the example.
In Comparative Example 2 using a polyfunctional monomer that does not contain a phosphorus atom and contains an isocyanurate group, in the NMP resistance evaluation, NMP was placed on the cross-cut surface and the cured film was peeled off after 9 minutes. Moreover, the brightness | luminance after high temperature heating in a color filter manufacturing process was low, and the color difference became large. Moreover, the film thickness of the colored layer was increased to obtain the same chromaticity as that of the example.
In Comparative Example 3 using a phosphorus atom-containing polyfunctional monomer having an isocyanurate group and having an acidic group, the coating film was dissolved in the NMP resistance evaluation. Moreover, the polyfunctional monomer reacted with a basic photoinitiator or dispersant, and the binder composition became cloudy. Further, when the color material dispersion and the binder composition were mixed, the dispersibility deteriorated and the luminance value was low.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 13a, 13b Alignment film 15 Liquid crystal layer 20 Opposite substrate 25a, 25b Polarizing plate 30 Backlight 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection Layer 73 hole transport layer 74 light emitting layer 75 electron injection layer 76 cathode 80 light emitter 100 light emitting display device

Claims (11)

(A) a coloring material, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent,
The photosensitive coloring resin composition in which the said (D) polyfunctional monomer contains the phosphorus atom containing polyfunctional monomer containing a phosphorus atom and an isocyanurate group.   The photosensitive coloring resin composition of Claim 1 whose acid value of the phosphorus atom containing monomer contained in the said photosensitive coloring resin composition is less than 190 mgKOH / g.   The photosensitive coloring resin composition of Claim 1 or 2 in which the said (A) coloring material contains the salt-forming coloring material of dye.   The photosensitive coloring resin composition of Claim 3 in which the salt-forming color material of the said dye contains the salt-forming color material of at least 1 type of dye chosen from a triarylmethane type | system | group basic dye and a xanthene type basic dye.   The photosensitive coloring resin composition of Claim 3 or 4 in which the salt-forming color material of the said dye contains the salt-forming color material of dye and a polyacid. The photosensitive coloring resin composition of Claim 4 or 5 in which the salt-forming color material of the said dye contains the color material represented by the following general formula (I).
(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. aliphatic hydrocarbon radical having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, O in the carbon chain, S, may be contained N is .B ^c-'s c-valent poly R ^{i to} R ^v each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R good .Ar ¹ be ^iv and ^{R v} are bonded to form a ring structure represents a divalent aromatic group which may have a substituent. plural ^R i to R ^v and Ar ¹ each They may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )   A color filter comprising at least a transparent substrate and a colored layer on the transparent substrate, comprising a colored layer that is a cured product of the photosensitive colored resin composition according to any one of claims 1 to 6. Color filter. A method for producing a color filter comprising at least a transparent substrate and a colored layer on the transparent substrate,
The manufacturing method of a color filter which has the process of hardening the photosensitive colored resin composition of any one of Claims 1 thru | or 6, and forming at least 1 of the said colored layer.   A liquid crystal display device comprising: the color filter according to claim 7; a counter substrate; and a liquid crystal layer positioned between the color filter and the counter substrate.   A light-emitting display device comprising the color filter according to claim 7 and a light emitter. A phosphorus atom-containing polyfunctional monomer represented by the following general formula (II) or the following general formula (III).
(In General Formula (II), W ¹ , W ² and W ³ are each independently a direct bond or —O— bond, and when there are a plurality of W ¹ , W ² and W ³ , they may be the same as each other. R ¹ is a hydrocarbon group or a group obtained by bonding a hydrocarbon group with at least one of an ether bond and an ester bond, and when there are a plurality of R ^{1 s} , they are the same. Z ¹ is a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group or a group represented by the following general formula (IV), and at least ^one of all Z ¹ One is a group represented by the following general formula (IV), and when there are a plurality of Z ^{1 s} , they may be the same or different, and R ² is a hydrocarbon group or a hydrocarbon. The group has few ether bonds and ester bonds. A group attached by Kutomo one is a (meth) acryloyl group, (meth) acrylamide groups, either no group of the group represented by a vinyl group and the following general formula (IV), R ² is When there are a plurality of them, they may be the same or different from each other, each of the hydrocarbon groups may have a substituent, f is 1, 2 or 3, and g is 0 or 1 And f + g is 1, 2 or 3. When g and 3-f-g are each 0, no bond exists.
(In General Formula (III), W ⁴ , W ⁵ , W ⁶ , W ⁷ , W ⁸ and W ⁹ are each independently a direct bond or an —O— bond, and W ⁴ , W ⁵ , W ⁶ , W ⁷ , when there are a plurality of W ⁸ and W ⁹ , they may be the same or different, and R ³ and R ⁴ each independently represents a hydrocarbon group or a hydrocarbon group with an ether bond and It is a group bonded by at least one ester bond, and when there are a plurality of R ³ and R ⁴ , they may be the same or different, and Z ² and Z ³ are each independently (meta ) An acryloyl group, a (meth) acrylamide group, a vinyl group and a group represented by the following general formula (IV), and at least one of all Z ² and Z ³ is represented by the following general formula (IV ) with a group represented, ^{Z 2} and Z There may be cases where more than one each identical, each good .R ⁵ and R ⁶ may be different independently, a hydrocarbon group, or at least one hydrocarbon group having an ether bond and an ester bond A bonded group, which is a group having neither a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, or a group represented by the following general formula (IV), and there are a plurality of R ⁵ and R ⁶ The hydrocarbon groups may each have a substituent, h and h ′ are each independently 0, 1 or 2, and may be the same or different. i and i ′ are each independently 0 or 1, h + h ′ is 1, 2, 3 or 4, i + i ′ is 0 or 1, and h + i and h ′ + i ′ are each independently 1 or 2, h, h ′, i, i ′, 2-h When i and 2-h'-i 'is 0, respectively, not bonded to each exist.)
(In the general formula (IV), R ⁷ and R ⁸ are each independently a hydrocarbon group or a group in which a hydrocarbon group is bonded by at least one of an ether bond and an ester bond, and Z ⁴ and Z ⁵ are Each independently is —O— (C═O) —CR ⁹ ═CH ₂ and —NR ¹⁰ — (C═O) —CR ¹¹ ═CH ₂ , wherein R ⁹ and R ¹¹ are each Independently, it is a hydrogen atom or a methyl group, and R ¹⁰ is a hydrogen atom, a methyl group or an ethyl group, and each of the hydrocarbon groups may have a substituent.