JP2018180114A - Colored cured film, method for producing colored cured film, colored composition, color filter, method for producing color filter, liquid crystal display device, and light emitting display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a colored cured film, a coloring composition and a color filter that are excellent in heat resistance and improved in luminance; manufacturing methods thereof; and a liquid-crystal display and a light-emitting display that include the color filter.SOLUTION: The colored cured film, coloring composition and color filter contain a polymer of a monomer having ethylenically unsaturated group, and a metal lake color material of a dye. The polymer includes a structure represented by the general formula (1) in the figure, where R1 and R2 each independently represent a hydrogen atom or methyl group.SELECTED DRAWING: None

Description

  Embodiments of the present disclosure relate to a colored cured film and a method of manufacturing the same, a colored composition, a color filter and a method of 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 launched on the market, characterized by being thinner than a CRT display and taking up less space in the depth direction. The market price has become reasonable year by year with the evolution of production technology, the demand is further expanded, and the production volume is also increasing year by year. In particular, color LCD TVs almost reached the TV mainstream. Further, recently, a light emitting display device such as an organic light emitting display device such as an organic EL display having high visibility due to self light emission is 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 for 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, and the amount of light is controlled by electrically driving the liquid crystal, and color representation is performed by passing the light through a color filter. Therefore, the color expression of the liquid crystal television must be a color filter, and plays a large role in determining the performance of the display. In addition, 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.

As a trend in recent years, power saving of the image display apparatus is required, and in order to improve the utilization efficiency of the backlight, the luminance enhancement of the color filter is particularly required. This is particularly a big issue for mobile displays (mobile phones, smart phones, tablet PCs).
Although battery capacity has increased due to technological advances, mobile storage capacity remains the same, while power consumption tends to increase as screen size increases. An image display apparatus including a color filter influences the design and performance of the mobile terminal in order to directly connect to the usable time and charging frequency of the mobile terminal.

Here, the color filter is generally formed on a transparent substrate, a colored layer formed on the transparent substrate and made of colored patterns of three primary colors of red, green and blue, and a transparent substrate so as to separate each colored pattern. And a light shielding portion formed.
In the formation method of such a colored layer, the pigment dispersion method using the pigment excellent in heat resistance or light resistance as a coloring material has been widely used. However, with color filters using pigments, it has become difficult to achieve the current demand for higher brightness.

  As one means for achieving high brightness, a colored resin composition using a dye has been studied. Dyes can generally produce color filters with high transmittance and high brightness compared to pigments, but their heat resistance and light resistance are poor, and the chromaticity is likely to change during high temperature heating in the color filter manufacturing process, etc. There was a problem. In addition, the colored resin composition using the dye has a problem that the solvent resistance of the cured coating film is poor, and the dye transfers color to the cured film containing no coloring agent such as adjacent adjacent color pixels or protective film. . Furthermore, the colored resin composition used by dissolving the dye is used as a color filter application, such as the problem that foreign matter is easily deposited on the surface of the cured coating film in the drying step, and the contrast is significantly reduced due to the fluorescence of the dye. Had many problems.

As a method of improving various resistance of a dye, a method of forming a salt of a dye is known. However, even if a dye is formed, in the conventional colored resin composition, the salt forming colorant of the dye is discolored by the high temperature heating performed in forming the colored layer, and the luminance of the colored layer actually decreases. Therefore, it has still been difficult to achieve high luminance. The applicant of the present invention is, in Patent Document 1, a color filter or the like using a salt-forming coloring material of a specific dye containing a divalent or higher cation and a divalent or higher anion in which a plurality of dye skeletons are crosslinked by a crosslinking group. Is disclosed. According to the salt-forming coloring material of the above-mentioned dye, it is disclosed that a molecular association is formed by containing a cation having a valence of 2 or more and an anion having a valence of 2 to improve heat resistance and solvent resistance.
However, for the colored resin composition containing a salt-forming coloring material for dyes, the heat resistance for achieving high brightness by suppressing the discoloration due to high-temperature heating performed in forming the colored layer is required to be further improved. It is done.

On the other hand, in colored resin compositions for color filters, improvement in developability and formation of high definition patterns have been attempted by using a resin that expresses a polar group in the side chain by the action of an acid (patent document 2 to 5).
Further, Patent Document 6 is a coloring composition containing a pigment, and a resin obtained by copolymerizing a specific polymerizable monomer such as butyl (meth) acrylate and another polymerizable monomer, and the specific composition Disclosed is a colored composition characterized in that the amount of components derived from the polymerizable monomer is 56% by weight or more in the total solid content of the resin, and the amount of components derived from the specific polymerizable monomer is the total solid of the resin It is described that the effect of light resistance improvement is acquired by sufficient interaction with a pigment by being 56 weight% or more in minutes.
In addition, Patent Document 7 discloses a pigment dispersion using a diketopyrrolopyrrole pigment, which has a structural unit having an amide group in its main chain for the purpose of forming a cured film having excellent heat resistance and excellent contrast. A pigment dispersant comprising a graft polymer containing a constituent unit derived from t-butyl methacrylate in a side chain, wherein the weight ratio of the main chain to the side chain in the graft polymer is a specific value, and a specific organic A pigment dispersion comprising a solvent is disclosed.

International Publication No. 2012/144521 JP 10-160924 A Unexamined-Japanese-Patent No. 10-260532 Unexamined-Japanese-Patent No. 2000-221682 JP, 2014-170189, A JP, 2013-160817, A JP, 2013-125087, A

However, with a colored resin composition using a pigment as a coloring material, it is difficult to obtain a sufficiently bright colored layer. On the other hand, in the case of a colored resin composition using a lake color material of a dye as a coloring material, a change in chromaticity may occur due to high temperature heating performed in forming a colored layer, and the brightness of the colored layer may be reduced There is a problem that it is difficult to make the brightness of the colored layer sufficiently high. In addition, when the dye is converted to a lake color material, the coloring power is reduced, so that many coloring materials are required to obtain a desired chromaticity, and it is difficult to thin the colored film. In Patent Documents 6 and 7, such a problem in the case of using a dye lake material is not recognized at all.
The embodiment of the present disclosure has been made in view of the above problems, and is a colored cured film having excellent heat resistance and improved luminance, which suppresses chromaticity change after high temperature heating, improves luminance, and reduces film thickness. Method of producing a colored cured film, a colored composition which is excellent in heat resistance, can improve luminance, and can form a thinner colored cured film, a color filter provided with the colored cured film, the colored hard film An object of the present invention is to provide a method of manufacturing a color filter using the manufacturing method, and a liquid crystal display and a light emitting display having the color filter.

One embodiment of the present disclosure includes a polymer of a monomer having an ethylenically unsaturated group, and a metal lake color material of a dye,
The colored cured film is provided, wherein the polymer contains a structure represented by the following general formula (1).

(In general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group.)

In one embodiment of the present disclosure, a colored cured film having a maximum peak in the region of wave number 1790 cm ⁻¹ or more and 1820 cm ⁻¹ or less in the infrared absorption spectrum is provided.

One embodiment of the present disclosure includes a polymer of a monomer having an ethylenically unsaturated group, a metal lake color material of a dye, and a solvent, and the polymer has a carboxyl group protecting group R ^{P described} below. Providing a coloring composition comprising the structural unit represented by formula (1 ′);
Forming a coating of the colored composition;
A step of removing the protective group R ^P by heating the coating film to form a structure represented by the following general formula (1);
A method of producing a colored cured film is provided.

(In general formula (1 ′), R ³ represents a hydrogen atom or a methyl group, R ^P represents a protecting group, and the protecting group is a group represented by the following general formula (A). N ′ is Represents an integer of 2 or more.)

(In general formula (A), R ^P1 represents a carbon atom or a silicon atom, R ^P2 , R ^P3 and R ^P4 each independently represent a hydrogen atom or a hydrocarbon group, R ^P5 represents a hydrocarbon group or a hydrocarbon group or It represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)

(In general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group.)

  In one embodiment of the present disclosure, the polymer contained in the coloring composition contains 30 mol% or more of a constituent unit represented by the general formula (1 ′) in 100 mol% of all constituent units. Provided is a method for producing a colored cured film.

One embodiment of the present disclosure contains a polymer of a monomer having an ethylenically unsaturated group, a metal lake color material of a dye, and a solvent.
The coloring composition is provided, wherein the polymer comprises a constituent unit represented by the general formula (1 ′) having a protecting group R ^P of a carboxy group.

  In one embodiment of the present disclosure, there is provided a coloring composition in which the polymerizable substance contains 30 mol% or more of a constituent unit represented by the general formula (1 ′) in 100 mol% of all constituent units. .

  One embodiment of the present disclosure is a color filter comprising at least a transparent substrate and a colored layer on the transparent substrate, wherein at least one of the colored layers is the above-mentioned colored cured film. .

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 the step of forming at least one of the colored layers by the method for producing a colored cured film described above.

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

  One embodiment of the present disclosure provides a light emitting display including the color filter described above and a light emitter.

  The embodiment of the present disclosure is a colored cured film having excellent heat resistance and improved brightness, a method for producing a colored cured film with suppressed luminance change and reduced thickness change after heating at high temperature, and heat resistance A colored composition capable of forming a colored cured film which is excellent in brightness and improved in thickness and can be made thinner, a color filter provided with the colored cured film, a method of producing a color filter using the method of producing a colored cured film, Also, it is possible to provide a liquid crystal display and a light emitting display having the color filter.

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. It is an infrared absorption spectrum of the colored cured film obtained in Examples 1, 2, 3 and 5 and the comparative colored cured film obtained in Comparative Examples 1 and 3. Is an enlarged view of the wave number 1790 cm ^-1 or 1820 cm ^-1 near the following areas of the infrared absorption spectrum of FIG. It is a < ¹ > H-NMR spectrum before the heating of the homopolymer of the reference example 1. FIG. It is a < ¹ > H-NMR spectrum after the heating of the homopolymer of the reference example 1. FIG. 5 is a GPC chart before and after heating of the homopolymer of Reference Example 1;

Hereinafter, a colored cured film, a method of manufacturing the colored cured film, a colored composition, a color filter and a method of manufacturing the same, a liquid crystal display device, and a light emitting display device according to the present disclosure will be described in order.
In the present specification, (meth) acrylic represents each of acrylic and methacrylic, (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 of wavelengths in the visible and non-visible regions, and also radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.

I. Colored cured film The colored cured film of the present disclosure contains a polymer of a monomer having an ethylenically unsaturated group and a metal lake color material of a dye,
It is a colored cured film in which the said polymer contains the structure represented by following General formula (1).

(In general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group.)

  The colored cured film according to the present disclosure generally has an effect of improving heat resistance while containing a metal lake color material of a dye having lower heat resistance compared to a pigment, and under high temperature heating such as post-baking. Also, since the fading of the color material can be suppressed, the luminance can be improved.

It is estimated as follows as an effect | action in which the coloring cured film which concerns on this indication exhibits the above effects.
In the colored cured film according to the present disclosure, the structure represented by the general formula (1) contained in the polymer in the colored cured film has a ring structure in the main chain, is rigid, and has a high glass transition temperature (Tg) It is considered that heat resistance is improved because it is a skeleton. Moreover, the structure represented by the said General formula (1) is considered to be a structure expressed by the heat processing performed in the manufacture process in the coloring cured film which concerns on this indication. That is, the polymer contains a structural unit having a carboxy protective group, and the protective group is removed by heating to form a carboxy group. Moreover, it is thought that the structure represented by the said General formula (1) is expressed by carrying out partial dehydration condensation of the carboxy groups which the mutually adjacent structural units have. Therefore, since the colored cured film according to the present disclosure is a film in which the carboxy group having a high glass transition temperature and the structure represented by the general formula (1) are expressed by heating and the heat resistance is improved, It is represented by the above-mentioned general formula (1) in which the solvent solubility is high due to the protective group, the dispersibility of the coloring material is good, the alkali developability does not become too high, and the hydrogen bond of the carboxy group The rigid structure makes it possible to suppress the molecular motion of the coloring material due to heating and suppress the color fading, so that the reduction in the luminance of the coloring layer is suppressed, and a colored layer with high luminance can be formed. Conceivable.

  The colored cured film of the present disclosure contains at least a polymer of a monomer having an ethylenically unsaturated group, and a metal lake color material of a dye, and may optionally contain other components. Typically, it is used as a colored layer of a color filter.

<Polymer of Monomer Having Ethylenically Unsaturated Group (1)>
The polymer of the monomer having an ethylenically unsaturated group contained in the colored cured film of the present disclosure includes the structure represented by the general formula (1). In the present disclosure, a polymer of a monomer having an ethylenically unsaturated group, which is a polymer including a structure represented by the general formula (1), is referred to as “a polymer of a monomer having an ethylenically unsaturated group (1)
The polymer (1) of the monomer having an ethylenically unsaturated group may be a binder resin or a dispersant, and is not particularly limited. However, the binder resin may be a colored cured film It is preferable from the point of improving the heat resistance and the brightness of the above and making the colored cured film more likely to be thinner.

Further, the polymer (1) of the monomer having an ethylenically unsaturated group contained in the colored cured film of the present disclosure is a homopolymer obtained using only one kind of monomer having an ethylenically unsaturated group. The copolymer may be a copolymer obtained by using two or more monomers having an ethylenically unsaturated group.
The structure represented by the general formula (1) is derived from a (meth) acrylate monomer, but when the polymer (1) of the monomer having an ethylenically unsaturated group is a copolymer, the general formula ( The monomer having an ethylenically unsaturated group other than the monomer that induces the structure represented by 1) may be other than the (meth) acrylate monomer. As a monomer which has an ethylenically unsaturated group other than a (meth) acrylate monomer, a (meth) acrylamide type monomer, a styrene-type monomer, a maleimide-type monomer is mentioned, for example. Among them, when the polymer (1) of the monomer having an ethylenically unsaturated group is a copolymer, it has an ethylenically unsaturated group other than the monomer that induces the structure represented by the general formula (1). The monomer is preferably a (meth) acrylate monomer.

That the colored cured film according to the present disclosure contains the polymer (1) of the monomer having an ethylenically unsaturated group is IR, thermal decomposition GC-MS, NMR, XPS, TOF-SIMS, and a combination thereof. It can be analyzed by the method. In particular, including the structure represented by the general formula (1) is confirmed, for example, by the colored cured film having a maximum peak in the region of wave number 1790 cm ⁻¹ or more and 1820 cm ⁻¹ or less in the infrared absorption spectrum. can do. The maximum peak appearing in the region of wave number 1790 cm ⁻¹ or more and 1820 cm ⁻¹ or less in the infrared absorption spectrum is derived from the structure represented by the general formula (1). Note that the maximum peak in the region of wave numbers 1790 cm ^{-1 to} 1820 cm ^-1 refers to the peak having the maximum peak intensity locally in the region, and the peak intensity of the maximum peak is the peak intensity at wave number 1790 cm ^-1. And it is preferable that it is larger than the peak intensity in wavenumber 1820cm < ^-1 >.
In addition, the infrared absorption spectrum of a colored cured film can be measured, for example, by a measuring apparatus: FT / IR-6100 manufactured by JASCO Corporation.

  In addition, the content ratio of the polymer (1) of the monomer having an ethylenically unsaturated group in the colored cured film of the present disclosure is 2% by mass or more from the viewpoints of heat resistance and luminance and thinning. Is preferably 4% by mass or more.

<Metal lake color material of dye>
The colored cured film according to the present disclosure contains the metal lake color of the dye. In the present disclosure, the metal lake coloring material of the dye refers to a coloring material in which a dye soluble in a solvent is insolubilized by forming a salt with a laking agent which is a counter ion containing a metal. A lake color material can usually be obtained by mixing a dye and a lake forming agent in a solvent.
The dye may be appropriately selected according to the desired color tone, and any of azo dyes, anthraquinone dyes, triarylmethane dyes, phthalocyanine dyes, xanthene dyes, cyanine dyes, indigo dyes, etc. It may be a dye having a skeleton (coloring site). Further, the dye may be a dye classified into any group such as an acid dye having an anionic substituent or a basic dye having a cationic substituent.
In the present disclosure, the metal lake color material of the dye is at least one color selected from the group consisting of triarylmethane-based colorants and xanthene-based colorants in terms of color developability, light transmittance, heat resistance, etc. It is preferable to use a material.

  Specific examples of acid dyes include C.I. I. Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72, C.I. I. Acid Blue 13, 5, 7, 9, 22, 22, 83, 90, 93, 100, 103, 104, 109, C.I. I. Triarylmethane-based acid dyes such as Acid Green 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 18, 22, 50, 50: 1, etc .; I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, sulforhodamine 101, C.I. I. Examples thereof include xanthene acid dyes such as Acid Blue 19 and the like. Among 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. Rhodamine acid dyes such as Acid Blue 19 are preferred.

  The basic dye is a cationic dye such as azine dyes, oxazine dyes, thiazine dyes, azo dyes, anthraquinone dyes, xanthene dyes, triarylmethane dyes, phthalocyanine dyes, Auramine dyes, acridine dyes, methine dyes and the like can be mentioned. Specifically, those having the following color index (CI) names can be mentioned.

C. I. Basic red 2, 5, 6, 10, C.I. I. Basic Violet 5, 6
8, 12, C.I. I. Azine dyes such as Basic Yellow 14;
C. I. Oxazine dyes such as Basic Blue 3, 6, 10, 12, 74, 122;
C. I. Basic Blue 9, 17, 24, C.I. I. Thiazine dyes such as Basic Green 5;
C. I. Basic reds 18, 22, 23, 24, 29, 30, 31, 32, 34, 38, 39, 46, 51, 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 15, 16, 18, 21, 22, 36, C.I. I. Basic yellow 15, 19, 24, 25, 28, 29, 38, 39, 49, 51, 52, 53, 57, 62, 73, C.I. I. Azo dyes such as Basic Orange 1, 2, 24, 25, 29, 30, 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, etc .;
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. Basic green 1, 4 etc. triarylmethane dyes;
C. I. Phthalocyanine dyes such as Basic Blue 140;
C. I. Basic yellow 2, 3, 37 auramine dyes such as;
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;
C. I. Basic red 12, 13, 14, 15, 27, 28, 37, 52, 90, C.I. I. Basic Blue 62, 63, C.I. I. Basic yellow 11, 13, 21, 22, 28, 29, 49, 51, 52, 53, C.I. I. Methine dyes such as Basic Violet 7, 15, 16, 20, 21, 22 and the like.
Moreover, as the triarylmethane-based basic dye and the xanthene-based basic dye in the present disclosure, cationic dyes that constitute the general formula (I) described later are also mentioned as preferable ones.
These dyes can be used singly or in combination of two or more.

  In the metal lake color material of the dye used in the present disclosure, the counter ion is appropriately selected from metal-containing counter ions according to the type of the dye, and the counter ion of the acid dye is a cation, The counter ion of the basic dye is an anion. That is, when the acid dye is to be insolubilized, a metal compound that produces a counter cation of the dye is used as a lake agent, and to insolubilize the basic dye, the counter anion of the dye is used as a lake agent. The resulting metal compound is used.

  As a counter cation of the acid dye, for example, metal ions such as calcium ion, barium ion, strontium ion, manganese ion, aluminum ion, cesium ion, lanthanum ion, neodymium ion, cerium ion, polyaluminum chloride, zirconium oxychloride and the like Inorganic polymers are mentioned.

On the other hand, as the counter anion of the basic dye, for example, anion of oxo acid (chromate ion, tungstate ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ), etc.), and a plurality of oxo acids Inorganic anions such as condensed polyacid anions and mixtures thereof can be mentioned.
The polyacid may be an isopolyacid anion (M _m O _n ) ^c- or a heteropolyacid anion (X _l M _m O _n ) ^c- . In the above ion formula, M represents a poly atom, X represents a hetero atom, 1 represents a composition ratio of hetero atoms, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. As poly atom M, Mo, W, V, Ti, Nb etc. are mentioned, for example. Moreover, as hetero atom X, Si, P, As, S, Fe, Co etc. are mentioned, for example.
Among them, from the viewpoint of heat resistance, a polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polyacid anion containing at least tungsten is more preferable.

As polyacid anions containing at least one of molybdenum and tungsten, for example, tungstate ions [W ₁₀ O ₃₂ ] ⁴⁻ , molybdate ions [Mo ₆ O ₁₉ ] ²⁻ , which are isopoly acids, and heteropoly acids there, ion phosphotungstic acid _{[PW 12 O} ^{40] 3-,} silicotungstic acid ion _{[SiW 12 O} ^{40] 4-,} phosphomolybdic acid ion _{[PMo 12 O} ^{40] 3-,} phosphorus tongue strike molybdate _{[PW 12- x} Mo _x O _40] ^3-, Keita ring strike molybdate _{[SiW 12-x Mo x O} 40] 4- , and the like. The polyacid anion containing at least one of molybdenum and tungsten is preferably a heteropolyacid among the above from the viewpoint of heat resistance and easiness of obtaining raw materials, and is further a heteropolyacid containing phosphorus (P) It is more preferable that

Examples of the lake agent that generates an inorganic anion include alkali salts and alkali metal salts of the above-mentioned inorganic anions.
The counter anion of the basic dye in the metal lake color material of the dye can be used singly or in combination of two or more.
In the present disclosure, the metal lake color material of the dye is preferably at least one metal lake color material of triarylmethane series basic dye and xanthene series basic dye from the viewpoint of brightness, and it is preferable to use triarylmethane series basic dye It is more preferable that it is a metal lake color material.

  In the present disclosure, the metal lake color material of the dye is excellent in heat resistance and light resistance, and at least one of triarylmethane-based basic dye and xanthene-based basic dye from the viewpoint of achieving high brightness of the color filter. Among the metal lake color materials, it is preferable to contain a color material represented by the following general formula (I).

(In general formula (I), A is an a-valent organic group in which a carbon atom directly bonded to N does not have a π bond, and the organic group is a saturated aliphatic carbon group at the end directly linked to N It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, N may be contained in the carbon chain B ^c- is a c-valent poly R ^{i to} R ^v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure R ^vi and R ^vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen Ar ¹ represents a divalent aromatic group which may have a substituent.
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. f and g represent integers of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less.
Plural R ^{i to} R ^vii , Ar ¹ , e, f and g may be the same or different. )

  Since the coloring material represented by the above general formula (I) contains a divalent or higher anion and a divalent or higher cation, in the aggregate of the coloring material, only 1 molecule to 1 molecule of anion and cation are present. It is presumed that, rather than being ionically bonded, they form a molecular assembly in which a plurality of molecules associate via ionic bonding. Therefore, the apparent molecular weight of the colorant represented by the general formula (I) significantly increases as compared with the molecular weight of the conventional lake colorant. The formation of such a molecular association further increases the cohesion in the solid state, reduces the thermal movement, can suppress the dissociation of the ion pair and the decomposition of the cation part, and is presumed to improve the heat resistance.

A in the general formula (I) is an a-valent organic group in which a carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is a saturated fat at the end directly linked to N Represents an aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and O (oxygen atom), S (sulfur atom), N (nitrogen atom) is contained in the carbon chain It may be Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic color forming site are not affected by the linking group A and other color forming sites, and the monomer Similar colors can be maintained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N has a linear, branched or cyclic structure if the terminal carbon atom directly bonded to N has no π bond. And any carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and O, S, N are contained in the carbon chain It is also good. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amido group or the like may be contained, and a hydrogen atom may be further substituted by a halogen atom or the like.
The aromatic group having the above 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 end directly bonded to N at least And may have a substituent, and may be a heterocyclic ring containing O, S and N.
Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of backbone fastness.
Among them, a bridged alicyclic hydrocarbon group is preferable as the cyclic aliphatic hydrocarbon group from the viewpoint of the fastness of the skeleton. The bridged alicyclic hydrocarbon group is a polycyclic aliphatic hydrocarbon group having a crosslinked structure in an aliphatic ring and having a polycyclic structure, and examples thereof include norbornane and bicyclo [2,2,2]. Examples include octane and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferred. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Especially, the group containing a benzene ring is preferable. For example, when A is a divalent organic group, a straight chain, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group having two alkylene groups of 1 to 20 carbon atoms such as xylylene group substituted Group groups and the like.

  The valence number a in the general formula (I) is the number of chromogenic cation sites constituting the cation, and a is an integer of 2 or more. In the color material of the present disclosure, since the valence number a of the cation is 2 or more, the heat resistance is excellent. The upper limit of a is not particularly limited, but in terms of easiness of production, a is preferably 4 or less, more preferably 3 or less.

The alkyl group in R ^{i to} R ^v is not particularly limited. Examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, and the like, among which a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and 1 to 5 carbon atoms. The following linear or branched alkyl groups are more preferable from the viewpoint of brightness and heat resistance. Among them, the alkyl group in R ^{i to} R ^v is particularly preferably an ethyl group or a methyl group. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and the like, and a substituted alkyl group includes a benzyl group and the like.
The aryl group in R ^{i to} R ^v is not particularly limited. For example, a phenyl group, a naphthyl group etc. are mentioned. As a substituent which an aryl group may have, an alkyl group, a halogen atom, etc. are mentioned, for example.

The fact that R ⁱⁱ and R ⁱⁱⁱ , and R ^iv and R ^v are combined to form a ring structure means that R ⁱⁱ and R ⁱⁱⁱ , and R ^iv and R ^v are forming a ring structure via a nitrogen atom. Say The ring structure is not particularly limited, and examples include pyrrolidine ring, piperidine ring, morpholine ring and the like.

Among them, from the viewpoint of chemical stability, R ^{i to} R ^v each independently represent 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 It is preferable that they combine to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

R ⁱ to R ^v may take the structure are each independently but, among them, it is preferable that in terms of color purity R ⁱ is a hydrogen atom, further R ⁱⁱ ~ in terms of manufacturing and ease of procurement of raw materials More preferably, all R ^v are identical.

Each of R ^vi and R ^vii independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom. The alkyl group in R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and is an alkyl having 1 to 4 carbon atoms. More preferred is a group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group, which may be linear or may have a branch. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group.
The alkoxy group in R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and 1 to 4 carbon atoms. More preferably, it is an alkoxy group of Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, which may be linear or may have a branch. Although it does not specifically limit as a substituent which an alkoxy group may have, For example, an aryl group, a halogen atom, a hydroxyl group etc. are mentioned.
As a halogen atom in R ^vi and R ^vii , a chlorine atom, a bromine atom, etc. are mentioned, for example.
Among them, R ^vi and R ^vii are preferably an electron donating group such as a methyl group or an ethyl group from the viewpoint of heat resistance.
The substitution number of R ^vi and R ^vii , that is, f and g each independently represent an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less, and more preferably 0 or more and 1 or less.
Further, R ^vi and R ^vii may be substituted at any position of the aromatic ring having a resonance structure in the triarylmethane skeleton or xanthene skeleton, but among them, —NR ⁱⁱ R ⁱⁱⁱ or —NR ^iv It is preferable that the meta position is substituted based on the substitution position of the amino group represented by R ^v .

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group in Ar ¹ can be the same as those listed for the aromatic group in A.
Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group composed of a fused polycyclic carbon ring having 10 to 14 carbon atoms. Among them, a phenylene group or a naphthylene group is more preferable in view of the simple structure and the inexpensive raw materials.

Plural R ^{i to} R ^vii , Ar ¹ , e, f and g in one molecule may be the same or different. When a plurality of R ^{i to} R ^vii , Ar ¹ , e, f and g are identical to each other, the color forming site exhibits the same color development, so that the color similar to that of the single color forming site can be reproduced and the color purity It is preferable from the point of view. On the other hand, when at least one of R ^{i to} R ^vii , Ar ¹ , e, f and g is a different substituent, it is possible to reproduce a mixed color of plural kinds of monomers, and desired It can be adjusted to the color.

In the colorant represented by the general formula (I), the anion part (B ^c− ) is a polyacid anion having a valence of 2 or more. As a polyacid anion, the thing similar to the polyacid anion mentioned above is used suitably.

  The polyacid anion in the coloring material represented by the general formula (I) can be used singly or in combination of two or more of the above anions, and when used in combination of two or more, the polyacid anion It is preferable from the viewpoint of heat resistance and light resistance that the ratio of tungsten to molybdenum in the whole is 90:10 to 100: 0.

  In the general formula (I), b represents the number of cations, d represents the number of anions in the molecular assembly, and b and d each represent an integer of 1 or more. When b is 2 or more, a plurality of cations in the molecular association may be used alone or in combination of two or more. When d is 2 or more, one or more anions in the molecular association may be used alone or in combination of two or more, and organic and inorganic anions may be used in combination. .

  E in the general formula (I) is an integer of 0 or 1. e = 0 represents a triarylmethane skeleton, and e = 1 represents a xanthene skeleton. The plurality of e may be the same or different. That is, for example, it may be a cation moiety having only a triarylmethane skeleton or only a xanthene skeleton, or may be a cation moiety containing both a triarylmethane skeleton and a xanthene skeleton in one molecule. From the viewpoint of color purity, it is preferable that the cation moiety has only the same skeleton. On the other hand, the coloring material represented by General formula (I) can be adjusted to a desired color by setting it as the cation part containing both a triaryl methane frame and a xanthene frame.

In addition, as a metal lake color material of a dye used in the present disclosure, a metal lake color material using a dye having a thermal decomposition temperature of 230 ° C. or more has a structure represented by the above general formula (1 ′) and the above general formula Since it has a thermal decomposition temperature higher than the heating temperature at which the structure represented by (1) is expressed, it is preferable from the point of being able to suppress fading by heating before the structure represented by the general formula (1) is expressed . Examples of metal lake color materials using dyes having a thermal decomposition temperature of 230 ° C. or higher include the color materials described in Japanese Patent No. 5403175 and the like.
The thermal decomposition temperature of the dye can be measured by thermogravimetric-differential thermal analysis (TG-DTA). Specifically, using, for example, DTG-60A manufactured by Shimadzu Corporation, the temperature is raised to 30 ° C. to 600 ° C. in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min, and the thermal decomposition temperature is measured.

  In addition, it is confirmed that the colored cured film according to the present disclosure contains the metal lake color material of the dye, for example, by elemental analysis by ICP emission spectroscopy (ICP-AES) or X-ray photoelectron spectroscopy (XPS). can do.

  In addition, the content ratio of the metal lake pigment of the dye in the colored cured film of the present disclosure is preferably 5% by mass or more, and more preferably 10% by mass or more from the viewpoint of achieving desired chromaticity. The content is preferably 50% by mass or less, and more preferably 40% by mass or less, from the viewpoint of making the colored cured film sufficient.

<Other ingredients>
The colored cured film according to the present disclosure may further contain other components as needed in addition to the polymer of the monomer having the ethylenically unsaturated group and the metal lake color material of the dye. As the other components, a polymer different from the polymer of the monomer having an ethylenically unsaturated group, a color material different from the metal lake color material of the dye, and an appropriately selected according to the application of the colored cured film Although it is not particularly limited, for example, polymerizable monomers, polymerization initiators, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, silane coupling agents, antifoaming agents, antirepelling agents And antioxidants, aggregation inhibitors, ultraviolet light absorbers, adhesion promoters and the like.

  Moreover, the colored cured film which concerns on this indication can be 5 micrometers or less in film thickness. On the other hand, the thickness of the colored cured film according to the present disclosure is preferably 0.5 μm or more, and more preferably 1 μm or more from the viewpoint of strength.

II. Method for Producing Colored Cured Film A method for producing a colored cured film according to the present disclosure comprises a polymer of a monomer having an ethylenically unsaturated group, a metal lake color material of a dye, and a solvent, and the polymer is carboxy Preparing a colored composition comprising a constituent unit represented by the following general formula (1 ′) having a protecting group R ^P of a group (hereinafter referred to as “colored composition preparation step”),
A step of forming a coating film of the coloring composition (hereinafter referred to as a “coating film forming step”);
A step of removing the protective group R ^P by heating the coating film to form a structure represented by the general formula (1) (hereinafter referred to as “coating film heating step”);
Have.

(In general formula (1 ′), R ³ represents a hydrogen atom or a methyl group, R ^P represents a protecting group, and the protecting group is a group represented by the following general formula (A). N ′ is Represents an integer of 2 or more.)

(In general formula (A), R ^P1 represents a carbon atom or a silicon atom, R ^P2 , R ^P3 and R ^P4 each independently represent a hydrogen atom or a hydrocarbon group, R ^P5 represents a hydrocarbon group or a hydrocarbon group or It represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)

Since the colored cured film obtained by the method for producing a colored cured film according to the present disclosure has a structure represented by the general formula (1), it is excellent in heat resistance similarly to the colored cured film according to the present disclosure, It is a colored cured film with improved brightness.
Furthermore, in the method for producing a colored cured film according to the present disclosure, the protective group of the carboxy group removed by heating is removed from the inside of the colored cured film, and the carboxy groups adjacent to each other are dehydrated and condensed. The colored cured film can be made thinner while increasing the colorant concentration.

1. Coloring Composition Preparation Step The coloring composition preparation step contains a polymer of a monomer having an ethylenically unsaturated group, a metal lake color material of a dye, and a solvent, and the polymer is a carboxyl group protecting group R ^P A colored composition comprising the constituent unit represented by the above general formula (1 ′) having
That is, the coloring composition used in the present disclosure contains a polymer of a monomer having an ethylenically unsaturated group, a metal lake color material of a dye, and a solvent, and the polymer is a protecting group R of a carboxy group. It is a coloring composition containing the structural unit represented by the said General formula (1 ') which has ^P.
In the present disclosure, a polymer of a monomer having an ethylenically unsaturated group, which is a polymer containing a structural unit represented by the general formula (1 ′), is referred to as “a monomer having an ethylenically unsaturated group. Polymer (1 ') ".

The coloring composition contains at least a polymer (1 ′) of a monomer having an ethylenically unsaturated group, a metal lake color material of a dye, and a solvent, and further contains other components as necessary. May be
Hereinafter, each component which the said coloring composition contains is demonstrated.

<Polymer (1 ′) of Monomer Having Ethylenically Unsaturated Group>
In the polymer (1 ′) of the monomer having an ethylenically unsaturated group contained in the coloring composition, n ′ represents an integer of 2 or more, preferably 5 or more, more preferably from the viewpoint of heat resistance and brightness. 10 or more. The upper limit of n ′ is not particularly limited, but can be, for example, 1000 or less.
Among others, R ^{P1 in the} general formula (A) is preferably a carbon atom from the viewpoint of high versatility and stability of the protective group.
The hydrocarbon group in R ^P2 , R ^P3 , R ^P4 , R ^P5 and R ^P6 in the general formula (A) may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, Although there is no particular limitation, aliphatic hydrocarbon groups are preferred, and among them, linear, branched, cyclic and alkyl combinations of these combinations are preferred. Examples of the alkyl group include methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, isopropyl group, isobutyl group, t-butyl group, 2- Ethylhexyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclohexylmethyl group and the like can be mentioned.
Among them, R ^P2 and R ^P3 in the general formula (A) are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. In R ^P2 and R ^P3, the alkyl group of 1 to 3 carbon atoms, among them, more preferably a methyl group and an ethyl group, a methyl group is particularly preferred.
R ^{P4 in the} general formula (A) is preferably an alkyl group having 1 to 3 carbon atoms, or forms a ring structure by bonding to R ^P5, and is an alkyl group having 1 to 3 carbon atoms Is more preferred. Among the alkyl groups having 1 or more and 3 or less carbon atoms in R ^P4 , a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.
R ^{P5 in the} general formula (A) is an alkyl group having 1 or more and 3 or less carbon atoms, -OR ^P6 and the R ^P6 is bonded to an alkyl group having 1 or more and 18 or less carbon atoms or R ^P4 to form a ring structure The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Among the alkyl groups having 1 or more and 3 or less carbon atoms in R ^P5 , among these, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable. As for R ^P6 , an alkyl group having 3 to 10 carbon atoms is more preferable.
The fact that R ^P4 and R ^P5 are linked to each other to form a ring structure means that R ^P4 and R ^P5 form a ring structure via R ^P1 . When R ^P1 is a carbon atom, examples of the ring structure formed by bonding R ^P4 and R ^P5 to each other include a cycloalkane having 3 to 6 carbon atoms and adamantane. When R ^P1 is a silicon atom, for example, a heterocyclic ring in which a carbon atom located in R ^P1 of the above-mentioned ring structure is replaced by a silicon atom can be mentioned.

  Specific examples of the monovalent protecting group represented by the general formula (A) include t-butyl group, sec-butyl group, trimethylsilyl group, 2-methyl-2-adamantyl group, and the following general formula ( The structure derived from the vinyl ether compound represented by A-1), etc. are mentioned.

(In General Formula (A-1), R ^P6 represents a hydrocarbon group.)

Examples of the hydrocarbon group for R ^P6 in the general formula (A-1), the general formula (A) the same as the hydrocarbon group in R ^P6 in. Among them, an alkyl having 1 to 18 carbon atoms A group is preferable, and an alkyl group having 3 to 10 carbon atoms is more preferable. Specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, cyclohexylmethyl group and the like are mentioned. Among them, from the viewpoint of solvent solubility, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, n-hexyl group and cyclohexyl group are preferable, methyl group, ethyl group, propyl group and isopropyl group, An n-butyl group is more preferred.

The polymer (1 ′) of the monomer having an ethylenically unsaturated group preferably has a structure in which two or more structural units represented by the general formula (1 ′) are positioned adjacent to each other. In the constituent unit represented by the general formula (1 ′), the protecting group R ^P of the carboxy group is released by heating to become a carboxy group. Therefore, when the structural units represented by the general formula (1 ′) are positioned adjacent to each other, the carboxy groups possessed by the structural units adjacent to each other are dehydrated and condensed, whereby the general formula (1) can be obtained. The depicted structure is formed.

  In the polymer (1 ′) of the monomer having an ethylenically unsaturated group, the content ratio of the structural unit represented by the general formula (1 ′) when the total structural unit is 100 mol% is the same as the general formula From the viewpoint of easily forming the structure represented by (1), improving the heat resistance and the brightness, and the point of thinning the colored cured film, it is preferably 20 mol% or more, and preferably 25 mol% or more Is more preferably 30 mol% or more, and from the viewpoint of solvent resistance, it is preferably 85 mol% or less, more preferably 80 mol% or less.

Moreover, it is preferable that polymer (1 ') of the monomer which has the said ethylenically unsaturated group is binder resin. When it is a binder resin, it is possible to use, as an alkali-soluble resin, a copolymer having a structural unit represented by the general formula (1 ′) and a structural unit having an acidic group in the side chain, among others. It is preferable in point. The structural unit having an acidic group in the side chain is introduced by copolymerizing a monomer having an ethylenically unsaturated group and an acidic group with a monomer that derives a structural unit represented by the general formula (1 ′). Can.
From the viewpoint that the polymer (1 ′) of the monomer having an ethylenically unsaturated group can be used as an alkali-soluble resin, the acid value of the polymer (1 ′) of the monomer having an ethylenically unsaturated group is 30 mg KOH / G or more is preferable, 40 mg KOH / g or more is more preferable, and 200 mg KOH / g or less is preferable and 190 mg KOH / g or less is more preferable from the viewpoint of solubility.
In addition, the said acid value represents the mass (mg) of potassium hydroxide required in order to neutralize the acidic component contained in solid content 1g of a polymer, and is a value measured by the method as described in JIS K 0070. is there.

  Further, in the copolymer, as an acid group of a constituent unit having an acid group in a side chain, a carboxy group has an alkali solubility, and together with the constituent unit represented by the general formula (1 ′), the general formula It is easy to form the structure represented by (1), which is preferable from the viewpoint of the heat resistance and the brightness of the colored cured film.

  As a monomer which derives the structural unit represented by the said General formula (1 '), the monomer represented by following General formula (1' ') is mentioned. Specifically, For example, t-butyl (meth) acrylate is mentioned. , (Meth) acrylic acid sec-butyl, (meth) acrylic acid trimethylsilyl, (meth) acrylic acid 2-methyl-2-adamantyl, (meth) acrylic acid 1-methoxyethyl, (meth) acrylic acid 1-ethoxyethyl, (Meth) acrylic acid 1-propoxyethyl, (meth) acrylic acid 1-n-butoxyethyl, (meth) acrylic acid 1-tert-butoxyethyl, (meth) acrylic acid 1-isobutoxyethyl, (meth) acrylic acid 1-cyclohexyl oxyethyl etc. are mentioned.

(In the general formula (1 ′ ′), R ³ represents a hydrogen atom or a methyl group, R ^P represents a protecting group, and the protecting group is a group represented by the general formula (A)).

In the general formula (1 ′ ′), R ³ and R ^P are the same as the general formula (1 ′).

  Specific examples of the monomer having an ethylenically unsaturated group and a carboxy group include acrylic acid and methacrylic acid.

  In the polymer (1 ′) of the monomer having an ethylenically unsaturated group, the content ratio of the constituent unit having an acidic group in the side chain when the total constituent unit is 100 mol%, the copolymer is alkali soluble From the viewpoint that it can be used as a resin, the solubility of the resulting coating film in an alkali developer is good, and pattern formation becomes easy, it is preferably 10 mol% or more, and 15 mol% or more. More preferable. In addition, the content ratio of the structural unit having an acidic group in the side chain is 95 mol% or less from the viewpoint of suppressing dropping of the formed pattern from the substrate and film roughness of the pattern surface during development with an alkaline developer. Is preferably 90 mol% or less.

The polymer (1 ′) of the monomer having an ethylenically unsaturated group further contains a constituent unit having an ester group or an amide group different from the constituent unit represented by the general formula (1 ′) It is also good. The structural unit having an ester group or an amide group not only functions as a component that suppresses the alkali solubility of the coloring composition, but also functions as a component that improves the solubility in a solvent. As a monomer which derives the structural unit which has such an ester group or an amido group, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate are mentioned, for example N-Butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, vinyl (meth) acrylate, (meth) acrylamide, N-tert-butyl (meth) acrylate And acrylamide).
The polymer (1 ′) of the monomer having an ethylenically unsaturated group may further contain a structural unit having an aromatic carbon ring or an aliphatic carbon ring. The aromatic carbon ring functions as a component to improve the coating film strength of the coloring composition.
As a monomer which derives the structural unit which has such an aromatic carbon ring, alpha-methyl styrene, styrene, a benzyl (meth) acrylate, etc. are mentioned, for example.

Moreover, the polymer (1 ′) of the monomer having an ethylenically unsaturated group is, among others, a constituent unit represented by the general formula (1 ′), a constituent unit having an acidic group in a side chain, and a side chain It is possible to use as the alkali-soluble resin that the copolymer has a structural unit having an ethylenically unsaturated group, and because the ethylenically unsaturated group contained in the side chain can form a crosslinked structure. Furthermore, it is preferable from the point which a film strength improves and heat resistance and solvent resistance improve. As a method of introducing a structural unit having an ethylenically unsaturated group in a side chain, a conventionally known method can be appropriately selected and used, for example, after polymerizing a structural unit having an acidic group in a side chain, Introducing a structural unit having an ethylenically unsaturated group in the side chain, for example, by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the acid group of the side chain it can.
When the polymer (1 ′) of the monomer having an ethylenically unsaturated group is a copolymer having a constituent unit having an ethylenically unsaturated group in a side chain, the ethylenically unsaturated group equivalent is the same as that of the colored cured film The film strength is preferably in the range of 100 or more and 5,000 or less, and particularly preferably in the range of 140 or more and 4,500 or less, from the viewpoint of improving the film strength and improving the development resistance and making the film strength sufficient.

Here, the ethylenically unsaturated group equivalent is a weight average molecular weight per mole of the ethylenically unsaturated group in the copolymer, and is represented by the following formula (1).
Formula (1)
Ethylenically unsaturated group equivalent (g / mol) = W (g) / M (mol)
(In the formula (1), W represents the mass (g) of the copolymer, and M represents the number of moles (mol) of the ethylenically unsaturated group contained in the copolymer W (g).)

  The said ethylenically unsaturated group equivalent is measured by, for example, measuring the number of the ethylenically unsaturated groups contained per 1 g of copolymers based on the test method of the iodine value of JIS K 0070: 1992. It may be calculated.

  From the viewpoint of film strength, the weight average molecular weight of the polymer (1 ′) of the monomer having an ethylenically unsaturated group is preferably 1000 or more, more preferably 1500 or more, and on the other hand, solubility From the point of point to point, it is preferably 50000 or less, more preferably 45000 or less. The mass average molecular weight is determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent value.

  The polymer (1 ′) of the monomer having an ethylenically unsaturated group is a known polymer using each monomer that derives the polymer (1 ′) containing the monomer represented by the general formula (1 ′ ′) It can be obtained by polymerizing by a method.

In the coloring composition, the polymer (1 ′) of the monomer having an ethylenically unsaturated group may be used singly or in combination of two or more.
The content of the polymer (1 ′) of the monomer having an ethylenically unsaturated group in the total solid content of the coloring composition is from the viewpoints of heat resistance and brightness, and thinning of the colored cured film. The content is preferably 5% by mass or more, more preferably 6% by mass or more, and on the other hand, preferably 50% by mass or less, and 45% by mass or less from the viewpoint of solvent resistance. preferable.
In the present disclosure, solid content means all components other than the solvent.
When the polymer (1 ′) of the monomer having an ethylenically unsaturated group is used as the alkali-soluble resin, the amount is preferably 10 parts by mass or more with respect to 100 parts by mass of the coloring material contained in the coloring composition. And more preferably 25 parts by mass or more, and preferably 100 parts by mass of the coloring material contained in the coloring composition in that the coloring material can be sufficiently contained and sufficient coloring density can be obtained. Is 500 parts by mass or less, more preferably 300 parts by mass or less.

<Metal lake color material of dye>
The metal lake coloring material of the dye contained in the coloring composition is the same as the metal lake coloring material of the dye contained in the colored cured film according to the above-mentioned present disclosure, and is dispersed in the coloring composition.
The average dispersed particle diameter of the metal lake color material of the dye in the coloring composition is not particularly limited as long as it is capable of desired color development, and varies depending on the type of the coloring material used, but the coloring material It is preferable to be in the range of 5 nm or more and 300 nm or less, and more preferable to be in the range of 30 nm or more and 250 nm or less from the viewpoint of obtaining satisfactory dispersion stability and sufficient coloring power.

  In addition, the content of the metal lake color material of the dye in the total solid content of the coloring composition is appropriately adjusted so as to achieve a desired chromaticity, and is not particularly limited, and varies depending on the type of coloring material Is preferably in the range of 5% by mass to 50% by mass, and more preferably in the range of 8% by mass to 40% by mass.

<Solvent>
The solvent contained in the coloring composition does not react with each component in the coloring composition, and can be appropriately selected and used from solvents capable of dissolving or dispersing these. Specifically, alcohol type; ether alcohol type; ester type; ketone type; ether alcohol acetate type; ether type; aprotic amide type; lactone type; unsaturated hydrocarbon type; organic solvent such as saturated hydrocarbon type Among them, it is preferable to use an ester solvent from the viewpoint of solubility at the time of 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, Diethylene glycol monobutyl ether acetate etc. are mentioned.
Above all, it is preferable to use propylene glycol monomethyl ether acetate (PGMEA) from the viewpoints of low danger to human body and low volatility at around room temperature but good heat drying property.
These solvents may be used alone or in combination of two or more.

  The content of the solvent may be set as appropriate as long as the colored cured film can be formed with high accuracy. From the viewpoint of achieving excellent coatability with respect to the total amount of the coloring composition containing the solvent, it is usually preferably in the range of 55% by mass to 95% by mass, and in particular, 65% by mass or more It is more preferable to be in the range of 88 mass% or less. When the content of the solvent is within the above range, the coloring composition can be made excellent in coatability.

<Other ingredients>
The coloring composition may further contain other components as necessary in addition to the polymer (1 ′) of the monomer having an ethylenically unsaturated group described above, the metal lake color material of the dye, and the solvent. good. As the other components, for example, a binder component other than the polymer (1 ′) of the monomer having the ethylenically unsaturated group, a coloring material other than the metal lake color material of the dye, a dispersant, and other optional additions An ingredient is mentioned.

(Binder component)
As binder components other than the polymer (1 ') of the monomer which has the said ethylenically unsaturated group, well-known alkali-soluble resin, a polyfunctional monomer, photoinitiator etc. are mentioned, for example.
A known alkali-soluble resin is one having an acidic group, which functions as a binder resin and is appropriately selected and used as a resin which is soluble in a developing solution used in forming a pattern, particularly preferably an alkaline developing solution. can do. Specific examples thereof include acrylic copolymers having a carboxyl group such as those described in WO 2012/144521.

  Content of alkali-soluble resin other than the polymer (1 ') of the monomer which has the said ethylenically unsaturated group in the total solid of the said coloring composition is a point of heat resistance and a brightness, and thin film formation of a colored cured film From the point of point of view, it is preferably 30% by mass or less, and more preferably 20% by mass or less.

Any polyfunctional monomer may be used as long as it can be polymerized by the later-described photoinitiator, and a compound having two or more ethylenically unsaturated double bonds is usually used, and in particular, two or more (meth) acryloyl groups It is preferable that it is a polyfunctional (meth) acrylate which it has.
As polyfunctional (meth) acrylate, it may select suitably from what is conventionally known, and may be used. As a specific example, the thing etc. which are described in international publication 2012/144521 gazette are mentioned, for example.

  One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. In addition, when a high crosslinking density is required for the colored cured film, it is preferable that the polyfunctional monomer has three or more (trifunctional) or more polymerizable double bonds, and a trivalent or higher polyvalent monomer. Poly (meth) acrylates of polyhydric alcohols and their dicarboxylic acid modified products are preferable, and specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and succinic acid of pentaerythritol tri (meth) acrylate Acid modified product, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate Viscoat (manufactured by Osaka Organic Chemical Industry) # 3PA, Viscoat # 3PMA (manufactured by Osaka Organic Chemical Industry) and the like are preferable.

  The content of the polyfunctional monomer in the total solid content of the coloring composition is not particularly limited, but from the viewpoint of sufficiently advancing photocuring and suppressing the elution of the exposed portion, a total of 100 mass of the alkali soluble resin Preferably it is 5 mass parts or more with respect to part, More preferably, it is 20 mass parts or more. Further, the content of the polyfunctional monomer is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, based on 100 parts by mass in total of the alkali-soluble resin, from the viewpoint of improving the alkali developability. .

  Moreover, in the coloring composition, the total content of the polyfunctional monomer is preferably 5% by mass to 70% by mass, and more preferably 10% by mass to 50% by mass, in the total solid content of the coloring composition. It is more preferable that

  There is no restriction | limiting in particular as photoinitiator, It can be used combining 1 type, or 2 or more types out of conventionally known various photoinitiators. As a specific example, the thing etc. which are described in international publication 2012/144521 gazette are mentioned, for example.

  The content of the photo-initiator used in the coloring composition is preferably 0 with respect to 100 parts by mass of the polyfunctional monomer from the viewpoint of sufficiently causing a polymerization reaction to make the cured cured film sufficiently hard. The content is 0.11 parts by mass or more, more preferably 5 parts by mass or more. In addition, the content of the photoinitiator relative to 100 parts by mass of the polyfunctional monomer is preferable in that the content of the coloring material and the like in the solid content of the coloring composition is sufficient and the sufficient coloring concentration is obtained. Preferably it is 100 mass parts or less, More preferably, it is 60 mass parts or less.

  In the coloring composition, the total amount of the alkali-soluble resin as the binder component, the polyfunctional monomer, and the photoinitiator relative to the total solid content of the coloring composition has sufficient hardness and adhesion with the substrate. It is preferably 10% by mass or more, more preferably 30% by mass or more from the viewpoint of obtaining a colored cured film having, and excellent in developability, and the occurrence of micro wrinkles due to heat shrinkage is also suppressed. Preferably, the content is 90% by mass or less, and more preferably 80% by mass or less.

(Color material)
Examples of the colorant other than the metal lake color material of the dye include known organic pigments and inorganic pigments.

As the organic pigment, for example, insoluble azo pigment, soluble azo pigment, phthalocyanine organic pigment, quinacridone organic pigment, perylene organic pigment, dioxazine organic pigment, nickel azo pigment, isoindolinone organic pigment, pyranthrone organic pigment As organic solid solution pigments such as thioindigo organic pigment, condensed azo organic pigment, benzimidazolone organic pigment, quinophthalone organic pigment, isoindoline organic pigment, quinacridone solid solution pigment, perylene solid solution pigment, and other pigments Carbon black etc. are mentioned.
When organic pigments are exemplified by color index (C.I.) numbers, C.I. I. Pigment yellow 1, 2, 3, 12, 13, 14, 15, 16, 17, 20, 24, 49, 55, 60, 61, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 120, 123, 124, 125, 126, 127, 127, 127, 127, 128, 129, 130, 133, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 166, 167, 168, 169, 170, 172, 173, 175, 176, 179, 180, 181, 182, 183, 185, 191, 193, 194, 199, 213, 214, 215, 219; I. Pigment red 5, 7, 9, 12, 48, 49, 52, 53, 57, 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5, 83, 88, 89, 97, 112, 122, 123, 144, 146, 147, 149, 166, 169, 170, 171, 172, 175, 176, 177, 178, 179, 180, 181, 184, 185, 187, 190, 192, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 215, 216, 217, 220, 221, 223, 224, 227, 228, 238, 240, 242, 245, 247, 251, 253, 254, 255, 256, 257, 258, 260, 262, 263, 264, 266, 268, 2 9,270,272,279; C. I. Pigment orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 24, 31, 34, 36, 38, 43, 46, 48, 51, 55, 59, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 81; I. Pigment violet 1, 2, 3, 3: 1, 3: 3, 5, 13, 19, 23, 25, 27, 29, 30, 31, 32, 36, 37, 38, 40, 42, 50; I. Pigment blue 1, 15, 15: 1, 15: 3, 15: 4, 15: 6, 16, 17: 1, 22, 24, 24: 1, 25, 26, 56, 60, 61, 62, 63, C.I. 64, 75, 79, 80; I. Pigment green 1, 4, 7, 8, 10, 36, 58, 59; C.I. I. Pigment brown 5, 23, 25, 26, 41 and the like.

  Specific examples of the above-mentioned inorganic pigments are barium sulfate, iron oxide, zinc oxide, barium carbonate, barium sulfate, silica, clay, talc, titanium oxide, calcium carbonate, synthetic mica, alumina, zinc flower, lead sulfate, yellow lead, Zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, inorganic solid solution pigments and the like can be mentioned.

Moreover, as a coloring material other than the metal lake color material of the said dye, the lake color material of the dye obtained using a lake-forming agent which does not contain a metal can also be mentioned. Examples of the metal-free lake forming agent include ammonium cations as counter cations of acid dyes, organic anions as counter anions of basic dyes, and the like.
As a compound which generate | occur | produces an ammonium ion, a primary amine compound, a secondary amine compound, a tertiary amine compound etc. are mentioned as a suitable thing, for example, Among them, the point which is excellent in heat resistance and light resistance, a secondary amine compound Alternatively, it is preferable to use a tertiary amine compound.
Examples of the organic anion include organic compounds having an anionic group as a substituent. The Examples of the anionic group, for ^{_{example, -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. Among these, from the viewpoint of heat resistance and light resistance, and imidate ^{_{groups, -SO 3 -, -CF 2 SO}} 3 - , more preferably a, -SO ₃ ^- (sulfonato group) is more preferable.

In the total 100 parts by mass of the coloring material contained in the coloring composition, the content of the coloring material other than the metal lake color material of the dye is preferably 70 parts by mass or less from the viewpoint of heat resistance and brightness.
The amount is more preferably 60 parts by mass or less, and still more preferably 50 parts by mass or less.

(Dispersant)
As a dispersing agent, it can select suitably from what is conventionally used as a dispersing agent, and can be used. As a specific example of a dispersing agent, surfactant, such as cationic type, anionic type, nonionic type, amphoteric, silicone type, a fluorine type, can be used, for example. Among the surfactants, polymer surfactants (polymer dispersants) are preferable in that they can be dispersed uniformly and finely. These dispersants may be used alone or in combination of two or more.

  As the polymer dispersant, for example, (co) polymers of unsaturated carboxylic acid ester such as polyacrylic acid ester; (partial) amine salt of (co) polymer of unsaturated carboxylic acid such as polyacrylic acid (Partially) ammonium salts and (partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and modified products thereof; polyurethanes; unsaturated polyamides; Long-chain polyamino amide phosphates; Polyethylenimine derivatives (amides obtained by reaction of poly (lower alkylenimine) with free carboxyl group-containing polyesters and their bases); Polyallylamine derivatives (polyallylamine and free carboxyls) Co-Condensation of Polyester, Polyamide or Ester Having a Group The reaction product obtained by reacting one or more compound selected from among the three compounds of (polyester amide)), and the like.

  As commercially available products of such dispersants, for example, Disperbyk-2000, 2001, BYK-LPN 6919, 21116, 21324 (above, made by BIC Chemie Japan), Ajispar PB 821, 881 (made by Ajinomoto Fine Techno Co., Ltd.) etc. it can. Among them, BYK-LPN 6919 and 21116 are preferable in terms of heat resistance, electrical reliability, and dispersibility.

Among these, as the polymer dispersant, a polymer having at least a constitutional unit represented by the following general formula (II) from the viewpoint of being able to suitably disperse the above-mentioned coloring material and having good dispersion stability, the following general formula A phosphate dispersant having at least one selected from a constituent unit represented by (III) and a constituent unit represented by the following general formula (III ′), and one or more urethane bonds (— 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 NH-COO-), Among them, the polymer which had the structural unit represented by the following general formula (II) at least And 1 selected from the group consisting of a phosphorus-based acidic dispersant having at least one selected from a constituent unit represented by the following general formula (III) and a constituent unit represented by the following general formula (III ′) Or more at a wavelength of 550 nm.
The above-mentioned preferable dispersants will be described in detail below.

  In the coloring composition of the present disclosure, a polymer having at least a constituent unit represented by the following general formula (II) can be suitably used as a dispersant.

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

(In general formula (II-a), R ²² and R ²³ each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom, and R ²² and R ²³ are the same or different from each other May be

In the general formula (II), A is a direct bond or a divalent linking group. The direct bonding means that Q is directly bonded to a carbon atom in the general formula (II) without a linking group.
Examples of the divalent linking group for 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 represent an alkylene group), a combination thereof and the like.
Among them, from the viewpoint of dispersibility, A in the general formula (II) is preferably a direct bond, a -CONH- group, or a divalent linking group containing a -COO- group.

  In addition, it can be particularly suitably used by forming a constituent unit represented by the above general formula (II) of these dispersants in an arbitrary ratio with a salt forming agent described below.

Among the polymers having a structural unit represented by the general formula (II), among them, WO 2011/108495, JP-A 2013-054200, JP-A 2010-237608, JP-A 2011-75661 The block copolymer and graft copolymer having the structure described in the above can improve the dispersibility and dispersion stability of the color material and the heat resistance of the resin composition, and can form a colored cured film with high brightness and high contrast. It is preferable from the point of view.
Moreover, BYK-LPN6919 etc. are mentioned as a commercial item of the polymer which has a structural unit represented by General formula (II).

Moreover, the polymer having a structural unit represented by General Formula (II) may further have a structural unit represented by General Formula (1 ′). Thereby, the heat resistance and the brightness of the colored cured film of the present disclosure can be further improved.
In the polymer having the structural unit represented by the general formula (II), the content of the structural unit represented by the general formula (1 ′) is 20 mol% or more from the viewpoint of heat resistance and luminance. It is preferably 30 mol% or more, and from the viewpoint of dispersibility and dispersion stability, it is preferably 95 mol% or less, and more preferably 90 mol% or less.

(Salt forming agent)
In the coloring composition, a preferable dispersant is a polymer in which at least a part of the nitrogen moiety of the constituent unit represented by the general formula (II) forms a salt.
As a salt formation agent, the acidic organophosphorus compound of WO2011 / 108495, Unexamined-Japanese-Patent No. 2013-054200, an organic sulfonic acid compound, a quaternizing agent etc. can be used conveniently. In particular, when the salt forming agent is an acidic organophosphorus compound, a colored cured film with higher brightness can be formed even after the high temperature heating step in the color filter manufacturing step.

<Phosphorus based acidic dispersant>
The phosphorus-based acidic dispersant suitably used as a dispersant in the present disclosure has at least one selected from a constitutional unit represented by the following general formula (III) and a constitutional unit represented by the following general formula (III ′) It is a phosphorus based acidic dispersant. By using the phosphorus-based acidic dispersant, the dispersibility of the metal lake color material can be particularly improved, and a colored cured film having excellent heat resistance, high luminance, and excellent alkali resistance can be formed.

(In the general formula (III) and the general formula (III ′), L ¹ is a direct bond or a divalent linking group, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydrocarbon group, — [CH ( A monovalent group represented by R ¹⁶ ) -CH (R ¹⁷ ) -O] _{x 1} -R ¹⁸ or-[(CH ₂ ) _{y 1} -O] _z 1 -R ¹⁸ , R ¹⁶ and R ¹⁷ are each independently A hydrogen atom or a methyl group, R ¹⁸ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ¹⁹ R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon group may have a substituent, x 1 is an integer of 1 to 18, y1 represents an integer of 1 to 5, and z1 represents an integer of 1 to 18.
In general formula (III '), X ⁺ represents an organic cation. )

  The phosphorus-based acidic dispersant having at least one selected from the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III ′) includes, for example, those described in Japanese Patent No. 5895925 Dispersants and the like can be mentioned.

<Urethane-based dispersant>
The urethane type dispersing agent suitably used as a dispersing agent is a dispersing agent which consists of a compound which has one or more urethane bond (-NH-COO-) in 1 molecule.
By using a urethane dispersant, good dispersion can be achieved with a small amount. By setting the amount of the dispersing agent to a small amount, it is possible to relatively increase the blending amount of the curing component and the like, and as a result, it is possible to form a colored cured film excellent in heat resistance.

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

  Commercially available urethane dispersants include Disperbyk-161, 162, 163, 164, 166, 167, 168, 170, 171, 174, 182, 183, 184, 185, BYK-9077 (all by Big Chemie Japan) ), Addispur PB711 (manufactured by Ajinomoto Fine Techno Co., Ltd.), EFKA-46, 47, 48 (manufactured by EFKA CHEMICALS), and the like. Among them, Disperbyk-161, 162, 166, 170, and 174 are preferable in terms of heat resistance, electrical reliability, and dispersibility.

  In the coloring composition, the content of the dispersing agent is not particularly limited as long as the coloring material can be uniformly dispersed, but it is excellent in dispersibility and dispersion stability of the coloring material, and is stored. From the viewpoint of excellent stability, the content is preferably 3% by mass or more, and more preferably 5% by mass or more, with respect to the total solid content of the coloring composition. In addition, the content of the dispersant is preferably 50% by mass or less, and more preferably 40% by mass or less based on the total solid content of the coloring composition, from the viewpoint of achieving good developability. And still more preferably 30% by mass or less.

(Optional additives)
The coloring composition may contain various additives as needed as long as the effects of the present disclosure described above are not impaired.

(Antioxidant)
It is preferable that the coloring composition further contains an antioxidant from the viewpoint of heat resistance and light resistance. The antioxidant may be appropriately selected from those known in the art. Specific examples of the antioxidant include, for example, hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc. From the point of view, it is preferable to use a hindered phenolic antioxidant.
A hindered phenolic antioxidant contains at least one phenol structure, and a structure in which at least one of the 2- and 6-positions of hydroxyl groups of the phenol structure is substituted with a substituent having 4 or more carbon atoms It means the antioxidant which it has. Moreover, the latent antioxidant in which the hindered phenol as described in Unexamined-Japanese-Patent No. 2015-132791 was latent may be sufficient.

  When using antioxidant, the compounding quantity will not be specifically limited if it is a range which does not impair the effect of the said coloring composition. The compounding amount of the antioxidant is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more based on the total solid content in the coloring composition, from the viewpoint of excellent heat resistance. More preferably, it is preferably 5.0% by mass or less and 4.0% by mass or less based on the total solid content in the coloring composition, from the viewpoint that the coloring composition can be made highly sensitive. Is more preferred.

(Other additives)
As the additive, in addition to the above-mentioned antioxidants, for example, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet light absorbers, adhesion promoters, etc. Can be mentioned.
Specific examples of the surfactant and the plasticizer include, for example, those described in WO 2012/144521.

The method for producing the coloring composition contains a polymer (1 ′) of a monomer having the ethylenically unsaturated group, a metal lake color material of a dye, a solvent, and other components optionally used. The coloring material is not particularly limited as long as the coloring material can be uniformly dispersed in the solvent than the dispersing agent, and is not particularly limited, and can be prepared by mixing using a known mixing means.
As a method of preparing the coloring composition, for example, (1) a binder component containing a polymer (1 ′) of a monomer having an ethylenically unsaturated group is optionally used in a coloring material dispersion described later (2) A method of mixing two or more colorants separately with a dispersant separately in a solvent or dissolving other colorants in a solvent without using a dispersant. A method of mixing a binder component containing a material dispersion and optionally a colorant solution, the polymer (1 ′) of the monomer having an ethylenically unsaturated group, and various additive components optionally used; (3) A method of simultaneously charging and mixing a coloring material, a binder component containing a polymer (1 ′) of a monomer having an ethylenically unsaturated group, and various additive components optionally used in a solvent (4) In the solvent, a binder component containing the polymer (1 ′) of the monomer having an ethylenically unsaturated group, and optionally added various additive components are added and mixed, and then a color material is added. A method of mixing and the like;
Among these methods, the method of preparing the colorant dispersion in advance of the above (1) or (2) is preferable from the viewpoint of effectively preventing aggregation of the colorant and enabling uniform dispersion.

  The colorant dispersion that can be used as a pre-preparation for preparing the coloring composition of the present disclosure is (mass of colorant component in composition) / (mass of solid content other than colorant component in composition) Colorant dispersion with high ratio. Specifically, the ratio (mass of color material component in the composition) / (mass of solid content other than the color material component in the composition) is usually 1.0 or more. By mixing the coloring material dispersion and at least the binder component, a colored resin composition having excellent dispersibility can be prepared.

The method for producing the coloring material dispersion is a method which contains a coloring material, a dispersing agent, a solvent, and various additive components optionally used, and the coloring material can be uniformly dispersed in the solvent by the dispersing agent. It can be uniformly dispersed by mixing using known mixing means.
For example, after a dispersant is mixed in a solvent and stirred to prepare a dispersant solution, the colorant solution and other components as needed are mixed in the dispersant solution and dispersed using a known stirrer or disperser. There is a way to In addition, the other component may contain the polymer (1 ′) of the monomer having an ethylenically unsaturated group.

  Examples of the disperser for performing the dispersion treatment include roll mills such as 2 rolls and 3 rolls, ball mills such as ball mill and vibration ball mill, paint conditioners, bead mills such as continuous disc type bead mill and continuous annular type bead mill. As a preferable dispersion condition of a bead mill, 0.03 mm or more and 2.00 mm or less of a bead diameter to be used are preferable, More preferably, they are 0.10 mm or more and 1.0 mm or less.

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

2. Step of Forming a Coating Film of the Colored Composition The method of forming a coating film is not particularly limited, but at least the step of applying the coloring composition onto a substrate and drying it After drying, if necessary, further exposure is carried out to polymerize the binder component.
As the method of application, known application means such as spray coating, dip coating, bar coating, roll coating, spin coating, slit coating, die coating can be used.
The said drying is performed below the temperature of the coating film heating process mentioned later, and the conditions which can remove the solvent in the said coloring composition can be set suitably. Among them, it is preferable to carry out at 150 ° C. or less, more preferably at 130 ° C. or less. On the other hand, it is preferable to carry out at 50 ° C. or higher, more preferably at 60 ° C. or higher, from the viewpoint of sufficiently removing the solvent. In the temperature range, the drying time is preferably 1 minute or more and 30 minutes or less, and more preferably 2 minutes or more and 20 minutes or less. In addition, the said drying can be performed using a hot plate, oven, etc., for example.

As a light source used for the said exposure, ultraviolet rays, such as a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an electron beam etc. are mentioned, for example. The exposure amount is appropriately adjusted depending on the light source to be used, the thickness of the coating film, and the like.
Moreover, a pattern-like coating film can be formed by exposing the coating film of the colored composition after drying through a mask of a predetermined pattern, and the colored cured film according to the present disclosure can be formed into a pattern. Can.

When the coating film is formed into a pattern, and the colored cured film according to the present disclosure is formed into a pattern, after the exposure, development is performed using a developing solution to dissolve and remove the unexposed part, thereby obtaining the desired. A coating film is formed in a pattern. As a developing solution, usually, a solution in which an alkali is dissolved in water or a water-soluble solvent is used. An appropriate amount of surfactant or the like may be added to the alkaline solution. Moreover, the developing method can employ | adopt a general method.
After development, washing of the developer and drying of the coloring composition are usually performed.

3. Coating film heating step In the method for producing a colored cured film of the present disclosure, the polymer (1 ′) of the monomer having an ethylenically unsaturated group is obtained by heating the coating film obtained in the coating film forming step. wherein the protecting group R ^P elimination to form the structure represented by the general formula (1) with.
The heating is preferably 200 ° C. or more, more preferably 230 ° C. or more, from the viewpoint that the protecting group R ^P of the carboxy group is easily desorbed, and on the other hand, it is 260 ° C. or less from the viewpoint of suppressing a decrease in luminance. Is preferred.
The heating time is preferably 5 minutes or more from the viewpoint that the protecting group R ^P of the carboxy group is easily released, and is preferably 3 hours or less from the viewpoint of suppressing a decrease in luminance.
In addition, the said heating can be performed, for example using a clean oven.

III. Color filter A color filter according to the present disclosure is a color filter including at least a transparent substrate and a colored layer on the transparent substrate, and at least one of the colored layers is the colored cured film according to the present disclosure.
Further, a method of manufacturing a color filter according to 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,
At least one of the colored layers is formed by the method for producing a colored cured film 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 showing 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 portion 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 the colored cured film according to the present disclosure.
In addition, at least one colored layer used in the color filter of the present disclosure is formed by the method for producing a colored cured film according to the present disclosure.
The colored layer is usually formed at an opening of a light shielding portion on a transparent substrate described later, and is usually formed of a coloring pattern of three or more colors.
Moreover, it does not specifically limit as arrangement | sequence of the said colored layer, For example, it can be set as general arrangement, such as stripe type, mosaic type, triangle type, 4 pixel arrangement | positioning type | mold. In addition, the width, area, and the like of the colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration of the colored composition, the viscosity and the like, but in general, it is preferably in the range of 1 μm to 5 μm.

(Light blocking part)
The light shielding portion 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 portion in a general color filter.
It does not specifically limit as a pattern shape of the said light-shielding part, For example, shapes, such as stripe form and a matrix form, are mentioned. Examples of the light shielding portion 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, CrO _x film (x is an arbitrary number) may be one and the Cr film is two-layered, also, CrO _x film (x is an arbitrary number) with reduced more reflectivity Alternatively, three layers of CrN _y films (y is an arbitrary number) and Cr films may be stacked.
When the light shielding portion is obtained by dispersing or dissolving a black color material in a binder resin, a method of forming the light shielding portion is not particularly limited as long as the light shielding portion can be patterned. For example, the photolithographic method using the coloring composition for light-shielding parts, the printing method, the inkjet method etc. can be mentioned.

  The film thickness of the light shielding portion is set to about 0.2 μm or more and 0.4 μm or less in the case of a metal thin film, and is 0.5 μm or more and 2 μm or less when the 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 transparent substrate to visible light, and a transparent substrate used for a general color filter can be used. Specifically, it has flexibility and flexibility such as transparent non-flexible rigid material such as quartz glass, non-alkali glass, synthetic quartz plate, or transparent resin film, resin plate for optics, flexible glass, etc. 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.
In the color filter of the present disclosure, in addition to the transparent substrate, the light shielding portion, and the colored layer, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning a liquid crystal material, and columnar spacers are formed. It may be done. The color filter of the present disclosure is not limited to the configuration exemplified above, and a known configuration generally used for the color filter can be appropriately selected and used.

IV. Liquid Crystal Display Device The liquid crystal display device of 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 view showing an example of the liquid crystal display device of the present disclosure. As exemplified in FIG. 2, the liquid crystal display device 40 of the present disclosure includes a color filter 10, an opposing substrate 20 having a TFT array substrate and the like, a liquid crystal layer 15 positioned between the color filter 10 and the opposing substrate 20. And. In FIG. 2, an example in which the alignment film 13a is located on the colored layer 3 side of the color filter 10 and the alignment film 13b is located on the opposite substrate 20 side, and the liquid crystal layer 15 is located between the two alignment films 13a and 13b. Is shown. Furthermore, in FIG. 2, the liquid crystal display device 40 includes the polarizing plate 25 a located outside the color filter 10, the polarizing plate 25 b located outside the counter substrate 20, and the liquid crystal display device 40 facing the counter substrate 20. The example which has the back light 30 located outside the polarizing plate 25b located is shown.
The liquid crystal display device of the present disclosure is not limited to the configuration shown in FIG. 2 and can be generally known as a liquid crystal display device using a color filter.

The drive method of the liquid crystal display device of the present disclosure is not particularly limited, and a drive method generally used for a liquid crystal display device can be adopted. As such a driving method, for example, a TN method, an IPS method, an OCB method, an MVA method and the like can be mentioned. In the present disclosure, any of these systems can be suitably used.
In addition, the opposite substrate can be appropriately selected and used in accordance with the driving method and the like 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 a mixture thereof can be used according to the driving method and the like of the liquid crystal display device of the present disclosure.

As a method of forming a liquid crystal layer, a method generally used as a method of 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 an opposite substrate, and the liquid crystal is heated to be an isotropic liquid, and the liquid crystal cell is isotropic liquid is made using the capillary effect. The liquid crystal layer can be formed by injecting in the state of and sealing with an adhesive. Thereafter, by gradually cooling the liquid crystal cell to room temperature, the enclosed liquid crystal can be aligned.
In the liquid crystal dropping method, for example, a sealing agent is applied to the peripheral edge of the color filter, the color filter is heated to a temperature at which the liquid crystal is isotropic, and the liquid crystal is dropped in the isotropic liquid state using a dispenser or the like. The liquid crystal layer can be formed by overlapping the color filter and the opposite substrate under reduced pressure and adhering them through a sealing agent. Thereafter, by gradually cooling the liquid crystal cell to room temperature, the enclosed liquid crystal can be aligned.

Moreover, as a backlight used for the liquid crystal display device of this indication, according to the use of a liquid crystal display device, it can select suitably and can use. As the backlight, for example, a cold cathode fluorescent lamp (CCFL), a backlight unit using a white LED or a white organic EL as a light source can be provided in addition to a cold cathode fluorescent lamp (CCFL).
As the white LED, for example, a white LED which obtains white light by color mixing by combining red LED, green LED and blue LED, a white LED which obtains white light by color mixing combining blue LED, red LED and green phosphor, blue LED White LED to obtain white light by color mixing by combining red, green and red light emitting phosphors, White LED to obtain white light by mixing blue LED and YAG phosphor, ultraviolet light LED and red light emitting phosphor and green light emitting fluorescent light A white LED etc. which obtain white light by color-mixing combining a body and a blue light emission fluorescent substance can be mentioned. A quantum dot may be used as the phosphor.

V. 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 emitting body as the light emitting body. A light-emitting body is not limited to an organic light-emitting body, An inorganic light-emitting body can also be used suitably.
Such a light emitting display device of the present disclosure will be described with reference to the drawings. FIG. 3 is a schematic view showing 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 a color filter 10 and a light emitter 80. The organic protective layer 50 or the 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 color filter Alternatively, the light-emitting body 80 formed on another substrate may be attached to the inorganic oxide film 60. 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 the other components in the light emitting body 80 may be appropriately known ones. The light emitting display device 100 manufactured in this manner is applicable to, for example, an organic EL display of a passive drive system and an organic EL display of an active drive system.
Note that the light emitting display device of the present disclosure is not limited to the light emitting display device having the configuration shown in FIG. 3, and can generally have a known configuration 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.
In addition, about the weight average molecular weight of the binder resin which did not use the trimethylsilyl methacrylate as a monomer in the following, about the weight average molecular weight of the binder resin, it uses GPC (gel permeation chromatography), using Tosoh HLC-8220. N-methyl pyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard condition confirmed, while the weight average molecular weight of the binder resin using trimethylsilyl methacrylate as a monomer The weight average molecular weight of the resin is confirmed by GPC in the same manner as described above, and the weight average molecular weight of the binder resin in which the constitutional unit derived from methacrylic acid is replaced with the constitutional unit derived from trimethylsilyl methacrylate from the weight average molecular weight of the binder resin It was determined by calculating the molecular weight.

(Synthesis Examples 1, 2, 5 to 10, Comparative Synthesis Examples 1 to 4: Synthesis of Binder Resins A, B, E to J, Comparative Binder Resins A to D)
In a reactor equipped with a cooling pipe, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 120 parts by mass of PGMEA is charged as a solvent, and the temperature is raised to 90 ° C. under a nitrogen atmosphere. Monomer 1, monomer 2, and methacrylic acid in amounts shown in Tables 1 and 2, 2.0 parts by weight of azobisisobutyronitrile (AIBN) as initiator, and n-dodecyl mercaptan 4 as chain transfer agent A mixture containing .5 parts by weight was continuously added dropwise over 1.5 hours.
Thereafter, the reaction is continued while maintaining the synthesis temperature, and 2 hours after the end of dropping, 0.05 parts by mass of p-methoxyphenol as a polymerization inhibitor and PGMEA as a solvent for dilution are used. It added so that it might become.
Next, glycidyl methacrylate is added in the amount shown in Table 1 while blowing in dry air, and after raising the temperature to 110 ° C., 0.2 parts by mass of triethylamine is added to carry out addition reaction at 110 ° C. for 15 hours, Binder resins A, B and E to J and comparative binder resins A to D having an ethylenically unsaturated group in the side chain were obtained.
The weight average molecular weight, the acid value, and the solid content concentration of the binder resins A, B and E to J and the comparative binder resins A to D are shown in Tables 1 and 2.

Synthesis Examples 3 and 4: Synthesis of Binder Resins C and D
120 parts by mass of PGMEA as a solvent is charged in a reactor equipped with a cooling pipe, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and after raising the temperature to 90 ° C under a nitrogen atmosphere, the amounts shown in Table 1 A mixture containing trimethylsilyl methacrylate and methacrylic acid in the amounts shown in Table 1, 2.0 parts by mass of AIBN as an initiator and 4.5 parts by mass of n-dodecyl mercaptan as a chain transfer agent over 1.5 hours Dripped into the
Thereafter, the synthesis temperature was maintained for 2 hours and the reaction was continued to obtain binder resins C and D.
The weight average molecular weight and solid content concentration of the binder resins C and D are shown in Table 1. As for the acid value, an accurate value could not be measured because the trimethylsilyl group was deprotected by the basic titration solution.

Here, each abbreviation in the table is as follows.
tBMA: tert-butyl methacrylate tBuA: tert-butyl acrylate BVEMAA: 1-n-butoxyethyl methacrylate TMSMAA: trimethylsilyl methacrylate CHMA: cyclohexyl methacrylate NtBMAm: N-tert-butyl methacrylamide BzMA: benzyl methacrylate MAA: Methacrylic acid AA: acrylic acid MMA: methyl methacrylate GMA: glycidyl methacrylate

Synthesis Example 11 Synthesis of Blue Color Material α
(1) Synthesis of Intermediate 1 15.9 parts by mass of Intermediate 1 represented by the following chemical formula (2) with reference to the method for producing Intermediate 3 and Intermediate 4 described in WO 2012/144521 (Yield 70%) was obtained.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), Divalent Elemental Analysis: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (7)
8.06%, 7.75%, 7.69%)
Further, the thermal decomposition temperature of the obtained compound was measured by DTG-60A manufactured by Shimadzu Corporation, and it was 239 ° C. as determined from the intersection of tangents near the weight loss temperature.

(2) Synthesis of blue color material α Add 15.00 parts by mass of Intermediate 1 to 300 parts by mass of water, and dissolve at 90 ° C. to obtain an Intermediate 1 solution. Next, 10.44 parts by mass of phosphotungstic acid · n-hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O (n = 30) (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) are added to 100 parts by mass of water, The mixture was stirred to prepare an aqueous solution of phosphotungstic acid. The prepared phosphotungstic acid aqueous solution was mixed with the above Intermediate 1 solution at 90 ° C., and the formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 parts by mass of a blue coloring material α of a metal lake color material of a triarylmethane basic dye represented by the following chemical formula (3).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 510 (+), Divalent Elemental Analysis: CHN found (41.55%, 5.34%, 4.32%); theoretical value (41.66%) , 5.17%, 4.11%)

Synthesis Example 12 Preparation of Salt-Type Block Polymer Dispersant A Solution
60.74 parts by mass of PGMEA and a block copolymer containing tertiary amino groups (trade name: BYK-LPN6919, manufactured by BYK-Chemie) in a reactor (amine value 120 mg KOH / g, solid content 60% by weight) 35.64 parts by mass ( 21.38 parts by mass of effective solids) are dissolved, 3.62 parts by mass of PPA (0.5 molar equivalent relative to the tertiary amino group of the block copolymer) is added, and the mixture is 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)
13.00 parts by mass of the blue coloring material α of Synthesis Example 11 as the coloring material, 20.80 parts by mass of the dispersant A solution of Synthesis Example 12 as the dispersing agent (solid content: 5.2 parts by mass) The amount of PGMEA is adjusted to 100 parts by mass in the comparative binder resin D of Comparative Synthesis Example 4 in an amount to be 100 parts by mass, and mixed. Further, the resultant was dispersed for 4 hours with 0.1 mm zirconia beads as main dispersion, to obtain a colorant dispersion.

(Comparative Production Example 1: Production of Comparative Colorant Dispersion)
As a colorant, C.I. I. Pigment blue 15: 6 (primary particle diameter 40 nm) in 11.18 parts by mass, C.I. I. Pigment violet 23 (primary particle diameter 60 nm), 20.80 parts by mass of the dispersant A solution of Synthesis Example 12 as a dispersant (solid content 5.20 parts by mass), and solid content 5.20 parts by mass; The amount of PGMEA is adjusted to 100 parts by mass in the comparative binder resin D of Comparative Synthesis Example 4 and mixed, and the mixture is preliminarily dispersed with a paint shaker (Asada Iron Works Co., Ltd.) for 1 hour with 2 mm zirconia beads Furthermore, as a main dispersion, it was dispersed for 4 hours with 0.1 mm zirconia beads to obtain a comparative coloring material dispersion.

(Preparation Examples 1 to 10, Comparative Preparation Examples 1 to 3: Preparation of Binder Compositions A to J, Comparative Binder Compositions A to C)
Binder Resins A to J of Synthesis Examples 1 to 10 or Comparative Binder Resins A to C of Comparative Synthesis Examples 1 to 3 in a Solid Content of 8 Parts by Mass, 5 to 6 Functional Acrylate Monomers (trade name: ALONIX M402, TOA Synthetic product) 24 parts by mass, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF) 6 parts by mass, 2,4 diethylthioxanthone (Trade name: Kayacure-DETX-S, manufactured by Nippon Kayaku Co., Ltd.) and 2 parts by mass of PGMEA so as to be 100 parts by mass in total and binder compositions A to J, and comparative binder compositions A to C Was prepared.

Example 1
(1) Production of Colored Composition 32.06 parts by mass of the color material dispersion obtained in Production Example 1, 24.22 parts by mass of the binder composition A obtained in Preparation Example 1, 43.67 parts by mass of PGMEA, surfactant 0.05 parts by mass of an agent R08MH (manufactured by DIC) was added and mixed, and pressure filtration was performed to obtain a coloring composition of Example 1. In addition, in the total solid content of the colored composition of Example 1, the content of the binder resin A obtained in Synthesis Example 1 was 11.3 mass%.

(2) Production of Colored Cured Film A spin coater was prepared by using the colored composition of Example 1 obtained in the above (1) on a glass substrate having a thickness of 0.7 mm (manufactured by Nippon Electric Glass, "OA-10G"). It applied using. After that, heat drying was performed on a hot plate at 80 ° C. for 3 minutes, and ultraviolet light of 40 mJ / cm ² was irradiated using an ultra-high pressure mercury lamp. Then, the colored cured film of Example 1 was obtained by post-baking treatment in a clean oven at 230 ° C. for 90 minutes.

(Examples 2 to 10, Comparative Examples 1 to 3)
(1) Production of Colored Composition In (1) of Example 1, in place of the binder composition A, the binder compositions B to J obtained in Preparation Examples 2 to 10 or Comparative Preparation Examples 1 to 3 were obtained. The colored compositions of Examples 2 to 10 and Comparative colored compositions of Comparative Examples 1 to 3 were obtained in the same manner as (1) of Example 1 except that the comparative binder compositions A to C were used. In addition, content of binder resin BJ in the total solid of the coloring composition of Examples 2-10, and comparison binder resin AC in the total solid of the comparison coloring composition of Comparative Examples 1-3 Each content was 11.3 mass%.

(2) Production of Colored Cured Film In (2) of Example 1, the colored composition or comparison of Examples 2 to 10 obtained in the above (1) instead of the colored composition obtained in Example 1 Comparative colored cured films of Examples 2 to 10 and Comparative Examples 1 to 3 are obtained in the same manner as in Example 1 (2) except that the comparative colored compositions of Examples 1 to 3 are used respectively. The

(Comparative example 4)
(1) Production of Colored Composition The comparative colorant dispersion obtained in Comparative Production Example 1 was used in place of the colorant dispersion obtained in Production Example 1 in (1) of Example 1. In the same manner as in (1) of Example 1, a comparative coloring composition of Comparative Example 4 was obtained. In addition, in the total solid of the comparative coloring composition of Comparative Example 4, the content of the binder resin A was 11.3% by mass.

(2) Production of Colored Cured Film In (2) of Example 1, the comparative colored composition of Comparative Example 4 obtained in (1) above was used in place of the colored composition obtained in Example 1. A comparative colored cured film of Comparative Example 4 was obtained in the same manner as (2) of Example 1 except for the above.

(Comparative example 5)
(1) Production of Colored Composition In (1) of Comparative Example 1, except that the comparative colorant dispersion obtained in Comparative Production Example 1 was used instead of the colorant dispersion obtained in Production Example 1. In the same manner as in (1) of Comparative Example 1, a comparative coloring composition of Comparative Example 5 was obtained. In addition, in the total solid content of the comparative coloring composition of Comparative Example 5, the content of the comparative binder resin A was 11.3% by mass.

(2) Production of Colored Cured Film In (2) of Comparative Example 1, the comparative colored composition of Comparative Example 5 obtained in (1) above was used instead of the colored composition obtained in Comparative Example 1. A comparative colored cured film of Comparative Example 5 was obtained in the same manner as (2) of Comparative Example 1 except for the difference.

[Evaluation]
<Measurement of infrared absorption spectrum>
The infrared absorption spectrum (IR spectrum) was measured about the colored cured film of each Example and each comparative example. In addition, IR spectrum was measured using JASCO Corporation FT / IR-6100.
In the IR spectra of the colored cured film of each example and the comparative colored cured film of Comparative Example 4, a maximum peak is observed in a region of wave number 1790 cm ⁻¹ or more and 1820 cm ⁻¹ or less, while Comparative Examples 1 to 3 and 5 In the IR spectrum of the colored cured film of the above, a maximum peak was not observed in the region of wave number 1790 cm ⁻¹ or more and 1820 cm ⁻¹ or less. The colored cured film in which the maximum peak is observed in the region of wave number 1790 cm ⁻¹ or more and 1820 cm ⁻¹ or less of the IR spectrum indicates that the structure represented by the general formula (1) is included.
As representative examples of the IR spectrum results, IR spectra of Examples 1, 2, 3 and 5 and Comparative Examples 1 and 3 are shown in FIG. 4 and FIG. FIG. 5 is an enlarged view of the 1820 cm ^-1 vicinity following areas wavenumber 1790 cm ^-1 or more in FIG.

<Measurement of optical property evaluation>
The chromaticity (x, y) and the luminance (Y) of the colored cured film obtained in each of the examples and the comparative examples were measured using "Microspectrophotometer OSP-SP200" manufactured by Olympus. Moreover, when producing a colored cured film in each Example and each Comparative Example, L, a, b (L ₀ , a ₀ , b ₀ ) after exposure and before post-baking treatment, and L after post-baking treatment , A, b (L ₁ , a ₁ , b ₁ ) were measured, and a color difference (ΔEab) was calculated from the following equation as heat resistance evaluation.
ΔEab = {(L ₁ −L ₀ ) ² + (a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² } ^1/2
The chromaticity (x, y) and luminance (Y) of the colored cured film after post-baking, and the color difference (ΔEab) before and after post-baking are shown in Tables 3 and 4.

<Measurement of film thickness>
The film thickness of the colored cured film obtained in each Example and each Comparative Example was measured using a fine shape measuring machine ET4000A manufactured by Kosaka Laboratory. The measurement results are shown in Tables 3 and 4.

(Summary of results)
From Tables 3 and 4, in the colored cured films of Examples 1 to 10, which are the colored cured films of the present disclosure, a maximum peak is observed in a region of wave number 1790 cm ⁻¹ or more and 1820 cm ⁻¹ or less of IR spectrum, Since it contains the structure represented by 1), compared with the comparative example containing the binder resin of the same quantity, the chromaticity change before and after post-baking is small, It was a high-intensity and was a thinner colored cured film.
On the other hand, in the comparative colored cured films of Comparative Examples 1 to 3, the maximum peak is not observed in the region of wave number 1790 cm ⁻¹ or more and 1820 cm ⁻¹ or less of IR spectrum, and the structure represented by the general formula (1) is included. As compared with the example containing the same amount of binder resin, the change in chromaticity before and after post-baking was large, the luminance was inferior, and the film thickness was large.
In addition, from Comparative Examples 4 and 5 in Table 4, when a pigment was used as the coloring material, it was confirmed that the change in chromaticity before and after post-baking was small, and the problem of the change in chromaticity due to heating did not occur. Furthermore, from the comparison between Example 1 and Comparative Example 4 and the comparison between Comparative Example 1 and Comparative Example 5, it was shown that when a pigment was used as the coloring material, the luminance was inferior.

(Reference Example 1)
In a reactor equipped with a cooling pipe, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 120 parts by mass of PGMEA is charged as a solvent, heated to 90 ° C. under a nitrogen atmosphere, and tert-butyl methacrylate A mixture containing 100 parts by mass, 2.0 parts by mass of AIBN as an initiator, and 4.5 parts by mass of n-dodecyl mercaptan as a chain transfer agent was dropped continuously over 1.5 hours. Thereafter, the reaction was continued while maintaining the synthesis temperature for 2 hours to obtain a homopolymer solution of t-butyl methacrylate (solid content: 47% by mass).
The weight average molecular weight of the obtained homopolymer was 6400. Moreover, ¹ H-NMR spectrum of the obtained homopolymer is shown in FIG. ^{The 1} H-NMR spectrum is
Measured by AVANCE 400 MHz manufactured by BRUKER.
Subsequently, the obtained homopolymer solution is coated on a 0.7 mm thick glass substrate ("OA-10G" manufactured by Nippon Electric Glass) using a spin coater and dried under reduced pressure to form a coating film. And the coating was heated at 230 ° C. for 30 minutes.
After heating, the coating was redissolved in N-methylpyrrolidone and the weight average molecular weight and NMR spectrum of the heated homopolymer were measured. The weight average molecular weight of the homopolymer after heating was 6,800. Moreover, ¹ H-NMR spectrum of the homopolymer after heating is shown in FIG.
The weight average molecular weight was confirmed by GPC under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide addition / polystyrene standard. The GPC chart of the homopolymer before and after heating is shown in FIG.
According to the GPC chart before and after heating of the obtained homopolymer, there is no significant change in weight average molecular weight before and after heating, and from the ¹ H-NMR spectrum, heating by 230 ° C. for 30 minutes It was shown that the tert-butyl group of tert-butyl methacrylate homopolymer was eliminated, and the reaction between adjacent carboxy groups formed the acid anhydride structure represented by the above general formula (1). .

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 opposing substrate 25a, 25b polarizing plate 30 back light 40 liquid crystal display 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

Claims (10)

A polymer of a monomer having an ethylenically unsaturated group, and a metal lake color material of a dye,
The colored cured film, wherein the polymer comprises a structure represented by the following general formula (1).
(In general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group.) The colored cured film according to claim 1, having a maximum peak in a region of wave number 1790 cm ^-1 or more and 1820 cm ^-1 or less in an infrared absorption spectrum. A polymer of a monomer having an ethylenically unsaturated group, a metal lake color material of a dye, and a solvent, and the polymer is represented by the following general formula (1 ′) having a protecting group R ^P of a carboxy group Preparing a colored composition comprising the structural units
Forming a coating of the colored composition;
A step of removing the protective group R ^P by heating the coating film to form a structure represented by the following general formula (1);
The manufacturing method of a coloring cured film which has.
(In general formula (1 ′), R ³ represents a hydrogen atom or a methyl group, R ^P represents a protective group, and the protective group is a group represented by the following general formula (A).)
(In general formula (A), R ^P1 represents a carbon atom or a silicon atom, R ^P2 , R ^P3 and R ^P4 each independently represent a hydrogen atom or a hydrocarbon group, R ^P5 represents a hydrocarbon group or a hydrocarbon group or It represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)
(In general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group.)   The colored cured film according to claim 3, wherein the polymer contained in the coloring composition contains 30 mol% or more of a constituent unit represented by the general formula (1 ′) in 100 mol% of all constituent units. Manufacturing method. A polymer of a monomer having an ethylenically unsaturated group, a metal lake material of a dye, and a solvent
It said polymer comprises a structural unit represented by the following general formula having a protecting group R ^P carboxy group (1 '), the colored composition.
(In general formula (1 ′), R ³ represents a hydrogen atom or a methyl group, R ^P represents a protective group, and the protective group is a group represented by the following general formula (A).)
(In general formula (A), R ^P1 represents a carbon atom or a silicon atom, R ^P2 , R ^P3 and R ^P4 each independently represent a hydrogen atom or a hydrocarbon group, R ^P5 represents a hydrocarbon group or a hydrocarbon group or It represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)   The coloring composition of Claim 5 in which the said polymerizable body contains 30 mol% or more of structural units represented by the said General formula (1 ') in 100 mol% of total structural units.   A color filter comprising at least a transparent substrate and a colored layer on the transparent substrate, wherein at least one of the colored layers is the colored cured film according to claim 1 or 2. A method for producing a color filter comprising at least a transparent substrate and a colored layer on the transparent substrate,
A method for producing a color filter, comprising the step of forming at least one of the colored layers by the method for producing a colored cured film according to claim 3 or 4.   A liquid crystal display device comprising the color filter according to claim 7, an opposing substrate, and a liquid crystal layer positioned between the color filter and the opposing substrate.   A light emitting display device comprising the color filter according to claim 7 and a light emitter.