JP6534523B2 - Colored resin composition for color filter, color filter, and display device - Google Patents

Description

  The present invention relates to a colored resin composition for a color filter, a color filter, and a 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, an organic light emitting display device such as an organic EL display having high visibility due to self light emission is also 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 organic 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, color adjustment of pixels may be performed using a color filter, or a color image may be formed similarly to a liquid crystal display device using a color filter for an organic light emitting element emitting white light.

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 conventional pigments, it has become difficult to achieve the current demand for higher brightness.

  As one means for achieving high luminance, a photosensitive resin composition for a color filter 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 photosensitive resin composition using a dye has a problem that foreign matters are easily deposited during the drying process. When foreign matter is deposited on the coating film, the contrast is significantly deteriorated and it is difficult to use as a colored layer.

Patent Document 1 discloses a specific colored photosensitive resin composition containing a colorant containing a specific dye and a pigment, and a specific solvent. According to Patent Document 1, it is supposed that a coating film having high heat resistance and little coating unevenness is obtained by the colored photosensitive resin composition.
In addition, Patent Document 2 discloses a specific blue-sensitive resin composition containing, as a colorant, an organic solvent-soluble dye having a specific structure and an organic pigment. According to Patent Document 2, it is supposed that a high brightness color filter can be obtained by using the colored photosensitive resin composition.
The above-mentioned specific dyes in Patent Documents 1 and 2 are used by being dissolved in a solvent and contain a polar solvent for dissolving the dye, so the stability of the viscosity is poor or only a solvent-soluble coloring material can be used There was such a problem.

  Patent Document 3 discloses a colored resin composition for a color filter containing a specific coloring material containing a divalent or higher valent cation in which a plurality of dye skeletons are cross-linked by a crosslinking group, and a divalent or higher valent anion. . It is disclosed that the colored layer formed of the colored resin composition for a color filter containing the above-mentioned coloring material has high contrast, and is excellent in solvent resistance and electrical reliability.

JP, 2010-211198, A JP, 2010-32999, A International Publication No. 2012/144521 brochure

  When a dye is used in a colored resin composition, a polar solvent is usually used. The inventors of the present invention have the problem that the colored resin composition using a polar solvent has problems such as the viscosity becomes unstable and foreign matter is generated in the colored resin composition because the polarity of the solvent is strong. I got the knowledge. In addition, when the dye is dispersed and used, it is difficult to ensure the dispersion stability of the dye, and a process such as stabilization is required, which increases the process load.

  Although the colored layer obtained by the colored resin composition containing the specific coloring material described in Patent Document 3 has higher luminance than before, the luminance drop at the time of high temperature heating is large, and the heat resistance is insufficient. Yes, further improvement was desired. In addition, the coloring composition containing the above-mentioned specific coloring material causes salt dissociation and the like because of the salt-formed coloring material, so that the stability of viscosity is poor, and further stability of viscosity is desired.

  This invention is made in view of the said situation, is excellent in the temporal viscosity stability of a coloring resin composition, and is a coloring resin composition for color filters which can form a coloring layer which heat resistance improved, and the said coloring resin composition It is an object of the present invention to provide a high-intensity color filter using an object and a display device having the color filter.

The colored resin composition for a color filter according to the present invention comprises a coloring material represented by the following general formula (I), a urethane dispersant, an alkali soluble resin, a polyfunctional monomer, an initiator, and a solvent. Contains
The alkali-soluble resin is a resin having an acid value of 90 mg KOH / g or more and 300 mg KOH / g or less,
The solvent is characterized in that the solubility of the coloring material at 23 ° C. is 0.1 (g / 10 ml solvent) or less.

(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- contains at least tungsten .R ⁱ to R ^v indicating the c-valent poly anion each independently represent a hydrogen atom, which may have an optionally substituted alkyl group or a substituted aryl group, and R ⁱⁱ R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure, Ar ¹ represents a divalent aromatic group which may have a substituent, and a plurality of R ^{i to} R ^v and Ar ¹ may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. The plurality of e may be the same or different. )

  In the colored resin composition for color filters of the present invention, the acid value of the urethane dispersant is preferably 10 mg KOH / g or more because of excellent heat resistance.

  In the colored resin composition for a color filter of the present invention, the amine value of the urethane dispersant is preferably 10 mg KOH / g or more from the viewpoint of excellent heat resistance.

  In the colored resin composition for a color filter of the present invention, the alkali-soluble resin is preferably a resin having an ethylenic double bond from the viewpoint of excellent development resistance.

  In the colored resin composition for color filters of the present invention, it is preferable that the alkali-soluble resin further has a hydrocarbon ring from the viewpoint of more excellent heat resistance.

  In the colored resin composition for color filter of the present invention, the adhesion of the substrate to the substrate is such that the content of the silane coupling agent is 1% by mass or less based on the total solid content in the colored resin composition. It is preferable from the point which can suppress the sensitivity change of a coloring composition at a little.

  The colored resin composition for a color filter of the present invention is further preferable because it can be adjusted to a desired color tone by further containing one or more selected from a dioxazine-based coloring material and a xanthene-based coloring material.

  The colored resin composition for a color filter of the present invention is preferably that the xanthene-based coloring material is a xanthene-based coloring material, from the viewpoint of excellent heat resistance.

The method for producing a colored resin composition for a color filter according to the present invention comprises the color material represented by the general formula (I), a xanthene type color material, a urethane type dispersant, an alkali soluble resin, and a polyfunctional monomer. , An initiator, and a solvent, wherein the alkali-soluble resin is a resin having an acid value of 90 mg KOH / g or more and 300 mg KOH / g or less, and the solvent has a solubility of 0.2. It is a manufacturing method of the coloring resin composition for color filters which is a solvent of 1 (g / 10 ml solvent) or less,
The colorant represented by the general formula (I), the xanthene colorant, and the dispersant are added to the solvent, and the colorant represented by the general formula (I), and the xanthene colorant It is characterized by having the process of co-dispersing with a material.

  The color filter according to the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is a colored resin composition for a color filter according to the present invention. It is characterized by having a colored layer formed by curing an object.

  A display device according to the present invention includes the color filter according to the present invention.

  According to the present invention, a colored resin composition for a color filter which is excellent in the temporal viscosity stability of the colored resin composition and can form a colored layer having improved heat resistance, and a high brightness color filter using the colored resin composition And a display device having the color filter.

FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the display device of the present invention. FIG. 3 is a schematic cross-sectional view showing another example of the display device of the present invention. FIG. 4 is a schematic view showing the molecular association state of the coloring material represented by the general formula (I).

Hereinafter, the colored resin composition for color filters according to the present invention, the color filter, and the display device will be described in order.
In the present invention, light includes electromagnetic waves of wavelengths in the visible and non-visible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves having a wavelength of 5 μm or less and electron beams.
In the present invention, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.
In the present invention, an organic group refers to a group having one or more carbon atoms.
Moreover, in this invention, solid content means all components other than the solvent which comprises a coloring resin composition, and even if it is a liquid monomer, it shall be contained in the said solid content.

1. Colored resin composition for color filter The colored resin composition for color filter according to the present invention comprises a color material represented by the following general formula (I), a urethane dispersant, an alkali soluble resin, a polyfunctional monomer, Contains an initiator and a solvent,
The alkali-soluble resin is a resin having an acid value of 80 mg KOH / g or more and 300 mg KOH / g or less,
The solvent is characterized in that the solubility of the coloring material at 23 ° C. is 0.1 (g / 10 ml solvent) or less.

(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- contains at least tungsten .R ⁱ to R ^v indicating the c-valent poly anion each independently represent a hydrogen atom, which may have an optionally substituted alkyl group or a substituted aryl group, and R ⁱⁱ R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure, Ar ¹ represents a divalent aromatic group which may have a substituent, and a plurality of R ^{i to} R ^v and Ar ¹ may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. The plurality of e may be the same or different. )

  The colored resin composition for a color filter of the present invention disperses the specific coloring material using a urethane dispersant, and combines and uses an alkali-soluble resin having the specific acid value to achieve long-term storage It is possible to obtain a colored layer which is excellent in the temporal viscosity stability of the colored resin composition and improved in heat resistance.

The action that exerts the above effects by the above specific combination is estimated as follows, though there are unresolved parts.
The coloring material represented by the general formula (I) contains, as shown in FIG. 4, an anion 202 having a valence of 2 or more and a cation 201 having a valence of 2 or more. It is presumed that the cation is not merely ionically bonded in one molecule to one molecule, but forms a molecular assembly 210 in which a plurality of molecules are associated via the ionic bond 203. 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.
The colored resin composition of the present invention is used in combination with an alkali soluble resin having an acid value of 80 mg KOH / g or more and 300 mg KOH / g or less. In the present invention, since it is a resin having a relatively large number of acidic groups, such as an acid value of 80 mg KOH / g or more, a dye or lake existing near the surface of the molecular aggregate of the coloring material represented by the general formula (I) As a result, it is presumed that the alkali-soluble resin is likely to be adsorbed to the surface of the molecular association body, as it is likely to interact with the basic group of the agent. Since the alkali-soluble resin has a relatively high acid value, once it is adsorbed, it is difficult to dissociate even at high temperature heating, and decomposition of the color material can be further suppressed, and a decrease in luminance is suppressed, and heat resistance is significantly improved. It is presumed that.
Furthermore, the colored resin composition for a color filter of the present invention comprises a urethane based dispersant for the colorant represented by the general formula (I) in such a molecular association state in a solvent having a low solubility of the colorant. It is distributed using. A urethane type dispersing agent is a dispersing agent which consists of a compound which has one or more urethane bond (-NH-COO-) in 1 molecule here.
The urethane compound contained in the urethane-based dispersant interacts with the specific coloring material forming the molecular association state, whereby the coloring material is stably held in the solvent having a low solubility while maintaining the molecular association state. Distributed to Generally, a urethane based dispersant has a relatively flexible structure among polymer dispersants, so that the urethane bond and the specific colorant are deformed so as to easily interact with each other, and the molecular association state of the colorant It is presumed that the adsorption state of the dispersant and the coloring material is improved by suppressing the liberation of the counter ion that forms the. Therefore, it is excellent in good temporal viscosity stability even under long-term storage.
As a result, the obtained colored layer has excellent heat resistance, and can maintain high brightness even after the heating step. From these things, the coloring resin composition for color filters of this invention is excellent in a time-lapse | temporal viscosity stability, and can obtain the coloring layer which heat resistance improved.

The colored resin composition for color filter of the present invention contains at least a color material represented by the general formula (I), a urethane dispersant, an alkali soluble resin, a polyfunctional monomer, an initiator, and a solvent. As long as the effects of the present invention are not impaired, the composition may further contain other components as necessary.
Hereinafter, each component of such a colored resin composition for color filters of the present invention will be described in detail in order.

[Colorant Represented by General Formula (I)]
The colored resin composition for color filters of the present invention contains a coloring 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- contains at least tungsten .R ⁱ to R ^v indicating the c-valent poly anion each independently represent a hydrogen atom, which may have an optionally substituted alkyl group or a substituted aryl group, and R ⁱⁱ R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure, Ar ¹ represents a divalent aromatic group which may have a substituent, and a plurality of R ^{i to} R ^v and Ar ¹ may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. The plurality of e may be the same or different. )

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. From the viewpoint of heat resistance, A preferably has no siloxane bond, and more preferably does not have Si (silicon atom).
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, it is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group in which two alkylene groups having 1 to 20 carbon atoms such as xylylene group are substituted. Etc.

  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. The colorant of the present invention is excellent in heat resistance because the valence number a of the cation is 2 or more. 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. For example, a linear or branched alkyl group having 1 to 20 carbon atoms and the like can be mentioned, and among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is preferable. It is more preferable that it is a chain or branched alkyl group 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 examples of the substituted alkyl group include 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 , and R ^iv and R ^v It is preferable that a pyrrolidine ring, a piperidine ring and a morpholine ring are formed.

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.

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 consisting 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 ^v and Ar ¹ in one molecule may be the same or different. A desired color can be adjusted by the combination of R ^{i to} R ^v and Ar ¹ .

In the coloring material represented by the general formula (I), the anion (B ^c- ) represents a c-valent polyacid anion containing at least tungsten, and a poly containing another metal within a range not impairing the effects of the present invention. It may be an acid anion. As another metal, molybdenum etc. are mentioned from a heat resistant point.

The polyacid anion may be isopolyacid anion (M _m O _n ) ^c- or heteropolyacid anion (X _l M _m O _n ) ^c- . In the above ion formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. The poly atom M contains at least W (tungsten) and may contain two or more elements including Mo (molybdenum). Examples of the hetero atom X include Si, P, As, S, Fe, Co and the like. In addition, a counter cation such as Na ⁺ or H ⁺ may be partially contained.

Specific examples of the polyacid anion include, for example, Keggin-type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ^3- , Dawson-type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [ P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , Keggin type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ⁴⁻ , β- [SiW ₁₂ O ₄₀ ] ⁴⁻ , γ- [SiW ₁₂ O ₄₀ ] ⁴⁻ , Other examples include [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- , α- [PMo ₁₂ O ₄₀ ] ^3- , α- [PW ₁₁ MoO ₄₀ ] ^3- , α- [PW ₉ Mo ₃ O ₄₀ ] ^3- , α- [ PW ₃ Mo ₉ O ₄₀ ] ^3- , α- [SiMo ₁₂ O ₄₀ ] ^4- , α- [P ₂ Mo ₁₈ O ₆₂ ] ^6- , [Mo ₂ O ₇ ] ^2- , [Mo ₆ O ₁₉ ] ^{2 And} [Mo ₈ O ₂₆ ] ^{4- and the} like.
Among the polyacid anions containing molybdenum and / or tungsten, heteropolyacids are preferable among the above from the viewpoint of heat resistance and light resistance and availability of raw materials, and heteropoly acids further containing P (phosphorus). It is more preferable that it is an acid.
As preferable phosphotungstic acid, Keggin-type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ^3- , Dawson-type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ^6- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^{14 In} particular, Keggin-type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ^3- is preferred. Further, as preferred phosphomolybdic acids, Keggin-type phosphomolybdate ions α- [PMo ₁₂ O ₄₀ ] ³⁻ , α- [P ₂ Mo ₁₈ O ₆₂ ] ⁶⁻ , β- [P ₂ Mo ₁₈ O ₆₂ ] ^{6 -} , [P ₂ Mo ₁₇ O ₆₁ ] ^10- , [P ₂ Mo ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ Mo ₁₂ O ₄₈ ] ^12- , [NaP ₅ Mo ₃₀ O ₁₁₀ ] ^14- From the viewpoint of heat resistance, Keggin-type phosphomolybdate ion α- [PMo ₁₂ O ₄₀ ] ^3- is particularly preferable.

  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 anion 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.
The coloring material represented by the general formula (I) may be included in a lake color material described later, but in the present invention, the coloring material represented by the general formula (I) corresponds to the coloring material represented by the general formula (I). It shall be treated as corresponding to the coloring material represented by (I).

  The method for producing the colorant represented by the general formula (I) is not particularly limited. For example, it can be obtained by the production method described in WO 2012/144520.

  In the present invention, the colorants represented by the general formula (I) can be used singly or in combination of two or more.

<Other color materials>
The colored resin composition for a color filter of the present invention may further contain other coloring materials for the purpose of controlling the color tone, as long as the effects of the present invention are not impaired. As other coloring materials, known pigments and dyes can be mentioned, and one or more kinds can be used.

  From the viewpoint of obtaining desired color tone, it is preferable to further contain one or more selected from dioxazine-based colorants and xanthene-based colorants as another colorant. Specific examples of preferred dioxazine pigments include Pigment Violet 23 and the like. As specific examples of preferable xanthene colorants, acid red 51, 52, 87, 92, 94, 289, 388, C.I. I. In addition to acid violet 9, 30, 102, sulforhodamine G, sulforhodamine B, sulforhodamine 101, sulforhodamine 640, etc., JP-A 2010-32999, JP-A 2010-211198, JP-A-4492760, etc. The xanthene dye of description, etc. are mentioned, and the xanthene type | system | group lake color material mentioned later may be sufficient. In the present invention, it is preferable to use a xanthene-based lake color material from the viewpoint of achieving both brightness and heat resistance.

  In the present invention, the lake color material means a color material in which a color material soluble in a solvent is insolubilized by forming a salt with a counter ion. The lake color material can be generally obtained by mixing a color material to be described later and a lake agent to be described later in a solvent. As the coloring material soluble in the solvent, it is preferable to use a dye having a high transmittance from the viewpoint of increasing the brightness of the color filter. The dye may be appropriately selected according to the desired color tone, and any basic skeleton (coloring site (coloring site, etc.) such as azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, cyanine dyes, indigo dyes, etc. And the like. 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.

As an acid dye, for example, C.I. I. Acid Violet 29, 31, 33, 34, 36, 36: 1, 39, 41, 42, 43, 47, 51, 63, 76, 103, 118, 126, C.I. I. Acid Blue 2, 8, 14, 25, 27, 35, 37, 40, 41, 41: 1, 41: 2, 43, 45, 46, 47, 49, 50, 51, 51, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 78, 79, 80, 81, 96, 111, 124, 127, 127: 1, 129, 137, 138, 143, 145, 150, 175, 176, 183, 198, 203, 204, 205, 208, 215, 220, 221, 225, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 264, 270, 271, 272, 273, 274, 277: 1, 278, 280, 281, 282, 286, 87, 288, 289, 290, 291, 291, 292, 293, 295, 298, 301, 302, 304, 306, 307, 313, 316, 318, 322, 324, 327, 331, 333, 336, 339, 340, 343, 344, 350, C.I. I. Anthraquinones such as acid green 10, 17, 25, 25: 1, 27, 36, 37, 38, 40, 41, 42, 44, 45, 59, 69, 71, 81, 84, 95, 101, 110, 117, etc. Acid dyes; C.I. I. Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 25, 49, 72, C.I. I. Acid Blue 1, 3, 5, 7, 9, 19, 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 G, sulforhodamine B, sulforhodamine 101, xanthene acid dyes such as sulforhodamine 640, etc. may be mentioned. 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.
Moreover, as a commercially available basic dye, for example, C.I. I. Basic Violet 1, 3, 14, C.I. I. Basic Blue 1, 5, 7, 8, 11, 26 C.I. I. Basic green 1, 4 etc. triaryl methane series basic dyes such as C.I. I. Basic Yellow 13, C.I. I. Cyanine basic dyes such as Basic Red 14; I. Azo basic dyes such as Basic Red 29; I. Examples thereof include xanthene basic dyes such as Basic Violet 11 and the like. Among the triarylmethane-based basic dyes, C.I. I. Basic Blue 1, 5, 7, 8, 11, 26 is preferred. These dyes can be used singly or in combination of two or more.
In the present invention, it is preferable to use one or more dyes selected from the xanthene acid dyes and the xanthene basic dyes, among others, because a desired color tone is easily obtained as the colored layer.

  In the lake color material, the counter ion differs depending on the type of the dye, the counter ion of the acid dye is a cation, and the counter ion of the basic dye is an anion. Therefore, the above-mentioned lake agent is suitably selected and used according to the above-mentioned dye. That is, when the acid dye is to be insolubilized, a compound that generates a counter cation of the dye is used as a lake agent, and when the base dye is to be insolubilized, a counter anion of the dye is generated as a lake agent. Compounds are used.

As a counter cation of the acid dye, in addition to ammonium cation, metal cation, inorganic polymer and the like can be mentioned.
Preferred examples of the lake generating agent that generates an ammonium cation include primary amine compounds, secondary amine compounds, tertiary amine compounds and the like, and among them, secondary ones from the viewpoint of excellent heat resistance and light resistance. It is preferable to use an amine compound or a tertiary amine compound.
Examples of primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, stearylamine, oleylamine, allylamine, aniline, benzylamine and the like.
Examples of secondary amine compounds include dimethylamine, diethylamine, methylethylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine and the like.
Examples of tertiary amine compounds include trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylaniline, diethylaniline and the like.
Moreover, as a lake agent which generate | occur | produces a metal cation, what is necessary is just to select suitably from the metal salt which has a desired metal ion.
The counter cation of the acid dye can be used singly or in combination of two or more.

Among them, a lake color material containing a xanthene dye is preferable as a lake color material containing an acid dye from the viewpoint of achieving high brightness.
Among them, the xanthene acid dye in the lake color material preferably has a compound represented by the following general formula (VI), that is, a rhodamine acid dye.

(In general formula (VI), R ^{10 to} R ¹³ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R ¹⁰ and R ¹² , and R ¹¹ and R ¹³ are bonded to each other R ¹⁴ may form a ring structure, R ¹⁴ represents an acid group, X represents a halogen atom, m represents an integer of 0 to 5. General formula (VI) has one or more acid groups, , N is an integer greater than or equal to 0.)

The alkyl group in R ^{10 to} R ¹³ is not particularly limited. Examples thereof include a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the like, among which a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. And a linear or branched alkyl group having 1 to 5 carbon atoms is more preferable. 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 examples of the substituted alkyl group include a benzyl group and the like, and further a substituent And may have a halogen atom or an acidic group.
The aryl group in R ^{10 to} R ¹³ is not particularly limited. For example, the aryl group which may have a C6-C20 substituent is mentioned, Especially, the group which has a phenyl group, a naphthyl group, etc. is preferable. The heteroaryl group in R ^{10 to} R ¹³ includes a heteroaryl group optionally having a carbon number of 5 to 20, and a hetero atom containing a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom is preferable. .
As a substituent which an aryl group or heteroaryl group may have, a C1-C5 alkyl group, a halogen atom, an acidic group, a hydroxyl group, an alkoxy group, a carbamoyl group, carboxylic acid ester group etc. are mentioned, for example .
R ^{10 to} R ¹³ may be the same or different.

Specific examples of the acidic group or a salt thereof, a carboxyl group (-COOH), a carboxylato group (-COO ^-), carboxylate (. -COOM, where M is a metal atom), a sulfonato group (-SO ₃ ^-), a sulfo group _(-SO 3 H), sulfonate _(-SO 3 M, wherein M represents a metal atom), and among them, a sulfonato group (-SO ₃ ^-.), a sulfo group it is preferred to have at least one _(-SO 3 H), or sulfonate _(-SO 3 M). In addition, as a metal atom M, a sodium atom, potassium atom, etc. are mentioned.

Among them, Acid Red 50, Acid Red 52, Acid Red 289, Acid Violet 9, Acid Violet 30, Acid Blue 19 and the like are preferable as the compound represented by the general formula (VI), from the viewpoint of achieving high brightness.
From the viewpoint of heat resistance, a compound having a betaine structure in which m = 1 and n = 0 in the general formula (VI) is preferable.

  As the metal lake color material of the above-mentioned xanthene acid dye, a material containing a metal atom is used as a lake agent. By using a lake agent containing a metal atom, the heat resistance of the colorant becomes high. As such a lake agent, a lake agent containing a metal atom to be a divalent or higher metal cation is preferable.

On the other hand, the counter anion of the basic dye may be an organic anion or an inorganic anion. Examples of the organic anion include organic compounds having an anionic group as a substituent. 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.

It does not specifically limit as an organic group by which an anionic substituent is substituted. The organic group includes a linear, branched or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, and a group obtained by combining them, and these include O, in the carbon chain, Heteroatoms such as S and N may be contained, and a carbonyl group, a carboxyl group, an oxycarbonyl group and an amido group may be contained, and a hydrogen atom may be substituted. As a substituent which the organic group may have, a halogen atom etc. are mentioned, for example.
As an organic group by which the said anionic substituent is substituted, For example, Aliphatic hydrocarbon groups, such as a cyclohexyl group, norbornyl group, bicyclo [2, 2, 2] hexyl group; Aromatic groups, such as a benzyl group and a naphthyl group And may further have a substituent such as a halogen atom or an alkyl group.
Among them, a monocyclic or polycyclic aromatic hydrocarbon group and a group obtained by combining these are preferable as the organic group to which the anionic substituent is substituted, from the viewpoint of easy introduction of the anionic substituent.
When it is intended not to change color due to anions, it is preferable to use an organic group having an absorption maximum in the wavelength region of 400 nm or less. The organic group having an absorption maximum in the wavelength region of 400 nm or less includes, for example, organic groups consisting of fused polycyclic carbon rings such as naphthalene, tetralin, indene, fluorene, anthracene, phenanthrene, etc .; biphenyl, terphenyl, diphenylmethane, triphenyl Organic group consisting of chained polycyclic hydrocarbon such as methane and stilbene; Organic group consisting of 5-membered heterocyclic ring such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole, pyran, pyrone, pyridine, pyridazine, pyrimidine And aromatic compounds consisting of 6-membered heterocycles such as pyrazine; from fused polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like Organic group, and the like that.
Moreover, you may use well-known acid dye as an organic anion. In this case, in the lake color material, the acid dye and the basic dye are present as an ion pair.
Examples of the lake forming agent that generates these organic anions include alkali metal salts and alkaline earth metal salts of the above-mentioned organic anions.

On the other hand, as the inorganic anion, for example, anion of oxo acid (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ), etc., plural Examples thereof include inorganic anions such as polyacid anions in which oxo acids are condensed, and mixtures thereof.
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, 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 a polyacid anion containing molybdenum and / or tungsten, for example, tungstate ion [W ₁₀ O ₃₂ ] ⁴⁻ , molybdate ion [Mo ₆ O ₁₉ ] ²⁻ or heteropolyacid which is an isopoly acid, phosphotungstic acid ion _{[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- , H ₃ [PW _2-x Mo _x O ₇ ] ^{4- and the} like. Among the polyacid anions containing molybdenum and / or tungsten, heteropolyacids are preferable among the above from the viewpoints of heat resistance and availability of raw materials, and P (phosphorus) -containing heteropolyacids. Is more preferred.

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 lake color material can be used singly or in combination of two or more.
In the present invention, a lake color material is preferably a lake color material consisting of a basic dye and an inorganic anion in terms of heat resistance and light resistance, and a lake color consisting of a basic dye and a polyacid anion. It is more preferable that it is a material. In the case of a lake color material containing a polyacid anion, the silane coupling agent is susceptible to change over time, but in the present invention, the content ratio of the silane coupling agent is the total solid content in the colored resin composition. On the other hand, since it is 1% by mass or less, the influence of the change over time is small, and the heat resistance and the light resistance are high, so it is particularly suitably used as the lake color material of the present invention.

  The blending ratio of the coloring material in the case of using another coloring material in combination with the coloring material represented by the general formula (I) may be appropriately adjusted so as to obtain a desired color tone. From the viewpoint of being excellent in heat resistance and light resistance, the general formula (I) is preferably contained in 100 parts by mass of the total of the coloring material represented by the general formula (I) and the other coloring materials. It is preferable that it is 30-100 mass parts, it is more preferable that it is 60-99 mass parts, and it is still more preferable that it is 70-98 mass parts.

[Urethane-based dispersant]
In the colored resin composition for a color filter of the present invention, the coloring material represented by the general formula (I) is used by being dispersed in a solvent by a urethane dispersant. By selecting and using a urethane dispersant, the coloring material represented by the above general formula (I) can be stably dispersed while forming a molecular association state, so it is excellent in viscosity stability over time, heat resistance It is possible to form a colored layer with improved properties.
In the present invention, a urethane dispersant is a dispersant composed of a compound having one or more urethane bonds (-NH-COO-) in one molecule.

  In the present invention, the urethane dispersant is preferably a reaction product of a polyisocyanate having two or more isocyanate groups in one molecule and a polyester having a hydroxyl group at one end or both ends.

  As polyisocyanates, it is preferable to have at least one isocyanate compound selected from diisocyanates and triisocyanates, and a polymer having a main chain skeleton obtained by polymerizing at least one of diisocyanates and triisocyanates. May be

  Examples of the main chain structure in which at least one of diisocyanates and triisocyanates is polymerized include a molecular structure in which isocyanate groups are bonded to each other between the molecules of the above-mentioned polyisocyanates to polymerize. In addition, the chain structure of the main chain skeleton may contain a ring structure such as an aromatic ring or a heterocyclic ring which may have a substituent.

The diisocyanate used in the urethane dispersant may be hexamethylene diisocyanate or an aliphatic diisocyanate such as isophorone diisocyanate, but aromatic diisocyanates are preferable from the viewpoint of heat resistance, for example, benzene 1,3-diisocyanate. Benzene diisocyanates such as benzene-1,4-diisocyanate; Toluene diisocyanates such as toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, toluene-3,5-diisocyanate 1,2-xylene-3,5-diisocyanate, 1,2-xylene-3,6-diisocyanate, 1,2-xylene-4,6-diisocyanate, 1,3-xylene-2,4-diisocyanate 1,3-xylene-2,5-diisocyanate, 1,3-xylene-2,6-diisocyanate, 1,3-xylene-4,6-diisocyanate, 1,4-xylene-2,5-diisocyanate, 1,3 Aromatic diisocyanates such as xylene diisocyanates such as 4-xylene-2,6-diisocyanate can be mentioned.
Also, as the triisocyanates, for example, benzene triisocyanates such as benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate, benzene-1,3,5-triisocyanate; toluene -2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate, toluene-2,4,6-triisocyanate, toluene-3,4,6 -Toluene isocyanates such as triisocyanate, toluene-3,5,6-triisocyanate, 1,2-xylene-3,4,6-triisocyanate, 1,2-xylene-3,5,6-triisocyanate 1,3-xylene-2,4,5-triisocyanate, 1,3-xylene-2,4,6 Xylene such as triisocyanate, 1,3-xylene-3,4,5-triisocyanate, 1,4-xylene-2,3,5-triisocyanate, 1,4-xylene-2,3,6-triisocyanate Aromatic triisocyanates such as triisocyanates can be mentioned. Among these, toluene diisocyanates are preferable from the viewpoint of high heat resistance. These diisocyanates and triisocyanates can be used alone or in combination of two or more. Among them, it is preferable from the viewpoint of high heat resistance to have a main chain structure in which toluene diisocyanates are polymerized alone. Examples of the dispersant having the above structure include BYK 161, BYK 167, BYK 170, BYK 174, and the like.

Among the polyesters having a hydroxyl group at one end or both ends, from the viewpoint of dispersibility, among others,-(O-R ^j CO) n- (R ^j is an alkylene group having 1 to 20 carbon atoms, n is 2 or more It is preferable that it is a compound containing the polyester chain represented by integer number of. Specific examples of polyester chains include polylactones such as polycaprolactone, polyvalerolactone and polypropiolactone, and polycondensation polyesters such as polyethylene terephthalate and polybutylene terephthalate. Among them, polylactones are preferable from the viewpoint of heat resistance, among which polycaprolactone [-(O-C ₅ CO) m-] (m is an integer of 2 or more) is preferable, and polycaprolactone is more preferable from the viewpoint of dispersibility. m of _{- [(O-C 5 CO} ) m-] is preferably an integer of 4 or more.
As dispersants containing polycaprolactone, BYK 170, BYK 171, BYK 174 and the like can be mentioned.

In the present invention, the acid value of the urethane dispersant is not particularly limited, but it is excellent in the dispersibility and dispersion stability of the coloring material represented by the general formula (I), and is excellent in heat resistance and has a high brightness colored layer It is preferable that it is 10 mgKOH / g or more from the point which can be formed, it is preferable that they are 20 mgKOH / g or more and 180 mgKOH / g or less, and it is more preferable that they are 30 mgKOH / g or more and 160 mgKOH / g or less. In addition, an acid value represents the mass (mg) of KOH required to neutralize 1 g of solid content, and says the value calculated | required by the potentiometric titration method according to JISK0070.
As dispersants having an acid value of 10 mg KOH / g or more, BYK 170 (acid number: 36.7 mg KOH / g, amine value 0 mg KOH / g), BYK 171 (32.9 mg KOH / g, amine value 0 mg KOH / g), BYK 174 ( 41.9 mg KOH / g, amine value 0 mg KOH / g)
Can be mentioned.

In the present invention, the amine value of the urethane dispersant is not particularly limited, but it is excellent in the dispersibility and dispersion stability of the coloring material represented by the general formula (I), is excellent in heat resistance, and has a high brightness. It is preferable that it is 10 mgKOH / g or more from the point which can be formed, it is preferable that they are 20 mgKOH / g or more and 130 mgKOH / g or less, and it is more preferable that they are 30 mgKOH / g or more and 100 mgKOH / g or less. The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of solid content, and may be measured by the method defined in JIS-K7237. it can.
Examples of dispersants having an amine value of 10 mg KOH / g or more include BYK 161, BYK 162, BYK 163, BYK 164, BYK 166, BYK 167, and BYK 168.

  The urethane dispersant may have an acid value of 10 mg KOH / g or more and an amine value of 10 mg KOH / g or more, but the increase in the viscosity of the colored resin composition is suppressed and the dispersion stability is excellent. From the above, a urethane dispersant having an acid value of 10 mg KOH / g or more and an amine value of 5 mg KOH / g or less, or an amine value of 10 mg KOH / g or more, and an acid value of 5 mg KOH / g or less It is preferable that it is any of the urethane type dispersing agent, and the urethane type dispersing agent whose acid value is 10 mgKOH / g or more and whose amine value is 5 mgKOH / g or less is more preferable among them. By using a urethane dispersant having a high acid value and only one of amine values, dispersion stability can be achieved by stably adsorbing on the surface of the molecular association formed by the color material represented by the general formula (I). It is estimated that it is excellent.

In the case of urethane dispersants having an acid value of 10 mg KOH / g or more, the increase in viscosity of the colored resin composition is suppressed, and from the viewpoint of being able to form a colored layer having excellent dispersion stability and high brightness, amine values are particularly high. It is more preferably 5 mg KOH / g or less, still more preferably 1 mg KOH / g or less, and particularly preferably substantially free of an amine value.
Moreover, in the case of a urethane dispersant having an amine value of 10 mg KOH / g or more, an increase in the viscosity of the colored resin composition is suppressed, and from the viewpoint of being able to form a colored layer having excellent dispersion stability and high luminance, acid is particularly preferable. More preferably, the acid value is 5 mg KOH / g or less, and even more preferably the acid value is 1 mg KOH / g or less. It is particularly preferable that the acid value is substantially zero.

Furthermore, it is preferable that a urethane type dispersing agent does not contain the polyether chain which is easy to be cut | disconnected by heating from a heat resistant point. Here, the polyether chain refers to a structure represented by — (O—R ⁱ ) n — (R ⁱ is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 2 or more). Specifically,-(O-CH ₂ CH ₂ ) n-,-(O-CH ₂ CH ₂ CH ₂ ) n-,-(O-CH ₂ CH ₂ CH ₂ CH ₂ ) n-,-(O _{-CH 2 CH 2 CH 2 CH 2} CH 2) n -, - (O-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2) n- can be mentioned.

Furthermore, the molecular weight of the urethane dispersant is preferably in the range of 500 to 30,000 in terms of mass average molecular weight from the viewpoint of heat resistance, electrical reliability, and dispersibility.
Here, the weight average molecular weight (Mw) is determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
In addition, the measuring method of the said weight average molecular weight can measure a weight average molecular weight by a Shodex GPC system -21H (Shodex GPC System -21H) by using polystyrene as a standard substance and THF as an eluting solvent.

As the urethane dispersant of the present invention, a urethane compound having a desired structure may be synthesized and used by a known method, or a commercially available product may be used. Examples of commercially available products include Disperbyk-161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174 (above, made by Big Chemie Japan Ltd.), Ajispar PB711 (made by Ajinomoto Co., Ltd.) And EFKA-46, 47, 48 (manufactured by EFKA CHEMICALS) and the like. Among them, Disperbyk-161, 162, 166, 170, 171, 174 are preferable in terms of heat resistance, electrical reliability, and dispersibility.
The urethane dispersant of the present invention can be used singly or in combination of two or more.

<Other dispersants>
The colored resin composition for color filter of the present invention may be used in combination with other dispersants as long as the effects of the present invention are not impaired. The other dispersant may be used to assist the dispersion of the colorant represented by the general formula (I), and may be used to disperse the other colorant. . As another dispersing agent, it can select suitably from what is conventionally used as a dispersing agent, and can be used. As the dispersant, for example, surfactants of cationic type, anionic type, nonionic type, amphoteric type, silicone type and fluorine type can be used. Among the surfactants, polymer surfactants (polymer dispersants) are preferable in that they can be dispersed uniformly and finely.

  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 knittings 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.

  Among other dispersing agents, block copolymers containing repeating units having a tertiary amine, and repeating units having a tertiary amine, among others, from the viewpoint that the dispersion stability of the coloring material represented by the general formula (I) is good. Graft copolymer containing a unit, and a salt block copolymer or salt graft copolymer in which the tertiary amine of the block copolymer or graft copolymer and the organic acid compound form a salt are preferable. The salt block copolymer or the salt graft copolymer is preferable. As a specific example of such a dispersing agent, for example, a salt-type block copolymer described in JP-A-2012-236882 or the like, a salt-type graft copolymer described in JP-A-2012-63429 or the like, etc. Is preferred.

  When another dispersant is used, the content thereof is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and 10 parts by mass or less with respect to 100 parts by mass of the total amount of the dispersant. Is particularly preferred.

[Alkali-soluble resin]
In the present invention, a resin having an acid value of 80 mgKOH / g or more and 300 mgKOH / g or less is selected and used as the alkali-soluble resin. The alkali-soluble resin acts as a binder resin, and is a resin soluble in a developer, preferably an alkaline developer, used in pattern formation. In the present invention, since the alkali-soluble resin is a resin of 80 mg KOH / g or more and 300 mg KOH / g or less, the number of acidic groups contained in the resin is relatively large, and the coloring material represented by the general formula (I) is It is estimated that the interaction between the molecular association and the urethane dispersant is stabilized, the temporal viscosity stability such as dispersion stability is improved, and the heat resistance of the colored layer obtained from the resin composition is improved. Ru.
Since the above-mentioned alkali-soluble resin is a resin having a relatively large number of acid groups and an acid value of 80 mg KOH / g or more, a dye existing near the surface of the molecular association body of the coloring material represented by the general formula (I) Alternatively, it is presumed that the alkali-soluble resin is easily adsorbed to the surface of the molecular association body as a result of interaction with the basic group possessed by the lake agent. Since the alkali-soluble resin has a relatively high acid value, once it is adsorbed, it is difficult to dissociate even at high temperature heating, and decomposition of the color material can be further suppressed, and a decrease in luminance is suppressed, and heat resistance is significantly improved. It is presumed that. In addition, by using an alkali-soluble resin having an acid value of 80 mg KOH / g or more, the acid group contributes to the adhesion to the substrate, and silane coupling which has been conventionally used to improve the adhesion to the substrate. The adhesion to the substrate is improved even without using an agent.

  The alkali-soluble resin in the present invention usually has a carboxyl group as an acidic group. Specifically, acrylic copolymers having a carboxyl group, epoxy (meth) acrylate resins having a carboxyl group, and the like can be mentioned. Among them, an acrylic copolymer having a structural unit having a carboxyl group at least in a side chain is preferable.

The acrylic copolymer having a structural unit having a carboxyl group is, for example, obtained by (co) polymerizing a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, another copolymerizable monomer, by a known method It is a (co) polymer obtained.
Examples of the carboxyl group-containing ethylenic unsaturated monomer include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl ester of maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer and the like. Be Also, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylate and the like can also be used. Further, as a precursor of a carboxyl group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride may be used. Among them, (meth) acrylic acid is particularly preferable in view of copolymerizability, cost, solubility, glass transition temperature and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of improving the heat resistance of the colored layer. Since the alkali-soluble resin has a bulky hydrocarbon ring, shrinkage at the time of curing is suppressed, peeling from the substrate is suppressed, and the film strength is improved.
As such a hydrocarbon ring, a cyclic aliphatic hydrocarbon ring which may have a substituent or an aromatic ring which may have a substituent can be mentioned. Among them, when an aliphatic ring is contained, the heat resistance and adhesion of the colored layer are improved, and the luminance of the obtained colored layer is improved.
Specific examples of the hydrocarbon ring include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2, 6)] decane (dicyclopentane), adamantane and the like Rings; and aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene and the like.
In the alkali-soluble resin used in the present invention, using a resin having a structural unit having a carboxyl group and a structural unit having the above-mentioned hydrocarbon ring makes it easy to adjust the amount of each structural unit, and has the above-mentioned hydrocarbon ring It is preferable from the point which is easy to increase the structural unit quantity and to improve the function which the said structural unit has.
An acrylic copolymer having a structural unit having a carboxyl group and the above-mentioned hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned “other copolymerizable monomer”. Can.
Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like.

In the alkali-soluble resin of the present invention, the film strength of the cured film is improved to improve the development resistance, and the thermal shrinkage of the cured film is suppressed to be excellent in the adhesion to the substrate. It is preferable to have In the case of having an ethylenic double bond, the alkali-soluble resins, or the alkali-soluble resin and the polyfunctional monomer may form crosslinks in the curing step of the resin composition at the time of producing the color filter. As a result, it is presumed that the film strength of the cured film of the colored layer is improved, the thermal contraction of the cured film is suppressed, and the adhesion to the substrate is excellent. By selecting and using an alkali-soluble resin having an ethylenic double bond, the colored layer formed of the colored resin composition for a color filter of the present invention can be a silane coupling agent to be described later Even when the amount is 1 part by mass or less with respect to the solid content, the adhesion to a substrate is excellent.
The method of introducing the ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method in which a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, is added to a carboxyl group of an alkali-soluble resin to introduce an ethylenic double bond in a side chain. Or introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond in the side chain Etc.

  The acrylic copolymer having a structural unit having a carboxyl group may further contain other structural units such as a structural unit having an ester group, such as methyl (meth) acrylate and ethyl (meth) acrylate. The structural unit having an ester group not only functions as a component that suppresses the alkali solubility of the colored resin composition for color filter, but also functions as a component that improves the solubility in a solvent and the solvent resolubility.

  The alkali-soluble resin in the present invention is preferably an acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, and has a structural unit having a carboxyl group and a hydrocarbon ring. It is more preferable that it is an acrylic copolymer having a structural unit and a structural unit having a double bond in the side chain.

  The alkali-soluble resin can be made an alkali-soluble resin having desired performance by appropriately adjusting the amount of each structural unit charged.

It is preferable that it is 5-50 mass% with respect to monomer whole quantity, and, as for the preparation amount of a carboxyl group-containing ethylenic unsaturated monomer, it is more preferable that it is 10-40 mass%.
When the proportion of the carboxyl group-containing ethylenic unsaturated monomer is less than 5% by mass, the solubility of the obtained coating film in an alkali developer decreases, and pattern formation becomes difficult. If the proportion of the carboxyl group-containing ethylenic unsaturated monomer exceeds 50% by mass, the formed pattern tends to be easily detached from the substrate or roughened on the surface of the pattern during development with an alkali developer.

  In addition, in an acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, which is preferably used as an alkali-soluble resin, the preparation amount of the carboxyl group-containing ethylenically unsaturated monomer is the total amount of monomers The amount is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. Moreover, in the said acryl-type copolymer, it is preferable that the preparation amount of hydrocarbon ring group containing ethylenic unsaturated monomer is 30-80 mass% with respect to the monomer whole quantity, and it is 40-75 mass%. More preferable.

An acrylic copolymer having a carboxyl group-containing structural unit, a hydrocarbon ring-containing structural unit, and an ethylenic double bond-containing structural unit, which is more preferably used as an alkali-soluble resin When an ethylenic double bond is introduced by adding a compound having an epoxy group and an ethylenic double bond in the molecule to the ethylenically unsaturated monomer, the amount of the carboxyl group-containing ethylenically unsaturated monomer is It is preferable that it is 5-50 mass% with respect to the monomer whole quantity, and it is more preferable that it is 10-40 mass%. In the said acryl-type copolymer, it is preferable that the preparation amount of hydrocarbon ring group containing ethylenically unsaturated monomer is 30-80 mass% with respect to the monomer whole quantity, and it is more preferable that it is 40-75 mass%. . In the acrylic copolymer, the compound having both an epoxy group and an ethylenic double bond is preferably 10 to 95% by mass with respect to the charged amount of the carboxyl group-containing ethylenically unsaturated monomer, It is more preferable that it is -90 mass%.
When an acryl-type copolymer has a structural unit which has a carboxyl group and a hydrocarbon ring, the said structural unit shall be contained in each of a structural unit which has a carboxyl group, and a structural unit which has a hydrocarbon ring.

  In the alkali-soluble resin of the present invention, the constituent unit having a carboxyl group, the constituent unit having a hydrocarbon ring, and the other constituent units contained in addition to the constituent unit having an ethylenic double bond in the side chain are all constituent units. It is preferable that it is 0-30 mass%, and it is more preferable that it is 0-20 mass%.

The alkali-soluble resin is selected from those having an acid value of 80 mg KOH / g or more and 300 mg KOH / g or less from the viewpoint of the developability (solubility) in an alkaline aqueous solution used for a developer and the heat resistance of the colored layer. Use. Among them, 90 mg KOH / g or more and 280 mg KOH / g or less is preferable, and 100 mg KOH / g or more and 250 mg KOH / g or less is more preferable. An alkali-soluble resin having an acid value of 100 mg KOH / g or more is preferable from the viewpoint of improving the brightness of the colored layer and improving the adhesion. When the coloring material represented by the general formula (I) and the metal lake color material of the acid dye are used in combination, an alkali-soluble resin having an acid value of 90 mg KOH / g or more from the viewpoint of improving heat resistance. It is preferable to use
An alkali-soluble resin having an acid value of the lower limit or more easily interacts with a basic group possessed by an anion present in the vicinity of the surface of the molecular aggregate of the coloring material represented by the general formula (I). It is presumed that the alkali-soluble resin is easily adsorbed to the surface of the molecular association body. Since the alkali-soluble resin has a relatively high acid value, once it is adsorbed, it is difficult to dissociate even at high temperature heating, and decomposition of the color material can be further suppressed, and a decrease in luminance is suppressed, and heat resistance is significantly improved. It is presumed that.
The acid value can be measured in accordance with JIS K 0070.

It is preferable that it is the range of 100-2000, and, in particular, it is preferable that it is the range of 140-1500 when it has an ethylenically unsaturated group in the side chain of alkali-soluble resin. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and the adhesion are excellent. In addition, if it is 100 or more, the proportion of other structural units such as the structural unit having a carboxyl group or the structural unit having a hydrocarbon ring can be relatively increased, so that it is excellent in developability and heat resistance. There is.
Here, the ethylenically unsaturated bond equivalent is the mass average molecular weight per mole of the ethylenically unsaturated bond in the above alkali-soluble resin, and is represented by the following formula (1).

(In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenic double bonds contained in the alkali-soluble resin W (g).)

  The above ethylenically unsaturated bond equivalent can be obtained, for example, by measuring the number of ethylenic double bonds contained in 1 g of the alkali-soluble resin in accordance with the test method for iodine value described in JIS K 0070: 1992. It can be calculated.

  Moreover, the said ethylenically unsaturated bond equivalent makes alkali-soluble resin calculated by following Formula (2) by making W in Formula (1) into the total mass (g) of the monomer which comprises alkali-soluble resin, and a compound By setting it as the number-of-moles (mol) of the ethylenic double bond in, it is simply calculated by the compounding quantity at the time of the synthesis | combination of alkali-soluble resin.

(In the formula (2), k is the number (number) of ethylenic double bonds that a compound having an epoxy group and an ethylenic double bond in the molecule has, and represents an integer of 1 or more. And the number of moles of the compound having an epoxy group and k ethylenic double bonds in the molecule).

The mass average molecular weight of the alkali-soluble resin is not particularly limited. Among them, preferably it is in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is significantly reduced, and if it exceeds 500,000, pattern formation may be difficult at the time of development with an alkali developer.
Here, the weight average molecular weight (Mw) is determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
In addition, the measuring method of the said weight average molecular weight made the polystyrene the standard substance, THF measured the weight average molecular weight by Shodex GPC system -21H (Shodex GPC System -21H) as an eluting solvent.

  The alkali-soluble resin used in the colored resin composition for a color filter of the present invention may be used alone or in combination of two or more, and is alkali-soluble to the total solid content of the colored resin composition. Although content of resin does not have a restriction | limiting in particular, 5-60 mass% is preferable, and 10-40 mass% is more preferable. If the content of the alkali-soluble resin is too small, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is too large, the proportion of the coloring material becomes relatively low, which is sufficient. In some cases, the color density can not be obtained. In the present invention, the solid content is all other than the above-mentioned solvents, and also includes liquid polyfunctional monomers and the like.

[Multifunctional monomer]
The polyfunctional monomer used in the colored resin composition for a color filter of the present invention is not particularly limited as long as it can be polymerized by an initiator described later, and usually, two or more ethylenically unsaturated double bonds are used. It is preferable that it is a polyfunctional (meth) acrylate in which the compound which it has is used and has especially 2 or more of acryloyl group or methacryloyl groups.
As such a polyfunctional (meth) acrylate, it may select suitably from conventionally well-known things, and may be used.

  Among the polyfunctional (meth) acrylates, examples of difunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, long-chain aliphatic di (meth) acrylate ) Acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, stearic acid modified pentaerythritol di (meth) acrylate, propylene di (meth) acrylate, propylene glycol di (meth) acrylate, Glycerol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, Tylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di ( Meta) acrylate, allylated cyclohexyl di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, acrylated isocyanurate, bis (acryloxy neopentyl glycol) adipate, bisphenol A di (meth) acrylate, tetrabromo bisphenol A di (Meth) acrylate, bisphenol S di (meth) acrylate, butanediol di (meth) acrylate, phthalic acid di (meth) acrylate, phosphoric acid di Meth) acrylate, zinc di (meth) acrylate.

  Also, as the trifunctional or higher polyfunctional (meth) acrylate, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, succinic anhydride modified pentaerythritol tetra (meth) acrylate, phosphoric tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacrylic) Roxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraa Lilate, alkyl modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) ) Acrylate, carboxylic acid modified dipentaerythritol penta (meth) acrylate, succinic anhydride modified dipentaerythritol penta (meth) acrylate, urethane tri (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, Ester hexa (meth) acrylate etc. are mentioned.

In the present invention, from the viewpoint of improving the alkali developability, the polyfunctional monomer preferably has a carboxyl group. As a polyfunctional monomer which has a carboxyl group, the carboxylic acid modified substance of poly (meth) acrylates of the following polyhydric alcohol etc. are mentioned, for example.
Specific examples of poly (meth) acrylates of polyhydric alcohol include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.
Moreover, these polyfunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type. For example, a polyfunctional monomer having a carboxyl group and a polyfunctional monomer having no carboxyl group may be used in combination.
Among these, a succinic acid modified product of pentaerythritol tri (meth) acrylate and a succinic acid modified product of dipentaerythritol penta (meth) acrylate are particularly preferable in that they are excellent in developability and improve heat resistance.

  The content of the polyfunctional monomer used in the colored resin composition for a color filter of the present invention is not particularly limited, but the content of the polyfunctional monomer is 5 to 60% by mass with respect to the total solid content of the colored resin composition. Is preferable, and 10 to 40% by mass is more preferable. If the content of the polyfunctional monomer is less than the above range, light curing may not proceed sufficiently, and the exposed portion may elute. If the content of the polyfunctional monomer is more than the above range, the alkali developability may be reduced. There is.

[Initiator]
There is no restriction | limiting in particular as an initiator used in the colored resin composition for color filters of this invention, It can be used combining 1 type, or 2 or more types out of conventionally known various initiators.

  Specific examples of the initiator include benzophenone, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, aromatic ketones such as phenanthrene, benzoin methyl ether, benzoin ethyl Benzoin ethers such as ether and benzoin phenyl ether, benzoin such as methylbenzoin and ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5- Di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-Triary Imidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- Halomethyl oxadiazole compounds such as (p-methoxystyryl) -1,3,4-oxadiazole; 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine; Bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino- -P-methoxystyryl-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6 Halomethyl-S-triazine compounds such as -bis-trichloromethyl-S-triazine and 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine; Dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-) Morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl- 4'-methyl diphenyl sulfide, benzyl methyl ketal, dimethylamino benzoate, p-dimethylamino isoamyl ester, 2-n-butoxyethyl-4-dimethylamino benzoate, 2-chlorothioxanthone, 2,4-diethyl thioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 4-benzoyl-methyldiphenyl Sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[( 4-Methylphenyl) methi -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- Examples include [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone and the like.

  In the present invention, among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and diethylthioxanthone are preferable.

  The content of the initiator used in the colored resin composition of the present invention is not particularly limited, but preferably 3 to 40% by mass, and more preferably 7 to 35% by mass with respect to the total solid content of the colored resin composition. Preferably, 10 to 30% by mass is particularly preferable. If this content is less than the above range, a sufficient polymerization reaction can not be generated, and therefore the hardness of the colored layer may not be sufficient. On the other hand, if it is more than the above range, the colored resin composition The content of the coloring material and the like in the solid content may be relatively small, and a sufficient coloring density may not be obtained.

[solvent]
In the present invention, as the solvent, a solvent having a solubility of not more than 0.1 (g / 10 ml solvent) at 23 ° C. of the coloring material represented by the general formula (I) is used. The colored resin composition according to the present invention can be prepared by using the coloring material represented by the general formula (I) in a solvent by using such a substantially insoluble or poorly soluble solvent for the coloring material. It can be dispersed and used in the state of association. The solvent used in the present invention has a solubility of 0.05 (g / 10 ml solvent) of the color material represented by the above general formula (I) at 23 ° C. from the viewpoint that a coating film with high brightness is obtained with excellent dispersibility. It is preferable that it is the following solvent.
In the present invention, solvents having a solubility of 0.1 (g / 10 ml solvent) or less at 23 ° C. for the coloring material and the xanthene dye can be simply determined by the following evaluation method.
First, it can be judged by the following method whether it is a solvent which does not substantially dissolve the coloring material represented by the general formula (I).
Into a 20 mL sample tube bottle, 0.1 g of a coloring material whose solubility is to be determined is charged, a solvent S is charged using a 10 ml hole pipette, and after being covered, ultrasonic treatment is performed for 3 minutes. The obtained solution is stored still in a water bath at 23 ° C. for 60 minutes. 5 ml of this supernatant is filtered with a PTFE 5 μm membrane filter, and further filtered with a 0.25 μm membrane filter to remove insolubles. The absorption spectrum of the obtained filtrate is measured using a 1 cm cell with a UV-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation). The absorbance (abs) at the maximum absorption wavelength of each color material is determined. At this time, if the absorbance (abs) is less than 40% of the upper limit of measurement (in the case of UV-2500PC manufactured by Shimadzu Corporation, the absorbance (abs) is less than 2), the solvent does not substantially dissolve the color material. It can be evaluated as a solvent. At this time, when the absorbance (abs) is 40% or more of the upper limit of measurement, the solubility is further determined by the following evaluation method.
First, instead of the above-mentioned solvent S, using a good solvent (for example, an alcohol such as methanol) of a coloring material whose solubility is to be determined, a filtrate is similarly obtained to prepare a coloring material solution, and then 10000 times The dilution is appropriately made to about 100 000 times, and the absorbance at the maximum absorption wavelength of the coloring material is similarly measured. The solubility of the color material in the solvent S is calculated from the absorbance and dilution ratio of the color material solution of the solvent S and the color material solution of the good solvent.
As a result, it is judged that the solvent whose solubility of the color material is 0.1 (g / 10 ml solvent) or less is a solvent which can be used in the present invention and the color material is poorly soluble.

In the colored resin composition of the present invention, among them, it is preferable from the viewpoint of dispersion stability to use appropriately selected from ester solvents.
Examples of the ester solvents include ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, 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 di Acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like can be mentioned. Among them, as a solvent used in the present invention, a group consisting of propylene glycol monomethyl ether acetate (PGMEA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate and 3-methoxybutyl acetate It is preferable from the point of the solubility of another component, and application | coating aptitude that it is 1 or more types selected from.
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. In this case, there is an advantage that a special cleaning step is not required even when switching to a colored resin composition using conventional PGMEA.
The solvent used in the present invention preferably contains 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more in all solvents.
These solvents may be used alone or in combination of two or more.

<Optional Additives>
The colored resin composition of the present invention may contain various additives as needed, as long as the object of the present invention is not impaired. Examples of the additive include an antioxidant, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoamer, a silane coupling agent, an ultraviolet absorber, an adhesion promoter, and the like. .

(Silane coupling agent)
In the present invention, a silane coupling agent may be used to improve the adhesion to the substrate. In the present invention, the silane coupling agent represents a compound having one or more groups selected from a silanol group and an alkoxysilyl group.
The silane coupling agent is usually used in an amount of 2% by mass or more based on the total solid content of the colored resin composition in terms of adhesion. On the other hand, the present inventors have found that when the silane coupling agent is used in combination with the colorant represented by the general formula (I), the silane coupling agent changes with time. Obtained. Therefore, the silane coupling agent is used as a solid in the colored resin composition in that the adhesion to the substrate is not lowered even after storage for a long period of time, and the change in sensitivity is suppressed and the patterned colored layer as designed can be obtained. The amount is preferably 1% by mass or less with respect to the component, more preferably 0.5% by mass or less with respect to the total solid content of the colored resin composition, and still more preferably substantially non-containing.

  Specific examples of the silane coupling agent include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc. (Meth) acrylsilanes, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltritrioxane Epoxysilanes such as ethoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyl Limethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxy Aminosilanes such as silane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane Among them, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-hydroxypropylmethyldiethoxysilane, and the like, from the viewpoint of adhesion to a substrate. Methacryloxy B pills triethoxysilane are preferred.

(Antioxidant)
The colored resin composition of the present invention preferably 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 viewpoint of light resistance, it is preferable to use a hindered phenolic antioxidant.

  Examples of hindered phenol-based antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF AG), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3) 5-Di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2′-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP-S, Sumitomo Chemical Co., Ltd.), 6,6'-thiobis (2-tert-butyl-4-methylphenol) Trade name: Irganox 1081, manufactured by BASF), 3,5-di -tert- butyl-4-hydroxybenzyl phosphonic acid diethyl (trade name: Irugamodo 195, manufactured by BASF), and the like. Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .

  When using an antioxidant, the compounding quantity will not be specifically limited if it is a range which does not impair the effect of this invention. As a compounding quantity of antioxidant, it is preferable that an antioxidant is 0.1-5.0 mass parts with respect to 100 mass parts of total solids in a coloring resin composition, and 0.5-4. More preferably, it is 0 parts by mass. If it is more than the said lower limit, it is excellent in heat resistance and light resistance. On the other hand, if it is below the said upper limit, the colored resin composition of this invention can be made into a highly sensitive photosensitive resin composition.

Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate And sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes and the like. In addition, fluorine surfactants can also be used.
Furthermore, as a plasticizer, dibutyl phthalate, dioctyl phthalate, tricresyl etc. are mentioned, for example. As an antifoamer and a leveling agent, a silicon type, a fluorine type, an acrylic type compound etc. are mentioned, for example.

<Mixing ratio of each component in colored resin composition>
The total content of the colorant represented by the general formula (I) and the other colorant is 3 to 65% by mass, more preferably 4 to 55% by mass with respect to the total solid content of the colored resin composition It is preferable to blend in proportions. If it is more than the said lower limit, the colored layer at the time of apply | coating a colored resin composition to a predetermined | prescribed film thickness (usually 1.0-5.0 micrometers) has sufficient color density. Moreover, if it is below the said upper limit, while it is excellent in dispersibility and dispersion stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. In the present invention, the solid content is all other than the above-mentioned solvents, and also includes liquid polyfunctional monomers and the like.
Further, the content of the dispersing agent is not particularly limited as long as the coloring material represented by the general formula (I) can be uniformly dispersed, but, for example, the solid content of the colored resin composition is 3-40 mass% can be used with respect to the whole quantity. Furthermore, 5-35 mass% is preferable with respect to solid content whole quantity of a coloring resin composition, and 5-25 mass% is especially more preferable. If it is more than the said lower limit, it is excellent in the dispersibility and dispersion stability of a lake color material, and is excellent in the temporal stability of viscosity. Moreover, if it is below the said upper limit, the brightness | luminance of a colored layer will become favorable.
The total content of the alkali-soluble resin, the polyfunctional monomer and the initiator is 10 to 92% by mass, preferably 15 to 87% by mass, based on the total solid content of the colored resin composition. preferable. If it is more than the said lower limit, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. Moreover, if it is below the said upper limit, it is excellent in developability, or generation | occurrence | production of the micro wrinkles by heat contraction is also suppressed.
Further, the content of the solvent may be appropriately set within the range in which the colored layer can be formed with high accuracy. It is preferable normally to exist in the range of 55-95 mass% with respect to whole quantity of the said coloring resin composition containing the said solvent, and it is more preferable to exist in the range of 65-88 mass% especially. When the content of the solvent is in the above range, the coating property can be excellent.

<Method of producing colored resin composition for color filter>
The process for producing a colored resin composition for color filter of the present invention comprises a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, an initiator, a solvent, and various additives optionally used. Any method may be used as long as the coloring material can be uniformly dispersed in the solvent by the dispersant, and it can be prepared by mixing using known mixing means.
As a method for preparing the resin composition, for example, (1) First, a dispersion of a coloring material is prepared, and an alkali-soluble resin, a polyfunctional monomer, an initiator, and various additives optionally used for the dispersion are prepared. (2) A method of simultaneously charging and mixing a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, an initiator, and optionally used various additive components in a solvent; (3) A method of adding a dispersant, an alkali-soluble resin, a polyfunctional monomer, an initiator, and various additive components optionally used and mixed in a solvent, and then adding and dispersing a coloring material; And the like.
Among these methods, the above method (1) is preferable from the viewpoint of effectively preventing aggregation of the coloring material and dispersing it uniformly.

  The method of preparing the dispersion of the coloring material represented by the general formula (I) can be appropriately selected and used from conventionally known dispersion methods. For example, after a urethane dispersant is mixed in a solvent and stirred to prepare a dispersant solution, the colorant solution represented by the general formula (I) is mixed with other components as needed in the dispersant solution. The dispersion can be prepared by dispersing the colorant represented by the general formula (I) using a known stirrer or disperser.

  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, as for the bead diameter to be used, 0.03-2.00 mm is preferable, More preferably, it is 0.10-1.0 mm.

  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 0.5-0.1 micrometer membrane filter after dispersion | distribution.

In the present invention, when the colorant represented by the general formula (I) and the xanthene colorant are used in combination, the solvent represented by the general formula (I) and the xanthene colorant are used as the solvent. It is preferable to add a dispersant and co-disperse the colorant represented by the general formula (I) and the xanthene colorant to obtain the colorant dispersion of the present invention.
That is, in the method for producing a colored resin composition for color filter according to the present invention, the colorant represented by the general formula (I), the xanthene colorant, the urethane dispersant, the alkali soluble resin, and A functional monomer, an initiator, and a solvent, wherein the alkali-soluble resin is a resin having an acid value of 80 mgKOH / g or more and 300 mgKOH / g or less, and the solvent has a solubility of 0.2% of the color material at 23 ° C. It is a manufacturing method of the coloring resin composition for color filters which is a solvent of 1 (g / 10 ml solvent) or less,
The colorant represented by the general formula (I), the xanthene colorant, and the dispersant are added to the solvent, and the colorant represented by the general formula (I), and the xanthene colorant It is characterized by having the process of co-dispersing with a material.

  According to the method of producing a colorant dispersion liquid according to the present invention, when the colorant represented by the general formula (I) and the xanthene colorant are codispersed, the cation contained in the colorant is The colorant represented by the general formula (I) and the xanthene colorant are combined by surface modification of the xanthene colorant by π-π interaction, electrical interaction, or acid-base interaction. The dispersion proceeds in the above state, whereby the dispersibility is improved, and it is presumed that the heat resistance and the light resistance are also excellent.

  In addition, according to the method for producing a colorant dispersion according to the present invention, the sulfonate of a xanthene-based coloring material having a sulfonate can be favorably dispersed without converting it into a sulfo group. From the viewpoint of dispersion stability, the colorant dispersion according to the present invention preferably uses a lake color material containing a xanthene dye and a polyaluminum chloride as the xanthene color material.

2. Color filter The color filter according to the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is the colored resin composition according to the present invention It has a colored layer formed by curing an object.

  Such a color filter according to the present invention 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 invention. According to FIG. 1, the color filter 10 of the present invention has 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 invention is a colored layer formed by curing the colored resin composition for a color filter according to the present invention.
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.
Although the thickness of the said colored layer is suitably controlled by adjusting solid content concentration, viscosity, etc. of a coating method and a coloring resin composition, it is preferable normally that it is the range of 1-5 micrometers.

The said colored layer can be formed by the following method, for example, when a colored resin composition is a photosensitive resin composition.
First, the above-mentioned colored resin composition for color filter of the present invention is applied to a transparent substrate described later using a coating method such as a spray coating method, dip coating method, bar coating method, coal coating method, spin coating method or die coating method. To form a wet coating.
Next, the wet coating film is dried using a hot plate, an oven or the like, exposed to light through a mask of a predetermined pattern, and photopolymerized with an alkali-soluble resin, a polyfunctional monomer, etc. It is a photosensitive coating film. As a light source used for exposure, ultraviolet rays, such as a low pressure mercury lamp, a high pressure mercury lamp, and 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.
Further, heat treatment may be performed to promote the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.

Next, development processing is performed using a developer, and the unexposed area is dissolved and removed to form a coating film in a desired 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 the development processing, washing of the developing solution and drying of the cured coating film of the colored resin composition are usually performed to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. There is no limitation in particular as heating conditions, According to the use of a coating film, it selects suitably.

  The chromaticity of the colored layer of the color filter may be appropriately adjusted according to the light source and the like, and is not particularly limited. For example, in the case of a blue colored layer, in the chromaticity (x, y) of the C light source, x is 0. It is preferable that 12 to 0.27 and y be in the range of 0.04 to 0.18.

(Light blocking part)
The light shielding portion in the color filter of the present invention is formed in a pattern on a transparent substrate to be 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 photolithography method, the printing method, the inkjet method etc. using the coloring resin composition for light-shielding parts can be mentioned.

The patterned light shielding portion can be manufactured, for example, by the following method.
First, a colored resin composition for light shielding part is applied on a transparent substrate by a known coating method such as spray coating, dip coating, bar coating, coal coating, spin coating, etc. to form a wet coating film. Do.
Next, the wet coating film is dried using a hot plate, an oven or the like, and then exposed to light through a mask having a predetermined pattern. As a light source used for exposure, ultraviolet rays, such as a low pressure mercury lamp, a high pressure mercury lamp, and 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.
Further, heat treatment may be performed to promote the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the black resin composition to be used, the thickness of the coating film, and the like.
Next, development processing is performed using a developer, and the unexposed area is dissolved and removed to form a coating film in a desired 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 the development processing, washing of the developing solution and drying of the cured coating film of the black resin composition are usually performed to form a resin black matrix. In addition, you may heat-process in order to fully harden a coating film after image development processing. There is no limitation in particular as heating conditions, According to the use of a coating film, it selects suitably.

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

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for general color filters can be used. Specifically, transparent non-flexible rigid material such as quartz glass, non-alkali glass, synthetic quartz plate or the like, or transparent transparent flexible film such as transparent resin film, resin plate for optics, flexible glass etc. Materials are included.
In the present invention, a substrate having a polar group on the surface is preferred from the viewpoint of adhesion to the colored resin composition. The substrate having a polar group on the surface means that the material of the substrate itself may have a polar group, such as glass, and it is a resin film having a polar group introduced by subjecting the surface to a hydrophilic treatment or the like. It may be.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, a thing about 100 micrometers-about 1 mm can be used, for example.
In the color filter of the present invention, 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, alignment protrusions, columnar spacers and the like are formed. May be

3. Display Device The display device according to the present invention is characterized by having the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device and an organic light emitting display device.

[Liquid crystal display device]
The liquid crystal display device is characterized by including the above-described color filter according to the present invention, an opposing substrate, and a liquid crystal layer formed between the color filter and the opposing substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device. As exemplified in FIG. 2, the liquid crystal display device 40 includes a color filter 10, an opposing substrate 20 having a TFT array substrate and the like, and a liquid crystal layer 30 formed between the color filter 10 and the opposing substrate 20. Have.
The liquid crystal display device of the present invention 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 invention 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 invention, 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 invention.
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 invention.

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.

[Organic light emitting display]
The organic light emitting display device is characterized by including the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display will be described with reference to the drawings. FIG. 3 is a schematic cross-sectional view showing an example of the organic light emitting display device. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention has a color filter 10 and an organic light emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitting body 80.

As a method of laminating the organic light emitting body 80, for example, 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 are sequentially formed on the upper surface of the color filter. The method, the method of bonding the organic light-emitting body 80 formed on another substrate on the inorganic oxide film 60, etc. are mentioned. 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 in the organic light emitting body 80 can be appropriately selected from other known constitutions. The organic light emitting display device 100 manufactured in this manner is applicable to, for example, a passive drive type organic EL display and an active drive type organic EL display.
The organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be generally known as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be specifically described by way of examples. These descriptions do not limit the present invention.
In addition, the average dispersion particle size of the particles contained in each dispersion liquid is suitably diluted to about 100 to 1000 times with propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and the laser light scattering particle size distribution The particle size distribution was measured at 23 ° C. by a dynamic light scattering method using a scale (Nanotrac particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.), and the 50% average particle size was determined by volume conversion (MV) It is a value. In the colorant dispersion, the average dispersed particle diameter is estimated to be the average dispersed particle diameter of the association of the colorant and the dispersant.
The mass average molecular weight is a value determined as a standard polystyrene equivalent by gel permeation chromatography (GPC).
The acid value (mg KOH / g) is a value determined by potentiometric titration according to JIS K 0070.

Synthesis Example 1: Synthesis of Intermediate 1
Wako Pure Chemical Industries, Ltd. product 1-iodonaphthalene 15.2 g (60 mmol), Mitsui Chemicals Co., Ltd. product norbornane diamine (NBDA) (CAS No. 56602-77-8) 4.
63 g (30 mmol), sodium-tert-butoxide 8.07 g (84 mmol), Aldrich 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl 0.09 g (0.2 mmol), Wako Pure Chemical Industries, Ltd. It dispersed in 0.021 g (0.1 mmol) of palladium acetate and 30 mL of xylene, and was made to react at 130-135 degreeC for 48 hours. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with water. Then, the resultant was dried over magnesium sulfate and concentrated to obtain 8.5 g (yield 70%) of an intermediate 1 represented by the following chemical formula (1).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 407 (M + H),
Elemental analysis value: CHN actual measurement value (85.47%, 8.02%, 6.72%); theoretical value (8
5.26%, 8.11%, 6.63%)

Synthesis Example 2: Synthesis of Intermediate 2
Intermediate 1 8.46 g (20.8 mmol), 13.5 g (41.6 mmol) of 4,4′-bis (dimethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 mL of toluene were added, and the mixture was stirred at 45 to 50 ° C. 6.38 g (51.5 mmol) of phosphorus oxychloride manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise, and the mixture was refluxed for 2 hours and cooled. After completion of the reaction, the toluene was decanted. The resinous precipitate was dissolved by adding 40 mL of chloroform, 40 mL of water and concentrated hydrochloric acid, and the chloroform layer was separated. The chloroform layer was washed with water, dried over magnesium sulfate and concentrated. To the concentrate, 65 mL of ethyl acetate was added and refluxed. After cooling, the precipitate was filtered to obtain 15.9 g (yield 70%) of an intermediate 2 (BB7-Nb-dimer) represented by the following chemical formula (2).
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%)

Synthesis Example 3 Synthesis of Color Material A
Intermediate 2 5.00 g (4.58 mmol) was added to 300 ml of water and dissolved at 90 ° C. to give an intermediate 2 solution. Next, 10.44 g (3.05 mmol) of phosphotungstic acid n hydrate H ₃ [PW ₁₂ O ₄₀ ] n H ₂ O (n = 30) manufactured by Japan Inorganic Chemical Industry Co., Ltd. is added to 100 mL of water and stirred at 90 ° C. And prepared an aqueous solution of phosphotungstic acid. An aqueous solution of phosphotungstic acid was mixed with the above Intermediate 2 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 g of a coloring material A represented by the following chemical formula (3) (yield: 98%).
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%)
In addition, it was confirmed by ³¹ P-NMR that the polyacid structure of phosphotungstic acid is maintained even after it becomes the coloring material A.

<Evaluation: Insoluble in solvent>
In a 20 mL sample tube bottle, 0.1 g of the above-mentioned coloring material A was put into 10 ml of PGMEA, covered, shaken well for 20 seconds, and allowed to stand for 10 minutes. 5 g of this supernatant was filtered to remove insolubles. The absorption spectrum of the obtained filtrate was measured using a 1 cm cell with a UV-visible spectrophotometer (UV-2500PC manufactured by Shimadzu Corporation), and the absorbance at the maximum absorption wavelength of each coloring agent was determined.
If the absorbance measured under the above conditions is 2 or less, it can be said that the substance does not substantially dissolve.
As a result, the absorbance of the coloring material A was 2 or less, and the solubility to PGMEA was 0.1 (g / 10 ml solvent) or less.

Production Example 1: Preparation of Colorant Dispersion (A)
In 30 ml mayonnaise bottles, 3.0 parts by mass of the color material A of Synthesis Example 1, byk 161 (manufactured by Bick Chemie, urethane type dispersant, solid content 30% by mass, amine value 36.7 mg KOH / g, acid value 0 mg KOH / g) Add 0 parts by mass, 21.0 parts by mass of PGMEA, and 30 parts by mass of zirconia beads of 2 mm in diameter, pre-disintegrate for 1 hour with a paint shaker (Asada Iron & Steel Co.), transfer the solution to another 30 ml mayonnaise bottle, 30 parts by mass of 0.1 mm zirconia beads were added and shaken for 5 hours with a paint shaker to obtain a color material dispersion (A). The average dispersed particle size of the particles in the colorant dispersion (A) was 123 nm.
In addition, the acid value and amine value of a dispersing agent are the value converted into solid content.

Preparation Example 2 Preparation of Colorant Dispersion (B)
In Production Example 1, 6.0 parts by mass of byk 170 (urethane dispersant, manufactured by Bick Chemie Co., urethane based dispersant, solid content 30 mass%, acid value 36.7 mg KOH / g, amine value 0 mg KOH / g) was used instead of byk 161 In the same manner as in Production Example 1, a colorant dispersion liquid (B) was obtained. The average dispersed particle size of the particles in the colorant dispersion (B) was 117 nm.
In addition, the acid value and amine value of a dispersing agent are the value converted into solid content.

Preparation Example 3 Preparation of Colorant Dispersion (C)
Production Example 2 is the same as Production Example 2 except that 2.4 parts by mass of coloring material A and 0.6 parts by mass of commercially available dioxazine violet pigment (PV23) are used instead of 3.0 parts by mass of coloring material A. , Colorant dispersion (C) was obtained. The average dispersed particle size of the particles in the colorant dispersion (C) was 95 nm.

Comparative Preparation Example 1: Preparation of Colorant Dispersion (D)
(1) Preparation of Dispersant Solution In a 225 mL mayonnaise bottle, 37.8 parts by mass of PGMEA and 55.4 parts by mass of Disperbyk LPN 6919 (manufactured by Bick Chemie, acrylic dispersant, 60% nonvolatile content) are placed, and then phenylphosphonic acid Add 6.7 parts by mass (PPA, manufactured by Nissan Chemical Industries, Ltd.) (0.6 molar equivalents relative to the amino group of the block copolymer), and stir for 30 minutes at room temperature to obtain a dispersant solution (solid content: 40%) Was prepared.
At this time, the amino group possessed by LPN6919 is salt formed by the acid-base reaction with the phosphonic acid group of PPA.
(2) Preparation of Colorant Dispersion (D) In Production Example 1, 4.5 parts by mass of the dispersant solution prepared in the above (1) was used instead of byk 161, and 19.5 parts by mass of PGMEA was used. In the same manner as in Production Example 1, a colorant dispersion liquid (D) of a comparative example was obtained. The average dispersed particle size of the particles in the colorant dispersion (D) was 114 nm.

Comparative Preparation Example 2: Preparation of Colorant Dispersion (E)
In the same manner as in Production Example 1 except that 4.5 parts by mass of BYK-N 21116 (manufactured by Bick Chemie, non-volatile content 40%) is used instead of byk 161 and PGMEA is 19.5 parts by mass. A colorant dispersion (E) of a comparative example was obtained. The average dispersed particle size of the particles in the colorant dispersion (E) was 121 nm.

  Table 1 below shows combinations of colorants and dispersants contained in the colorant dispersions (A) to (E).

Production Example 4 Synthesis of Alkali-Soluble Resin A
250 parts by mass of PGMEA is charged in a polymerization tank, and after raising the temperature to 100 ° C. under a nitrogen atmosphere, 13.9 parts by mass of methacrylic acid, 36.1 parts by mass of methyl methacrylate, 50.0 parts of cyclohexyl methacrylate (CHMA) Parts, 6 parts by mass of Perbutyl O (manufactured by NOF Corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction is continued while maintaining the temperature at 100 ° C., and 2 parts after completion of the dropping of the mixture for forming the main chain, 0.1 part by mass of p-methoxyphenol is added as a polymerization inhibitor to stop the polymerization, and alkali solubility is achieved. A PGMEA solution (solid content 40% by mass) of resin A was obtained. The weight average molecular weight of the said alkali-soluble resin A was 9,000, and the acid value was 90 mgKOH / g.

Preparation Example 5 Preparation of Alkali-Soluble Resin B
250 parts by mass of PGMEA is charged in a polymerization tank, and after raising the temperature to 100 ° C. under a nitrogen atmosphere, 13.9 parts by mass of methacrylic acid, 86.1 parts by mass of methyl methacrylate, and Perbutyl O (manufactured by NOF CORPORATION) 6 parts by mass and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction is continued while maintaining the temperature at 100 ° C., and 2 parts after completion of the dropping of the mixture for forming the main chain, 0.1 part by mass of p-methoxyphenol is added as a polymerization inhibitor to stop the polymerization, and alkali solubility is achieved. A PGMEA solution (solid content: 40% by mass) of resin B was obtained. The weight average molecular weight of the said alkali-soluble resin B was 9,000, and the acid value was 90 mgKOH / g.

Preparation Example 6 Preparation of Alkali-Soluble Resin C
250 parts by mass of PGMEA is charged in a polymerization tank, and after raising the temperature to 100 ° C. under a nitrogen atmosphere, 13.9 parts by mass of methacrylic acid, 36.1 parts by mass of methyl methacrylate, 50.0 parts of benzyl methacrylate (BzMA) Parts, 6 parts by mass of Perbutyl O (manufactured by NOF Corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction is continued while maintaining the temperature at 100 ° C., and 2 parts after completion of the dropping of the mixture for forming the main chain, 0.1 part by mass of p-methoxyphenol is added as a polymerization inhibitor to stop the polymerization, and alkali solubility is achieved. A PGMEA solution (solid content 40% by mass) of resin C was obtained. The weight average molecular weight of the said alkali-soluble resin C was 9,000, and the acid value was 90 mgKOH / g.

Preparation Example 7 Preparation of Alkali-Soluble Resin D
250 parts by mass of PGMEA is charged in a polymerization tank, and after raising the temperature to 100 ° C. under a nitrogen atmosphere, 13.9 parts by mass of methacrylic acid, 36.1 parts by mass of methyl methacrylate, and dicyclopentanyl methacrylate (DCPMA) 50 .0 parts by mass, 6 parts by mass of Perbutyl O (manufactured by NOF Corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction is continued while maintaining the temperature at 100 ° C., and 2 parts after completion of the dropping of the mixture for forming the main chain, 0.1 part by mass of p-methoxyphenol is added as a polymerization inhibitor to stop the polymerization, and alkali solubility is achieved. A PGMEA solution (solid content 40% by mass) of resin D was obtained. The weight average molecular weight of the said alkali-soluble resin D was 9,000, and the acid value was 90 mgKOH / g.

Preparation Example 8 Preparation of Alkali-Soluble Resin E
In a polymerization tank, 250 parts by mass of PGMEA is charged, and after raising the temperature to 100 ° C. under a nitrogen atmosphere, 15.4 parts by mass of methacrylic acid, 34.6 parts by mass of methyl methacrylate, 50.0 parts by mass of cyclohexyl methacrylate, Six parts by mass of Perbutyl O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction is continued while maintaining the temperature at 100 ° C., and 2 parts after completion of the dropping of the mixture for forming the main chain, 0.1 part by mass of p-methoxyphenol is added as a polymerization inhibitor to stop the polymerization, and alkali solubility is achieved. A PGMEA solution (solid content 40% by mass) of resin E was obtained. The weight average molecular weight of the said alkali-soluble resin E was 9,000, and the acid value was 100 mgKOH / g.

Preparation Example 9 Preparation of Alkali-Soluble Resin F
250 parts by mass of PGMEA is charged in a polymerization tank, and the temperature is raised to 100 ° C. under a nitrogen atmosphere, and then 20.0 parts by mass of methacrylic acid, 30.0 parts by mass of methyl methacrylate, 50.0 parts by mass of cyclohexyl methacrylate, Six parts by mass of Perbutyl O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction is continued while maintaining the temperature at 100 ° C., and 2 parts after completion of the dropping of the mixture for forming the main chain, 0.1 part by mass of p-methoxyphenol is added as a polymerization inhibitor to stop the polymerization, and alkali solubility is achieved. A PGMEA solution (solid content 40% by mass) of resin F was obtained. The weight average molecular weight of the said alkali-soluble resin F was 9,000, and the acid value was 130 mgKOH / g.

Preparation Example 10 Preparation of Alkali-Soluble Resin G
250 parts by mass of PGMEA is charged in a polymerization tank, and after raising the temperature to 100 ° C. under a nitrogen atmosphere, 27.7 parts by mass of methacrylic acid, 22.3 parts by mass of methyl methacrylate, 50.0 parts by mass of cyclohexyl methacrylate, and Six parts by mass of Perbutyl O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction is continued while maintaining the temperature at 100 ° C., and 2 parts after completion of the dropping of the mixture for forming the main chain, 0.1 part by mass of p-methoxyphenol is added as a polymerization inhibitor to stop the polymerization, and alkali solubility is achieved. A PGMEA solution (solid content 40% by mass) of resin E was obtained. The mass average molecular weight of the said alkali-soluble resin E was 9,000, and the acid value was 180 mgKOH / g.

Preparation Example 11 Preparation of Alkali-Soluble Resin H
250 parts by mass of PGMEA is charged in a polymerization tank, and after raising the temperature to 100 ° C. under a nitrogen atmosphere, 19.4 parts by mass of methacrylic acid, 20.6 parts by mass of methyl methacrylate, 50.0 parts by mass of cyclohexyl methacrylate, and perbutyl 6 parts by mass of O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction was continued while maintaining the temperature at 100 ° C., and 2 parts after completion of the dropping of the mixture for forming a main chain, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
Next, while blowing in air, 10 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound is added, and the temperature is raised to 110 ° C. 0.8 parts by mass of triethylamine is then added and 110 ° C. for 15 hours Addition reaction was performed to obtain a PGMEA solution (solid content: 40% by mass) of the alkali-soluble resin E. The weight average molecular weight of the said alkali-soluble resin E was 9,000, and the acid value was 90 mgKOH / g.

Comparative Preparation Example 3: Preparation of Alkali-Soluble Resin I
In a polymerization tank, 250 parts by mass of PGMEA is charged, and after raising the temperature to 100 ° C. under a nitrogen atmosphere, 10.8 parts by mass of methacrylic acid, 39.2 parts by mass of methyl methacrylate, 50.0 parts by mass of cyclohexyl methacrylate, Six parts by mass of Perbutyl O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction is continued while maintaining the temperature at 100 ° C., and 2 parts after completion of the dropping of the mixture for forming the main chain, 0.1 part by mass of p-methoxyphenol is added as a polymerization inhibitor to stop the polymerization, and alkali solubility is achieved. A PGMEA solution (solid content 40% by mass) of resin G was obtained. The weight average molecular weight of the said alkali-soluble resin G was 9,000, and the acid value was 70 mgKOH / g.

Preparation Example 1 Preparation of Photosensitive Binder Component (CR-1)
31.4 parts by weight of a PGMEA solution (solid content 40% by mass) of the alkali-soluble resin A obtained in Production Example 4; Succinic anhydride-modified dipentaerythritol penta (meth) acrylate (ALONIX M520 (TONA SYNTHESIS, as a polyfunctional monomer) ) 18.8 parts by mass, 5.9 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF, “IRGACURE 907”) as a photoinitiator. After adding 2.0 parts by mass of diethylthioxanthone ("DETX-S" manufactured by Nippon Kayaku Co., Ltd.), 0.8 parts by mass of Irganox 1010 as an antioxidant, and 41.2 parts by mass of PGMEA as a solvent, The mixture was mixed to obtain a photosensitive binder component (CR-1).

Preparation Examples 2 to 8: Preparation of Photosensitive Binder Components (CR-2) to (CR-8)
The same procedure as in Preparation Example 1 was repeated, except that PGMEA solutions (solid content 40% by mass) of alkali soluble resins B to H obtained in Preparation Examples 5 to 11 were used instead of Alkali soluble resin A. The photosensitive binder components (CR-2) to (CR-8) of Preparation Examples 2 to 8 were obtained.

Preparation Example 9 Preparation of Photosensitive Binder Component (CR-9)
A photosensitive binder component (CR) of Preparation Example 9 (CR) was prepared in the same manner as in Preparation Example 1 except that the polyfunctional monomer was changed to dipentaerythritol hexaacrylate ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.). -9) was obtained.

Comparative Preparation Example 1: Preparation of Photosensitive Binder Component (CR-10)
Comparative preparation in the same manner as in Preparation Example 1 except that PGMEA solution (solid content: 40% by mass) of alkali soluble resin I obtained in Comparative Preparation Example 3 was used instead of alkali soluble resin A. The photosensitive binder component (CR-10) of Example 1 was obtained.

Example 1 Preparation of Colored Resin Composition
8.03 parts by mass of the color material dispersion (A) of Production Example 1, 5.79 parts by mass of the photosensitive binder component (CR-1) of Preparation Example 1, 0.007 parts by mass of Megafac R08MH (manufactured by DIC) 6.18 parts by mass of PGMEA was added and stirred, followed by filtration through a 0.25 μm mesh to obtain a colored resin composition of Example 1.

(Examples 2 to 13: Preparation of Colored Resin Composition)
Colored resin compositions of Examples 2 to 13 were obtained in the same manner as in Example 1 except that the combination of the coloring material dispersion and the photosensitive binder component in Example 1 was changed as shown in Table 2.

(Example 14: Preparation of a colored resin composition)
8.03 parts by mass of the color material dispersion (A) of Production Example 1, 5.79 parts by mass of the photosensitive binder component (CR-1) of Preparation Example 1, 0.007 parts by mass of Megafac R08MH (manufactured by DIC) 0.036 parts by mass of KBM 503 (Shin-Etsu Chemical Co., Ltd., silane coupling agent) and 6.18 parts by mass of PGMEA were added and stirred, followed by filtration through a 0.25 μm mesh to obtain a colored resin composition of Example 14.

Example 15 Preparation of Colored Resin Composition
A colored resin composition of Example 15 was obtained in the same manner as in Example 14 except that the amount of KBM 503 added was changed to 0.072 parts by mass.

(Examples 16 to 17: Preparation of Colored Resin Composition)
Colored resin compositions of Examples 16 to 17 in the same manner as in Examples 14 to 15 except that the coloring material dispersion (B) was used instead of the coloring material dispersion (A) in Examples 14 to 15, respectively. I got

(Example 18: Preparation of a colored resin composition)
A colored resin composition of Example 18 is obtained in the same manner as in Example 1 except that the coloring material dispersion (C) of Production Example 3 is used instead of the coloring material dispersion (A) in Example 1. The

Comparative Examples 1-2: Preparation of Comparative Colored Resin Composition
Comparative Example 1 in the same manner as Example 1, except that the color material dispersions (D) to (E) of Comparative Production Examples 1 and 2 were used instead of the color material dispersion (A) in Example 1, respectively. A colored resin composition of ̃2 was obtained.

Comparative Example 3: Preparation of Comparative Colored Resin Composition
In Example 2, except using the photosensitive binder component (CR-10) of Comparative Production Example 1 in place of the photosensitive binder (CR-1), the coloring of Comparative Example 3 is carried out in the same manner as Example 2. A resin composition was obtained.

<Viscosity stability evaluation>
The viscosity of the colored resin composition obtained in Examples and Comparative Examples was measured immediately after dispersion and after storage for 6 months at normal temperature (25 ° C.). The viscosity was measured at 25.0 ± 1.0 ° C. using a vibrating viscometer (VM-200T2 manufactured by Seconik), and a value 30 seconds after the start of the measurement was adopted.
The viscosity immediately after dispersion was compared with the viscosity after storage for 6 months, and those having a viscosity change of 5% or less were regarded as A, and those having a viscosity change exceeding 5% as B. The results are shown in Table 1. If the viscosity change is within 5%, it is evaluated that the viscosity stability is excellent.

<Heat resistance evaluation>
About the colored resin composition of an Example and a comparative example, it apply | coated using the spin coater on the glass substrate (NH techno glass Co., Ltd. product, "NA35") of thickness 0.7 mm, respectively. Then, it heat-dried on the 80 degreeC hotplate for 3 minutes. A cured film (blue colored film) was obtained by irradiating ultraviolet light of 60 mJ / cm ² using an ultrahigh pressure mercury lamp without using a photomask. The film thickness after drying and curing (T; μm) was such that the chromaticity after post-baking described later was y = 0.092. The chromaticity (L ₀ , a ₀ , b ₀ ) of this colored film was measured. Thereafter, the glass plate on which the colored film was formed was post-baked in a clean oven at 230 ° C. for 75 minutes, and the chromaticity (L ₁ , a ₁ , b ₁ ) of the obtained colored film was measured again.
In addition, the chromaticity of a colored film was measured using Olympus Co., Ltd. "microspectroscopy measuring apparatus OSP-SP200".
The chromaticity change of the colored film before and after the post-baking was evaluated by the following equation. The results are shown in Table 2.
ΔEab = {(L ₁ −L ₀ ) ² + (a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² } ^1/2
(Heat resistance evaluation criteria)
A: ΔEab was less than 3.
B: ΔEab was 3 or more and less than 5.
C: ΔEab was 5 or more and less than 10.
D: ΔEab was 10 or more.
If heat resistance evaluation is A or B, it is evaluated that it is excellent in heat resistance.

<Development resistance evaluation>
The colored resin compositions of Examples and Comparative Examples were each coated on a glass substrate having a thickness of 0.7 mm ("NA 35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater. After drying by heating on a hot plate at 80 ° C. for 3 minutes, ultraviolet light of 40 mJ / cm ² was irradiated using an extra-high pressure mercury lamp. The film thickness at this point of time is measured to obtain T1 (μm). Thereafter, shower development was performed using a 0.05% by mass aqueous solution of potassium hydroxide as an alkaline developer. The film thickness after development is measured to obtain T2 (μm). T2 / T1 × 100 (%) was calculated, A for 97% or more, B for 95% or more and less than 97%, and C for less than 95%. The results are shown in Table 2. If the evaluation result is A or B, it is evaluated that the development resistance is excellent.

(Optical characteristics evaluation)
The colored resin compositions of Examples and Comparative Examples immediately after preparation were each coated on a glass substrate having a thickness of 0.7 mm ("NA 35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater. After drying by heating on a hot plate at 80 ° C. for 3 minutes, ultraviolet light of 60 mJ / cm ² was irradiated using an extra-high pressure mercury lamp. Thereafter, post-baking was carried out for 75 minutes in a clean oven at 230 ° C., and the obtained colored film chromaticity (x, y) and luminance (Y) were measured. The film thickness after drying and curing (T; μm) was such that the chromaticity after post-baking described later was y = 0.092. The chromaticity and the brightness were measured using “Microspectroscopic light measuring apparatus OSP-SP200” manufactured by Olympus Corporation. The results are shown in Table 2.

[Result Summary]
The colored resin compositions of Examples 1 to 18 containing a coloring material represented by the following general formula (I), a urethane dispersant and an alkali-soluble resin having an acid value of 80 mg KOH / g to 300 mg KOH / g are The dispersion stability of the colorant containing the colorant represented by the general formula (I) was excellent, the heat resistance was high, and the developability was excellent. Among the examples, the colored resin compositions of Examples 6 to 12 using an alkali-soluble resin having an acid value of 100 mg KOH / g or more proved to be particularly excellent in heat resistance. Moreover, it became clear that the coloring layer using the coloring resin composition of Example 12 which has an ethylenic double bond in alkali-soluble resin has the especially outstanding resistance with respect to an alkaline developing solution. Moreover, when the colored resin composition of Example 12 was stored at normal temperature for 3 months, and the colored layer was formed using the colored resin composition after the storage, the adhesion to the substrate was compared with other examples. It became clear that it was also excellent and the board | substrate adhesiveness over time was also excellent.

DESCRIPTION OF SYMBOLS 1 transparent substrate 2 light-shielding part 3 colored layer 10 color filter 20 opposing substrate 30 liquid crystal layer 40 liquid crystal display device 50 organic protective layer 60 inorganic oxide film 71 transparent anode 72 hole injection layer 73 hole transport layer 74 light emitting layer 75 electron injection layer 76 cathode 80 organic light emitter 100 organic light emitting display device 201 divalent or higher cation 202 divalent or higher anion 203 ion binding 210 molecular association

Claims (11)

It contains a coloring material represented by the following general formula (I), a urethane dispersant, an alkali soluble resin, a polyfunctional monomer, an initiator, and a solvent,
The alkali-soluble resin is a resin having an acid value of 90 mg KOH / g or more and 300 mg KOH / g or less,
The coloring resin composition for color filters whose said solvent is a solvent whose solubility of the said color material in 23 degreeC is 0.1 (g / 10 ml solvent) or less.
(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- contains at least tungsten .R ⁱ to R ^v indicating the c-valent poly anion each independently represent a hydrogen atom, which may have an optionally substituted alkyl group or a substituted aryl group, and R ⁱⁱ R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure, Ar ¹ represents a divalent aromatic group which may have a substituent, and a plurality of R ^{i to} R ^v and Ar ¹ may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. The plurality of e may be the same or different. )   The coloring resin composition for color filters of Claim 1 whose acid value of the said urethane type dispersing agent is 10 mgKOH / g or more.   The coloring resin composition for color filters of Claim 1 whose amine value of the said urethane type dispersing agent is 10 mgKOH / g or more.   The colored resin composition for color filters according to any one of claims 1 to 3, wherein the alkali-soluble resin is a resin having an ethylenic double bond.   The colored resin composition for color filters according to any one of claims 1 to 4, wherein the alkali-soluble resin further has a hydrocarbon ring.   The coloring resin composition for color filters as described in any one of Claims 1 thru | or 5 whose content rate of a silane coupling agent is 1 mass% or less with respect to the total solid in a coloring resin composition.   Furthermore, the coloring resin composition for color filters as described in any one of the Claims 1 thru | or 6 containing 1 or more types selected from a dioxazine type coloring material and a xanthene type coloring material.   The colored resin composition for color filters according to claim 7, wherein the xanthene colorant is a xanthene lake colorant. Contains a coloring material represented by the following following general formula (I), the a xanthene colorant, a urethane-based dispersant, an alkali-soluble resin, the polyfunctional monomer and initiator, and a solvent, the alkali-soluble The color filter, wherein the resin is a resin having an acid value of 90 mgKOH / g or more and 300 mgKOH / g or less, and the solvent is a solvent whose solubility of the color material at 23 ° C. is 0.1 (g / 10 ml solvent) or less A method for producing a colored resin composition for use in
The colorant represented by the general formula (I), the xanthene colorant, and the dispersant are added to the solvent, and the colorant represented by the general formula (I), and the xanthene colorant The manufacturing method of the colored resin composition for color filters which has the process of co-dispersing with material.
(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- contains at least tungsten .R ⁱ to R ^v indicating the c-valent poly anion each independently represent a hydrogen atom, which may have an optionally substituted alkyl group or a substituted aryl group, and R ⁱⁱ R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure, Ar ¹ represents a divalent aromatic group which may have a substituent, and a plurality of R ^{i to} R ^v and Ar ¹ may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. The plurality of e may be the same or different. )   A color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is a colored resin composition for a color filter according to any one of claims 1 to 8. A color filter characterized by having a colored layer formed by curing a substance.   A display device comprising the color filter according to claim 10.