TW201833243A - Color material dispersion liquid for color filter, color resin composition for color filter, color filter and display device - Google Patents

Abstract

Provided is a color resin composition for a color filter, which is configured to have high solvent resolubility and can form a color layer having a wide blue color reproduction range. Disclosed is a color resin composition for a color filter, comprising color materials, a dispersant, a binder component and a solvent, wherein the color materials include a blue color material, a violet color material and C.I. Pigment Green 59, and the dispersant is a polymer having a specific constitutional unit.

Description

 Colored material dispersion for color filter, colored resin composition for color filter, color filter, and display device  

The present invention relates to a color material dispersion liquid for a color filter, a colored resin composition for a color filter, a color filter, and a display device.

In recent years, with the development of personal computers, especially the development of portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs) has also increased, and the market for liquid crystal displays has been expanding. In addition, an organic light-emitting display device similar to an organic EL display having high visibility by self-luminescence has recently attracted attention as a next-generation image display device. In view of the performance of such image display devices, it is strongly desired to further improve the image quality or power consumption, such as improvement in contrast or color reproducibility.

Conventional display devices are mostly based on sRGB (IEC61966-2-1) of the international standard specification of color space. However, in order to require a performance closer to the physical object and to further improve the color reproducibility, Adobe RGB corresponding to a wider color reproduction domain than sRGB, or DIC (Digital Cinema Initiatives) or BT having a wider color reproduction domain is required. (Broadcasting Service Television). The demand for display devices of 2020 is increasing.

These liquid crystal display devices or organic light emitting display devices use color filters. For example, the color image of the liquid crystal display device is formed by directly coloring the light of the color filter into the color of each pixel constituting the color filter, and combining the light of the colors to form a color image. As a light source at this time, in addition to the conventional cold cathode tube, there are cases where an organic light-emitting element of white light emission or an inorganic light-emitting element of white light emission is used. Further, the organic light-emitting display device uses a color filter for color adjustment or the like.

Therefore, for the color filter, high luminance or high contrast, improvement in color reproducibility, and the like are expected to increase.

In the color filter, the area where the three points of the red, green, and blue pixels are connected is the limit of the reproducible color. That is, a color filter having a larger triangular shape composed of three points of red, green, and blue pixels has a wider range of colors that can be reproduced by the display device on the screen.

Therefore, in order to achieve a color space having a wider color reproduction domain, it is required to achieve a high color density chromaticity for each color pixel.

Patent Document 1 discloses a color filter which is a liquid crystal display device for a white LED light source having a color reproduction domain satisfying the NTSC standard, and is characterized in that it penetrates the 550 nm of the blue pixel in the color filter. The transmittance is 1% or less, and the maximum transmittance wavelength of visible light penetrating the color filter is in the range of 470 nm to 500 nm; the blue coloring composition forming the blue pixel described above contains CI Pigment Blue 15: 6 or at least one blue pigment of CI Pigment Blue 15:3, and at least one green pigment of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58.

 [Previous Technical Literature]    [Patent Literature]  

Patent Document 1: Japanese Patent Laid-Open Publication No. 2012-220817

In the blue pixel, if the blue color material concentration in the pixel is increased in order to achieve a high color density, there is a problem that the solvent resolubility is extremely deteriorated.

That is, in the manufacturing process of the color filter, it is required that the solid content of the dried colored resin composition is once again dissolved in the solvent and the solvent is resolubilized. For example, when the coating is applied by a die coater, if a colored resin composition adheres to the tip end of the lip, a cured product is formed by drying. However, when the coating is restarted, the cured product is less likely to be dissolved in the colored resin composition. Then, the cured product on the lip is partially peeled off and easily adheres to the coloring layer of the color filter, which is a cause of foreign matter defects. In particular, when the color material concentration of the colored resin composition is increased, the solvent resolubility is liable to be insufficient, and there is a problem that the yield due to the occurrence of the foreign matter in the manufacturing process of the color filter is lowered.

It is presumed that the blue color material used for the blue pixel of the color filter generally has a tendency to have a very poor solvent resolubility.

Further, the colored resin composition obtained by the technique of Patent Document 1 also has a problem that the solvent resolubility is poor.

An object of the present invention is to provide a color material dispersion liquid for a color filter which is excellent in dispersion stability of a color material, has improved solvent resolubility, and can form a colored resin composition in which a blue reproduction domain is enlarged, and is used for the color filter. A colored resin composition for a color filter which is capable of forming a color filter having a blue color reproduction domain and a coloring layer which is improved in re-solubility of a color material, and a colored resin composition for color filter, and excellent color reproducibility. A color filter that is improved in productivity; and a display device that is excellent in color reproducibility and improved in productivity by using the color filter.

The color material dispersion liquid for a color filter according to the present invention is a color material, a dispersant, and a color material dispersion liquid with a solvent, wherein the color material contains a blue color material, a purple color material, and a CI color green 59; The dispersant is a polymer having the following structural unit represented by the general formula (I).

Further, the colored resin composition for a color filter of the present invention contains a color material, a dispersant, a binder component, and a solvent; and the color material contains a blue color material, a purple color material, and a CI color green 59. The above dispersant is a polymer having the following structural unit represented by the general formula (I).

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ^{3 are} also They can be bonded to each other to form a ring structure.)

The color filter of the present invention includes at least a substrate and a coloring layer provided on the substrate, wherein at least one of the colored layers belongs to the hardening of the colored resin composition for a color filter of the present invention. The color layer of the object.

The present invention provides a display device characterized by having the above-described color filter of the present invention.

According to the present invention, it is possible to provide a color material dispersion liquid for a color filter which is excellent in dispersion stability of a color material, has improved solvent resolubility, and can form a colored resin composition in which a blue reproduction domain is enlarged, and is used for the color filter. A colored resin composition for a color filter which is capable of forming a color filter having a blue color reproduction domain and a coloring layer which is improved in re-solubility of a color material, and a colored resin composition for color filter, and excellent color reproducibility. A color filter that is improved in productivity; and a display device that is excellent in color reproducibility and improved in productivity by using the color filter.

1‧‧‧Substrate

2‧‧‧Lighting Department

3‧‧‧Colored layer

10‧‧‧Color filters

20‧‧‧ opposite substrate

30‧‧‧Liquid 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‧‧‧Lighting layer

75‧‧‧Electronic injection layer

76‧‧‧ cathode

80‧‧‧Organic emitters

100‧‧‧Organic light-emitting display device

Fig. 1 is a schematic view showing an example of a color filter of the present invention.

Fig. 2 is a schematic view showing an example of a display device of the present invention.

Fig. 3 is a schematic view showing another example of the display device of the present invention.

Hereinafter, the color material dispersion liquid for color filters, the coloring resin composition for color filters, the color filter, and the display device of the present invention will be described in detail.

Still, in the present invention, the light includes electromagnetic waves of wavelengths of visible and non-visible regions, and further includes radiation, and the radiation system includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.

In the present invention, the (meth)acrylic acid means acrylic acid and methacrylic acid, respectively, and the (meth)acrylic acid ester means acrylate and methacrylate, respectively.

Further, C.I. pigment blue is simply referred to as "PB", C.I. pigment purple is simply referred to as "PV", and C.I. pigment green is simply referred to as "PG".

 [Color material dispersion]  

The color material dispersion liquid for color filters of the present invention contains a color material, a dispersant, and a solvent, wherein the color material contains a blue color material, a purple color material, and CI color green 59; and the dispersant has The polymer of the constituent unit represented by the following general formula (I).

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ^{3 are} also They can be bonded to each other to form a ring structure.)

The color material dispersion liquid of the present invention is a combination of the above-mentioned specific color materials and a polymer having a structural unit represented by the general formula (I) as a dispersing agent, so that the dispersion stability of the color material is excellent, the solvent resolubility is improved, and A colored resin composition in which a blue reproduction domain is enlarged is formed.

The blue color material tends to deteriorate in solvent resolubility, but the reason for this is not known. When the color material concentration is increased, the solvent resolubility tends to be very poor. Further, with the blue color material, even if the color material concentration is increased, the expansion of the blue reproduction domain is limited and insufficient. As in Patent Document 1, when a blue color material and a green color material are mixed, the chromaticity of a high color density may be achieved, but the solvent resolubility is inferior. It is presumed that this is to achieve a high color density chromaticity in order to mix the blue color material and the green color material, and since the concentration of the color material in the composition must be increased, the solvent resolubility is deteriorated.

On the other hand, in the color material dispersion liquid of the present invention, a purple color material, a C.I. pigment green 59, and a dispersing agent which is specifically a polymer having a structural unit represented by the general formula (I) are used in combination with the blue color material.

In the present invention, C.I. Pigment Green 59 (hereinafter sometimes abbreviated as PG59), which is a color material, is monochromatic and has a blueish green color, and has a strong coloring power and a high luminance. The present inventors have found that if a purple color material is further combined in combination with such a PG59 and a blue color material, the content of the blue color material in the color material is suppressed, or the P/V ratio is suppressed ((the total mass of the color material in the composition) / / (total mass of solid content other than the color material in the composition), it is still possible to produce blue pixels covered in the blue color region of the above high color density. Therefore, it is suitable to use as a blue color material dispersion. Further, when the blue pixel is produced using PG59, the luminance tends to be higher than when the blue pixel is produced using PG58.

Further, since the polymer having the constituent unit represented by the following general formula (I) is used as a dispersing agent in combination with the specific color material combination described above, it is estimated that the specific color materials are firmly adsorbed to the general formula (I). The nitrogen portion contained in the unit is well dispersed, and the specific color material surrounded by the dispersing agent is easily washed away by the solvent having resolubility in a state of being adsorbed to the dispersing agent.

A colored resin composition for producing a blue pixel included in a blue color region of a high color density, which is capable of suppressing the content of the blue color material in the color material or suppressing P/V, and also having the above The role of a particular dispersant. By this, it is estimated that the coloring resin composition which can improve the solvent resolubility can be formed.

Further, since the total content of the color material components in the coloring resin composition for producing the blue pixel included in the blue color region of the high color density can be suppressed, the content of the binder component can be relatively increased, and The plate making property can be improved, and development defects can be easily suppressed. On the other hand, the development residue can be easily suppressed, and the adhesion to the substrate can be improved.

The color material dispersion liquid of the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components within the range not impairing the effects of the present invention.

Hereinafter, each component of the color material dispersion liquid of the present invention will be described in detail in order.

 <color material>  

In the present invention, the color material is characterized by containing a blue color material, a purple color material, and C.I. pigment green 59.

C.I. Pigment Green 59 (PG59) is an indigo zinc pigment.

PG59 is a chromaticity coordinate meter in the XYZ color system of JIS Z8701 which uses a C light source for color measurement, and is a color material which can represent x=0.10 or more and 0.30 or less, y=0.30 or more and 0.64 or less. Therefore, it belongs to a color material which can represent x=0.13 or more and 0.20 or less, y=0.32 or more and 0.60 or less.

The PG59 is characterized in that the XYZ colorimetric region surrounded by the following equations 1, 2, and 3 can be expressed in the XYZ color system of JIS Z8701, which uses a C light source for color measurement.

 (Equation 1) y=6.715×x-0.286  

Where, in Equation 1, 0.121<x<0.133

(Equation 2) y=7147.200×x ⁵ -8466.000×x ⁴ +3891.400×x ³ -854.200×x ² +86.380×x-2.579

Where, in Equation 2, 0.133<x<0.310

(Equation 3) y=1189.500×x ⁶ +1817.000×x ⁵ -3011.300×x ⁴ +1447.800×x ³ -307.420×x ² +27.628×x-0.285

Where, in Equation 3, 0.121<x<0.310

Among the xy chromaticity coordinate regions surrounded by the above equations 1, 2, and 3, the region having x=0.13 or more and 0.20 or less, y=0.32 or more and 0.60 or less is the most characteristic, and is effective.

In the PG59 used in the present invention, when the transmittance at 450 nm is 5%, the wavelength at which the transmittance of the spectral transmittance spectrum of 400 nm or more and 700 nm or less becomes maximum (Tmax) is 505 nm or more and 535 nm or less. . Further, the transmittance of the above wavelength (Tmax) is 70% or more. Further, the PG59 system used in the present invention has a transmittance of the spectral transmittance spectrum of 435 nm of 15% or less, and the transmittance of the spectral transmittance spectrum of 575 nm is 5% or less.

In order to coat PG59 with a monomer for color measurement, a suitable dispersing agent, a binder component, and a solvent are prepared for PG59 to prepare a coating liquid, which is applied onto a transparent substrate, dried, and hardened as needed. . As a binder component, a non-curable thermoplastic resin composition may be used, or a photocurable (photosensitive) or thermosetting resin may be used under the premise that a clear coating film capable of color measurement can be formed. Things. Further, in the colored resin composition of the present invention to be described later, a coating film containing only PG59 as a color material is formed by using a composition containing only PG59 as a color material, and color measurement can be performed. Specifically, for example, a solid component other than the color material used in the resin composition of Example 1 to be described later can be regarded as a binder component.

The transparent coating film containing a dispersing agent and a binder component and capable of color measurement can be, for example, a film thickness of 2.0 μm, a wavelength of 380 nm or more, and a transmittance of a spectral transmittance spectrum at 780 nm of 95% or more.

Further, the spectroscopic transmittance spectrum can be measured using a spectroscopic measuring device (for example, an Olympus microspectrophotometer OSP-SP200).

PG59 is a single color and has a blueish green color with strong tinting strength and high brightness. Further, PG59 tends to have better dispersibility such as PG7 than the conventional green pigment, and it is easy to improve the contrast and has a good resolubility.

Further, as the blue color material used in the present invention, when a spectroscopic transmittance spectrum is measured by forming a 2.5 μm coating film at P/V = 0.2, the transmittance at 440 nm is 60% or more and the transmittance at 520 nm is 560 nm. A color material of 10% or more and a transmittance of 580 nm of less than 10%.

Further, when the blue color material is coated by a single film to perform color measurement, it can be carried out like the above PG59.

The blue color material used for the colored resin composition for a color filter of the present invention is not particularly limited, and a known blue organic pigment, a blue dye, and a blue color of a salt-forming compound belonging to a blue dye can be used. Precipitate materials and the like. Here, the blue organic pigment has superior resistance to heat resistance and light resistance as compared with the dye or lake color material, and the blue dye is more soluble than the organic pigment because it is soluble. Further, since the lake color material is derived from a dye, the penetration rate is higher than that of a usual pigment, and a high luminance can be achieved.

Examples of the blue organic pigment include C.I. Pigment Blue 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 60, and the like. Among them, from the viewpoint of superior luminance, a blue pigment of beryllium bronze is preferred.

Examples of the blue dye include a methine dye, an anthraquinone dye, an azo dye, a triarylmethane dye, and an indigo dye.

In the blue lake coloring material belonging to the salt forming compound of the above blue dye, the relative ion type varies depending on the type of the dye, the relative ion of the acid dye is a cation, and the relative ion of the basic dye is an anion.

Examples of the relative cation of the acid dye include, in addition to the ammonium cation, a metal cation or an inorganic polymer.

The preferred range of the coloring agent for producing the ammonium ion is, for example, a primary amine compound, a secondary amine compound, a tertiary amine compound, and the like. Among them, from the viewpoint of superior heat resistance and light resistance, it is preferably A grade 2 amine compound or a grade 3 amine compound is used.

Further, as the coloring agent for producing metal cations, it may be appropriately selected from metal salts having a desired metal ion.

The relative cation of the acid dye may be used alone or in combination of two or more.

On the other hand, as the relative anion of the basic dye, it may be an organic anion or an inorganic anion. The organic anion may, for example, be an organic compound having an anionic group as a substituent.

Further, a known acid dye can also be used as the organic anion. At this time, the lake color material is an acid dye and the basic dye is present as an ion pair. The lake forming agent which produces such an organic anion may, for example, be an alkali metal salt or an alkaline earth metal salt of the above organic anion.

On the other hand, examples of the inorganic anion include an anion of an oxyacid (phosphoric acid ion, sulfate ion, chromic acid ion, tungstic acid ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ), etc.), or An inorganic anion or a mixture thereof in which a plurality of oxyacids are condensed, such as a polyoxometalate anion.

The polyoxo acid may be a heteropolyoxometalate ion (M _m O _n ) ^c- or a heteropolyoxometalate ion (X _l M _m O _n ) ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of polyatoms, and n represents a composition ratio of oxygen atoms. Examples of the polyatomic M include Mo, W, V, Ti, Nb, and the like. Further, examples of the hetero atom X include Si, P, As, S, Fe, Co, and the like.

Among them, from the viewpoint of heat resistance, it is preferred to contain at least one polyoxometalate anion of molybdenum (Mo) and tungsten (W), and more preferably a c-valent polyoxometalate anion containing at least tungsten.

The lake forming agent which produces an inorganic anion may, for example, be an alkali salt or an alkali metal salt of the above inorganic anion.

The relative anion of the basic dye in the lake coloring material may be used alone or in combination of two or more.

Examples of the blue lake color material include CI Pigment Blue 1, CI Pigment Blue 1: 2, CI Pigment Blue 2, CI Pigment Blue 3, CI Pigment Blue 8, CI Pigment Blue 9, CI Pigment Blue 10, and CI Pigment Blue. 12, CI pigment blue 14, CI pigment blue 17: 1, CI pigment blue 18, CI pigment blue 19, CI pigment blue 24, CI pigment blue 24: 1, CI pigment blue 53, CI pigment blue 56, CI pigment blue 56 : 1, CI Pigment Blue 61, CI Pigment Blue 61:1, CI Pigment Blue 62, CI Pigment Blue 63, CI Pigment Blue 78, and the like.

The blue dye and the blue lake color material are not particularly limited, and among them, a triarylmethane-based color material containing triarylmethane as a skeleton is preferable from the viewpoint of enhancing the brightness of the colored layer and the viewpoint of comparison.

Examples of the blue color material of the triarylmethane type include a triarylmethane dye having a triarylmethane skeleton represented by the following general formula (1), and a triarylmethane-based lake color material.

(In the general formula (1), R ⁱ to R ^vi each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, R ⁱ and R ⁱⁱ , R ⁱⁱⁱ and R ^iv , R ^v and R ^vi may also be bonded to form a ring structure. Ar ⁱ represents a divalent aromatic group which may have a substituent, and the plural R ⁱ ~ R ^vi and Ar ⁱ may be the same or different, respectively.

In the above general formula (1), the alkyl group of R ⁱ to R ^vi is not particularly limited, and examples thereof include a linear or branched alkyl group having 1 to 20 carbon atoms, and among them, a carbon number of 1 to 8 is preferred. A straight-chain or branched alkyl group; more preferably a linear or branched alkyl group having 1 to 5 carbon atoms from the viewpoint of ease of production and availability of a raw material, and particularly preferably an ethyl group and 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, and a hydroxyl group. Examples of the substituted alkyl group include a benzyl group.

The aryl group of R ⁱ to R ^vi is not particularly limited, and examples thereof include an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. The substituent which the aryl group may have is not particularly limited, and examples thereof include an alkyl group and a halogen atom.

The relationship between R ⁱ and R ⁱⁱ , R ⁱⁱⁱ and R ^iv , R ^v and R ^vi to form a ring structure means that R ⁱ and R ⁱⁱ , R ⁱⁱⁱ and R ^iv , R ^v and R ^vi form a ring via a nitrogen atom. structure. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring and a piperidine ring. A porphyrin ring or the like.

The divalent aromatic group in Ar ⁱ is not particularly limited, and may be a heterocyclic group in addition to the aromatic hydrocarbon group containing a carbocyclic ring. The aromatic hydrocarbon in the aromatic hydrocarbon group may, for example, be a condensed polycyclic aromatic hydrocarbon such as a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring or a phenanthrene ring, in addition to a benzene ring; A chain polycyclic hydrocarbon such as triphenyl, diphenylmethane, triphenylmethane or hydrazine. In the chain polycyclic hydrocarbon, O, S, and N may be present in the chain skeleton as in diphenyl ether or the like. On the other hand, examples of the heterocyclic ring in the heterocyclic group include furan, thiophene, and pyrrole. 5-membered heterocyclic ring such as azole, thiazole, imidazole or pyrazole; pyran, pyrone, pyridine, hydrazine Pyrimidine, pyridyl 6-membered heterocyclic ring; benzofuran, benzothiophene, anthracene, oxazole, coumarin, benzopiperone, quinoline, isoquinoline, acridine, anthracene Quinazoline, quinolin A condensed polycyclic heterocyclic ring such as a phenyl group. These aromatic groups may have a substituent.

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

Ar ^{i is} preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having a condensed polycyclic carbocyclic ring having 10 to 14 carbon atoms. Among them, a particularly preferred one is a phenyl or a naphthyl group.

Further, R ⁱ to R ^vi and Ar ⁱ in a complex number in one molecule may be the same or different.

Specific examples of the triarylmethane dye represented by the above general formula (1) include basic blue-7 and basic blue-26.

In addition, as the triarylmethane-based lake color material, the basic triarylmethane-based dye represented by the above general formula (1) contains one or a plurality of elements selected from the group consisting of molybdenum, tungsten, rhenium, and phosphorus. A lake color material composed of an anion having oxygen as an essential element is preferably used from the viewpoint of achieving high luminance of the color layer. As the anion, it is preferable to contain at least one of molybdenum and tungsten as an anion of a heteropolymetal oxyacid or a heteropolyoxoacid as an essential element. Among them, one or more selected from the group consisting of phosphotungstic acid, lanthanum tungstic acid, phosphotungstic acid, and samarium tungsten molybdate are suitably used.

As the above anion, it is particularly preferable to use (PMo _x W _12-x O ₄₀ ) ^3- /3 (here, an integer of x = 1, 2 or 3), (SiMoW ₁₁ ) from the viewpoint of improving heat resistance. O ₄₀ ) ^4- /4, (P ₂ Mo _y W _18-y O ₆₂ ) ^6- /6 (here, an integer of y = 1, 2 or 3). From the viewpoint of heat resistance improvement, it is preferred to use (SiMoW ₁₁ O ₄₀ ) ^4- /4 and (P ₂ Mo _y W _18-y O ₆₂ ) ^6- /6 (here, y = 1, 2 or At least one of the integers of 3).

Such a lake color material can be prepared by referring to, for example, the specification of International Patent Publication No. 2012/039416 and the specification of International Patent Publication No. 2012/039417.

Further, as the triarylmethane-based lake color material, from the viewpoint of achieving high luminance of the color layer, it is also suitable to use the following general formula (2).

(In the general formula (2), A is an a-valent organic group having no π bond to a carbon atom directly bonded to N, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, Or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain may further contain O, S, and N; B ^c- represents a c-valent anion. R ^XI to R ^XV each independently represent a hydrogen atom and an alkyl group which may have a substituent Or an aryl group which may have a substituent, R ^XII and R ^XIII , R ^XIV and R ^XV may also be bonded to form a ring structure; Ar ¹ represents a divalent aromatic group which may have a substituent; and a plurality of R ^XI ~ R ^XV And Ar ¹ may be the same or different, respectively.

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 the bond does not exist when e is 0. The plural e can be the same or different. )

A in the general formula (2) is an a-valent organic group having no π bond to a carbon atom directly bonded to N (nitrogen atom), and the organic group represents a fat having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. A hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain may further include O (oxygen atom), S (sulfur atom), and N (nitrogen atom). Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone or transmittance of the cationic color-developing portion are not affected by the linking group A or other color-developing portions, and can be maintained and single. The same color.

In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be a straight chain, a branch or a ring if the carbon atom at the terminal directly bonded to N does not have a π bond. The carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and may further contain O, S, and N in the carbon chain. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, a guanamine group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.

Further, the aromatic group having the above aliphatic hydrocarbon group in A may, for example, be a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and may have a substituent. It may also be a heterocyclic ring containing O, S, and N.

Among them, from the viewpoint of the robustness of the skeleton, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group.

The cyclic aliphatic hydrocarbon group is preferably a bridged alicyclic hydrocarbon group from the viewpoint of the robustness of the skeleton. The bridged alicyclic hydrocarbon group refers to a polycyclic aliphatic hydrocarbon group having a bridge structure in an aliphatic ring and having a polycyclic structure, and for example, Alkane, bicyclo[2,2,2]octane, adamantane, and the like. Among the bridged alicyclic hydrocarbon groups, it is preferred to lower alkyl. In addition, examples of the aromatic group include a benzene ring and a naphthalene ring. Among them, a group containing a benzene ring is preferred. For example, when A is a divalent organic group, a carbon number of 1 to 20 such as a straight chain, a branched or a cyclic alkyl group having 1 to 20 carbon atoms or a benzoyl group An aromatic group obtained by substituting an alkyl group.

The valence number a of A is the number of chromogenic cation sites constituting a cation, and a is an integer of 2 or more. In the lake color material, since the valence number a of the cation is 2 or more, heat resistance is excellent, and among them, the valence number a of the cation is preferably 3 or more. The upper limit of a is not particularly limited, and a is preferably 4 or less, more preferably 3 or less from the viewpoint of easiness of production.

Specific examples of Ar ¹ and R ^XI to R ^{XV in} the general formula (2) include those described in the specification of International Patent Publication No. 2012/144520.

In the lake color material of the general formula (2), the anion portion (B ^c- ) is not particularly limited, and may be an organic anion or an inorganic anion. The term "organic anion" as used herein means an anion containing at least one carbon atom. Further, the inorganic anion means an anion which does not contain a carbon atom. In the present invention, B ^{c- is} preferably an inorganic anion from the viewpoint of high luminance and excellent heat resistance.

Specific examples of the organic anion and the inorganic anion include those described in the specification of International Patent Publication No. 2012/144520.

Among them, from the viewpoint of high luminance and excellent heat resistance, an anion of a mineral acid containing at least one of tungsten (W) and molybdenum (Mo) is preferred.

In the general formula (2), b represents the number of cations, d represents the number of anions in the molecular combination, and b and d represent an integer of 1 or more. In the case where b is 2 or more, the plural cations in the molecular combination may be used alone or in combination of two or more. Further, when d is 2 or more, the plural anions in the molecular combination may be used alone or in combination of two or more kinds, and an organic anion may be used in combination with an inorganic anion.

In the general formula (2), e is an integer of 0 or 1. e=0 represents a triarylmethane skeleton, and e=1 represents skeleton. The plural e can be the same or different. In the lake color material of the general formula (2) used in the present invention, those containing at least a triarylmethane skeleton are suitably used.

Further, as the coloring matter material of the general formula (2), for example, it can be prepared by referring to the specification of International Patent Publication No. 2012/144520.

The blue color material is preferably selected from the group consisting of CI Pigment Blue 15:6, CI Pigment Blue 15:3, CI Pigment Blue 15:4, and Triarylmethane-based lake color material from the viewpoint of hue. One or more.

Further, as the blue color material, C.I. Pigment Blue 16 is preferable from the viewpoint of the hue, particularly the color reproduction domain. C.I. Pigment Blue 16 can reduce the P/V ratio because of the strong coloring power, so that the plate-making property is improved and the development defects are easily suppressed. On the other hand, the development residue is easily suppressed, and the adhesion to the substrate is improved.

Further, as the purple color material used in the present invention, when a spectroscopic transmittance spectrum is formed by forming a 2.5 μm coating film at P/V = 0.2, the transmittance at 440 nm is 40% or more and the transmittance at 520 nm. A color material of less than 10% and a transmittance of 680 nm of 40% or more.

The purple color material used in the present invention also contains a reddish purple color material called a red dye.

Further, when the purple color material is coated by a single film to perform color measurement, it can be carried out like the above PG59.

The purple color material used for the colored resin composition for a color filter of the present invention is not particularly limited, and a known purple organic pigment, a violet dye, a purple lake color material, or the like can be used.

The purple organic pigment may, for example, be C.I. Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, 38 or the like. Among them, from the viewpoint of superior coloring power, C.I. Pigment Violet 23 is preferred.

Examples of the violet dye include CI Acid Violet 29, 31, 33, 34, 36, 36:1, 39, 41, 42, 43, 47, 51, 63, 76, 103, 118, 126 and the like. Acid dye, CI alkaline red 12 and other cyanine acid dyes, acid purple 15,16,17,19,21,23,24,25,38,49,72, etc. triarylmethane acid dye, CI acid red 289, CI acid purple 9, CI acid purple 30 and other rose red acid dyes; or CI alkaline purple 1, 3, 14 and other triaryl methane basic dyes, CI alkaline purple 11 etc. It is a basic dye or the like.

The purple lake coloring material may, for example, be one in which the purple dye is laked by a lake forming agent.

In the lake color material, the relative ion type varies depending on the type of the dye, the relative ion of the acid dye is a cation, and the relative ion of the basic dye is an anion. As the relative anion of the acid dye and the relative anion of the basic dye, the same as those exemplified above for the blue dye can be used.

As the purple lake color material, from the viewpoint of hue, it is preferably selected from the group consisting of a lanthanum color material, a cyan color material, and One or more types of the constituents of the color materials are used.

Further, as the purple dye and the purple lake color material, it is preferable to contain the brightness and contrast of the colored layer. As a basic skeleton, containing rose red color material Color material.

As the color lake material The acid dye is preferably a compound represented by the following general formula (3), that is, a rosin-based acid dye.

(In the general formula (3), R ^a to R ^d each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R ^a and R ^b , R ^c and R ^d may be bonded to form a ring structure, R ^e represents an acidic group, X represents a halogen atom, and m represents an integer of 0 to 5. The general formula (3) has one or more acidic groups, and n is an integer of 0 or more.

The alkyl group in R ^a to R ^d is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent may be used. Among them, a linear or branched alkyl group having a carbon number of 1 to 8 is preferred, and a carbon number is preferably A linear or branched alkyl group of 1 to 5. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group. Examples of the substituted alkyl group include a benzyl group and the like, and may further have a halogen atom or an acidic group as a substituent. base.

The aryl group in R ^a to R ^d is not particularly limited. For example, an aryl group having a substituent of 6 to 20 carbon atoms may be mentioned, and among them, a group having a phenyl group, a naphthyl group or the like is preferable. Examples of the heteroaryl group in R ^a to R ^d include a heteroaryl group having a substituent of 5 to 20 carbon atoms, and a hetero atom preferably contains a nitrogen atom, an oxygen atom or a sulfur atom.

Examples of the substituent which the aryl group or the heteroaryl group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group, a hydroxyl group, an alkoxy group, an amine carbenyl group, and a carboxylate group.

Also, R ^a ~ R ^d may be the same or different.

Specific examples of the acidic group or a salt thereof include a carboxyl group (-COOH), a carboxyl group (-COO-), a carboxylate group (-COOM, where M represents a metal atom), and a sulfonate group (-SO). ₃ ^- ), a sulfo group (-SO ₃ H), a sulfonate group (-SO ₃ M, where M represents a metal atom), and the like, among which a sulfonate group (-SO ₃ ^- ) and a sulfonate are preferred. At least one of a group (-SO ₃ H) or a sulfonate group (-SO ₃ M). Further, examples of the metal atom M include a sodium atom and a potassium atom.

The compound represented by the general formula (3) is preferably an acid red 289, an acid violet 9, an acid violet 30 or the like from the viewpoint of high luminance.

Further, from the viewpoint of heat resistance, in the general formula (3), a compound having a betaine structure of m=1 and n=0 is preferred.

Further, among them, from the viewpoint of forming a coloring layer excellent in luminance and light resistance, m=1 and n=0 are preferable, and R ^a and R ^c are each independently an alkyl group or an aryl group, and R ^b and R ^d are each independently. Individually independent of aryl or heteroaryl.

The method for producing the compound of the above formula (3) is not particularly limited. For example, it can be obtained by referring to JP-A-2010-211198.

As above It is a coloring material for acid dyes, suitable for metal lake color materials. The metal lake coloring material uses a metal atom-containing one as a lake former. By using a metal atomizing agent containing a metal atom, the heat resistance of the color material becomes high. As such a lake-forming agent, a lake-forming agent containing a metal atom of a metal cation of two or more valences is preferable.

In the color material dispersion liquid of the present invention, a blue color material, a purple color material, and PG59 are used in combination as a color material, but other color materials as exemplified in the colored resin composition described later may be used in combination. As the other color material, for example, a red color material, an orange color material, a green color material, or the like is used, and from the viewpoint of the hue, a red color material or a green color material as exemplified in the colored resin composition described later is suitably used.

In the color material dispersion liquid of the present invention, the content ratio of each of the blue color material, the purple color material, and the PG59, and the content ratio when the other color material is used, is preferably the same as the content ratio of the colored resin composition to be described later. In particular, since the color material dispersion liquid can be used in a mixture of two or more kinds to form a colored resin composition, it is suitably used even if it is not contained in the same ratio as the coloring resin composition described later.

The average primary particle diameter of the color material used in the present invention is not particularly limited as long as it is a coloring layer of a color filter, and the color material used is not particularly limited. The type is preferably 10 nm or more and 100 nm or less, more preferably 15 nm or more and 60 nm or less. When the average primary particle diameter of the color material is within the above range, a display device having a color filter manufactured using the color material dispersion of the present invention can be highly contrasted and of high quality.

Further, the average dispersed particle diameter of the color material in the color material dispersion liquid varies depending on the type of the color material, and is preferably in the range of 10 nm or more and 100 nm, more preferably 15 nm or more and 60 nm or less.

The average dispersed particle diameter of the color material in the color material dispersion is a dispersed particle diameter of the color material particles dispersed in the dispersion medium containing at least the solvent, and is measured by a laser light scattering particle size distribution meter. As the particle diameter measurement by the laser light scattering particle size distribution meter, the color material dispersion liquid is appropriately diluted to a concentration which can be measured by a laser light scattering particle size distribution meter by using a solvent used for the color material dispersion liquid (for example, 1000) The measurement was carried out at 23 ° C by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring apparatus UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle diameter here is a volume average particle diameter.

In the color material dispersion liquid of the present invention, the color material content is not particularly limited. The color material content is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 8 parts by mass based on 100 parts by mass of the total solid content in the color material dispersion liquid, from the viewpoint of dispersibility and dispersion stability. The ratio is more than the mass part and 70 parts by mass or less.

In particular, in the case of forming a coating film or a colored layer having a high color material concentration, it is preferably 30 parts by mass or more and 80 parts by mass or less, more preferably 40 parts by mass based on 100 parts by mass of the total solid content in the color material dispersion liquid. The ratio is greater than or equal to 75 parts by mass.

 <dispersant>  

In the present invention, as the dispersant, a polymer having the structural unit represented by the above general formula (I) is used. The constituent unit represented by the above general formula (I) is alkaline, and functions as a absorbing portion of the color material.

In the color material dispersion liquid of the present invention, by using the polymer having the structural unit represented by the above general formula (I), the absorbing property of the color material is improved, and the dispersibility and dispersion stability of the color material are improved.

In the general formula (I), A is a divalent linking group. Examples of the divalent linking group in A include an alkylene group having 1 or more and 10 or less carbon atoms, an extended aryl group, a -CONH- group, a -COO- group, and an ether group having 1 or more and 10 or less carbon atoms. (-R'-OR"-: R' and R" are each independently an alkylene group) and combinations thereof.

Among them, from the viewpoint of dispersibility, A in the general formula (I) is preferably a -CONH- group or a divalent linking group containing a -COO- group.

R ² and R ³ may further contain a hydrocarbon group in a hydrocarbon group of a hetero atom, and examples thereof include an alkyl group, an aralkyl group, and an aryl group.

The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group or a cyclohexyl group; and the alkyl group preferably has a carbon number; It is 1 or more and 18 or less, and more preferably, it is a methyl group or an ethyl group.

The aralkyl group may, for example, be a benzyl group, a phenethyl group, a naphthylmethyl group or a biphenylmethyl group. The carbon atom of the aralkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 14 or less.

Further, examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less. Further, the above preferred carbon number does not include the number of carbon atoms of the substituent.

The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the above-mentioned radial group is substituted by a hetero atom. Examples of the hetero atom which may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a ruthenium atom.

Further, the hydrogen atom in the hydrocarbon group may be substituted by a halogen atom such as an alkyl group having 1 or more and 5 or less carbon atoms, a fluorine atom, a chlorine atom or a bromine atom.

R ² and R ³ may also be bonded to each other to form a ring structure, which means that R ² and R ³ form a ring structure via a nitrogen atom. The ring structure formed by R ² and R ³ may also contain a hetero atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring and a piperidine ring. A porphyrin ring or the like.

In the present invention, each of R ² and R ^{3 is} independently a hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or R ² and R ^{3 are} bonded to each other to form a pyrrolidine ring or a piperidine ring. More preferably, at least one of R ² and R ^{3 is} an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or R ² and R ^{3 are} bonded to each other to form a pyrrolidine ring or a piperidine ring. A porphyrin ring.

The constituent unit represented by the above general formula (I) may, for example, be dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate or diethylaminoethyl. (meth) acrylate containing an alkyl-substituted amine group such as (meth) acrylate or diethylamino propyl (meth) acrylate, etc., dimethylaminoethyl (meth) propylene oxime A (meth)acrylamide or the like containing an alkyl-substituted amine group such as an amine or dimethylaminopropyl (meth) acrylamide. Among them, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethyl is preferably used from the viewpoint of improvement in dispersibility and dispersion stability. Aminopropyl (meth) acrylamide.

The constituent unit represented by the general formula (I) may contain one type or two or more types of constituent units.

As the polymer having the structural unit represented by the general formula (I), it is preferred to further contain a solvent-affinitive site from the viewpoint of enhancing the dispersibility. The solvent affinity site is preferably a solvent having a solvent affinity by a monomer having an ethylenically unsaturated bond which can be polymerized with a monomer derived from a unit of the formula (I). And choose to use it properly. As a standard, a solvent affinity site is introduced with respect to the solvent to be used in combination so that the solubility of the polymer at 23 ° C is 50 (g/100 g solvent) or more.

The polymer used in the present invention is preferably a block from the viewpoints of dispersibility and dispersion stability of the color material and heat resistance of the resin composition, and formation of a high-luminance and high-comparison coloring layer. A copolymer or a graft copolymer, particularly preferably a block copolymer. The following is a detailed description of the preferred block copolymer.

 (block copolymer)  

When the block containing the structural unit represented by the above general formula (I) is an A block, the structural unit represented by the above general formula (I) of the A block is alkaline, and exhibits absorption as a color material. The function of the part. On the other hand, the B block which does not contain the structural unit represented by the above general formula (I) exhibits a function as a block having solvent affinity. In the present invention, the arrangement of the respective blocks of the block copolymer is not particularly limited, and examples thereof include an AB block copolymer, an ABA block copolymer, and a BAB block copolymer. Among them, from the viewpoint of superior dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

The constituent unit constituting the B block may, for example, be a monomer having an unsaturated double bond copolymerizable with a monomer derived from a structural unit represented by the general formula (I), and preferably the following general formula ( II) The constituent units shown.

[Chemical 6]

(In general formula (II), A' is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, -[CH(R ⁶ )-CH(R ⁷ )-O] _X -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ represents a monovalent group. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, a hydrocarbon group, -CHO And a monovalent group represented by -CH ₂ CHO or -CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms.

The above hydrocarbon group may have a substituent.

x represents an integer of 1 or more and 30 or less, y represents an integer of 1 or more and 5 or less, and z represents an integer of 1 or more and 18 or less. )

The divalent linking group A' of the general formula (II) can be the same as A in the general formula (I). Among them, A' is preferably a direct bond, a -CONH- group or a divalent linking group containing a -COO- group from the viewpoint of solubility in an organic solvent. From the viewpoint of heat resistance of the obtained polymer or a solubility suitable for use as a solvent of propylene glycol monomethyl ether acetate (PGMEA) or a relatively inexpensive material, A' is preferably a -COO- group.

The hydrocarbon group in R ⁵ is preferably an alkyl group having 1 or more and 18 or less carbon atoms, an alkenyl group having 2 or more and 18 or less carbon atoms, an aralkyl group or an aryl group.

The alkyl group having 1 or more and 18 or less carbon atoms may be any of a linear chain, a branched chain, and a cyclic group, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. 2-ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl, Basis A group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, a lower alkyl group-substituted adamantyl group or the like.

The alkenyl group having 2 or more and 18 or less carbon atoms may be any of a linear chain, a branched chain, and a cyclic chain. Examples of such an alkenyl group include a vinyl group, an allyl group, and an allyl group. The position of the double bond of the alkenyl group is not limited, and from the viewpoint of the reactivity of the obtained polymer, it is preferred to have a double bond at the terminal of the alkenyl group.

Examples of the substituent of the aliphatic hydrocarbon such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

The aryl group may, for example, be a phenyl group, a biphenyl group, a naphthyl group, a tolyl group or a xylyl group, and may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less.

Further, examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, and the like, and may further have a substituent. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 14 or less.

The substituent of the aromatic ring such as an aryl group or an aralkyl group may, for example, be an alkyl group, a nitro group or a halogen atom, in addition to a linear or branched alkyl group having 1 or more and 4 or less carbon atoms.

Further, the above preferred carbon number does not include the number of carbon atoms of the substituent.

In the above R ⁵ , x is an integer of 1 or more and 30 or less, preferably an integer of 1 or more and 26 or less, more preferably an integer of 1 or more and 18 or less, still more preferably an integer of 1 or more and 4 or less. It is preferably an integer of 1 or more and 2 or less; y is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, more preferably 2 or 3. z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less.

The hydrocarbon group in the above R ⁸ may be the same as those shown in the above R ⁵ . In particular, the hydrocarbon group in the above R ⁸ is preferably an alkyl group having 1 or more and 18 or less carbon atoms from the viewpoint of excellent developability.

R ⁹ is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, and may be any of a linear chain, a branched chain, or a cyclic group.

Further, R ⁵ in the structural unit represented by the above general formula (II) may be the same or different.

Examples of R ^5, wherein, in accordance with the preferred system embodiment becomes the selected location by said compatibility between the solvent and the rear, specifically, for example, in the above-described solvent is used as a color filter colored resin composition of the solvent is generally used in the composition In the case of a solvent such as a glycol ether acetate type, an ether type or an ester type, a methyl group, an ethyl group, an isobutyl group, a n-butyl group, a 2-ethylhexyl group, a benzyl group or the like is preferable.

Further, in the structural unit constituting the B block, the R ⁵ is preferably -[CH(R ⁶ )-CH(R ⁷ )-O from the viewpoint of excellent developability and excellent development residue. ] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ .

Further, the R ⁵ may be substituted by a substituent such as an alkoxy group, a hydroxyl group, an epoxy group or an isocyanate group, without impeding the dispersion property of the block copolymer or the like. After the synthesis of the segment copolymer, it may be reacted with a compound having the above substituent to form the above substituent.

In the present invention, the glass transition temperature (Tg) of the block portion of the solvent affinity of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the block portion of the solvent affinity is preferably 80 ° C or higher, more preferably 100 ° C or higher.

The glass transition temperature (Tg) of the block portion of the solvent affinity of the present invention can be calculated by the following formula. Further, the glass transition temperature of the color material affinity block portion and the block copolymer can be similarly calculated.

1/Tg=Σ(Xi/Tgi)

Here, the block portion of the solvent affinity is a copolymerization of n monomer components of i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, the lanthanide adopts the sum of i=1 to n. Further, the value (Tgi) of the homopolymer glass transition temperature of each monomer can be a value of Polymer Handbook (3rd Edition) (J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).

The number of constituent units of the block portion constituting the solvent affinity may be appropriately adjusted within the range in which the dispersibility of the color material is improved. In particular, the number of constituent units of the block portion constituting the solvent affinity is preferably 10 or more and 200 or less, from the viewpoint that the solvent affinity portion and the color material affinity portion effectively act to enhance the dispersibility of the color material. It is preferably 10 or more and 100 or less, and more preferably 10 or more and 70 or less.

The block portion of the solvent affinity may be selected so as to function as a solvent affinity site, and the repeating unit of the block portion constituting the solvent affinity may be contained in one type or may contain two or more types of repeating units.

In addition, in the present invention, the dispersant is preferably composed of the above-described general formula (II) and having an amine value of 40 mgKOH from the viewpoint of good dispersibility, no precipitation of foreign matter during coating film formation, and improvement in brightness and contrast. a polymer of /g or more and 120 mgKOH/g or less.

When the amine value is within the above range, the viscosity stability or heat resistance is excellent, and alkali developability or solvent resolubility is also excellent. In the present invention, the amine valence of the dispersing agent is preferably from 60 mgKOH/g or more, more preferably 90 mgKOH/g or more, from the viewpoints of dispersibility and dispersion stability. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersant is preferably 115 mgKOH/g or less, more preferably 105 mgKOH/g or less.

The amine value is the number of mg of potassium hydroxide equivalent to perchloric acid required for neutralization of the amine component contained in 1 g of the sample, and can be measured by a method defined in JIS-K7237. In the measurement by the method, even if the amine group which forms a salt with the organic acid compound in the dispersant is usually dissociated from the organic acid compound, the amine valence of the block copolymer itself as the dispersing agent can be measured.

The acid value of the dispersing agent used in the present invention is preferably 1 mgKOH/g or more from the viewpoint of the effect of suppressing the development residue. Among them, the acid value of the dispersing agent is more preferably 2 mgKOH/g or more from the viewpoint of further suppressing the effect of the development residue. On the other hand, the acid value of the dispersing agent may be less than 1 mgKOH/g, preferably 0 mgKOH/g from the viewpoint of dispersibility and dispersion stability. In addition, the acid value of the dispersing agent used in the present invention is preferably 18 mg KOH/g or less as the upper limit of the acid value of the dispersing agent from the viewpoint of preventing deterioration of development adhesiveness or deterioration of solvent resolubility. . In particular, the acid value of the dispersing agent is preferably 12 mgKOH/g or less, and more preferably 8 mgKOH/g or less, from the viewpoints of good development adhesiveness and solvent resolubility.

In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more. This is due to an increase in the suppression effect of the development residue. On the other hand, the acid value of the block copolymer before salt formation may be less than 1 mgKOH/g, preferably 0 mgKOH/g from the viewpoint of dispersibility and dispersion stability. Further, the upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH/g or less, more preferably 12 mgKOH/g or less, still more preferably 8 mgKOH/g or less. This is because the development adhesiveness and the solvent resolubility become good.

Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C or higher from the viewpoint of improving the development adhesiveness. That is, the dispersing agent is preferably a glass transition temperature of 30 ° C or more, regardless of the block copolymer before salt formation or the salt block copolymer. If the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C), and the development adhesiveness is lowered. It is presumed that if the glass transition temperature is close to the developer temperature, the movement of the dispersant during development becomes large, and as a result, the development adhesiveness is deteriorated. When the glass transition temperature is 30 ° C or higher, it is estimated that the molecular motion of the dispersing agent during development is suppressed, so that the deterioration of the developing adhesiveness is suppressed.

The glass transition temperature of the dispersant is preferably 32 ° C or higher, more preferably 35 ° C or higher, from the viewpoint of developing adhesion. On the other hand, from the viewpoint of ease of use such as accurate weighing, etc., it is preferably 200 ° C or lower.

The glass transition temperature of the dispersant of the present invention can be determined by measurement by differential scanning calorimetry (DSC) according to JIS K7121.

When the concentration of the color material is increased and the content of the dispersant is increased, the amount of the binder is relatively reduced, so that the colored resin layer is easily peeled off from the base substrate during development. When the dispersing agent contains a B block having a constituent unit derived from a carboxyl group-containing monomer and has the above specific acid value and glass transition temperature, the development adhesiveness is improved. It is presumed that if the acid value is too high, although the developability is excellent, the polarity is too high, and peeling is likely to occur during development.

From the above, in the present invention, the dispersion stability of the color material is superior and the contrast is improved, and the development residue is suppressed when the colored resin composition is formed, and the solvent resolubility is superior and the development adhesiveness is high. The dispersing agent is preferably a polymer containing the structure represented by the above general formula (I) and having an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less, and the acid value is 1 mgKOH/g or more and 18 mgKOH/g or less, and the glass transition temperature is Above 30 °C.

As the carboxyl group-containing monomer, a monomer which can be copolymerized with a monomer having a structural unit represented by the general formula (I) and contains an unsaturated double bond and a carboxyl group can be used. Examples of such a monomer include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, isaconic acid, crotonic acid, and the like. Cinnamic acid, acrylic acid dimer, and the like. Further, an addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride, or ω- may be used. Carboxy-polycaprolactone mono(meth)acrylate and the like. Further, an acid anhydride group-containing monomer such as maleic anhydride, isaconic anhydride or citraconic anhydride may be used as the carboxyl precursor. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

In the block copolymer before salt formation, the content ratio of the constituent unit derived from the carboxyl group-containing monomer is appropriately set so that the acid value of the block copolymer is within the range of the specific acid value, and is not particularly limited. The total mass of the total constituent units of the block copolymer is preferably 0.05% by mass or more and 4.5% by mass or less, more preferably 0.07% by mass or more and 3.7% by mass or less.

When the content ratio of the constituent unit derived from the carboxyl group-containing monomer is at least the above lower limit value, the effect of suppressing the development residue is expressed, and if it is at most the above upper limit value, deterioration of development adhesiveness or solvent redissolution can be prevented. Sexual deterioration.

In addition, the constituent unit derived from the carboxyl group-containing monomer may be one or more kinds of constituent units, and may be one or more constituent units.

Further, from the viewpoint that the glass transition temperature of the dispersant used in the present invention is a specific value or more and the development adhesiveness is improved, it is preferred that the value of the glass transition temperature (Tgi) of the monomer homopolymer is The monomer of 10 ° C or more is 75% by mass or more, and more preferably 85% by mass or more based on the total of the B block.

In the block copolymer, the ratio m/n of the unit number m of the constituent units of the A block and the unit number n of the constituent units of the B block is preferably 0.05 or more and 1.5 or less; From the viewpoint of dispersibility and dispersion stability of the color material, it is more preferably in the range of 0.1 or more and 1.0 or less.

The weight average molecular weight Mw of the above-mentioned block copolymer is not particularly limited, and is preferably 1,000 or more and 20,000 or less, more preferably 2,000 or more and 15,000 or less, from the viewpoint of satisfactory color material dispersibility and dispersion stability. More preferably, it is 3,000 or more and 12,000 or less.

Here, the weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) in terms of standard polystyrene. Further, the macromonomer, the salt block copolymer, and the graft block copolymer which are the raw materials of the block copolymer are also subjected to the above conditions.

The method for producing the above block copolymer is not particularly limited. The block copolymer can be produced by a known method, and it is preferably produced by a living polymerization method. This is because it is difficult to cause chain movement or deactivation, and it is possible to produce a copolymer having a uniform molecular weight and to improve dispersibility and the like. The living polymerization method may, for example, be a living anionic polymerization method such as a living radical polymerization method or a base transfer polymerization method, or a living cationic polymerization method. By sequentially polymerizing the monomers by such methods, a copolymer can be produced. For example, the A block is first produced, and the A block is polymerized with the constituent unit constituting the B block to produce a block copolymer. Further, in the above production method, the polymerization order of the A block and the B block may be reversed. Further, the A block and the B block may be separately produced, and then the A block and the B block may be coupled.

Specific examples of the block copolymer having the block portion having the structural unit represented by the above formula (I) and the block portion having a solvent affinity include, for example, block copolymerization described in Japanese Patent No. 4911253. Fit as appropriate.

In the present invention, from the viewpoint of dispersibility or dispersion stability of the color material, it is preferred to use at least a part of the amine group in the polymer containing the structural unit represented by the above general formula (I), and an organic acid. The salt formed by the compound or the halogenated hydrocarbon is used as a dispersing agent (hereinafter, such a polymer is referred to as a salt type polymer).

Among them, from the viewpoint of superior dispersibility and dispersion stability of the color material, it is preferred that the polymer having a repeating unit having a tertiary amine is a block copolymer, and the organic acid compound is a phenylphosphonic acid or a phenyl group. An acidic organophosphorus compound such as phosphinic acid. Specific examples of the organic acid compound to be used as such a dispersing agent include, for example, an organic acid compound described in JP-A-2012-236882.

Further, as the halogenated hydrocarbon, at least one of a halogenated allyl group such as a brominated allyl group or a benzyl chloride group and a halogenated aralkyl group is preferred from the viewpoint of excellent dispersibility and dispersion stability of the color material. Kind.

In the color material dispersion liquid of the present invention, at least one type of the polymer having the structural unit represented by the above general formula (I) is used as the dispersing agent, and the content thereof is blended with the type of the color material to be used, and further, the color filter described later. The light sheet is appropriately selected by the solid content concentration or the like in the colored resin composition.

The content of the dispersant is preferably from 3 parts by mass to 45 parts by mass, more preferably from 100 parts by mass based on the total solid content in the color material dispersion, from the viewpoint of dispersibility and dispersion stability. 5 parts by mass or more and 35 parts by mass or less are blended.

In particular, in the case of forming a coating film or a colored layer having a high color material concentration, the content of the dispersing agent is preferably 3 parts by mass or more and 25 parts by mass or less based on 100 parts by mass of the total solid content in the color material dispersion liquid. More preferably, it is formulated in a ratio of 5 parts by mass or more and 20 parts by mass or less.

Further, in the present invention, the solid portion is all other than the above solvent, and includes a monomer dissolved in a solvent or the like.

 <solvent>  

The solvent to be used in the present invention is not particularly limited as long as it is an organic solvent which does not react with each component in the color material dispersion liquid and can be dissolved or dispersed. The solvent may be used singly or in combination of two or more.

Specific examples of the solvent include an alcohol solvent such as methanol, ethanol, isopropanol or methoxy alcohol; a carbitol solvent such as methoxyethoxyethanol or ethoxyethoxyethanol; and ethyl acetate B; Ester, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate An ester solvent such as isobutyl acetate, n-butyl butyrate or cyclohexanol acetate; a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone or 2-heptanone; methoxy B Acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl ethyl a glycol ether acetate solvent such as an acid ester; a card such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, or butyl carbitol acetate (BCA) Alcohol acetate solvent; diacetate such as propylene glycol diacetate or 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether a glycol ether solvent such as diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether or dipropylene glycol dimethyl ether; N,N-dimethylformamide, N,N- An aprotic guanamine solvent such as dimethylacetamide or N-methylpyrrolidone; a lactone solvent such as γ-butyrolactone; a cyclic ether solvent such as tetrahydrofuran; benzene, toluene, and xylene An unsaturated hydrocarbon solvent such as naphthalene; a saturated hydrocarbon solvent such as N-heptane, N-hexane or N-octane; or an organic solvent such as an aromatic hydrocarbon such as toluene or xylene. Among these solvents, a glycol ether acetate solvent, a carbitol acetate solvent, a glycol ether solvent, and an ester solvent are preferably used from the viewpoint of solubility of other components. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 2-methyl from the viewpoint of solubility or coating suitability of other components. Oxyethyl acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl One or more of the group consisting of acetate, ethyl lactate, methyl 2-hydroxypropionate, and 3-methoxybutyl acetate.

Further, from the viewpoints of developability, solvent resolubility, and the like, a mixed solvent containing two or more kinds of solvents is preferably used.

In the case of using a mixed solvent, the above-mentioned glycol ether acetate-based solvent is preferably used as the first solvent because of high safety, moderate volatility, and good dispersibility due to moderate solubility. Further, among them, 2-methoxyethyl acetate or propylene glycol monomethyl ether acetate which is more preferably a boiling point (refer to a boiling point at atmospheric pressure, the same applies hereinafter) of less than 150 ° C, particularly preferably a propylene glycol single Methyl ether acetate (PGMEA).

The second solvent (solvent other than the first solvent) is preferably a solvent having an alcoholic hydroxyl group or a solvent having a boiling point of 150 ° C or higher. The second solvent may be used singly or in combination of two or more.

When a solvent having an alcoholic hydroxyl group is used as the second solvent, the dispersibility is improved and the solvent resolubility is likely to be good.

Examples of the solvent having an alcoholic hydroxyl group include the above-described alcohol solvent, the carbitol solvent, and the glycol ether solvent. Specific examples thereof include propylene glycol monomethyl ether (boiling point: 121 ° C), 3-methyl Oxy-3-methyl-1-butanol (boiling point 174 ° C) and the like.

In the case of using a mixed solvent, the content of the solvent having an alcoholic hydroxyl group is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less, based on the total solvent. Further, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 1% by mass or more.

When it is in the above range, the solubility of the dispersing agent is likely to be good, and the dispersing agent does not inhibit the dissolution of the first solvent, so that the dispersion stability is likely to be good.

When the first solvent is a solvent having a boiling point of less than 150 ° C, when a solvent having a boiling point of 150 ° C or higher is used as the second solvent, drying unevenness is less likely to occur, and foreign matter is less likely to occur, and solvent resolubility is also likely to be good.

Examples of the solvent having a boiling point of 150 ° C or higher include diethylene glycol ethyl methyl ether (boiling point: 179 ° C) and 3-methoxy-3-methyl-1-butyl acetate (boiling point: 188 ° C). ), diethylene glycol ethyl methyl ether (boiling point: 179 ° C), 3-methoxybutyl acetate (boiling point: 172 ° C), and the like.

In the case of using a mixed solvent, the content of the solvent having a boiling point of 150 ° C or higher is preferably 40% by mass or less, and more preferably 30% by mass or less based on the total solvent. Further, it is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more.

When it is in the above range, drying unevenness is less likely to occur, and the drying time is not too long, and the productivity is likely to be good.

The boiling point of the "solvent having a boiling point of 150 ° C or higher" is preferably 240 ° C or less, and particularly preferably 200 ° C or less from the viewpoint that the drying time is not too long.

The color material dispersion liquid of the present invention is preferably contained in the range of 55 mass% or more and 95 mass% or less of the above solvent, based on the total amount of the color material dispersion liquid containing the solvent, and preferably 65 mass%. It is more preferably in the range of 90% by mass or less, more preferably 70% by mass or more and 88% by mass or less. If it is in the above range, the dispersibility is improved and the viscosity stability is obtained, and the target chromaticity coordinate can be achieved.

 <Other ingredients>  

In the color material dispersion liquid of the present invention, it is possible to further disperse the dispersion auxiliary resin and other components as needed without impairing the effects of the present invention.

The dispersing auxiliary resin may, for example, be an alkali-soluble resin exemplified as a colored resin composition for a color filter to be described later. Since the steric hindrance of the alkali-soluble resin makes the color material particles hardly contact each other, there is a case where the effect of the dispersing agent is reduced by dispersion stabilization or by the effect of stabilizing the dispersion.

Further, examples of the other component include a surfactant for improving wettability, a decane coupling agent for improving adhesion, an antifoaming agent, a shrinkage preventing agent, an antioxidant, an anti-aggregating agent, an ultraviolet absorber, and the like. .

The color material dispersion liquid of the present invention is used as a preliminary preparation for preparing a colored resin composition for a color filter to be described later. In other words, the color material dispersion liquid is prepared in a stage before the preparation of the colored resin composition for a color filter described later, P/V (total mass of the color material in the composition) / (other than the color material in the composition) A relatively high color material dispersion of the total mass of the solids. Specifically, the ratio of (the total mass of the color material in the composition) / (the total mass of the solid portion other than the color material in the composition) is usually 1.0 or more. By mixing the color material dispersion liquid and each component described later, it is possible to prepare a colored resin composition for a color filter excellent in dispersibility.

 [Manufacturing method of color material dispersion]  

In the present invention, the method for producing a color material dispersion liquid is not particularly limited as long as the color material is obtained by dispersing the color material to obtain a color material dispersion liquid dispersed in a solvent. Among them, from the viewpoint of excellent dispersibility and dispersion stability of the color material, it is preferably one of the following two production methods.

That is, the first method for producing the color material dispersion of the present invention comprises the steps of: preparing the dispersant; and dispersing the color material in the presence of the dispersant in a solvent. In the solvent, two or more kinds of color materials may be co-dispersed in the presence of the dispersant, or one or more color materials may be dispersed or co-dispersed, and then two or more kinds of color material dispersions may be mixed. This also gives the color material dispersion of the present invention.

Moreover, the second production method of the color material dispersion liquid of the present invention in the case of using a dispersant which is a salt type block copolymer has a solvent, the above block copolymer, the above organic acid compound or a halogenated hydrocarbon, and The color material is mixed, and at least a part of the nitrogen portion at the terminal end of the structural unit represented by the above general formula (I) is formed by salting the coloring material with the organic acid compound or the halogenated hydrocarbon. When the salt material is dispersed on one side, two or more color materials may be co-dispersed, or one or more color materials may be dispersed or co-dispersed, and then two or more color materials may be mixed and dispersed. The liquid material can also be used to obtain the color material dispersion of the present invention.

In the first manufacturing method and the second manufacturing method described above, the color material can be dispersed using a conventionally known disperser.

Specific examples of the dispersing machine include a roll mill such as a twin roll machine and a three roll machine; a ball mill such as a ball mill or a vibrating ball mill; a paint conditioner, a continuous disk type bead mill, a continuous ring type bead mill, and the like. Bead mill. The preferred dispersion conditions of the bead mill are preferably 0.03 mm or more and 3.0 mm or less, more preferably 0.05 mm or more and 2.0 mm or less.

 [Colored resin composition for color filter]  

The colored resin composition for a color filter of the present invention contains a color material, a dispersant, a binder component, and a solvent; and the color material contains a blue color material, a purple color material, and a CI color green 59; The dispersant is a polymer having the structural unit represented by the above general formula (I).

The coloring resin composition for a color filter of the present invention is superior in dispersion of color material similarly to the above-described color material dispersion liquid of the present invention, and can be improved as described in the item of the color material dispersion liquid of the present invention. It has resolubility and can form a colored layer in which the blue reproduction domain is enlarged.

The colored resin composition for a color filter of the present invention contains a color material, a dispersant, a binder component, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. In the following, the components contained in the colored resin composition for a color filter of the present invention are described, but the blue color material, the purple color material, the PG59, the dispersant, and the solvent which are essential components in the color material are described in the above Since the description of the color material dispersion is the same, the description thereof is omitted.

 <color material>  

The color material in the colored resin composition for a color filter of the present invention contains a blue color material, a purple color material, and C.I. pigment green 59 as essential components. However, in order to adjust the color tone, other color materials may be further used in combination.

In the case of forming the colored layer of the color filter, the desired color development is not particularly limited, and various organic pigments, inorganic pigments, and dispersible dyes may be used alone or in combination of two or more. Among them, organic pigments are suitable for use because of their high color developability and high heat resistance. The organic pigment may, for example, be a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), and specifically has a color index (C.I.) value as described below.

Further, as the dispersible dye, for example, various substituents may be added to the dye, or a known disintegration (salting) method may be used to form a dispersible dye by insolubilizing a solvent, or by combination. A solvent of low solubility is used to become a dispersible dye. By using such a dispersible dye in combination with the above dispersant, the dispersibility or dispersion stability of the dye can be improved.

As the dispersible dye, it can be suitably selected from known dyes. Examples of such a dye include an azo dye, a metal salt azo dye, an anthraquinone dye, and a triphenylmethane dye. Dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, indigo dyes, and the like.

Further, as a standard, when the amount of the dye dissolved is 10 mg or less based on 10 g of the solvent (or mixed solvent), it can be judged that the dye is dispersible in the solvent (or mixed solvent).

As other color materials, other green color materials and red color materials are preferably used.

The other color material may, for example, be the following, but is not limited thereto.

As the red color material, there are C.I. Pigment Red 177, 168, 254 and the like.

As a green color material, it is like C.I. Pigment Green 7, 7, 58, and the like.

In the colored resin composition for a color filter of the present invention, the content ratio of the blue color material to the entire color material is appropriately adjusted depending on the desired chromaticity, and is not particularly limited.

In the above, from the viewpoint of enhancing the solvent resolubility and forming the coloring layer in which the blue reproduction region is enlarged, it is preferable to contain the blue color material in an amount of 15% by mass or more and 98% by mass or less, and more preferably, from the total amount of the coloring material. The content is preferably 20% by mass or more and 90% by mass or less, more preferably 25% by mass or more and 80% by mass or less, and particularly preferably 27% by mass or more and 70% by mass or less.

In the photosensitive colored resin composition for a color filter of the present invention, the content ratio of the purple color material to the blue color material is appropriately adjusted depending on the desired chromaticity, and is not particularly limited. In the case of the coloring layer which is capable of forming a blue coloring region, it is preferable to contain the purple coloring material in an amount of 3 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the blue coloring material. More preferably, it is contained in an amount of 5 parts by mass or more and 80 parts by mass or less.

In addition, it is preferable that the total amount of the color material is 1% by mass or more and 45% by mass or less, more preferably 3% by mass or more and 40% by mass or less, and still more preferably 5% by mass or more. 40% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.

In the photosensitive colored resin composition for a color filter of the present invention, the content ratio of PG59 to the blue color material is appropriately adjusted in accordance with the desired chromaticity, and is not particularly limited. In particular, it is preferable to contain PG59 2 parts by mass or more and 250 parts by mass or less, and more preferably 100 parts by mass of the blue color material, from the viewpoint of enhancing the solvent resolubility and forming the coloring layer in which the blue reproduction region is enlarged. The amount is preferably 5 parts by mass or more and 200 parts by mass or less.

In addition, it is preferable to contain PG59 of 1% by mass or more and 65% by mass or less, more preferably 2% by mass or more and 60% by mass or less, and still more preferably 10% by mass or more and 50% by mass based on the total amount of the color material. %the following.

In the photosensitive colored resin composition for a color filter of the present invention, the content ratio of the purple color material to the PG59 is appropriately adjusted depending on the desired chromaticity, and is not particularly limited. In the above, from the viewpoint of the solvent re-solubility and the formation of the coloring layer in which the blue reproduction region is enlarged, it is preferable to contain the purple color material in an amount of 0.03 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass of the PG59. The content is preferably 0.05 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 7 parts by mass or less.

From the viewpoint of improving the solvent resolubility and forming the coloring layer in which the blue reproduction region is enlarged, the blending ratio or combination is preferably 15% by mass or more based on the total amount of the coloring material. 98% by mass or less, the purple color material is 1% by mass or more and 45% by mass or less, PG59 is 1% by mass or more and 65% by mass or less, and more preferably the blue coloring material is 20% by mass or more and 90% by mass or less, and purple color The material is 1% by mass or more and 45% by mass or less, PG59 is 1% by mass or more and 65% by mass or less, and more preferably, the blue color material is 25% by mass or more and 80% by mass or less, and the purple color material is 3% by mass or more. 40% by mass or less, PG59 is 2% by mass or more and 60% by mass or less, and particularly preferably, the blue color material is 27% by mass or more and 70% by mass or less, and the purple color material is 10% by mass or more and 40% by mass or less, and PG59 It is 10% by mass or more and 50% by mass or less.

Further, in the photosensitive colored resin composition for a color filter of the present invention, when a green color material other than PG59 is further contained, the content ratio of the green color material of PG59 to the entire color material is included, and the desired color is blended. The degree can be appropriately adjusted, and is not particularly limited.

In the case of further containing a green color material other than PG59, PG59 is preferably more than 50% by mass, more preferably 70% by mass or more, and still more preferably 80% by mass or more based on the total amount of green color material containing PG59.

The content ratio of the green color material including PG59 to the entire color material, and the content ratio of the purple color material to the green color material containing PG59 are respectively proportional to the content ratio of the PG59 to the entire color material, and the purple color material is relative to the PG59. The content ratio is the same.

Further, in the photosensitive colored resin composition for a color filter of the present invention, the yellow color material is preferably 0.1 with respect to the total amount of the color material from the viewpoint of forming a coloring layer in which the blue reproduction region is enlarged. The mass% or less, more preferably less than 0.01% by mass.

Further, in the photosensitive colored resin composition for a color filter of the present invention, the color material may further contain a blue color material, a purple color material, and other colors other than PG59 in a range that does not impair the effects of the present invention. The total content of the blue color material, the purple color material, and the PG59 is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less based on the total amount of the color material.

 <Binder composition>  

The colored resin composition for a color filter of the present invention contains a binder component for film formability or adhesion to a surface to be coated. In order to impart sufficient hardness to the coating film, it is preferred to contain a curable binder component. The curable binder component is not particularly limited, and a curable binder component known in the art for forming a color layer of a color filter can be suitably used.

As the curable binder component, for example, a photocurable binder component containing a photocurable resin which can be polymerized and cured by visible light rays, ultraviolet rays, electron beams or the like can be used, or can be heated by heating. A thermosetting binder component of a thermosetting resin which is polymer cured.

In the case where a photolithography step is used in forming the coloring layer, a photosensitive adhesive component having alkali developability is suitably used. Further, a thermosetting adhesive component may be further used in the photosensitive adhesive component.

Examples of the photosensitive adhesive component include a positive photosensitive adhesive component and a negative photosensitive adhesive component. The positive-type photosensitive adhesive component may, for example, be an alkali-soluble resin or a system containing an ortho-quinonediazide-based compound as a photosensitive component.

On the other hand, as the negative photosensitive adhesive component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is suitably used.

In the colored resin composition for a color filter of the present invention, a negative photosensitive adhesive component is preferred from the viewpoint that a pattern can be easily formed by photolithography using an existing process.

In order to expand the blue reproduction region, a photosensitive coloring resin for a blue colored layer is prepared by combining a negative color photosensitive adhesive component with a blue color material and a green color material such as PG58, PG7 or PG36 as in Patent Document 1. In the composition, the photosensitive colored resin composition absorbs about 300 nm of the absorption wavelength (radical generation wavelength) of the photoinitiator, so that the inside of the colored layer is insufficiently hardened during exposure, and the hollowing during development is liable to occur. This is accompanied by defects and peeling during development. Further, when the surface is solidified by the hollowing out to generate a void (a space inside the colored layer), color unevenness caused by the disordered reflection of light when the colored layer is viewed obliquely occurs. Further, when the hollowed-out portion is present in the colored layer, when the next color layer or protective coating layer is applied, the resin composition flows into the hollowed-out portion, and the coating liquid is interrupted, which tends to cause uneven coating.

On the other hand, in the present invention, the purple color material and the PG59 are mixed with the blue color material. Since the combination of the purple color material and the PG59 does not easily absorb the wavelength of about 300 nm, even the negative photosensitive adhesive is combined. The composition of the photosensitive colored resin composition for the blue colored layer is not likely to cause insufficient hardening of the inside of the colored layer during exposure. Therefore, when the colored resin composition of the present invention is used as a photosensitive colored resin composition for a blue colored layer, voiding during development, defects and peeling during development are less likely to occur, and voids are less likely to occur. It is not easy to occur in the color unevenness caused by the disordered reflection of light when the colored layer is viewed obliquely.

Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator which constitute the negative-type photosensitive adhesive component will be specifically described.

 (alkali soluble resin)  

The alkali-soluble resin of the present invention has an acidic group and can function as a binder resin, and can be appropriately selected from those which are soluble in the alkali developer used for pattern formation.

In the present invention, the alkali-soluble resin may have an acid value of 40 mgKOH/g or more.

The alkali-soluble resin which is preferable in the present invention is a resin having an acidic group and usually a carboxyl group, and specific examples thereof include an acrylic resin having a carboxyl group and an acrylic resin having a carboxyl group and a styrene-acrylic copolymer. An epoxy group (meth) acrylate resin having a carboxyl group or the like. Among these, those having a carboxyl group in the side chain and further having an ethylenically unsaturated group in the side chain are preferred. The reason for this is that the film strength of the formed cured film can be enhanced by containing a photopolymerizable functional group. Further, two or more kinds of the acrylic resin and the epoxy acrylate resin such as the acryl-based copolymer and the styrene-acrylic copolymer may be used in combination.

An acrylic resin having an acryl-based copolymer having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group, for example, a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, copolymerizable The other monomer is a (co)polymer obtained by (co)polymerization by a known method.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, and itaconic acid. , butenoic acid, cinnamic acid, acrylic acid dimer, and the like. Further, an addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride, or ω- may be used. Carboxy-polycaprolactone mono(meth)acrylate and the like. Further, an acid anhydride-containing monomer such as maleic anhydride, isaconic anhydride or citraconic anhydride may be used as the carboxyl precursor. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring belonging to a bulky group in the alkali-soluble resin, shrinkage during hardening, relaxation and peeling from the substrate, and adhesion of the substrate are improved. Moreover, the present inventors have found that by using an alkali-soluble resin having a hydrocarbon ring, the solvent resistance of the obtained colored layer, particularly the swelling of the colored layer, can be suppressed. Although the effect has not yet been elucidated, it is presumed that the molecular action in the colored layer can be suppressed by the large-volume hydrocarbon ring in the colored layer, and as a result, the coating film strength is increased and the swelling due to the solvent is suppressed.

Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and combinations thereof, and the hydrocarbon ring may have an alkyl group, a carbonyl group, a carboxyl group, or an oxygen group. a substituent of a carbonyl group, a guanamine group, a hydroxyl group, a nitro group, an amine group, a halogen atom or the like.

The hydrocarbon ring may be contained as a monovalent group or may be contained as a divalent or higher group.

Specific examples of the hydrocarbon ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and descending. An aliphatic hydrocarbon ring such as alkane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane) or adamantane; an aromatic hydrocarbon ring of benzene, naphthalene, anthracene, phenanthrene, anthracene or the like; biphenyl, A chain polycyclic ring such as terphenyl, diphenylmethane, triphenylmethane or hydrazine, or a cardo structure (9,9-diarylfluorene).

The hydrocarbon ring preferably contains an aliphatic hydrocarbon ring from the viewpoint of improving the heat resistance or adhesion of the colored layer and improving the luminance of the obtained colored layer.

Moreover, from the viewpoint of improving the hardenability of the colored layer and improving the solvent resistance ((NMP swelling inhibition), it is particularly preferable to contain the above-described ruthenium structure.

The alkali-soluble resin is preferably a crosslinked cyclic hydrocarbon ring which is an aliphatic hydrocarbon ring having a structure in which two or more rings have two or more atoms.

Specific examples of the crosslinked cyclic hydrocarbon ring include, for example, a lowering Alkane, different Alkane, adamantane, tricyclo[5.2.1.0(2,6)]decane, tricyclo[5.2.1.0(2,6)]nonene, tricyclopentene, tricyclopentane, tricyclopentadiene Dicyclopentadiene; a group in which one of these groups is substituted by a substituent.

The substituent may, for example, be an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amine group or a halogen atom.

The carbon number of the crosslinked cyclic hydrocarbon ring is preferably 5 or more, and particularly preferably 7 or more, from the viewpoint of compatibility with other materials or solubility to an alkali developer. The upper limit is preferably 12 or less, and particularly preferably 10 or less.

Further, the alkali-soluble resin preferably has a maleimide structure represented by the following general formula (III).

[In the general formula (III), R ^M is a hydrocarbon ring which may also be substituted. ]

In the case where the alkali-soluble resin has a maleic acid imide structure represented by the general formula (III), since the hydrocarbon ring has a nitrogen atom, it is a base which belongs to the polymer having the structural unit represented by the above general formula (I). The compatibility between the dispersants is very good, the development speed is fast, and the suppression effect of the development residue is enhanced.

In the R ^M of the general formula (III), specific examples of the hydrocarbon ring which may be substituted may, for example, be the same as the specific examples of the hydrocarbon ring described above.

For example, an aliphatic hydrocarbon ring such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, or a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group or a methoxybenzene group. An aromatic hydrocarbon ring such as a group, a benzyl group, a hydroxyphenyl group or a naphthyl group, or a group in which one of these groups is substituted by a substituent.

In the alkali-soluble resin used in the present invention, in addition to the constituent unit of the carboxyl group, it is easy to adjust the respective constituent unit amounts and increase the constituent unit amount of the hydrocarbon ring, and it is easy to improve the function of the constituent unit. In other words, an acrylic copolymer having a constituent unit having the above hydrocarbon ring is preferably used.

The acrylic copolymer having a carboxyl group and the above hydrocarbon ring can be produced by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other monomer copolymerizable".

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, and (meth)acrylic acid. The ester, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, etc., are more effective in maintaining the cross-sectional shape of the colored layer after development in the heat treatment. It is preferable to use at least one selected from the group consisting of cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene.

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in a side chain. In the case of having an ethylenic double bond, in the hardening step of the resin composition at the time of production of the color filter, the alkali-soluble resins or the alkali-soluble resin and the polyfunctional monomer may form a cross-linking bond. The film strength of the cured film is further improved, the development resistance is improved, and the heat shrinkage of the cured film is suppressed to be excellent in adhesion to the substrate.

The method of introducing an ethylenic double bond into the alkali-soluble resin can be appropriately selected by a conventionally known method. For example, a carboxyl group having an alkali-soluble resin is added to a compound having an epoxy group and an ethylenic double bond in the molecule, for example, glycidyl (meth)acrylate, and the like, and an ethylenic double is introduced into the side chain. A method of introducing a constituent unit having a hydroxyl group into a copolymer, a compound having an isocyanate group and an ethylenic double bond in the molecule, and a method of introducing an ethylenic double bond into a side chain.

The alkali-soluble resin of the present invention may further contain other constituent units such as methyl (meth)acrylate, ethyl (meth)acrylate, and the like, and constituent units having an ester group. The constituent unit having an ester group has a function as a component which suppresses the alkali solubility of the coloring resin composition for a color filter, and also has a function as a component which improves the solubility in a solvent and further resolves the solvent.

The alkali-soluble resin of the present invention preferably has an acrylic resin having a constituent unit of a carboxyl group, an acrylic copolymer having a structural unit of a hydrocarbon ring, and a styrene-acrylic copolymer, and more preferably has a carboxyl group. An acrylic resin such as an acrylic copolymer or a styrene-acrylic copolymer having a unit of a hydrocarbon ring, an acrylic copolymer having a constituent unit of an ethylenic double bond, or the like.

The alkali-soluble resin can be made into an alkali-soluble resin having a desired property by appropriately adjusting the amount of each constituent unit.

The amount of the carboxyl group-containing ethylenically unsaturated monomer to be filled is preferably 5% by mass or more, and more preferably 10% by mass or more based on the total amount of the monomers, from the viewpoint of obtaining a good pattern. On the other hand, the amount of the carboxyl group-containing ethylenically unsaturated monomer to be filled is preferably 50% by mass or less, more preferably from the viewpoint of suppressing film roughness of the surface of the pattern after development. It is 40% by mass or less.

When the ratio of the carboxyl group-containing ethylenically unsaturated monomer is at least the above lower limit value, the solubility of the obtained coating film to the alkali developing solution is sufficient; and, if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is the above upper limit When the value is below the value, there is a tendency that the formed pattern is less likely to fall off from the substrate or the film on the surface of the pattern is rough during development of the alkali developer.

In addition, an acrylic resin having an acryl-based copolymer having a structural unit of an ethylenic double bond and a styrene-acrylic copolymer or the like, which is an alkali-soluble resin, can be more preferably used. The compounding amount of the saturated monomer and the compound having an epoxy group and an ethylenic double bond are preferably 10% by mass or more and 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less.

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. In the case where the curing agent is hardened at a temperature of less than 1,000, the function of the binder is remarkably lowered. If it exceeds 50,000, the pattern is difficult to form during the development of the alkali developer.

Further, the above weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be determined by using Shodex GPC System-21H (Shodex GPC System-21H) using THF as an eluent.

The epoxy group-containing (meth) acrylate resin having a carboxyl group is not particularly limited, and an epoxy obtained by reacting an epoxy compound with a monocarboxylic acid containing an unsaturated group with an acid anhydride is preferable. A (meth) acrylate compound.

The epoxy compound, the monocarboxylic acid containing an unsaturated group, and the acid anhydride can be appropriately selected from known ones. The epoxy group-containing (meth) acrylate resin having a carboxyl group may be used alone or in combination of two or more.

The alkali-soluble resin is preferably one having an acid value of 50 mgKOH/g or more from the viewpoint of developability (solubility) of the aqueous alkali solution used in the developer. The acid value of the alkali-soluble resin is preferably 70 mgKOH/g or more and 300 mgKOH/g or less from the viewpoint of the developability (solubility) of the aqueous alkali solution used in the developer and the adhesion to the substrate. More preferably, it is 80 mgKOH/g or more and 280 mgKOH/g or less.

Further, in the present invention, the acid value can be measured in accordance with JIS K 0070.

The ethylenically unsaturated bond equivalent in the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group is obtained from the viewpoint of obtaining the film strength of the cured film and improving the development resistance and the adhesion to the substrate. It is preferably in the range of 100 to 2,000, and particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 2,000 or less, development resistance or adhesion is excellent. In addition, when the ratio is 100 or more, the ratio of the constituent unit having the carboxyl group or the other constituent unit having the constituent unit of the hydrocarbon ring can be relatively increased, so that the developability or heat resistance is excellent.

Here, the ethylenically unsaturated bond equivalent means the weight average molecular weight per 1 mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

Formula (1) Ethylene Unsaturated Bond Equivalent (g/mol)=W(g)/M(mol)

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

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

The alkali-soluble resin to be used for the color filter resin composition may be used singly or in combination of two or more kinds, and the content thereof is not particularly limited, and it is a coloring resin composition for a color filter. The total amount of the solid content of the alkali-soluble resin is preferably 5% by mass and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less. When the content of the alkali-soluble resin is at least the above lower limit value, sufficient alkali developability is easily obtained, and when the content of the alkali-soluble resin is at most the above upper limit value, film roughening or pattern peeling during development is easily suppressed.

 (multifunctional monomer)  

The polyfunctional monomer used in the coloring resin composition for a color filter is not particularly limited as long as it is polymerizable by the above photoinitiator, and it is usually suitable to use two or more ethylenic unsaturation. The compound having a double bond is particularly preferably a polyfunctional (meth) acrylate having two or more acryloyl fluorenyl groups or methacryl fluorenyl groups.

Such a polyfunctional (meth) acrylate can be appropriately selected from known ones. Specific examples include those described in Japanese Laid-Open Patent Publication No. 2013-029832.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more. Further, when the colored resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer preferably has three (trifunctional) or more polymerizable double bonds, and more preferably A poly(meth)acrylate of a trihydric or higher polyhydric alcohol or a modified dicarboxylic acid, specifically, preferably: trimethylolpropane tri(meth)acrylate, pentaerythritol III ( Methyl) acrylate, succinic acid modification of pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, two A succinic acid modification of pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like.

The content of the above polyfunctional monomer used for the coloring resin composition for a color filter is not particularly limited, and the polyfunctional monomer is preferably 5 in terms of the total amount of the solid content of the colored resin composition for a color filter. It is in the range of % by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less. When the content of the polyfunctional monomer is at least the above lower limit value, the photocuring is sufficiently performed, and the elution of the exposed portion at the time of development can be suppressed. When the content of the polyfunctional monomer is at most the above upper limit, the alkali developability is sufficient. .

 <Photoinitiator>  

The initiator to be used in the coloring resin composition for a color filter of the present invention is not particularly limited, and one type of the various initiators known in the art may be used, or two or more types may be used in combination.

The starting agent may, for example, be an aromatic ketone, a benzoin ether or a halomethyl group. Diazole compound, α-amino ketone, biimidazole, N,N-dimethylaminodiphenyl ketone, halomethyl-S-three Compound, 9-oxosulfur Wait. Specific examples of the initiator include aromatics such as diphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, and 4-methoxy-4'-dimethylaminodiphenyl ketone. a ketone ketone, a benzoin ether such as benzoin methyl ether, a benzoin such as ethyl benzoin, or a double of 2-(o-chlorophenyl)-4,5-phenylimidazole dimer Imidazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halomethyl group such as oxadiazole Diazole compound, 2-(4-butoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-S-three Halomethyl-S-three Compound, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-N- Polinylacetone, 1,2-benzyl-2-dimethylamino-1-(4-N- Phenylphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzhydrylbenzoic acid, methyl benzhydrylbenzoate, 4-benzylidene-4' -methyldiphenyl sulfide, benzyl methyl ketal, dimethylamino benzoate, p-amylamino benzoate, 2-n-butoxyethyl-4- Methylaminobenzoic acid ester, 2-chloro 9-oxo sulfur 2,4-diethyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxosulfur , 4-benzylidene-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4- Phenyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4- Polinyl)-1-propanone and the like.

Among them, 2-methyl-1-[4-(methylthio)phenyl]-2-N- is preferably used. Polinyl propan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-N- Polinylphenyl)-1-butanone, 4,4'-bis(diethylamino)acetophenone, diethyl 9-oxosulfur . From the viewpoints of sensitivity adjustment, suppression of water bleeding, and improvement of development resistance, it is more preferable to combine 2-methyl-1-[4-(methylthio)phenyl]-2-N- Alkyl propan-1-one-like α-aminoacetophenone-based initiator and diethyl 9-oxosulfur 9-oxygen sulfur Is the initiator.

Using α-aminoacetophenone initiator and 9-oxosulfur In the case of the initiator, the total content of these is preferably 5% by mass or more and 15% by mass or less based on the total amount of the solid content of the colored resin composition. If the starting dose is 15% by mass or less, it is preferable because the sublimate in the manufacturing process is reduced. When the starting dose is 5% by mass or more, development resistance such as water bleeding is improved.

In the present invention, from the viewpoint of enhancing sensitivity, the initiator preferably contains an oxime ester photoinitiator. By using an oxime ester-based photoinitiator, it is easy to suppress variations in line width in the plane when forming a fine line pattern. Further, by using an oxime ester photoinitiator, the development resistance is improved and the water permeation suppressing effect tends to be high. Further, the term "water permeation" refers to a phenomenon in which, after alkali development, after washing with pure water, a trace such as water bleeding occurs, when a component which improves alkali developability is used. Since such water permeation disappears after post-baking, there is no problem as a product. However, when the appearance of the pattern surface is examined after development, an abnormality is detected, and the problem that the normal product and the abnormal product cannot be distinguished is generated. . Therefore, if the inspection sensitivity of the inspection apparatus is lowered at the time of visual inspection, the result is that the yield of the final color filter product is lowered, which is a problem.

The oxime ester-based photoinitiator is preferably one having an aromatic ring, from the viewpoint of reducing contamination by a colored resin composition for a color filter due to a decomposition product or contamination of a device. The condensed ring having an aromatic ring is more preferably a condensed ring containing a benzene ring and a hetero ring.

As the oxime ester photoinitiator, it can be composed of 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzylidene fluorenyl)], ethyl ketone, 1-[9- Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(o-ethylindenyl), Japanese Patent Laid-Open No. 2000-80068, JP-A-2001 An oxime ester photoinitiator described in the above-mentioned Japanese Patent Publication No. 233-842, No. 2010-527339, No. 2010-527338, and No. 2013-041153 is appropriately selected. As a commercially available product, Irgacure OXE-02 (manufactured by BASF Corporation), ADEKA ARKLS NCI-831 (made by Adeka Co., Ltd.), and TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) having a carbazole skeleton can be used. ADEKA ARKLS NCI-930 (made by ADEKA), TR-PBG-345, TR-PBG-3057 (made by Changzhou Strong Electronic New Materials Co., Ltd.) and Irgacure OXE-01 (made by BASF), TR-PBG-365 (manufactured by Changzhou Strong Electronic New Material Co., Ltd.) having a skeleton. From the viewpoint of luminance, an oxime ester photoinitiator having a diphenyl sulfide skeleton or an anthracene skeleton is particularly preferably used. Further, from the viewpoint of high sensitivity, an oxime ester photoinitiator having a carbazole skeleton is preferably used.

Moreover, it is preferable to use two or more types of oxime-based photoinitiators in view of the fact that the development resistance or the luminance is easily improved and the effect of suppressing the occurrence of water bleeding is high. From the viewpoint of high luminance and high heat resistance, it is preferable to use two kinds of oxime ester-based photoinitiators having a diphenyl sulfide skeleton or a combination of an oxime ester-based photopolymer having a diphenyl sulfide skeleton. The initiator and the oxime ester photoinitiator having an anthracene skeleton. Further, from the viewpoint of superior sensitivity and water permeation inhibition effect, it is preferred to use an oxime ester photoinitiator having a carbazole skeleton, an oxime ester photoinitiator having an anthracene skeleton, or a diphenyl group. An oxime ester of a thioether is a photoinitiator.

Further, from the viewpoint of suppressing water bleeding and improving sensitivity, it is preferred to use a photoinitiator having a tertiary amine structure in combination with an oxime ester photoinitiator. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure of an oxygen quencher in the molecule, the radical generated by the initiator is not easily deactivated by oxygen, and the sensitivity can be improved. As a commercially available product of the above-mentioned photoinitiator having a tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2-N- Lolinylpropan-1-one (for example, Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-N- Polinylphenyl)-1-butanone (for example, Irgacure 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)diphenyl ketone (for example, Hicure ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), and the like.

Further, from the viewpoints of sensitivity adjustment, suppression of water bleeding, and improvement of development resistance, it is preferred to combine 9-oxosulfuric acid with an oxime ester photoinitiator. It is preferred to combine two or more kinds of oxime-based photoinitiators and 9 in terms of brightness, development resistance, easy adjustment sensitivity, high water permeation inhibition effect, and improvement of development resistance. - Oxygen sulfur Is the initiator.

The content of the photoinitiator used in the colored resin composition for a color filter of the present invention is usually 0.01 parts by mass or more and 100 parts by mass or less, preferably 100 parts by mass or less based on 100 parts by mass of the above polyfunctional monomer. 5 parts by mass or more and 60 parts by mass or less. When the content is at least the above lower limit value, the photocuring is sufficiently performed, and the elution of the exposed portion at the time of development is suppressed. On the other hand, when the content is at most the above upper limit, the yellowing property of the obtained colored layer is weak, and the luminance can be suppressed. reduce.

In addition, as a photoinitiator used in the colored resin composition for a color filter of the present invention, the total content of two or more kinds of oxime ester photoinitiators is such that the photoinitiator is sufficiently exhibited. From the viewpoint of the effect, the total amount of the solid content of the colored resin composition for a color filter is preferably 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less. Within the scope.

In the coloring resin composition for a color filter of the present invention, the total amount of the binder component is preferably 35 mass% or more based on the total amount of the solid content of the coloring resin composition for a color filter. Further, 97% by mass or less, more preferably 40% by mass or more and 96% by mass or less. When it is more than the above lower limit value, a coloring layer excellent in hardness or adhesion to a substrate can be obtained. Moreover, when it is at most the above upper limit value, the developability is excellent, and the occurrence of minute wrinkles due to heat shrinkage is also suppressed.

 <arbitrarily added ingredients>  

The colored resin composition for a color filter may contain various additives as needed.

As an additive, for example, an antimony compound, for example, a mercapto compound, a polymerization stopper, a chain shifting agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a decane coupling agent, an ultraviolet absorber, and a dense adhesion promotion are mentioned. Agents, etc.

In the colored resin composition for a color filter of the present invention, it is preferred to further contain an antioxidant from the viewpoint of improving heat resistance, suppressing fading of the color material, and improving the luminance.

The antioxidant may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and lanthanoid antioxidants, and are preferably blocked from the viewpoint of heat resistance. Phenolic antioxidants.

The hindered phenol-based antioxidant refers to an antioxidant having a structure in which at least one phenol structure is contained, and at least one of the two or six positions of the hydroxyl group of the phenol structure is substituted with a substituent having 4 or more carbon atoms. Construction.

Specific examples of the hindered phenol-based antioxidant include dibutylhydroxytoluene (BHT) and pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (products) Name: Irganox 1010, manufactured by BASF), 1,3,5-gin (3,5-di-t-butyl-4-hydroxybenzyl)-polyisocyanate (trade name: Irganox 3114, manufactured by BASF), 2, 4 , 6-gin (4-hydroxy-3,5-di-t-butylbenzyl)-symmetrical trimethylbenzene (trade name: Irganox 1330, manufactured by BASF), 6-(4-hydroxy-3,5-di-3rd Alkylamino)-2,4-bis(octylthio)-1,3,5-three (trade name: Irganox 565, manufactured by BASF), 2,2'-thiodiethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox) 1035, manufactured by BASF), 1,2-bis[3-(4-hydroxy-3,5-di-t-butylphenyl)propanyl]anthracene (trade name: Irganox MD1024, manufactured by BASF), 3-( Octyl 4-hydroxy-3,5-diisopropylphenyl)propanoate (trade name: Irganox 1135, manufactured by BASF), 4,6-bis(octylthiomethyl)-o-cresol (trade name: Irganox) 1520L, manufactured by BASF), N,N'-hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanamide] (trade name: Irganox 1098, manufactured by BASF) 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 259, manufactured by BASF), 1-dimethyl- 2-[(3-Tertibutyl-4-hydroxy-5-methylphenyl)propanoxy]ethyl]2,4,8,10-tetraoxaspiro[5.5]undecane (Commodity Name: ADK STAB AO-80, manufactured by ADEKA), bis(3-t-butyl-4-hydroxy-5-methylphenylpropionic acid) ethylene bis(ethylene oxide) (trade name: Irganox 245, manufactured by BASF), 1,3,5-gin[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-tri -2,4,6(1H,3H,5H)-trione (trade name: Irganox 1790, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: SUMILIZER MDP-S, manufactured by 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-hydroxybenzylphosphonic acid diethyl ester (trade name: Irgamod 195, manufactured by BASF), 2-tert-butyl-4-methyl-6-(2-hydroxy-3-acrylate Third butyl-5-methylbenzyl)phenyl ester (trade name: SUMILIZER GM, manufactured by Sumitomo Chemical Co., Ltd.), 4,4'-thiobis(6-t-butyl-m-cresol) (trade name: SUMILIZER WX-R, manufactured by Sumitomo Chemical Co., Ltd., 6,6'-di-tert-butyl-4,4'-butylene m-cresol (trade name: ADEKASTAB AO-40, manufactured by ADEKA). Other compounds having an oligomeric type and a polymer type having a hindered phenol structure can also be used.

Among them, from the viewpoint of heat resistance and light resistance, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, BASF) is preferred. Company system).

Further, from the viewpoint of forming a coloring layer which is capable of forming a luminance and a contrast, it is preferably a molecular weight of 1,000 or less, and a molecular weight of one or more phenolic hydroxyl groups is 280 equivalents or less, more preferably 500 or less, and one phenolic hydroxyl group per one. The hindered phenol-based antioxidant having a molecular weight of 200 equivalent or less. It is presumed that such an antioxidant has high fluidity and a large number of active points per weight unit, thereby suppressing color material agglomeration caused by rapid hardening shrinkage during exposure or post-baking by radical trapping, or inhibiting resin, etc. The yellowing is easy to obtain the above effects. As such an antioxidant, for example, 6,6'-di-t-butyl-4,4'-butylene-m-cresol (trade name: ADEKASTAB AO-40, manufactured by ADEKA) can be mentioned.

Further, in the present invention, it is preferred to use a latent antioxidant as an antioxidant from the viewpoint of forming a comparatively enhanced coloring layer. When a latent antioxidant is used, it is presumed that since the radical trapping effect is particularly high in post-baking, the coloring of the color material due to the rapid hardening shrinkage during post-baking is suppressed, and the above effects are easily obtained. The latent antioxidant in the present invention is a compound having a protective group which can be detached by heating, and exhibits an antioxidant function by being detached from the protective group. Among them, it is preferred that the protecting group is easily detached by heating at 150 ° C or higher. For example, a latent antioxidant as described in International Patent Publication No. 2014/021023 can be mentioned.

The latent antioxidant which is suitably used in the present invention is, for example, a latent hindered phenol-based antioxidant which protects the phenolic hydroxyl group of the hindered phenol-based antioxidant with a protective group which can be removed by heating. Examples of the latent hindered phenol-based antioxidant include a phenolic hydroxyl group of a hindered phenol-based antioxidant, an acid anhydride, an acid chloride, a Boc reagent, an alkyl halide compound, a mercapto chloride compound, or an allyl ether compound. Etc. As a latent hindered phenol-based antioxidant, a structure in which a hydrogen of a phenol group of a hindered phenol-based antioxidant is substituted with a protective group such as a third butoxycarbonyl-based amine-based ester is suitably used. Specific examples are as follows: The chemical formulae (a) to (c) and the like are described, but are not limited thereto.

[化8]

The method for producing the above-mentioned latent antioxidant is not particularly limited. For example, Japanese Patent Laid-Open No. Sho 57-111375, JP-A-3-173833, JP-A-6-128195, JP-A-7-20771, JP-A-7-252191 The phenolic compound produced by the method described in each of the publications of JP-A-2004-501128 is obtained by reacting with an acid anhydride, an acid chloride, a Boc reagent, an alkyl halide compound, a mercapto chloride compound, an allyl ether compound, or the like. Further, a commercially available product can also be used.

When the colored resin composition for a color filter of the present invention contains the above-described oxime ester-based photoinitiator in combination with an antioxidant as a photosensitive colored resin composition, the effect of the multiplication effect is suppressed to invade into the mask opening. The portion where the outer portion of the portion is weakened and hardened; furthermore, the hollowing out during development, the defect during the development, and the peeling are less likely to occur; and it is less likely to occur due to the chaotic reflection of light when the colored layer is viewed obliquely. It is preferable from the viewpoint of color unevenness.

The content of the antioxidant is preferably 0.05 parts by mass or more and 10.00 parts by mass or less, more preferably 0.10 parts by mass or more and 5.00 parts by mass or less based on 100 parts by mass of the total solid content in the colored resin composition. When it is more than the above lower limit, heat resistance and light resistance are excellent. On the other hand, if it is at most the above upper limit value, the colored resin composition of the present invention can be used as a highly sensitive photosensitive resin composition.

When the antioxidant is used in combination with the above-mentioned oxime ester-based photoinitiator, the content of the antioxidant is preferably 100 parts by mass or more based on the total amount of the oxime ester-based photoinitiator, and the antioxidant is preferably 1 part by mass or more. Further, it is 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, still more preferably 5 parts by mass or more and 45 parts by mass or less. If it is within the above range, the effect of the above combination is excellent.

The colored resin composition for a color filter of the present invention preferably further contains a mercapto compound from the viewpoint of enhancing the effect of suppressing water permeation.

In addition, when the oxime ester-based photoinitiator and the mercapto compound are contained as a photosensitive colored resin composition in combination with the colored resin composition for a color filter of the present invention, the water osmosis is further enhanced from the viewpoint of improving development resistance. It is preferable from the viewpoint of the effect of suppressing the occurrence of dyeing, and the improvement in linearity when the fine line pattern is formed, or the ability to form a fine line pattern as in the design of the mask line width. Further, when the oxime ester-based photoinitiator and the mercapto compound are contained in combination, the hollowing out during development and the defects and peeling during development are less likely to occur due to the multiplication effect, and it is less likely to occur in the oblique direction. It is preferable from the viewpoint of color unevenness caused by the disordered reflection of light when viewing the colored layer.

In addition, the term "linear improvement" means that the end portion of the coloring layer formed in the developing step after the application of the colored composition is less irregular, and is formed linearly or linearly.

The mercapto compound can function as a chain shifting agent, and has a property of receiving a radical by a radical having a slow reaction, thereby accelerating the reaction and improving the curability.

As the mercapto compound, for example, 2-mercaptobenzothiazole and 2-mercaptobenzoic acid can be mentioned. Oxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, 3 - ethyl mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis(3-mercaptobutyloxy)butane, 1,3,5-gin (3-mercaptobutyloxyethyl)- 1,3,5-three -2,4,6(1H,3H,5H)-trione, trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol bismuth (3-mercaptobutyrate), pentaerythritol bismuth (3-mercaptopropyl acrylate) Acid ester), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

The thiol compound may be used alone or in combination of two or more. From the viewpoint of increasing the crosslinking density and improving the water permeation inhibiting effect, it is preferably selected from the group consisting of two or more sulfhydryl groups in one molecule. One or more kinds of the group consisting of functional mercapto compounds.

Further, from the viewpoint of easily maintaining a good water permeation inhibiting effect even in the case of long-term storage, it is preferred to have a secondary sulfhydryl group in which the carbon atom to which the thiol group is bonded is a secondary carbon atom. The mercapto compound is more preferably a polyfunctional secondary mercapto compound having two or more such mercapto groups in one molecule.

The content of the mercapto compound used in the coloring resin composition for a color filter is not particularly limited, and the total amount of the solid content of the colored resin composition for a color filter is obtained from the viewpoint of sufficiently exerting the above effects. The mercapto compound is preferably in a range of 0.2% by mass or more and 7% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less.

Further, in the colored resin composition for a color filter of the present invention, it is preferable to further contain an ultraviolet absorber from the viewpoint of forming a comparatively enhanced coloring layer. The effect of improving these characteristics can be presumed to be caused by the agglomeration of the color material caused by the rapid hardening shrinkage in the exposure step. The ultraviolet absorber may be appropriately selected from conventionally known ones. Specific examples of the ultraviolet absorber include a benzotriazole-based compound, a diphenylketone-based compound, and three. A compound or the like. Among them, a benzotriazole-based compound is preferably used from the viewpoint of forming a comparatively enhanced coloring layer.

The benzotriazole-based compound may, for example, be 2-(5-methyl-2-hydroxyphenyl)benzotriazole or 2-(2-hydroxy-5-t-butylphenyl)-2H-benzene. And triazole, octyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethyl a mixture of hexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[2-hydroxy- 3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5 -Chlorobenzotriazole, 2-(3,5-di-t-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-trioctylphenyl)benzene And triazole, 5% 2-methoxy-1-methylethyl acetate and 95% phenylpropionic acid, 3-(2H-benzotriazol-2-yl)-(1,1- Dimethylethyl)-4-hydroxyl, C7-9 side chain and linear alkyl ester compound, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl -1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3, 3-tetramethylbutyl phenol or the like, but is not limited thereto.

Commercial products include, for example, "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 384-" manufactured by BASF. 2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130", etc.

The benzotriazole-based compound is preferably a benzotriazole-based compound represented by the following general formula (IV) from the viewpoint of forming a comparatively enhanced colored layer.

(In the general formula (IV), R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may be substituted by a phenyl group, and X represents a hydrogen atom or a chlorine atom.)

In the general formula (IV), R ^{12 is} preferably a methyl group, a tert-butyl group, a third pentyl group, a third octyl group, or an α,α-dimethylbenzyl group, and R ^{11 is} preferably a hydrogen atom. , a third butyl group, a third pentyl group, or an α,α-dimethylbenzyl group.

The content of the ultraviolet absorber to be used in the coloring resin composition for a color filter is not particularly limited, and the ultraviolet absorber is preferably 0.05 parts by mass or more and 10.00% by weight based on 100 parts by mass of the total solid content in the colored resin composition. It is preferably 0.10 parts by mass or more and 5.00 parts by mass or less by mass or less. When it is more than the above lower limit, heat resistance and light resistance are excellent. On the other hand, when it is at most the above upper limit value, the colored resin composition of the present invention can be used as a photosensitive resin composition having high sensitivity.

When the colored resin composition for a color filter of the present invention contains the above-described oxime ester-based photoinitiator in combination with the ultraviolet ray absorbing agent as a colored resin composition, the hollowing out during development is less likely to occur due to the multiplication effect. Defects and peeling at the time of development accompanying this are more preferable because it is less likely to occur in the case of color unevenness caused by the disordered reflection of light when the colored layer is viewed obliquely.

In the case where the ultraviolet absorber is used in combination with the above-mentioned oxime ester photoinitiator, the content of the ultraviolet absorber is preferably 1 in terms of 100 parts by mass of the total amount of the oxime ester photoinitiator. The mass part or more is 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, still more preferably 5 parts by mass or more and 45 parts by mass or less. If it is in the above range, the effect of the above combination is excellent.

Further, as a specific example of the surfactant and the plasticizer, for example, those described in JP-A-2013-029832 can be cited.

Further, the colored resin composition for a color filter of the present invention preferably further contains a decane coupling agent from the viewpoint of suppressing the release of the coating film. Examples of the decane coupling agent include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, and KBE-403. KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Lee Co., Ltd.). Among them, from the viewpoint of the adhesion of the SiN substrate, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 having a methacrylic group and an acrylic group are preferable.

The content of the decane coupling agent is 0.05 parts by mass or more and 10.0 parts by mass or less, more preferably 0.1 parts by mass or more and 5.0 parts by mass or less based on 100 parts by mass of the total solid content in the colored resin composition. When it is more than the above lower limit value and not more than the above upper limit value, the peeling of the coating film is excellent.

 <Preparation ratio of each component in the colored resin composition for color filter>  

The total content of the color materials is preferably 3% by mass or more and 65% by mass or less, and more preferably 4% by mass or more and 60% by mass or less based on the total amount of the solid content of the colored resin composition for a color filter. Proportional allocation. When the color filter resin composition is applied to a predetermined film thickness (usually 1.0 μm or more and 5.0 μm or less), the color layer has a sufficient color density. Moreover, when it is at most the above upper limit value, the storage stability is excellent, and a coloring layer having sufficient hardness and adhesion to the substrate can be obtained. In particular, in the case of forming a coloring layer having a high coloring material concentration, the content of the coloring material is preferably 15% by mass or more and 65% by mass or less, based on the total amount of the solid content of the colored resin composition for a color filter. Jiawei is blended in a ratio of 25 mass% or more and 60 mass% or less.

In addition, the content of the dispersant is not particularly limited as long as the color material can be uniformly dispersed. For example, the content of the solid content of the colored resin composition for a color filter can be 1% by mass or more and 40% by mass or less. . In addition, the total amount of the solid content of the colored resin composition for a color filter is preferably 2% by mass or more and 30% by mass or less, and particularly preferably 3% by mass or more and 25% by mass or less. Proportional allocation. When it is more than the above lower limit value, the dispersibility and dispersion stability of the color material are superior, and the storage stability of the colored resin composition for a color filter is superior. Moreover, when it is below the said upper limit, the developability becomes favorable. In particular, in the case of forming a coloring layer having a high coloring material concentration, the content of the dispersing agent is preferably 2% by mass or more and 25% by mass or less, based on the total amount of the solid content of the colored resin composition for a color filter. Jiawei is formulated in a ratio of 3 mass% or more and 20 mass% or less.

Further, the content of the solvent may be appropriately set depending on the range in which the coloring layer can be formed with high precision. The total amount of the colored resin composition for a color filter containing the solvent is usually preferably in the range of 55% by mass or more and 95% by mass or less, more preferably 65% by mass or more and 88% by mass or less. Inside. When the content of the solvent is within the above range, it is possible to obtain a coating property superior.

When a negative photosensitive adhesive component is combined to form a photosensitive colored resin composition for a blue colored layer, the blue color material in the color material is suppressed from the viewpoint of suppressing defects, peeling, and color unevenness during development. The color material ratio (mass ratio) of the purple color material and PG59 is preferably set to a color material ratio satisfying the following average transmittance.

The test color material dispersion liquid is prepared by using a suitable dispersing agent and a solvent in a manner of a predetermined color material ratio, and the test color material dispersion liquid is diluted by PGMEA in such a manner that the total content of the color material is 0.001% by mass, and the diluted test color is obtained. The material dispersion was placed in a quartz cell having an optical path length of 10 mm to measure the spectral transmittance. In the measurement of the spectral transmittance, the average transmittance in the range of 280 nm or more and 360 nm or less is preferably 36% or more, more preferably 39% or more, still more preferably 40% or more. The spectral transmittance can be measured using an ultraviolet-visible spectrophotometer (for example, an ultraviolet-visible near-infrared spectrophotometer UV-3150 manufactured by Shimadzu Corporation).

Further, as a suitable dispersing agent and solvent, for example, a dispersing agent and a solvent used in the color material dispersion liquid of Example 1 to be described later, for example, the test color material dispersion liquid and the color material dispersion liquid of Example 1 can be used. Modulate the same.

In addition, when the negative photosensitive adhesive component is combined to form a photosensitive colored resin composition for a blue colored layer, the blue color in the color material is suppressed from the viewpoint of suppressing defects, peeling, and color unevenness during development. The color ratio (mass ratio) of the material, the purple color material, and the PG59 is preferably set to a color material ratio satisfying the average average transmittance described below.

In the chromaticity coordinates of the XYZ color system of JIS Z8701 whose film thickness is 2.8 μm or less and the color measured by the C light source is a single pixel, the chromaticity coordinates in the XYZ color system of JIS Z8701 can be expressed as x=0.120 or more and 0.147 or less, and y=0.038 or more. Further, the cured film of the color space in the range of 0.180 or less is preferably a blue color material in a color material of a cured film of a color space of x=0.125 or more and 0.147 or less, y=0.038 or more and 0.120 or less, The ratio of the color material of the purple color material and the PG59, the color material concentration of the color material concentration (total mass of the color material / the total mass of the solid portion of the cured film) of the cured film (the total mass/color of the color material) The diluted test color material dispersion of the solvent color material dispersion liquid was placed in a quartz cell having an optical path length of 10 mm to measure the spectral transmittance. In the measurement of the spectral transmittance, the average transmittance in the range of 280 nm or more and 360 nm or less is preferably 42% or more, more preferably 44% or more, still more preferably 46% or more. The spectral transmittance can be measured in the same manner as described above using an ultraviolet-visible spectrophotometer.

In the above-mentioned dilute test color material dispersion liquid, for example, the blue color material, the purple color material, and the PG59 are set to a desired ratio according to the color material ratio in the cured film, and the color material dispersion liquid of the first embodiment described later is used. The dispersant and the solvent to be used were prepared in the same manner as in Example 1 to prepare a color material dispersion liquid, which was a color material of one-six thousandth of the color material concentration (total mass of the color material / total mass of the solid portion of the cured film) of the cured film. The concentration (the total mass of the color material / the total mass of the solvent-containing color material dispersion) can be adjusted by diluting with a solvent such as PGMEA.

In the colored resin composition for a color filter of the present invention, the P/V ratio ((the total mass of the color material in the composition) / (the total mass of the solid content other than the color material in the composition)) is determined by the blue color From the viewpoint of expanding the color reproduction domain, it is preferably 0.10 or more, more preferably 0.15 or more, still more preferably 0.20 or more; on the other hand, solvent resolubility, development residue, development adhesion, development resistance, development The viewpoint of suppressing the occurrence of defects or unevenness and the viewpoint of superiority such as contrast are preferably 0.60 or less, more preferably 0.50 or less, still more preferably 0.45 or less, and particularly preferably 0.35 or less.

 <Cured film of colored resin composition for color filter>  

In the colored resin composition for color filters, it is preferable that the chromaticity coordinates in the XYZ color system of JIS Z8701 which can be formed by using the C light source are x=0.110 or more and 0.150 or less and y=0.035 or more. A cured film in the range of 0.190 or less.

Among them, from the viewpoint of enhancing color reproducibility, it is preferable that the chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source are x=0.120 or more and 0.147 or less, and y=0.038 or more. Further, the cured film in the range of 0.180 or less is more preferably formed into a cured film having a range of x=0.122 or more and 0.147 or less, y=0.038 or more and 0.150 or less, and more preferably x=0.125 or more and 0.147 or less. A cured film in the range of y=0.038 or more and 0.120 or less.

In the cured film of the colored resin composition for a color filter, in the chromaticity coordinates of the XYZ color system of JIS Z8701 having a film thickness of 2.8 μm or less and a color measured by a single light source, it is preferable. The color space in the range of x=0.120 or more and 0.147 or less, y=0.038 or more and 0.180 or less may be expressed as a color range of x=0.122 or more and 0.147 or less, y=0.038 or more and 0.150 or less. Further, the space can be expressed as a color space in the range of x=0.125 or more and 0.147 or less, y=0.038 or more and 0.120 or less.

In the cured film of the colored resin composition for a color filter, the chromaticity coordinates in the XYZ color system of JIS Z8701 whose film thickness is 2.8 μm or less and the color measured by the C light source is measured as a single pixel are used as The ratio or combination of the color ratios of the color spaces in the range of x=0.137 or more and 0.147 or less, y=0.038 or more, and less than 0.060 is preferably 43% by mass or more based on the total amount of the color materials. 85 mass% or less, the purple color material is 14% by mass or more and 40% by mass or less, and PG59 is 1% by mass or more and 24% by mass or less.

Similarly, a good blending ratio or combination for expressing a color space in the range of x=0.132 or more and 0.145 or less, y=0.060 or more, and less than 0.080 is preferably a blue color material with respect to the total amount of the color material. 43% by mass or more and 93% by mass or less, more preferably 43% by mass or more and 90% by mass or less, and the purple color material is 5% by mass or more and 39% by mass or less, and PG59 is 1% by mass or more and 30% by mass or less.

Similarly, a good blending ratio or combination for expressing a color space in the range of x=0.128 or more and 0.138 or less, y=0.080 or more, and less than 0.100 is preferably a blue color material with respect to the total amount of the color material. 35% by mass or more and 98% by mass or less, more preferably 35% by mass or more and 90% by mass or less, and the purple color material is 1% by mass or more and 23% by mass or less, and PG59 is 1% by mass or more and 49% by mass or less.

Similarly, a good blending ratio or combination for expressing a color space in the range of x=0.125 or more and 0.147 or less, y=0.100 or more, and less than 0.120 is preferably a blue color material with respect to the total amount of the color material. 25 mass% or more and 98 mass% or less, more preferably 27 mass% or more and 90 mass% or less, the purple color material is 1 mass% or more and 26 mass% or less, and PG59 is 1 mass% or more and 53 mass% or less.

Similarly, a good blending ratio or combination for expressing a color space in the range of x=0.122 or more and 0.147 or less, y=0.120 or more, and less than 0.150 is preferably a blue color material with respect to the total amount of the color material. 27% by mass or more and 89% by mass or less, the purple color material is 1% by mass or more and 26% by mass or less, and the PG59 is 10% by mass or more and 60% by mass or less.

Similarly, as a good blending ratio or combination for expressing a color space in the range of x=0.120 or more and 0.147 or less, y=0.150 or more and 0.180 or less, it is preferable that the blue color material is 26 with respect to the total amount of the color material. The mass% or more and 73 mass% or less, the purple color material is 1% by mass or more and 13% by mass or less, and the PG59 is 21% by mass or more and 65% by mass or less.

Further, the film thickness of the cured film herein is obtained by coating and drying a color filter with a colored resin composition, and then exposing the polyfunctional monomer to exposure, and then performing the dust-free furnace at 230 ° C. The film thickness after baking for 30 minutes.

 <Method for Producing Colored Resin Composition for Color Filter>  

The method for producing the colored resin composition for a color filter of the present invention is not particularly limited. For example, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator may be added to the color material dispersion of the present invention. Other components as needed are obtained by mixing them by a known mixing means. Alternatively, the color material dispersion liquid of each color material may be separately prepared by using the above dispersant, and various color material dispersion liquids, binder components, and other components as necessary may be obtained by mixing by using a known mixing means.

 [Color Filter]  

The color filter of the present invention includes at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers has a cured product of the colored resin composition for a color filter of the present invention. Colored layer.

The color filter of the present invention will be described with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a substrate 1, a light shielding portion 2, and a coloring layer 3.

 (colored layer)  

At least one of the coloring layers used in the color filter of the present invention is a cured product of the colored resin composition for a color filter of the present invention, and a colored layer formed by curing the colored resin composition.

The colored layer is usually formed in an opening of a light-shielding portion on a substrate to be described later, and is usually composed of a color pattern of three or more colors.

In addition, the arrangement of the colored layer is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangular type, or a four-pixel arrangement type. Further, the width, area, and the like of the colored layer can be arbitrarily set.

The thickness of the colored layer is appropriately controlled by the coating method, the solid content concentration or the viscosity of the colored resin composition for color filters, and the like, and is usually preferably in the range of 1 μm or more and 5 μm or less.

This colored layer can be formed, for example, by the following method.

First, the colored resin composition for a color filter of the present invention is applied to a substrate to be described later by a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. On top, a wet coating film is formed. Among them, spin coating or die coating is preferably used.

Next, using a hot plate or an oven, the wet coating film is dried, and then exposed to a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized to form a hard coating. membrane. Examples of the light source used for the exposure include ultraviolet rays such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the thickness of the light source or coating film to be used and the like.

Further, in order to promote the polymerization reaction after the exposure, heat treatment may be performed. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition for color filters to be used, the thickness of the coating film, and the like.

Next, development processing is carried out using a developing solution, and the unexposed portion is dissolved and removed to form a coating film in a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. In the alkali solution, an interface agent or the like may be added in an appropriate amount. Further, the development method can be carried out by a general method.

After the development treatment, the developer is usually washed, and the color filter is dried with a cured coating film of the colored resin composition to form a colored layer. Further, after the development treatment, heat treatment may be performed in order to sufficiently cure the coating film. The heating conditions are not particularly limited and may be appropriately selected in accordance with the use of the coating film.

 (lighting part)  

The light-shielding portion of the color filter of the present invention is formed into a pattern on a substrate to be described later, and can be used in the same manner as a light-shielding portion used in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and may be, for example, a stripe shape or a matrix shape. The light shielding portion may be a metal thin film such as chromium formed by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the resin binder. In the case of a resin layer containing light-shielding particles, there is a method of patterning by using a photosensitive resist by development, a method of patterning using an inkjet ink containing light-shielding particles, and heat-transfering a photosensitive resist. Printing method, etc.

The film thickness of the light-shielding portion is set to be 0.2 μm or more and 0.4 μm or less in the case of the metal thin film, and is set to be 0.5 μm or more and 2 μm or less in the case where the black pigment is dispersed or dissolved in the binder resin.

 (substrate)  

As the substrate, a transparent substrate or a tantalum substrate to be described later is used, and an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed on the substrate. Other color filter layers, resin layers, TFTs such as TFTs, circuits, and the like may be formed on the substrates.

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples thereof include a transparent rigid material that is not flexible such as quartz glass, an alkali-free glass, and a synthetic quartz plate, or a flexible transparent material such as a transparent resin film, an optical resin sheet, or a flexible glass.

The thickness of the transparent substrate is not particularly limited, and may be, for example, 100 μm or more and 1 mm or less in combination with the use of the color filter of the present invention.

Further, in the color filter of the present invention, in addition to the substrate, the light shielding portion, and the coloring layer, for example, a protective layer or a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, or the like may be formed.

 [display device]  

The display device of the present invention is characterized by having the above-described color filter of the present invention. The configuration of the display device in the present invention is not particularly limited, and may be appropriately selected from known display devices, and examples thereof include a liquid crystal display device and an organic light-emitting display device. In the present invention, in the liquid crystal display device of the horizontal electric field type, various display defects such as the disorder of alignment of the liquid crystal due to the electrical characteristics of the green pixel and the image sticking phenomenon caused by the threshold value of the switching are suppressed. Suitable for selecting a liquid crystal display device.

 <Liquid crystal display device>  

A liquid crystal display device of the present invention is characterized by comprising the above-described color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

The 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 a display device of the present invention, and is a schematic view showing an example of a liquid crystal display device. As shown in FIG. 2, the liquid crystal display device 40 of the present invention has a color filter 10, an opposite substrate 20 having a TFT array substrate, and the like, and a color filter 10 and the opposite substrate 20 are formed between the color filter 10 and the counter substrate 20. Liquid crystal layer 30.

Further, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and can be a known configuration of a liquid crystal display device in which a color filter is generally used.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used in a general liquid crystal display device can be employed. Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be suitably used.

Moreover, the counter substrate can be appropriately selected in accordance with the driving method of the liquid crystal display device of the present invention.

As a method of forming the liquid crystal layer, a method generally used as a method of producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.

 <Organic light-emitting display device>  

The organic light-emitting display device of the present invention is characterized by comprising the above-described color filter of the present invention and an organic light-emitting body.

The organic light-emitting display device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic view showing another example of the display device of the present invention, and is a schematic view showing an example of an 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. The organic protective layer 50 or the 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, a method of sequentially forming the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 on the color filter may be mentioned. Or a method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60 or the like. 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 used. The organic light-emitting display device 100 thus produced can also be applied to, for example, an organic EL display of a passive driving type or an organic EL display of an active driving type.

Further, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be used as a known configuration of an organic light-emitting display device in which a color filter is generally used.

 [Examples]  

The examples are shown below to specifically illustrate the invention. The invention is not limited by the description.

Further, the acid value of the block copolymer before salt formation is determined by the method described in JIS K 0070.

The amine valence of the block copolymer before salt formation is determined by the method described in JIS K 7237.

The weight average molecular weight (Mw) of the block copolymer before salt formation is determined by GPC (gel permeation chromatography) as a standard polystyrene conversion value according to the above-described measurement method of the present invention.

The glass transition temperature (Tg) of the block copolymer before salt formation and after salt formation is determined by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII TECHNOLOGY Co., Ltd.) according to the method described in JIS K 7121. .

 (Synthesis Example 1: Modulation of Dispersant a)  

In a 500 mL round bottom four-neck separation flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to -60 ° C, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 3.3 parts by mass of 1-ethoxyethyl methacrylate (EEMA) of the B block, 18.2 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 2-ethylhexyl methacrylate ( EHMA) 4.2 parts by mass, 7.0 parts by mass of n-butyl methacrylate (BMA), 24.7 parts by mass of benzyl methacrylate (BzMA), and 13.3 parts by mass of methyl methacrylate (MMA), using an addition funnel for 60 minutes dropping. After 30 minutes, the A block was dropped with a monomer of dimethylaminoethyl methacrylate (DMMA) in an amount of 30.8 parts by weight over 20 minutes. After allowing to react for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was purified by reprecipitation in hexane, filtration, and vacuum drying, and diluted with PGMEA to prepare a 30% by mass solid solution. 32.5 parts by mass of water was added, and the mixture was heated to 100 ° C and reacted for 7 hours to deprotect the constituent unit derived from EEMA to form a constituent unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is purified by reprecipitation in hexane, filtration, and vacuum drying to obtain an A block containing a structural unit represented by the general formula (I) and a composition containing a carboxyl group-containing monomer. The unit is a solvent-soluble B block block copolymer A-1 (acid value: 12 mgKOH/g, Tg: 44 ° C). The block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 8,100. Further, the amine value was 110 mgKOH/g.

Into a 100 mL round bottom flask, 29.35 parts by mass of PGMEA was dissolved in 29.35 parts by mass of the block copolymer A-1, and phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in an amount of 1.59 parts by mass (relative to the DMMA of the block copolymer A-1). The unit 1 mol, phenylphosphonic acid was 0.1 mol, and stirred at a reaction temperature of 30 ° C for 20 hours, thereby obtaining a salt type block copolymer A-1 (dispersant a) solution. The amine value after salt formation is specifically calculated as follows.

1 g of a solution in which a salt-type block copolymer A-1 (solid matter after reprecipitation) was mixed with 91 parts by mass of chloroform-D1 NMR was added to the NMR sample tube, and a nuclear magnetic resonance apparatus (FTM, manufactured by JEOL Ltd.) was used. NMR, JNM-AL400) The ¹³ C-NMR spectrum was measured under the conditions of room temperature and cumulative number of times of 10,000 times. In the obtained spectral data, the nitrogen moiety (amine group) at the terminal is calculated from the ratio of the peak of the carbon atom adjacent to the nitrogen atom which is not salted, and the integral value of the peak of the carbon atom adjacent to the nitrogen atom of the salt. The ratio of the number of amine groups of salt to the total number of amine groups was confirmed to be the same as the theoretical salt formation ratio (the nitrogen sites of the two acidic groups of all phenylphosphonic acids and the DMMA of the block copolymer A-1) A salt).

The amine value (22 mg KOH/g) of 0.20 mole parts of the DMMA unit was subtracted from the amine price of 110 mgKOH/g before salt formation, and the amine value after salt formation was calculated to be 88 mgKOH/g. The acid value of the block copolymer A-1 after salt formation is the same as that of the pre-salt block copolymer A-1. The acid value, amine value and Tg of the block copolymer A-1 before and after salt formation are shown in Table 1.

 (Synthesis Examples 2 to 4: Production of Dispersant b~d)  

In the synthesis example 1, except that the content shown in Table 1 was changed, the same as in Synthesis Example 1, and the salt pre-block copolymers A-2 to A-4 and the salt block copolymer A-2 were synthesized. (Dispersant b) ~ A-4 (dispersant d) solution. Further, 1-ethoxyethyl methacrylate (EEMA) was used in Synthesis Example 2 in an amount of 2.8 parts by mass, in Synthesis Example 3, 2.2 parts by mass, and in Synthesis Example 4, 1.1 parts by mass. The acid value, amine value and Tg of the block copolymer obtained before and after salt formation are shown in Table 1.

 (Synthesis Example 5: Modulation of Dispersant e)  

The 500-ml four-necked flask was dried under reduced pressure, and then subjected to Ar (argon) replacement.

Under a stream of Ar, 100 g of dehydrated THF, 2.0 g of methyltrimethyldecyl dimethyl ketene acetal, and 1 M acetonitrile solution of tetrabutylammonium 3-chlorobenzoate (TBACB) were added in an amount of 0.15 ml, 1, 3, 5 - Trimethylbenzene 0.2 g. 13.4 parts by mass of 2-ethylhexyl methacrylate (EHMA), 14.3 parts by mass of n-butyl methacrylate (BMA), benzyl by weight of benzyl methacrylate (BzMA), methacrylic acid, using a dropping funnel Methyl ester (MMA) 35.7 parts by mass was dropped over 45 minutes. Since the reaction was heated, the temperature was kept below 40 ° C by ice cooling. After 1 hour, 26.7 g of dimethylaminoethyl methacrylate (DMMA) was dropped over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to give a block copolymer A-5. The weight average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 8,350, and the amine value was 95 mgKOH/g.

Into a 100 mL round bottom flask, 29.35 parts by mass of PGMEA was dissolved in 29.35 parts by mass of block copolymer A-5, and phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry Co., Ltd.) was added in an amount of 3.17 parts by mass (relative to the block copolymer A-5). The DMMA unit was 1 mol, and the phenylphosphonic acid was 0.20 mol. The mixture was stirred at a reaction temperature of 30 ° C for 20 hours to obtain a salt-type block copolymer A-5 (dispersant e) solution. The amine value after salt formation was calculated in the same manner as in Synthesis Example 1. The acid value, amine value and Tg of the block copolymer obtained before and after salt formation are shown in Table 1.

 (Synthesis Example 6: Modulation of Dispersant f)  

In addition to the phenylphosphonic acid, 3.80 parts by mass of chlorotoluene (manufactured by Tokyo Chemical Industry Co., Ltd.) (1 mol of DMMA unit of the block copolymer A-5, and 0.3 mol of chlorotoluene) was used. The same procedure as in Synthesis Example 5 was carried out to synthesize a salt block copolymer A-6 (dispersant f) solution. The acid value, amine value and Tg of the block copolymer obtained before and after salt formation are shown in Table 1.

 (Synthesis Example 7: Modulation of Dispersant g)  

In Synthesis Example 5, in place of 13.4 parts by mass of 2-ethylhexyl methacrylate (EHMA), 14.3 parts by mass of n-butyl methacrylate (BMA), 9.9 parts by mass of benzyl methacrylate (BzMA), and Methyl methacrylate (MMA) 35.7 parts by mass, using 7.6 parts by mass of n-butyl methacrylate (BMA), 32.9 parts by mass of methyl methacrylate (MMA), and PME-1000 (methoxypolyethylene glycol) Monomethacrylate (polyethylene glycol chain repeat number n≒23), trade name BLEMMER PME-1000, manufactured by Nippon Oil Co., Ltd., 39.9 parts by mass, and substituted dimethylaminoethyl methacrylate (DMMA) 26.7 The salt preblock copolymer A-7 and the salt block copolymer A-7 (dispersant g) solution were synthesized in the same manner as in Synthesis Example 5 except that the amount was 19.96 parts by mass. The amine group after salt formation was calculated in the same manner as in Synthesis Example 1. The acid value, amine value and Tg of the block copolymer obtained before and after salt formation are shown in Table 1.

 (Synthesis Example 8: Preparation of alkali-soluble resin A solution)  

40 parts by mass of BzMA, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of AIBN were placed in a polymerization tank filled with 150 parts by mass of PGMEA, and dropped at 100 ° C for 3 hours under a nitrogen stream. After completion of the dropwise addition, the mixture was further heated at 100 ° C for 3 hours to obtain a polymer solution. The polymer solution had a weight average molecular weight of 7,000.

Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and heated at 110 ° C for 10 hours in the reaction solution. The air is bubbled. The obtained alkali-soluble resin A is a resin obtained by introducing a side chain having an ethylenic double bond to a main chain formed by copolymerization of BzMA with MMA and MAA, and has a solid content of 42.6 mass% and an acid value of 74 mgKOH/g. The weight average molecular weight is 12,000. The weight average molecular weight was determined by using Shodex GPC System-21H (Shodex GPC System-21H) using polystyrene as a standard material and THF as an eluent. Further, the method for measuring the acid value is measured in accordance with JIS K 0070.

 (Synthesis Example 9: Preparation of alkali-soluble resin B solution)  

In Synthesis Example 8, except for 40 parts by mass of BzMA which is a comonomer species in the polymerization, 20 parts by mass of styrene and N-phenyl maleimide (Tokyo Chemical Industry Co., Ltd.) 20 were used. The same procedure as in Synthesis Example 8 was carried out except for the mass portion, and an alkali-soluble resin B solution was obtained. The solid content was 42.6 mass%, the acid value was 74 mgKOH/g, and the weight average molecular weight was 12,000.

 (Synthesis Example 10: Synthesis of Blue Color Material 1)    (1) Synthesis of Intermediate 1  

According to the production method of Intermediate 3 and Intermediate 4 described in International Patent Publication No. 2012/144521, 15.9 g of the intermediate 1 represented by the following chemical formula (A) (yield 70%) was obtained.

The obtained compound was confirmed to be the target compound by the following analysis.

‧MS(ESI)(m/z): 511(+), 2 price

‧ Elemental analysis values: CHN measured values (78.13%, 7.48%, 7.78%); theoretical values (78.06%, 7.75%, 7.69%)

 (2) Synthesis of blue color material 1  

5.00 g (4.58 mmol) of Intermediate 1 was added to 300 ml of water, and dissolved at 90 ° C to prepare a solution of Intermediate 2. Next, a phosphotungstic acid ‧n hydrate H ₃ [PW ₁₂ O ₄₀ ]‧nH ₂ O (n=30) 10.44 g (3.05 mmol) manufactured by Nippon Chemical Industry Co., Ltd. was added to 100 mL of water, and stirred at 90 ° C to prepare a phosphorus tungsten Aqueous acid solution. The aqueous solution of phosphotungstic acid was mixed at 90 ° C in the previous intermediate 2 solution, and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g of a blue color material 1 (yield 98%) represented by the following chemical formula (B).

The obtained compound was confirmed to be the target compound by the following analysis. (Morby W/Mo=100/0)

‧MS(ESI)(m/z): 510(+), 2 price

‧ Elemental analysis values: CHN measured values (41.55%, 5.34%, 4.32%); theoretical values (41.66%, 5.17%, 4.11%)

Further, it was confirmed by ³¹ P-NMR that the polyoxo acid structure of the phosphotungstic acid remained after the blue color material 1 was obtained.

 (Synthesis Example 11: Synthesis of purple color material 2)  

5.0 g of Acid Red 289 (AR289; Purple Color Material 1, manufactured by Tokyo Chemical Industry Co., Ltd.) of the following formula was added to 500 ml of water, and dissolved at 80 ° C to prepare a dye solution. Polyaluminum chloride ("trade name: Takibine #1500" manufactured by Toki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, alkalinity 83.5 mass%, alumina fraction: 23.5% by mass) 3.85 g was added to water 200 ml. The mixture was stirred at 80 ° C to prepare an aqueous solution of polyaluminum chloride. The prepared aqueous solution of polyaluminum chloride was dropped to the above dye solution at 80 ° C for 15 minutes, and further stirred at 80 ° C for 1 hour. The resulting precipitate was filtered off and washed with water. The obtained cake was dried to obtain 6.30 g (yield 96.2%) of a metallic lake color material (purple color material 2) of a rosin-based acid dye.

 (Synthesis Example 12: Synthesis of latent antioxidant (compound a))  

0.01 mol of the phenol compound represented by the following chemical formula (4), 0.05 mol of dibutyl succinate and 30 g of pyridine are mixed, and 0.025 mol of 4-dimethylaminopyridine is added at room temperature under a nitrogen atmosphere at 60 ° C. Stir for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added thereto to carry out oil-water separation. After drying the organic layer with anhydrous sodium sulfate, the solvent was evaporated, and 100 g of methanol was added to the residue for crystallization. The obtained white powdery crystals were dried under reduced pressure at 60 ° C for 3 hours to obtain a latent antioxidant (compound a) represented by the above formula (a). Further, the structure of the obtained latent antioxidant was confirmed by IR and NMR.

 (Example 1)    (1) Manufacture of color material dispersion B1  

6.23 parts by mass of a dispersing agent a solution of Synthesis Example 1 as a dispersing agent, and 6.42 parts by mass of CI Pigment Blue 15:6 (trade name: FASTOGEN BLUE A510 DIC Co., Ltd.) as a blue color material, CI as a purple color material Pigment Violet 23 (trade name: Hostaperm Violet RL-NF, manufactured by CLARIANT) 1.61 parts by mass, CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100, manufactured by DIC) 4.97 parts by mass, and alkali soluble in Synthesis Example 8. 14.59 parts by mass of the resin A solution, 66.12 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a cannabis bottle, and shaken for 1 hour with a pigment shaker (made by Asada Iron Works Co., Ltd.) as a preliminary crush. Then, zirconia beads having a particle diameter of 2.0 mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and dispersion was carried out for 4 hours in the same manner as a powder shaker to obtain a color material dispersion B1.

 (2) Manufacture of colored resin composition B1 for color filter  

8.18 parts by mass of the color material dispersion liquid B1 obtained in the above (1), 1.08 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8, and a polyfunctional monomer (trade name: ARONIX M-403, manufactured by Toagosei Co., Ltd.) 0.71 mass. , 2-methyl-1-(4-methylthiophenyl)-2-N- Lolinylpropan-1-one (photoinitiator: trade name Irgacure 907 (IRG907), manufactured by BASF Co., Ltd.) 0.07 parts by mass, 2-benzyl-2-dimethylamino-1-(4-N- Phenylphenyl)-butanone-1 (photoinitiator: trade name Irgacure 369 (IRG369), manufactured by BASF) 0.04 parts by mass, diethyl 9-oxosulfuric acid ("DETX-S" (DETX)), manufactured by Nippon Kasei Co., Ltd., 0.02 parts by mass, oxime ester-based starter ("TR-PBG-3057" (PBG3057) 0.02 parts by mass, manufactured by Changzhou Strong Electronic New Materials Co., Ltd. 0.07 parts by mass of a surfactant (trade name: MEGAFACE F559, manufactured by DIC Co., Ltd.), a decane coupling agent (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.07 parts by mass, a mercapto compound (pentaerythritol oxime (3-mercaptobutyric acid) Ester)) 0.05 parts by mass, PGMEA 58.85 parts by mass, and 3-methoxy-3-methyl-1-butyl acetate 3.92 parts by mass to obtain a colored resin composition B1 for a color filter.

 (3) Formation of colored layer  

The colored resin composition B1 obtained in the above (2) was applied to a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") having a thickness of 0.7 mm and coated with a spin coater, and then used. The heating plate was dried at 80 ° C for 3 minutes, irradiated with ultraviolet rays of 60 mJ/cm ² using an ultrahigh pressure mercury lamp, and further post-baked in a dust-free furnace at 230 ° C for 30 minutes, thereby adjusting the film thickness after hardening to 2.50 μm. The color layer B1 is formed by the film thickness.

 (Examples 2 to 12, Comparative Examples 1 to 4)    (1) Manufacture of color material dispersions B2~B9, CB1~CB4  

In Examples 2 to 6 and Comparative Example 1, in (1) of Example 1, except that the dispersant a solution was replaced as shown in Table 2, and the type and amount of the dispersant were changed to the same solid content. The color material dispersions B2 to B6 and the color material dispersion liquid CB1 were obtained in the same manner as in the above (1) except that the PGMEA amount was adjusted in a total amount of 100 parts by mass.

Further, in Examples 7 to 9, in (1) of Example 3, except that the type and amount of the color material were changed as shown in Table 2, the same procedure as in (1) of Example 3 was carried out. Color material dispersion B7~B9.

Further, in Comparative Examples 2 to 4, in the first example (1), the dispersant a solution was replaced as shown in Table 2, and the type and amount of the dispersing agent were changed to the same mass parts as the solid content. In the same manner as (1) of Example 1, except that the amount of PGMEA was adjusted to 100 parts by mass in total, and the type and amount of the color material were changed, the color material dispersions CB2 to CB4 were obtained.

 (2) Manufacture of colored resin composition B2~B12, CB1~CB4 for color filters  

In each of Examples 2 to 9 and Comparative Examples 1 to 4, the above-described color material dispersions B2 to B9 and CB1 were used as shown in Table 2, except for the color material dispersant B1 in (2) of Example 1. In the method of (3) of the first embodiment, in order to adjust the film thickness to 2.50 μm, the amount of the alkali-soluble resin is adjusted so that the P/V ratio is the value shown in Table 2, respectively. (2) In the same manner, colored resin compositions B2 to B9 and CB1 to CB4 for color filters were obtained.

Further, in Example 10, except that 0.03 parts by mass of the antioxidant IRGANOX 1010 (manufactured by BASF Corporation) was added in the same manner as in Example 3, the same procedure as in (2) of Example 3 was carried out, and a coloring resin for a color filter was obtained. B10.

Further, in Example 11, except that the alkali-soluble resin B solution obtained in Synthesis Example 9 was used instead of the alkali-soluble resin A solution in Example 3, and the antioxidant IRGANOX 1010 (manufactured by BASF Corporation) was further added in an amount of 0.03 parts by mass. In the same manner as (2) of Example 3, a colored resin composition B11 for a color filter was obtained.

Further, in Example 12, except for the photoinitiator, as shown in Table 2, in place of 0.04 parts by mass of IRG369, an oxime ester photoinitiator (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) was used. In the same manner as in (2) of Example 11, except that "TR-PBG-365" (PBG365) was used in an amount of 0.04 parts by mass, a colored resin composition B12 for a color filter was obtained.

Further, in the combination of the color materials of Comparative Examples 3 to 4, the coloring resin composition having a film thickness of 2.5 μm and having a chromaticity of x = 0.130 and y = 0.119 could not be obtained by the method of (3) of Example 1.

 (3) Formation of colored layer  

In (3) of Example 1, except that the colored resin composition B1 was used instead of the colored resin compositions B2 to B12 and CB1 to CB2, respectively, the same procedure as in (3) of Example 1 was carried out to obtain a colored layer B2. ~B12, CB1~CB2.

Here, each of the abbreviations in the table is as follows.

PB15:3:C.I. Pigment Blue 15:3 (trade name: CHROMOFINE BLUE A-220JC Da Ri Jing Chemical Co., Ltd.)

Blue color material 1: Blue color material 1 of Synthesis Example 10

Purple color material 1: Acid red 289 (AR289, manufactured by Tokyo Chemical Industry Co., Ltd.)

Purple color material 2: purple color material of Synthesis Example 11

PG58: C.I. Pigment Green 58 (trade name: FASTOGEN GREEN A110, manufactured by DIC Corporation)

Byk161: trade name Disperbyk-161 (manufactured by BYK Chemie, urethane dispersant, solid content 30% by mass)

Byk2001: trade name Disperbyk-2001 (manufactured by BYK Chemie, a polymer having a structural unit represented by the general formula (I), a solid content of 46% by mass)

Solvent A: Propylene glycol monomethyl ether acetate (PGMEA)

Solvent B: 3-methoxy-3-methyl-1-butyl acetate

 (Examples 13 to 15)    (1) Manufacture of color material dispersion B13~B15  

In the first to third embodiments, the amount of the color material and the blending amount are changed as shown in Table 3, and the amount of the PGMEA is adjusted so as to become 100 parts by mass in total. The color material dispersion liquids B13 to B15 were obtained in the same manner as in the above (1).

 (2) Manufacture of colored resin composition B13 to B15 for color filters  

In place of the color material dispersion liquid B3 in (2) of Example 12, the color material dispersion liquids B13 to B15 were respectively used, and the film thickness was 2.50 μm by the method of (3) of Example 1 The coloring resin compositions B13 to B15 for color filters were obtained in the same manner as in (2) of Example 12 except that the amount of the alkali-soluble resin was adjusted so that the P/V ratio was the value shown in Table 3.

 (3) Formation of colored layer  

In (3) of Example 12, the colored layers B13 to B15 were obtained in the same manner as in (3) of Example 12, except that the colored resin composition B12 was used instead of the colored resin composition B13 to B15.

 (Comparative examples 5 to 7)    (1) Manufacture of color material dispersion CB5~CB7  

In Comparative Examples 5 to 7, in (1) of Example 1, the dispersant a solution was replaced as shown in Table 3, and the type and amount of the dispersant were changed to the same mass parts as the solid portion. The color material dispersion liquids CB5 to CB7 were obtained in the same manner as in the first embodiment (1) except that the amount of the color material and the blending amount were changed as shown in Table 3, and the amount of PGMEA was adjusted to 100 parts by mass.

 (2) Manufacture of colored resin composition CB5~CB7 for color filters  

In place of the color material dispersion liquid B3 in (2) of Example 12, the color material dispersion liquids CB5 to CB7 were respectively used, and the film thickness was 2.50 μm by the method of (3) of Example 1 The coloring resin compositions CB5 to CB7 for color filters were obtained in the same manner as in (2) of Example 12 except that the amount of the alkali-soluble resin was adjusted so that the P/V ratio was the value shown in Table 3.

 (3) Formation of colored layer  

In (3) of Example 12, except for the substitution of the colored resin composition B12, the colored resin compositions CB5 to CB7 were used, and the same procedure as in (3) of Example 12 was carried out to obtain colored layers CB5 to CB7.

Here, each of the abbreviations in the table is as follows.

PG36: C.I. Pigment Green 36 (trade name: FASTOGEN GREEN 2YK-50, manufactured by DIC Corporation)

PG7: C.I. Pigment Green 7 (trade name: CHROMOFINE GREEN 6428EC, manufactured by Daisei Seika Chemical Co., Ltd.)

 (Examples 16 to 33)    (1) Manufacture of color material dispersion B16~B33  

In the examples (1) to (3), the types and the blending amounts of the color materials were changed as shown in Table 4, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. The color material dispersion liquids B16 to B33 were obtained in the same manner as in the above (1).

 (2) Manufacture of colored resin composition B16 to B33 for color filters  

In place of the color material dispersion liquid B3 in (2) of Example 12, the color material dispersion liquids B16 to B33 were respectively used, and the film thickness was 2.80 μm by the method of (3) of Example 1 The coloring resin compositions B16 to B33 for color filters were obtained in the same manner as in (2) of Example 12 except that the amount of the alkali-soluble resin was adjusted so that the P/V ratio was the value shown in Table 4.

 (3) Formation of colored layer  

In (3) of the example 12, the colored layer B16 to B33 were obtained in the same manner as in the above (3) except that the colored resin composition B12 was used instead of the colored resin composition B12.

Here, each of the abbreviations in the table is as follows.

PB16: C.I. Pigment Blue 16 (trade name: Heliogen Blue D7490, manufactured by BASF)

 (Example 34)    (1) Manufacture of color material dispersion  

6.23 parts by mass of a dispersant c solution of Synthesis Example 3 as a dispersing agent, 13.0 parts by mass of CI Pigment Blue 15:6 (trade name: FASTOGEN BLUE A510, manufactured by DIC) as a color material, and the base obtained in Synthesis Example 8. 14.59 parts by mass of the soluble resin A solution, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a cannabis bottle and shaken for 1 hour with a pigment shaker (made by Asada Iron Works Co., Ltd.). After disintegrating, zirconia beads having a particle diameter of 2.0 mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and dispersion was carried out for 4 hours in the same manner as a powder shaker to obtain a blue color material dispersion b1.

In the above-mentioned blue color material dispersion liquid b1, CI color violet 23 (trade name: Hostaperm Violet RL-NF, manufactured by CLARIANT Co., Ltd.) as a color material was used instead of 13.0 parts by mass of CI color blue 15:6 as a color material. In the same manner as the blue color material dispersion liquid b1 described above, the purple color material dispersion liquid v1 was obtained.

In the above-mentioned blue color material dispersion liquid b1, CI color green 59 (PG59, trade name FASTOGEN GREEN C100, manufactured by DIC) which is a color material is used instead of 13.0 parts by mass of CI color blue 15:6 as a color material. The green color material dispersion liquid g1 was obtained in the same manner as the above-described blue color material dispersion liquid b1 except for 13.0 parts by mass.

 (2) Manufacture of colored resin composition B34 for color filter  

4.00 parts by mass of the blue color material dispersion liquid b1 obtained in the above (1), 1.01 parts by mass of the purple color material dispersion liquid v1, 3.12 parts by mass of the green color material dispersion liquid g1, and 1.08 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8. Functional monomer (trade name: ARONIX M-403, manufactured by Toagosei Co., Ltd.) 0.71 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-N- Lolinylpropan-1-one (photoinitiator: trade name Irgacure 907 (IRG907), manufactured by BASF Co., Ltd.) 0.07 parts by mass, 2-benzyl-2-dimethylamino-1-(4-N- Phenylphenyl)-butanone-1 (photoinitiator: trade name Irgacure 369 (IRG369), manufactured by BASF) 0.04 parts by mass, diethyl 9-oxosulfuric acid ("DETX-S" (DETX) 0.02 parts by mass, oxime ester-based initiator ("TR-PBG-3057" (PBG3057)), 0.02 parts by mass, fluorine 0.07 parts by mass of a surfactant (trade name: MEGAFACE F559, manufactured by DIC Co., Ltd.), a decane coupling agent (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.07 parts by mass, a mercapto compound (pentaerythritol oxime (3-mercaptobutyric acid) Ester)) 0.05 parts by mass, PGMEA 58.85 parts by mass, and 3-methoxy-3-methyl-1-butyl acetate 3.92 parts by mass to obtain a colored resin composition B34 for a color filter.

 (3) Formation of colored layer  

In (3) of the first embodiment, the colored layer B34 was obtained in the same manner as in the above (3) except that the colored resin composition B1 was used instead of the colored resin composition B1.

The colored resin composition B34 obtained by the color filter has the same composition as the colored resin composition B3 of the color filter of Example 3, and the evaluation results of the colored resin composition B34 and the colored layer B34 of the color filter are The evaluation results of the colored resin composition B3 and the coloring layer B3 of the color filter were the same.

 (Examples 35 to 40)    (1) Manufacture of color material dispersion B39  

In Example 39, in (1) of Example 1, the dispersant a solution was replaced with the dispersant g solution and changed to the same mass fraction as the solid portion, as shown in Table 5, and was 100 in total. The color material dispersion liquid B39 was obtained in the same manner as in the above (1) except that the amount of the PGMEA was adjusted in the amount of the mass.

 (2) Manufacture of colored resin composition B35~B40 for color filters  

In Example 35, except for the photoinitiator in Example 3, as shown in Table 5, an oxime ester photoinitiator (trade name Irgacure OXE 01 (OXE01), BASF was used instead of 0.04 parts by mass of IRG369. In the same manner as in (2) of Example 3, except that 0.02 parts by mass of PGB3057 was used instead of 0.02 parts by mass of PGB3057 and 0.04 parts by mass of an oxime ester photoinitiator (trade name: Irgacure OXE 02 (OXE02), manufactured by BASF) was used. A colored resin composition B35 for a color filter was obtained.

Further, in Example 36, an antioxidant (trade name ADEKA STAB AO-40 (AO-40) was used instead of the antioxidant 10 (trade name: IRGANOX 1010 (1010), manufactured by BASF Corporation) in an amount of 0.03 parts by mass. In the same manner as (2) of Example 10 except that 0.03 parts by mass of ADEKA was used, a colored resin composition B36 for a color filter was obtained.

Further, in Example 37, in addition to 0.03 parts by mass of the antioxidant (trade name: IRGANOX 1010 (1010), manufactured by BASF Corporation) in Example 10, the latent antioxidant (Compound a) of Synthesis Example 12 was used. In the same manner as in the above (2), the coloring resin composition B37 for a color filter was obtained.

Further, in Example 38, in addition to the addition of 0.03 parts by mass of an antioxidant (trade name: IRGANOX 1010 (1010), manufactured by BASF Corporation) in Example 10, a UV absorber (benzotriazole-based compound, trade name) was added. The coloring resin composition B38 for a color filter was obtained in the same manner as (2) of Example 10 except that it was 0.03 parts by mass of TINUVIN 329, manufactured by BASF.

In the same manner as in (2) of Example 3 except that the color material dispersion liquid B39 was used instead of the color material dispersion liquid B3 in Example 3, a colored resin composition for color filters B39 was obtained. .

In Example 40, the color material dispersion liquid B39 was used instead of the color material dispersion liquid B3 in Example 35, and the alkali-soluble resin B solution obtained in Synthesis Example 9 was used instead of the alkali-soluble resin A solution, and an anti-drug was added. 0.03 parts by mass of an oxidizing agent (trade name: ADEKA STAB AO-40 (AO-40), manufactured by ADEKA), and 0.03 parts by mass of a UV absorber (benzotriazole-based compound, trade name TINUVIN 329, manufactured by BASF) (2) of Example 35 was carried out in the same manner to obtain a colored resin composition B40 for a color filter.

 (3) Formation of colored layer  

In (3) of the first embodiment, the colored layer B35 to B40 were obtained in the same manner as in the above (3) except that the colored resin composition B1 was used instead of the colored resin composition B1.

 [Evaluation method]    <Dispersibility evaluation of color material dispersion>  

The viscosity of the color material dispersion obtained in the examples and the comparative examples was measured immediately after preparation and after storage at 25 ° C for 30 days, and the viscosity change rate was calculated from the viscosity before and after storage, and the viscosity stability was evaluated. The viscosity was measured using a vibrating viscometer to measure a viscosity of 25.0 ± 0.5 °C.

 (Standard of viscosity stability evaluation)  

A: The viscosity change rate before and after storage is less than 10%

B: The viscosity change rate before and after storage is 10% or more and less than 20%

C: The viscosity change rate before and after storage is 20% or more and less than 30%

D: The viscosity change rate before and after storage is 30% or more

In addition, it is a value when the color material is 13 mass % with respect to the total mass of the solvent containing the color material dispersion liquid.

In the evaluation result, the color material dispersion liquid of C is practically used. However, when the evaluation result is B, the color material dispersion liquid is more excellent, and when the evaluation result is A, the dispersion stability of the color material dispersion liquid is excellent.

 <Optical performance evaluation, comparative evaluation>  

The contrast and chromaticity (x, y) and luminance (Y) of the coloring layers obtained in the examples and the comparative examples were measured using a large-spectrum electronic spectroscopic characteristic measuring device LCF-1500M and a pot-and-yellow comparative measuring device CT-1B.

 (Comparative evaluation benchmark)  

The value of y is set to 0.038~0.070 under C light source.

AA: More than 5000

A: 3500~4999

B: 1500~3499

C: less than 1500

The value of y is set to 0.071~0.110 under C light source.

AA: More than 6000

A: 4000~5999

B: 2000~3999

C: less than 2000

The value of y is set to 0.111~0.140 under C light source.

AA: More than 7000

A: 4500~6999

B: 2500~4499

C: less than 2500

The value of y is set to 0.141~0.180 under C light source.

AA: More than 7500

A: 5000~7499

B: 3000~4999

C: less than 3000

When the above evaluation criteria are AA, A or B, the evaluation is good, and practically no problem, but if the evaluation result is A and further AA, the effect is superior.

 <Solvent resolubility evaluation>  

The front end of the glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the colored resin composition for color filters obtained in the examples and the comparative examples, and applied to the 1 cm long portion of the glass substrate. The glass substrate which was pulled up was placed in a constant temperature and humidity machine so that the glass surface was horizontal, and dried at a temperature of 23 ° C and a humidity of 80% RH for 10 minutes. Next, the glass substrate to which the dried coating film adhered was immersed in PGMEA for 15 seconds. The re-dissolved state of the dried coating film at this time was visually discriminated and evaluated.

 (Solvent resolubility evaluation standard)  

AA: Dry film is completely dissolved below 8 seconds

A: The dry coating film is completely dissolved

B: a thin film of a dried coating film is produced in a solvent, and the solution is colored.

C: no thin film of the dried coating film was produced in the solvent, and the solution was not colored.

When the evaluation criteria are AA, A or B, it is evaluated that the solvent resolubility is good, and it can be used practically without problems. When the evaluation result is A and further AA, the effect is further improved.

 <Development residue evaluation>  

The color filter composition for the color filter obtained in the examples and the comparative examples was applied to a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm and 100 mm × 100 mm, respectively, using a spin coater. After coating, it was dried at 60 ° C for 3 minutes using a hot plate, thereby forming a coloring layer having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 60 seconds. The unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer was visually observed, and then thoroughly wiped with a lens cleaning cloth (manufactured by Toray Industries, Inc., trade name: TORAYSEE MK cleaning cloth) containing ethanol, and the lens was visually observed. The degree of coloring of the cleaning cloth.

 (Development residue evaluation standard)  

AA: Even if the color layer of 3.5 μm thick was subjected to the same evaluation, the development residue was not visually observed, and the lens cleaning cloth was completely free from coloring.

A: The development residue was not visually confirmed, and the lens cleaning cloth was completely colorless.

B: The development residue was not visually confirmed, and it was confirmed that the lens cleaning cloth was slightly colored.

C: A slight development residue was visually confirmed, and the color of the lens cleaning cloth was confirmed.

D: Visually confirm the development residue and confirm the color of the lens cleaning cloth

If the above evaluation criteria are AA, A, B or C, although it can be used practically, if the evaluation result is B, further A, or even AA, the effect is more excellent.

 <Development resistance evaluation>  

The colored resin compositions for the color filters obtained in the examples and the comparative examples were coated on a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm, using a spin coater. After heating and drying on a hot plate at 80 ° C for 3 minutes, ultraviolet rays of 40 mJ/cm ^{2 were} irradiated with an ultrahigh pressure mercury lamp. The film thickness at this time was measured and set to T1 (μm). Thereafter, shower development was carried out using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution. The film thickness after development was measured and set to T2 (μm). Calculate T2/T1×100 (%).

 (Development resistance evaluation standard)  

AA: 98% or more

A: 95% or more and less than 98%

B: 90% or more and less than 95%

C: less than 90%

If the evaluation results are AA, A, and B, although they are available for practical use, if the above evaluation criteria are A or even AA, the effect is superior.

 <development defect>  

The color filter composition for each of the color filters of the respective examples and the comparative examples was used for a glass substrate ("NA35" manufactured by NH TECHNO GLASS Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm. After the applicator was applied, it was dried at 60 ° C for 3 minutes using a hot plate, and after baking (30 minutes in a dust-free furnace at 230 ° C), the number of rotations was adjusted to have a film thickness as described, and a colored layer was formed. The colored layer was irradiated with ultraviolet rays of 30 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask having a mask opening width of 80 μm and a masking width of 160 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 100 seconds. The developed substrate was observed with an optical microscope, and the number of defects at the edge portion of the color layer in the range of 50 mm × 50 mm was measured.

 (Development defect evaluation standard)  

AA: no defect

A: less than 20

B: 20 or more and less than 50

C: 50 or more

If the development defect evaluation standard is AA, A or B, although it is available for practical use, if the evaluation result is A or even AA, the effect is more excellent.

 <uneven>  

The color filter composition for each of the color filters of the respective examples and the comparative examples was used for a glass substrate ("NA35" manufactured by NH TECHNO GLASS Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm. After the applicator was applied, it was dried at 60 ° C for 3 minutes using a hot plate, and after baking, the number of rotations was adjusted to have a film thickness as described, and a colored layer was formed. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask having a mask opening width of 80 μm and a masking width of 160 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 60 seconds. Next, the substrate was post-baked in a 230 ° C dust-free oven for 30 minutes, and the unevenness of the colored layer was visually observed under a light projector, and the edge of the colored layer in the range of 50 mm × 50 mm was measured by an optical microscope. The number of gaps in the department.

 (uneven evaluation basis)  

AA: no gaps, no gaps in the edge

A: There is no unevenness, and the gap between the edges is less than 20

B: Unevenness is observed in one part

C: unevenness observed overall

If the evaluation criteria for unevenness are AA or A, although it can be used in actual use, if the evaluation result is A or even AA, the effect is more superior.

 [Results integration]  

As can be seen from the results of the table, Examples 1 to 33 and 39 in which a blue color material was combined with a purple color material, PG59, and a dispersant belonging to a polymer having a constituent monomer represented by the general formula (I). The color material dispersion has good viscosity stability. On the other hand, the color material dispersion liquid of Comparative Example 1 in which a purple color material, PG59, and a urethane-based dispersing agent were combined with the blue color material was clearly observed, and the viscosity stability was deteriorated.

Moreover, it was clarified that the color material dispersion liquid of Comparative Example 2 and 5 to 7 in which the blue color material was combined with the conventional green color material was displayed even when a dispersing agent having a polymer having a structural unit represented by the general formula (I) was used. Poor viscosity stability.

Further, it is known that the color filter of Examples 1 to 40 in which the purple color material and the PG59 are combined with the blue color material and the dispersing agent belonging to the polymer having the structural unit represented by the general formula (I) is further combined is known. The colored resin composition is a colored resin composition for a color filter which is improved in solvent resolubility and which forms a coloring layer in which the blue reproduction domain is enlarged. Moreover, it was found that the coloring layer using the photosensitive colored resin compositions of Examples 1 to 40 suppresses development defects or unevenness.

On the other hand, Comparative Example 1 in which a purple color material, a PG59, and a urethane-based dispersant were combined with a blue color material was compared with an example of the same chromaticity coordinate (x, y), and the solvent was further The solubility is deteriorated, and the contrast, further development residue, development resistance, development defects, and unevenness are deteriorated. When the urethane dispersant is combined with the above-mentioned color material, the dispersibility or dispersion stability is poor, so that the color material is not well surrounded by the dispersant, and the color material is not easily resolubilized in the solvent. It is washed out in the state of the dispersant.

Further, in the color materials of Comparative Examples 3 to 4, the coloring resin composition capable of realizing the chromaticity of x = 0.130 and y = 0.119 could not be prepared.

Further, in Comparative Examples 2 and 5 to 7, the P/V ratio of the colored resin composition tends to be larger than that of the examples of the same chromaticity coordinates (x, y), and the solvent resolubility deteriorates. Further, in Comparative Examples 2 and 5 to 7, the development defects and unevenness were liable to occur in comparison with the examples of the same chromaticity coordinates (x, y).

The color materials of the colored resin compositions of Examples 1 to 40 and the ratio thereof satisfy the following conditions (colors in the XYZ color system of JIS Z8701 having a film thickness of 2.8 μm or less and using a C-light source as a single pixel) In the degree coordinate, the ratio of the blue color material, the purple color material, and the PG59 in the color material of the cured film which can be expressed as a color space of x=0.120 or more and 0.147 or less, y=0.038 or more and 0.180 or less is prepared. Dilution test of the color material concentration (total mass of the color material / total mass of the solid portion of the cured film) of the cured film, the color concentration of the color material (the total mass of the color material / the total mass of the color material dispersion containing the solvent) In the color material dispersion liquid, when the diluted test color material dispersion liquid is placed in a groove having a thickness of 1 cm and the spectral transmittance is measured, the average transmittance in the range of 280 nm or more and 360 nm or less is preferably 42% or more. On the other hand, in the colored resin compositions of Comparative Examples 2 and 5 to 7, the average transmittance in the range of 280 nm or more and 360 nm or less was less than 41%.

In the examples, in the examples in which the alkali-soluble resin contains both the maleic acid imide structure having a hydrocarbon ring and the styrene structure, a coloring resin composition in which the development residue is suppressed from being improved is obtained.

In addition, it has been found that when two types of oxime ester photoinitiators are used in combination, a coloring resin composition having improved development resistance is obtained.

In the examples, the examples in which the oxime ester-based photoinitiator and the antioxidant were combined were used to obtain a coloring resin composition having an improved effect of suppressing development defects and unevenness. With respect to the embodiment in which the antioxidant is added, it is known that the coloring layer which is also improved in contrast is obtained. The comparison of Examples 10 to 12 is close to A of AA. Among them, Example 36 in which a hindered phenol-based antioxidant having a molecular weight of 500 or less and a molecular weight of 200 equivalents or less per phenolic hydroxyl group was used was used to obtain a coloring layer having high contrast.

Further, in Example 37, in which a latent antioxidant was used, a colored resin composition having an improved unevenness-inhibiting effect was obtained, and the development adhesiveness was good, and a coloring layer having improved contrast was obtained.

Further, in Example 38 in which an oxime ester-based photoinitiator and an ultraviolet absorber were combined, a coloring resin composition having an improved effect of suppressing development defects and unevenness was obtained. An embodiment in which a UV absorber is added is a comparatively enhanced coloring layer.

Further, an alkali-soluble resin containing both a maleic acid imide structure having a hydrocarbon ring and a styrene structure, an oxime ester photoinitiator having a carbazole skeleton, and a fluorene having diphenyl sulfide are used. The ester-based photoinitiator and the use of the hindered phenol-based antioxidant having a molecular weight of 500 or less and a molecular weight of 200 equivalents or less per phenolic hydroxyl group in combination with the ultraviolet absorber are used, and the development residue suppressing effect is obtained. A coloring resin composition in which the development defect and unevenness are suppressed, and the development resistance is improved, and a coloring layer which is improved in contrast is obtained.

Claims (14)

A color material dispersion liquid for color filters, comprising a color material, a dispersant, and a solvent, wherein the color material comprises a blue color material, a purple color material, and a CI color green 59; and the dispersant has the following a polymer of the constituent unit represented by the general formula (I); (In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ^{3 are} also They can be bonded to each other to form a ring structure).  The color material dispersion liquid for a color filter according to claim 1, wherein the purple color material is contained in the color material in an amount of 1% by mass or more and 45% by mass or less.    The color material dispersion liquid for a color filter according to claim 1 or 2, wherein the blue color material is selected from the group consisting of CI Pigment Blue 15:6, CI Pigment Blue 15:3, CI Pigment Blue 15:4, and Triarylmethane One or more types of the group of the coloring materials are used.   The color material dispersion liquid for a color filter according to claim 1 or 2, wherein the purple color material is selected from the group consisting of CI color violet 23, an anthraquinone color material, a cyanine color material, and One or more types of the constituents of the color materials. A coloring resin composition for a color filter, comprising a color material, a dispersing agent, a binder component, and a solvent; wherein the color material comprises a blue color material, a purple color material, and a CI color green 59; the dispersing agent a polymer having the following structural unit represented by the general formula (I); (In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ^{3 are} also They can be bonded to each other to form a ring structure).  The colored resin composition for a color filter according to claim 5, wherein the purple color material is contained in the color material in an amount of 1% by mass or more and 45% by mass or less.    The colored resin composition for a color filter according to claim 5 or 6, wherein the blue color material is selected from the group consisting of CI Pigment Blue 15:6, CI Pigment Blue 15:3, CI Pigment Blue 15:4, and Triarylmethane One or more types of the group of the coloring materials are used.   The colored resin composition for a color filter according to claim 5 or 6, wherein the purple color material is selected from the group consisting of CI Pigment Violet 23, Lanthanide Color Material, and Cyanine Color Material; One or more types of the constituents of the color materials.  The colored resin composition for a color filter according to claim 5, wherein the binder component contains an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and further contains a mercapto compound.    The coloring resin composition for a color filter according to claim 9, wherein the photoinitiator contains an oxime ester and further contains an antioxidant.    The coloring resin composition for a color filter according to claim 9 or 10, wherein the photoinitiator contains at least two oxime esters.    A colored resin composition for a color filter according to claim 5 or 6, which can form a cured film having a chromaticity coordinate of x=0.120 in the XYZ color system of JIS Z8701 color measured using a C light source. The above is in the range of 0.147 or less, y=0.038 or more and 0.180 or less.    A color filter comprising at least one of a transparent substrate and a coloring layer provided on the transparent substrate, wherein at least one of the colored layers is used for the color filter of any one of claims 5 to 12. A cured product of a colored resin composition.    A display device characterized by having a color filter of claim 13.