TWI743323B - 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 material dispersion liquid for a color filter, which can form a color filter having improved contrast. Disclosed is a color material dispersion liquid for a color filter, comprising a color material, a pigment derivative, a dispersant and a solvent, wherein the color material includes a diketopyrrolopyrrole-based color material; wherein the pigment derivative is a mixture of a monosulfonated derivative of the diketopyrrolopyrrole-based color material and a disulfonated derivative of the diketopyrrolopyrrole-based color material; wherein a ratio of a mole of the monosulfonated derivative to a total of the mole of the monosulfonated derivative and a mole of the disulfonated derivative {monosulfonated derivative/(monosulfonated derivative+disulfonated derivative)} is 0.10 or more and 0.90 or less; and wherein the dispersant is a polymer including a constitutional unit represented by the following general formula (I): (the symbols in the general formula (I) are as described in the specification.)

Description

Color material dispersion liquid 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 color filters, a colored resin composition for color filters, a color filter, and a display device.

The color filter is usually formed by forming three color pixels of red, blue, and green in a pattern on a transparent substrate. In order to improve color reproducibility, in recent years, display products using color filters formed by patterning pixels of four colors in which yellow is added to the above three colors have also been put on the market. Under such circumstances, the requirements for further enhancement of brightness or contrast of color filters, and improvement of color reproducibility have increased.

As a method of forming pixels in a color filter, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, etc. are known. Among them, from the viewpoints of spectroscopic properties, durability, pattern shape, and accuracy, the pigment dispersion method with excellent average properties is most widely used.

In a color filter with pixels formed using a pigment dispersion method, in order to achieve high brightness or high contrast, the miniaturization of pigments is being studied. It is thought that by miniaturizing the pigment, the scattering of light penetrating the color filter based on the pigment particles is reduced, thereby achieving high brightness or high contrast.

However, the miniaturized pigment particles have a problem that they are easy to agglomerate. In particular, if the diketopyrrolopyrrole pigments are refined in order to achieve high contrast, the pigment particles tend to agglomerate or crystallize when heated at high temperatures in the manufacturing process of the color filter. After the heating process, Pigment particles are deposited on the surface of the pixel in the form of foreign matter, which leads to a decrease in contrast or a problem that is recognized as a defect.

As an attempt to refine the pigment, a pigment formulation is used that combines a pigment and a pigment derivative with a substituent introduced into a part of the pigment skeleton. As the pigment derivative of the diketopyrrolopyrrole pigment, the sulfonate of the diketopyrrolopyrrole pigment or its metal salt or amine salt or the like is used (for example, Patent Document 1).

In addition, Patent Document 2 describes a method for selecting or designing a pigment derivative, which is a pigment derivative that imparts a pigment composition with good dispersibility in a pigment composition obtained by treating the pigment derivative in a pigment The method for selecting or designing a material is characterized by comprising: measuring or calculating the dipole moment of the pigment derivative; and selecting the pigment derivative according to the value of the measured or calculated dipole moment or according to the dipole moment The value of the moment is the process of designing pigment derivatives. In addition, it is disclosed that the results obtained by evaluating the dispersibility and storage stability in a pigment composition obtained by treating a pigment derivative in CI Pigment Red 254, which is a diketopyrrolopyrrole pigment, are used in CI Pigment Red 254. When the sulfonic acid mono-substituted product of Pigment Red 254, the sulfonic acid mono-substituted aluminum salt of CI Pigment Red 264, and the sulfonic acid mono-substituted product of CI Pigment Yellow 138 are used as pigment derivatives, they show good dispersibility and storage stability. When the sulfonic acid disubstituted product of CI Pigment Red 255 and the sulfonic acid disubstituted product of CI Pigment Red 177 are used as pigment derivatives, the dispersibility and storage stability are poor.

Patent Document 3 describes the following: In order to improve the color quality of pigment inks for color filters, reduce viscosity, and prevent the generation of foreign substances, a pigment composition containing pigments and resin varnishes contains pigment molecules containing a moiety A pigment composite of a component and a pigment molecular component that does not contain a turbidity base, and the average number of turbidity introductions per molecule converted from the total pigment molecules in the pigment composite is set to 0.05-0.5.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 7-173406

Patent Document 2: Japanese Patent Laid-Open No. 2012-77192

Patent Document 3: Japanese Patent Laid-Open No. 2007-23266

However, the coloring layer formed by using the coloring resin composition containing the binder component in the conventional color material dispersion liquid has the problem of lowering the contrast after post-baking. The present invention was completed in view of the above-mentioned actual situation, and its object is to provide a color material dispersion liquid for color filters that can form a coloring layer with improved contrast. Another object of the present invention is to provide a colored resin composition for a color filter that can form a colored layer with improved contrast. Furthermore, the object of the present invention is to provide a color filter having a coloring layer with improved contrast formed by using the colored resin composition for a color filter. Moreover, the object of the present invention is to provide a display device using the color filter.

The color material dispersion liquid for color filters of the present invention contains a color material, a pigment derivative, a dispersant, and a solvent, and is characterized in that the color material includes a diketopyrrolopyrrole color material, and the pigment derivative system Contains a mixture of a monosulfonated derivative of a diketopyrrolopyrrole color material and a disulfonated derivative of a diketopyrrolopyrrole color material, and the molar ratio of the above-mentioned monosulfonated derivative is relative to the above-mentioned monosulfonated derivative The ratio {monosulfonated derivative/(monosulfonated derivative+disulfonated derivative)} of the total molar ratio of the substance to the above-mentioned disulfonated derivative is 0.10 or more and 0.90 or less. The above-mentioned dispersant system has the following A polymer of the structural unit represented by the general formula (I).

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a heteroatom, R ² and R ³ may They are bonded to each other to form a ring structure.)

The colored resin composition for a color filter of the present invention contains a color material, a pigment derivative, a dispersant, a binder component, and a solvent, and is characterized in that the color material includes a diketopyrrolopyrrole color material. The pigment derivative is a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material, and the mole of the monosulfonated derivative is relative to the above The ratio of the total molar ratio of the monosulfonated derivative and the disulfonated derivative {monosulfonated derivative/(monosulfonated derivative + disulfonated derivative)} is 0.10 or more and 0.90 or less, the above dispersant It is a polymer having a structural unit represented by the above general formula (I).

The color filter of the present invention has at least a substrate and a coloring layer provided on the substrate, and is characterized in that: at least one layer of the coloring layer is a cured product of the coloring resin composition for a color filter of the present invention .

The display device of the present invention is characterized in that it has the above-mentioned 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 that can form a coloring layer with improved contrast. In addition, the present invention can provide a colored resin composition for a color filter that can form a colored layer with improved contrast. In addition, the present invention can provide a color filter having a coloring layer with improved contrast formed by using the colored resin composition for a color filter. In addition, the present invention can provide a display device using the color filter.

1‧‧‧Substrate

2‧‧‧Shading part

3‧‧‧Coloring layer

10‧‧‧Color filter

20‧‧‧Opposite substrate

30‧‧‧Liquid crystal layer

40‧‧‧LCD device

50‧‧‧Organic protective layer

60‧‧‧Inorganic oxide film

71‧‧‧Transparent anode

72‧‧‧hole injection layer

73‧‧‧Hole Transmission Layer

74‧‧‧Light-emitting layer

75‧‧‧Electron injection layer

76‧‧‧Cathode

80‧‧‧Organic luminous body

100‧‧‧Organic light emitting display device

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

Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.

FIG. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention.

Hereinafter, the color material dispersion liquid for color filters, the colored resin composition for color filters, the color filter, and the display device of the present invention will be described in detail in order. Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less. In the present invention, (meth)acrylic acid means each of acrylic acid and methacrylic acid, and (meth)acrylate means each of acrylate and methacrylate.

I. Color material dispersion liquid for color filter

The color material dispersion liquid for color filters of the present invention contains a color material, a pigment derivative, a dispersant, and a solvent, and is characterized in that the color material includes a diketopyrrolopyrrole color material, and the pigment derivative system Contains a mixture of a monosulfonated derivative of a diketopyrrolopyrrole color material and a disulfonated derivative of a diketopyrrolopyrrole color material, and the molar ratio of the above-mentioned monosulfonated derivative is relative to the above-mentioned monosulfonated derivative The ratio {monosulfonated derivative/(monosulfonated derivative+disulfonated derivative)} of the total molar ratio of the substance to the above-mentioned disulfonated derivative is 0.10 or more and 0.90 or less, and the above-mentioned dispersant system has the following The polymer of the structural unit represented by the general formula (I).

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may have a heteroatom, R ² and R ³ Can be bonded to each other to form a ring structure.)

Since the color material dispersion of the present invention will mix the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material in a predetermined ratio and serve as a dispersion The polymer having the structural unit represented by the above general formula (I) is contained in combination with a diketopyrrolopyrrole color material, so the coloring resin composition prepared by using the color material dispersion liquid can form a contrast that inhibits heating It reduces and improves the contrast of the colored layer. Generally, in the preparation of the color material dispersion liquid, when a pigment is used as the color material, the pigment is made finer by extending the dispersion time of the pigment in the solvent. The surface of the pigment exposed by the miniaturization has a strong adsorption force, and the pigments may adsorb each other and agglomerate. Here, it is considered that when a dispersant is used, the dispersant is adsorbed on the surface of the pigment exposed by the refinement, so that the pigment in the solvent can be stabilized, and the pigment can be uniformly refined. However, after the composition containing the diketopyrrolopyrrole color material (for example, CI Pigment Red 254 (PR254)) that has been uniformly miniaturized is made into a coating film, if the color filter is manufactured in the process When a high temperature of 230°C is applied to the coating film, the diketopyrrolopyrrole color material particles are deposited. It is estimated that if a high temperature of 230℃ is applied to the coating film, the thermal movement of the dispersant adsorbed on the diketopyrrolopyrrole color material will weaken the adsorption of the dispersant, the pigment agglomerates, and the pigment crystal grows to produce pyrrole on the surface of the coating film. Precipitation of diketopyrrole color material particles. It is speculated that the cohesive force between the pigment surfaces is enhanced and the pigment precipitates of PR254 are generated. The contrast of the coating film is reduced due to the generation of the pigment precipitates. As an attempt to inhibit the aggregation of diketopyrrolopyrrole color materials, pigment derivatives of diketopyrrolopyrrole color materials were used. The pigment derivative is a compound in which a substituent is introduced into a part of the color material skeleton, and an interaction occurs between the substituent and the dispersant. It is speculated that because the pigment derivative is adsorbed on the surface of the color material, the dispersant that interacts with the pigment derivative generates static electricity or steric repulsion, which prevents agglomeration of the color material and makes the color material stably dispersed. Among the sulfonated derivatives of diketopyrrolopyrrole color materials among the pigment derivatives of diketopyrrolopyrrole color materials, it is shown in Patent Document 2 above that, compared with disulfonated derivatives, monosulfonated Derivatives can easily improve the dispersion and storage stability of the dispersion. However, the inventors of the present invention found that a mixture of a monosulfonated derivative of a diketopyrrolopyrrole color material and a disulfonated derivative of a diketopyrrolopyrrole color material was mixed in a predetermined ratio And the combination of a dispersant with a specific structure and a diketopyrrolopyrrole color material can improve the contrast of the colored layer compared with the case of using a monosulfonated derivative monomer. Although it has not been clarified as to the effect of this effect, it is speculated that the above-mentioned monosulfonated derivative has a higher affinity for pigment molecules, and the above-mentioned disulfonated derivative has a higher affinity for the above-mentioned specific dispersant or resin. By mixing the above-mentioned monosulfonated derivative and the above-mentioned disulfonated derivative in a predetermined ratio, the components contained in the dispersion or the resin composition can easily become a more uniform and stable dispersion state, and it is estimated that When the resin composition is heated, it is easy to maintain a uniform and stable dispersion state, and it is not easy to produce changes in the form caused by heat such as sublimation and agglomeration, thereby suppressing the decrease in contrast when the colored layer is heated.

The color material dispersion of the present invention contains at least a color material, a pigment derivative, a dispersant, and a solvent, and may further contain other components within a range that does not impair 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 from the dye derivative of the present invention.

<Pigment Derivatives>

The pigment derivative used in the present invention contains a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material. The total molar ratio of the monosulfonated derivative of the monosulfonated derivative and the disulfonated derivative {monosulfonated derivative/(monosulfonated derivative + disulfonated derivative)} is 0.10 or more And below 0.90.

As the monosulfonated derivative of the diketopyrrolopyrrole color material, for example, the monosulfonated derivative represented by the following general formula (1-m) can be cited as the second sulfonation of the diketopyrrolopyrrole color material Examples of derivatives include disulfonated derivatives represented by the following general formula (1-d).

[化3]

(In general formula (1-m) and general formula (1-d), Y ₁ and Y ₂ are each independently selected from a halogen atom, a cyano group, a benzyl group, a phenyl group that may be substituted with an alkyl group, and carbon Substituents in a group consisting of an alkyl group of 1-10, n and m each independently represent an integer of 0-5; when n and m are 2 or more, several Y ₁ and Y ₂ can be respectively The same or different; Z means -OH, -OM ^+p /p, -ON ⁺ HR ¹¹ R ¹² R ¹³ , -NH-(CH ₂ ) _s -NR ¹⁴ R ¹⁵ , -NH-(CH ₂ ) _t -COOH or -NH-(CH ₂ ) _u -SO ₃ H, several Z may be the same or different; M represents a monovalent, divalent or trivalent metal cation, p represents 1, 2 or 3; R ¹¹ , R ¹² , R ¹³ , R ^14, and R ¹⁵ each independently represent a hydrogen atom, a substituted hydrocarbon group with 1 to 20 carbon atoms, or one that forms a heterocyclic ring together with an adjacent nitrogen atom; s, t, and u independently represents an integer from 1 to 6.)

In the above general formula (1-m) and the above general formula (1-d), Y ₁ and Y ₂ are each independently selected from a halogen atom, a cyano group, a benzyl group, a phenyl group that may be substituted with an alkyl group, and The substituents in the group consisting of alkyl groups with 1 to 10 carbon atoms can be appropriately selected according to the hue or structure of the diketopyrrolopyrrole color material used in combination. Among them, it is easy to increase the contrast of the colored layer. From the point of view, a halogen atom and an alkyl group having 1 to 3 carbon atoms are preferred. The reason is that the steric hindrance of the halogen atom or the linear or branched alkyl group with carbon number 1~3 is small and it is difficult to hinder the adsorption of the color material. Examples of the halogen atom in Y ₁ and Y ₂ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom and a bromine atom are preferable. In addition, the alkyl group as the substituent of the phenyl group is preferably a linear or branched alkyl group having 1 to 3 carbon atoms. Examples of linear or branched alkyl groups having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, and isopropyl.

In the above general formula (1-m) and the above general formula (1-d), n and m are each independently the number of substituents of the phenyl group bonded to the diketopyrrolopyrrole skeleton, which further improves the contrast From the aspect, it is preferably 0 or 1, respectively. It is speculated that by setting n and m to 0 or 1, the steric hindrance acting on the side of the diketopyrrolopyrrole color material is smaller, and more hydrogen can be bonded or adsorbed on the diketopyrrolopyrrole color material. The surface of the primary particles of the material can easily become a more uniform and stable dispersion state, and the effect of suppressing the decrease in contrast when the colored layer is heated is improved.

In the above general formula (1-m) and the above general formula (1-d), Z is -OH, -OM ^+p /p, -ON ⁺ HR ¹¹ R ¹² R ¹³ , -NH-(CH ₂ ) _s -NR ¹⁴ R ¹⁵ , -NH-(CH ₂ ) _t -COOH or -NH-(CH ₂ ) _u -SO ₃ H, as long as they are properly selected according to the hue or structure of the diketopyrrolopyrrole color material used in combination However, in terms of improving the contrast of the colored layer, Z is preferably -OH, -OM ^+p /p, or -NH-(CH ₂ ) _s -NR ¹⁴ R ¹⁵ , more preferably -OH.

In -OM ^+p /p, M represents a monovalent, divalent or trivalent metal cation, and p represents 1, 2, or 3. Examples of M ^+p include metal cations of alkali metals, alkaline earth metals or transition metals, preferably Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Mn ²⁺ , Zn ²⁺ , Cu ²⁺ , Ni ²⁺ , Cd ²⁺ , Co ²⁺ , Al ³⁺ and Cr ³⁺ .

-ON ⁺ HR ¹¹ R ¹² R ¹³ in R ¹¹ , R ¹² and R ¹³ , and -NH-(CH ₂ ) _s -NR ¹⁴ R ¹⁵ in R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom and carbon number The hydrocarbon group of 1-20 can be substituted, or the one that forms a heterocyclic ring together with the adjacent nitrogen atom. The above-mentioned hydrocarbon group may be either a saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, the heterocyclic ring may further include a nitrogen, oxygen, or sulfur atom. As R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ , among them, a hydrogen atom, an alkyl group with 1 to 20 carbons, an aralkyl group with 1 to 20 carbons, and a ring with 5 or 6 carbons are preferred. Alkyl, aryl with 6-10 carbons. In terms of solvent resolubility, among them, alkyl groups with 3 to 20 carbons, aralkyl groups with 3 to 20 carbons, cycloalkyls with 5 or 6 carbons, and 6 to 10 carbons are preferred. The aryl group is more preferably a straight-chain alkyl group with a carbon number of 3-20. Here, the solvent re-solubility refers to the property that the solid content of the color material dispersion liquid or photosensitive resin composition that has been dried once is re-dissolved in the solvent. If the solvent resolubility is good, the removal and cleaning of the dried matter of the photosensitive resin composition attached during the manufacture of the color filter becomes easier, which becomes a great advantage in the manufacture.

啉基乙基、哌啶基丙基、甲基哌啶基丙基、二乙胺基己基、二乙胺基乙氧基丙基、二乙胺基丁基、二甲胺基戊基、N-N-甲基-月桂基-胺基丙基、2-乙基己胺基乙基、硬脂胺基乙基、油胺基乙基等。 Representative examples of the amine component in -NH-(CH ₂ ) _s -NR ¹⁴ R ¹⁵ include piperidinyl methyl, dimethylaminoethyl, diethylaminoethyl, and dimethylamine. Propyl, diethylaminopropyl, dibutylaminopropyl, piperidinylethyl, methylpiperidinylethyl,

Alkylethyl, piperidinylpropyl, methylpiperidinylpropyl, diethylaminohexyl, diethylaminoethoxypropyl, diethylaminobutyl, dimethylaminopentyl, NN -Methyl-lauryl-aminopropyl, 2-ethylhexylaminoethyl, stearylaminoethyl, oleylaminoethyl, etc.

In the case of using a salt-type dispersant, since the interaction with the salt-forming site or the remaining amine group of the salt-type dispersant can be used to increase the color material adsorption capacity of the dispersant, it is preferable in terms of contrast improvement The monosulfonated derivative represented by the above general formula (1-m) and the disulfonated derivative represented by the above general formula (1-d) have a sulfonic acid group (-SO ₃ H) that does not form a salt. In addition, the monosulfonated derivative represented by the above general formula (1-m) and the disulfonated derivative represented by the above general formula (1-d) except for a sulfonic acid group, a sulfonamide group, and a sulfonate, It may be further substituted with other functional groups such as phthaliminomethyl.

In addition, in terms of improved solvent re-solubility, it is preferable that at least one of Z in the general formula (1-m) and the general formula (1-d) is -NH-(CH ₂ ) _s -NR ¹⁴ R ¹⁵ or -ON ⁺ HR ¹¹ R ¹² R ¹³ .

As the monosulfonated derivative represented by the above general formula (1-m) and the disulfonated derivative represented by the above general formula (1-d) suitably used in the present invention, the following general formula ( The monosulfonated derivative represented by im), and the disulfonated derivative represented by the following general formula (id).

(In the general formula (im) and the general formula (id), X represents a hydrogen atom, a chlorine atom or a bromine atom, and several Xs may be the same or different; Z'represents -OH, -OM ^+p /p, Or -NH-(CH ₂ ) _s -NR ¹⁴ R ¹⁵ , several Z's may be the same or different; M represents a monovalent, divalent or trivalent metal cation, and p represents 1, 2 or 3; R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a substituted hydrocarbon group with 1 to 20 carbon atoms, or one that forms a heterocyclic ring together with an adjacent nitrogen atom; s represents an integer of 1 to 6.)

The molar ratio of the monosulfonated derivative of the diketopyrrolopyrrole color material is relative to the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material The ratio of the total moles of the substance {monosulfonated derivative/(monosulfonated derivative + disulfonated derivative)} is not particularly limited as long as it is 0.10 or more and 0.90 or less. Among them, heating is suppressed In terms of reducing the contrast to improve the contrast of the colored layer and the dispersion stability of the color material dispersion liquid, it is preferably 0.20 or more, more preferably 0.30 or more, and even more preferably 0.50 or more. Furthermore, although it is not particularly limited, in terms of productivity, the above-mentioned ratio is preferably 0.80 or less, and more preferably 0.70 or less.

Furthermore, in the present invention, the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material may be used alone or in combination of two or more Mixed use.

In the color material dispersion of the present invention, in terms of suppressing the decrease in contrast caused by heating, the monosulfonated derivative of the diketopyrrolopyrrole color material and the second of the diketopyrrolopyrrole color material The total content of the sulfonated derivatives relative to 100 parts by mass of the diketopyrrolopyrrole color material is preferably 1 part by mass or more, preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more. In terms of further improving the brightness of the colored layer, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less.

In the color material dispersion of the present invention, the total content of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material is derived from the color material and the pigment The total content (100% by mass) of the substance is preferably 1% by mass or more and 20% by mass or less, more preferably 1.5% by mass or more and 15% by mass or less, and still more preferably 2% by mass or more and 10% by mass or less . By being more than the above-mentioned lower limit, it is possible to further suppress the decrease in contrast caused by heating, and by being less than the above-mentioned upper limit, the brightness of the colored layer can be further improved.

The monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material used in the present invention can be used, for example, by adding the diketopyrrolopyrrole color material Put it into a sulfonating agent such as concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or a mixture of these to perform sulfonation reaction, and manufacture as a mixture of monosulfonated derivatives and disulfonated derivatives. After the sulfonation reaction, it is preferable to use a large amount of water to dilute the reaction solution, or to neutralize the resulting suspension in an aqueous solution containing the metal salt or amine required for the production of the metal salt or amine salt. After filtration, use an aqueous cleaning solution to clean and dry. By appropriately selecting the metal salt or amine in the aqueous solution used, the sulfonic acid salt can be appropriately introduced as designed. In addition, in the production of sulfonamides, the sulfonated derivative obtained by the sulfonation reaction is made to act on sulfite chloride, and the sulfonate chloride is mixed with the amine, so that the sulfonate can be appropriately introduced as designed. Amide.

In the case of sulfonation using the above method, by adjusting the concentration of the reaction solution, reaction temperature, reaction time, etc., the introduction amount of sulfonic acid groups or sulfonamide groups per molecule, and monosulfonated derivatives can be controlled Mixing ratio with disulfonated derivatives. Specifically, by increasing the sulfuric acid concentration of the sulfonating agent, or increasing the reaction temperature of the sulfonation reaction, or prolonging the reaction time, the number of disulfonated derivatives can be increased.

As the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material, the diketopyrrolopyrrole color material, for example, preferably has The diketopyrrolopyrrole color material of the structure represented by the following general formula (2).

[化5]

(In the general formula (2), Y ₁ and Y ₂ , and n and m are independently the same as the general formula (1-m) and the general formula (1-d); when n and m are 2 or more , Several Y ₁ and Y ₂ can be the same or different respectively.)

In the above general formula (2), Y ₁ and Y ₂ , and n and m may be the same as the above general formula (1-m) and the above general formula (1-d), so the description here is omitted.

As a diketopyrrolopyrrole color material for producing a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material, the diketopyrrolopyrrole color material is As far as the effect of suppressing the decrease in contrast caused by heating is high, CI Pigment Orange 71, CI Pigment Red 254, 255, 264, and 272 are preferred, CI Pigment Red 254, 255 is more preferred, and CI Pigment Red 254, 255 is more preferred, and particularly preferred CI Pigment Red 254.

(Other pigment derivatives)

The pigment derivatives used in the present invention can also be within the range that does not impair the effects of the present invention, except for the monosulfonated derivatives of the diketopyrrolopyrrole color materials and the disulfonation of the diketopyrrolopyrrole color materials. In addition to derivatives, other pigment derivatives are further included. As other pigment derivatives, for example, in terms of hue, a pigment derivative having a pigment skeleton of a yellow color material can be preferably used. Among them, in terms of suppressing the decrease in contrast caused by heating and improving the contrast of the colored layer In general, the sulfonated derivative of CI Pigment Yellow 138 (PY138) can be preferably used.

As the sulfonated derivative of PY138, at least one selected from the group consisting of a sulfonic acid group, a sulfonamide group, and a sulfonate bonded to PY138 has the following general formula (S) Representation of the structure.

(In the general formula (S), Z" is selected from sulfonic acid group, -SO ₂ NH-(CH ₂ ) _v -NR'R", -SO ₂ NH-(CH ₂ ) _v -COOH, -SO ₂ One of the group consisting of NH-(CH ₂ ) _v -SO ₃ H and sulfonate, R'and R" each independently represent a hydrogen atom, a substituted hydrocarbon group with 1 to 20 carbon atoms, Or if it forms a heterocyclic ring together with adjacent nitrogen atoms, v is independently an integer from 1 to 6; w represents the number of substituents, and represents an integer from 1 to 4.)

^{R'and R" of the above general formula (S) are the same as R 14} and R ^{15 of the} above general formula (1-d) and the above general formula (1-m). As the above -SO ₂ NH-(CH ₂ ) Representative examples of amine components introduced in the form of substituents represented by _{v -NR'R" include, for example, -NH-(CH 2} ) The representative examples of the amine components in _s -NR ¹⁴ R ^{15 are the same.} In the case of using a salt-type dispersant, the interaction with the salt-forming site or the remaining amine group of the salt-type dispersant can be used to increase the color material adsorption capacity of the dispersant, so in terms of contrast improvement, it is PY138 The sulfonated derivative of the sulfonate is preferably the case where there is a sulfonic acid group that does not form a salt. In addition, in _{the case of the sulfonamide group represented by the above -SO 2} NH-(CH ₂ ) _v -NR'R", and the sulfonic acid that forms a salt with an amine group containing a long-chain alkyl group having 3 or more carbon atoms In the case of a salt, the solvent re-solubility becomes good, which is preferable in this point.

Examples of suitably used substituents include sulfonic acid groups, -SO ₂ NHC ₂ H ₄ COOH, -SO ₃ -N(CH ₃ ) ₂ (C ₁₈ H ₃₇ ) ₂ ⁺ , -SO ₂ NHC ₃ H ₆ N( C ₂ H ₅ ) ₂ and the like, among them, a sulfonic acid group is preferred.

Furthermore, in the general formula (S), the number of substituents w is preferably 1 to 2 in terms of improving the contrast and heat resistance of the colored layer, and among them, 1 is preferred.

The sulfonated derivative of PY138 can be used, for example, in a method for producing a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material. Manufactured instead of diketopyrrolopyrrole color materials.

As the sulfonated derivative of PY138, one kind can be used alone or two or more kinds can be used in combination. For example, two or more sulfonated derivatives different in the type, substitution position, or substitution number of the sulfonic acid group and/or the sulfonamide group may be used in combination.

In the color material dispersion of the present invention, when the sulfonated derivative of PY138 is contained, the content of the sulfonated derivative of PY138 is based on the total content (100% by mass) of the color material and the pigment derivative, preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, and still more preferably 2% by mass or more and 7% by mass or less. By using this content, a coloring layer that meets the requirements of high brightness and high contrast can be produced without greatly changing the color tone.

In addition, in the color material dispersion of the present invention, the content of the pigment derivative in the total content (100% by mass) of the color material and the pigment derivative is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 20% by mass or less. By using this content, the brightness and contrast of the colored layer can be further improved.

<color material>

The color material used in the present invention includes a diketopyrrolopyrrole color material. In the present invention, a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material is combined with the diketopyrrolopyrrole color material. The combination of materials can prevent the decrease of the contrast of the coating film. The diketopyrrolopyrrole color material used in the present invention is preferably a diketopyrrolopyrrole color material having a structure represented by the following general formula (2').

(In the general formula (2'), Y ₁ and Y ₂ are independently the same as the general formula (1-m) and the general formula (1-d); n'and m'each independently represent an integer from 0 to 5 ; When n'and m'are 2 or more, several Y ₁ and Y ₂ may be the same or different respectively.)

In the above general formula (2'), Y ₁ and Y ₂ may be the same as the above general formula (1-m) and the above general formula (1-d), therefore, the description here is omitted. In the above general formula (2'), n'and m'are each independently the number of substituents of the phenyl group bonded to the diketopyrrolopyrrole skeleton, more preferably 0 or 1, respectively. In the structure represented by the general formula (2') of the diketopyrrolopyrrole-based color material used as the color material instead of the raw material of the pigment derivative, n'and m'are particularly preferably 1 respectively . _{Regarding the substituents Y 1} and Y ₂ in the general formula (2'), they can be appropriately selected according to the desired color. Among them, halogen atoms, cyano groups, methyl groups, and phenyl groups are preferred, and chlorine is especially preferred. Atom, bromine atom.

As the average primary particle size of the diketopyrrolopyrrole color material used in the present invention, when the coloring layer of the color filter is formed, the desired color development can be achieved, and it can be adjusted appropriately. Among them, it is preferably in the range of 10 to 100 nm, and more preferably 15 to 60 nm. Furthermore, the average particle size of the above-mentioned color material can be obtained by directly measuring the size of the primary particles from electron micrographs. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average value is taken as the particle diameter of the particle. Then, the volume (mass) of the particles is obtained by approximating 100 or more particles to the rectangular parallelepiped of the obtained particle size, and the volume average particle size is obtained and used as the average particle size. Furthermore, the same result can be obtained by using either transmission type (TEM) or scanning type (SEM) for the electron microscope.

The diketopyrrolopyrrole color material used in the present invention can be produced by a known method such as a recrystallization method and a solvent salt grinding method. Commercially available C.I. Pigment Red 254, 255, 264, 272, C.I. Pigment Orange 71, etc. can also be used. In the case where the diketopyrrolopyrrole color material is CI Pigment Red 254, for example, the trade name Hostaperm Red D2B-COFLV3781 manufactured by CLARIANT, the trade name Irgaphor Red B-CF manufactured by BASF JAPAN and other commercially available CI pigments can be used. Red 254 is used after grinding.

In the color material dispersion of the present invention, the content of the diketopyrrolopyrrole color material contained in the entire color material is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass %above. In addition, in the color material dispersion of the present invention, the content of the diketopyrrolopyrrole color material contained in the total of the color material and the pigment derivative is preferably 20% by mass or more, more preferably 30% by mass or more , And more preferably 35% by mass or more.

(Other color materials)

In the present invention, in order to achieve the desired chromaticity, as the color material, in addition to the diketopyrrolopyrrole-based color material, other color materials may be further contained within a range that does not impair the effects of the present invention. There are no particular limitations on other color materials, and various organic pigments, inorganic pigments, and dispersible dyes can be cited. Among them, organic pigments have high color rendering properties and high heat resistance, so they can be preferably used. For example, by combining red pigments, orange pigments, or yellow pigments as other color materials with diketopyrrolopyrrole color materials, the desired chromaticity of the red color layer can be adjusted.

As the above-mentioned organic pigments used as other color materials, for example, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colourists), specifically labeled as the following color index (CI ) Numbered person.

CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155 , 156, 166, 168, 175; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31 , 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57 , 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102 , 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179 , 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 265.

As specific examples of the above-mentioned inorganic pigments, titanium oxide, titanium black, carbon black, and the like can be cited.

染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。 Examples of the above-mentioned dispersible dyes include: dyes that are made dispersible by imparting various substituents to the dyes to make them insoluble in a solvent, or dyes that are made dispersible by being used in combination with a solvent with lower solubility , Or a lake color material that forms a salt with a soluble dye and an opposite ion, but does not dissolve (lake) in the solvent. By using such a dispersible dye in combination with a dispersant, the dispersibility or dispersion stability of the dye can be improved. Furthermore, as a standard, as long as the dissolved amount of the dye is 100 mg or less relative to 10 g of the solvent (or mixed solvent), it can be determined that the dye can be dispersed in the solvent (or mixed solvent). The above-mentioned dispersible dyes can be appropriately selected from conventionally known dyes, and are not particularly limited. For example, azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes,

Dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc.

Among them, other color materials that can be preferably used in combination with diketopyrrolopyrrole color materials include those selected from the group consisting of CI Pigment Red 177, 242, CI Pigment Yellow 138, 139, and 150 At least one. Furthermore, in the present invention, in terms of suppressing the decrease in contrast caused by heating and improving the contrast of the colored layer, as the above-mentioned other color material, it is preferable to contain the following yellow color material: which is selected from the following general formulas (A) At least one anion in the group consisting of the mono-, di-, tri-, and tetra-anions of the azo compound and its tautomeric structure of the azo compound, selected from Cd, Co, Al, Cr, A composite molecule of at least two metal ions in the group consisting of Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a compound represented by the following general formula (B). In addition, if the specific yellow color material is used in combination, the P/V ratio ((the mass of the color material in the composition)/(the mass of the solid content other than the color material in the composition) ratio) can be suppressed, and it is easy to form The red colored layer is also better in terms of improved plate-making properties. Furthermore, the color material components mentioned here include color materials and pigment derivatives.

(In the general formula (A), R ^{a is} each independently -OH, -NH ₂ , -NH-CN, an acylamino group, an alkylamino group or an arylamino group, and R ^{b is} each independently -OH Or -NH ₂ )

(In the general formula (B), R ^{c is} each independently a hydrogen atom or an alkyl group)

Among the metal complexes composed of the anion of the azo compound represented by the above general formula (A) and the azo compound of its tautomeric structure and a specific metal ion, and the compound represented by the above general formula (B) In a composite molecule, the intermolecular bonds can be formed, for example, by intermolecular interactions, or by Lewis acid-base interactions, or by coordination bonds. In addition, it may also have a structure like an inclusion compound in which guest molecules are incorporated into the lattice constituting the host molecule. Alternatively, it can also be a mixed replacement crystal in which two substances form a common crystal, and the atoms of the second component are located in the regular lattice of the first component.

As the acyl group in the acylamino group in the above general formula (A), for example, an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, an alkyl group, a phenyl group, Or naphthyl substituted aminoformyl, alkyl, phenyl, or naphthyl substituted aminosulfonyl, alkyl, phenyl, or naphthyl substituted formamidino, etc. The carbon number of the above-mentioned alkyl group is preferably 1 or more and 6 or less. In addition, the above-mentioned alkyl group may be substituted with halogens such as F, Cl, and Br, -OH, -CN, -NH ₂ , and/or an alkoxy group having 1 to 6 carbon atoms, for example. In addition, the above-mentioned phenyl group and naphthyl group may be subjected to halogens such as F, Cl, Br, -OH, -CN, -NH ₂ , -NO ₂ , alkyl groups with 1 to 6 carbon atoms, and/or carbon atoms. Alkoxy substituted with 1 or more and 6 or less. The alkyl group in the alkylamino group in the general formula (A) preferably has a carbon number of 1 or more and 6 or less. The above-mentioned alkyl group may be substituted with halogens such as F, Cl, and Br, -OH, -CN, -NH ₂ , and/or an alkoxy group having 1 to 6 carbon atoms, for example. Examples of the aryl group in the arylamino group in the above general formula (A) include phenyl and naphthyl. These aryl groups may be substituted with halogens such as F, Cl, and Br, -OH, and carbon number of 1 or more. Substitutions such as alkyl groups of 6 or less, alkoxy groups of 1 to 6 carbon atoms, -NH ₂ , -NO _{2 and -CN.}

Azo compound and an azo compound of the structural configuration to the tautomers of formula (A) represented by the sum, as R ^a, in terms of aspect became red hues, preferably are each independently -OH, -NH _2, -NH-CN, or an alkyl group, two R ^a may be the same, respectively, or different. In the above-mentioned general formula (A), regarding two ^Ras , among them, in terms of hue, it is more preferable that both are -OH, both are -NH-CN, or one When it is -OH and the other is -NH-CN, it is more preferable that both are -OH.

In addition, in the azo compound represented by the general formula (A) and the azo compound of the tautomeric structure, as R ^b , in terms of color tone, it is more preferable that both are -OH.

As at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, it is preferable to include at least one of them to become divalent or 3 The metal of the valence cation preferably contains at least one selected from the group consisting of Ni, Cu, and Zn, and more preferably contains at least Ni. More preferably, it contains Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn, and more preferably contains Ni and further selected At least one metal from the group consisting of Zn, Cu, Al, and Fe. Among them, as the above-mentioned at least two kinds of metals, Ni and Zn or Ni and Cu are particularly preferred.

In the above-mentioned yellow color material, the content ratio of at least two kinds of metals may be appropriately prepared. Among them, in terms of the red hue, in the above-mentioned yellow color material, regarding Ni and further selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn The content ratio of at least one metal is preferably Ni: the other above-mentioned at least one metal is contained in a molar ratio of 97:3-10:90, and more preferably a molar ratio of 95:5-10:90. Include. Among them, in terms of the red hue, it is preferable to include Ni and Zn in a molar ratio of Ni:Zn of 90:10 to 10:90, and more preferably to have a molar ratio of 80:20 to 20:80. Than contains. Or, in terms of the red hue, it is preferable to include Ni and Cu with a molar ratio of Ni:Cu of 97:3 to 10:90, and more preferably a molar ratio of 96:4 to 20:80 Than contains. When the yellow color material has a red hue, even if the P/V ratio is suppressed, it is easy to produce the red pixels contained in the red chromaticity area with high color density.

The yellow color material may further include a metal ion different from the specific metal ion. The yellow color material may include, for example, at least one metal ion selected from the group consisting of Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La.

Examples of the aspect in which at least two metal ions are contained in the yellow color material include a case where at least two metal ions are contained in a common crystal lattice, and crystals each containing one metal ion in separate crystal lattices. The situation of agglutination. Among them, in terms of further improvement in contrast, the case where at least two types of metal ions are contained in a common crystal lattice is preferable. Furthermore, for the state where at least two metal ions are contained in a common crystal lattice or the state where crystals each containing one metal ion in separate crystal lattices are aggregated, please refer to, for example, Japanese Patent Laid-Open No. 2014-12838 Communiqué and use the X-ray diffraction method to make appropriate judgments.

^{The alkyl group in R c} in the general formula (B) is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and more preferably an alkyl group having 1 or more and 4 or less carbon atoms. The alkyl group may also be substituted by -OH group. Among them, R ^{c is} preferably a hydrogen atom.

Regarding the content of the compound represented by the above general formula (B), based on 1 mol of the azo compound represented by the above general formula (A) and the azo compound of its tautomeric structure, it is usually 5 mol or more And 300 mol or less, preferably 10 mol or more and 250 mol or less, and more preferably 100 mol or more and 200 mol or less.

啉、2,3-二羥基喹

啉-6-磺酸、咔唑、咔唑-3,6-二磺酸、2- 羥基喹啉、2,4-二羥基喹啉、己內醯胺、6-苯基-1,3,5-三

-2,4-二胺、6-甲基-1,3,5-三

-2,4-二胺、三聚氰酸等。又，於上述黃色色材中，亦可進而包含：水溶性聚合物、例如乙烯-環氧丙烷-嵌段聚合物、聚乙烯醇、聚(甲基)丙烯酸；例如如羧甲基纖維素、羥乙基纖維素、羥丙基纖維素、甲基-及乙基羥乙基纖維素般之改質纖維素等。 In addition, the above-mentioned yellow color material may further include: urea and substituted urea, such as phenylurea, dodecyl urea, etc., and its condensation polymer with aldehydes, especially formaldehyde; heterocycles, such as barbiturates Acid, benzimidazolone, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquine

Morpholine, 2,3-dihydroxyquine

Lin-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid, 2-hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactam, 6-phenyl-1,3, 5-Three

-2,4-diamine, 6-methyl-1,3,5-tri

-2,4-Diamine, cyanuric acid, etc. In addition, the yellow color material may further include: water-soluble polymers, such as ethylene-propylene oxide-block polymer, polyvinyl alcohol, poly(meth)acrylic acid; such as carboxymethyl cellulose, Modified cellulose like hydroxyethyl cellulose, hydroxypropyl cellulose, methyl- and ethyl hydroxyethyl cellulose, etc.

The yellow color material can be prepared by referring to Japanese Patent Laid-Open No. 2014-12838, for example.

When the color material dispersion of the present invention contains color materials other than diketopyrrolopyrrole color materials, the content of the other color materials is preferably 80% by mass or less of the entire color material, more preferably 70% by mass Hereinafter, it is more preferably 65% by mass or less. In addition, when the color material dispersion of the present invention contains color materials other than diketopyrrolopyrrole color materials, the content of the other color materials is preferably 80% by mass or less of the total of the color materials and pigment derivatives. , More preferably 70% by mass or less, and still more preferably 65% by mass or less.

<Dispersant>

The color material dispersion liquid for a color filter of the present invention contains a polymer having a structural unit represented by the above-mentioned general formula (I) as a dispersant. The structural unit represented by the above general formula (I) has basicity and functions as an adsorption site for the color material. The color material dispersion of the present invention uses a polymer having the structural unit represented by the general formula (I) to improve the adsorption performance of the above-mentioned specific color material and pigment derivatives, and the dispersibility and dispersion stability of the color material are improved , Which can improve the contrast of the colored layer.

In the general formula (I), A is a divalent linking group. Examples of the divalent linking group in A include: alkylene, arylene, -CONH-, -COO-, and carbon atoms of 1 to 10 and carbon atoms of 1 to 10 Ether group (-R'-OR"-: R'and R" are each independently an alkylene group) and combinations thereof. Among them, in terms of dispersibility, A in the general formula (I) is preferably a divalent linking group including a -CONH- group or a -COO- group.

The hydrocarbon group in the hydrocarbon group that may contain a hetero atom in R ² and R ³ includes, for example, an alkyl group, an aralkyl group, and an aryl group. Examples of alkyl groups include methyl, ethyl, propyl, butyl, isopropyl, tertiary butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc. The number of carbon atoms in the alkyl group is relatively high. It is preferably 1 or more and 18 or less, and among them, a methyl group or an ethyl group is more preferable. As an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, for example. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less. Moreover, as an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less. Furthermore, the above-mentioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent. The hydrocarbon group containing heteroatoms has a structure in which the carbon atoms in the above hydrocarbon group are substituted by heteroatoms. Examples of heteroatoms that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. In addition, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 or more and 5 or less carbon atoms, a fluorine atom, a chlorine atom, and a bromine atom.

啉環等。 R ² and R ³ are bonded to each other to form a ring structure 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 include heteroatoms.} The ring structure is not particularly limited, and examples include: pyrrolidine ring, piperidine ring,

Morpholino ring and so on.

啉環，其中，較佳為R²及R³之至少1 個為碳原子數1以上且5以下之烷基、苯基，或R²與R³鍵結而形成吡咯啶環、哌啶環、

啉環。 In the present invention, wherein R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R ² and R ^{3 are} bonded to form a pyrrolidine ring , Piperidine ring,

Among them, it is preferable that ^{at least one of R 2} and R ³ is an alkyl group or a phenyl group having 1 to 5 carbon atoms, or R ² and R ^{3 are} bonded to form a pyrrolidine ring or a piperidine ring ,

Morpholino ring.

As the structural unit represented by the above general formula (I), dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and diethylaminoethyl (meth)acrylate can be cited. (Meth)acrylates containing alkyl substituted amino groups, such as esters, diethylaminopropyl (meth)acrylate, etc.; dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl ( (Meth)acrylamide and other (meth)acrylamides containing alkyl substituted amino groups. Among them, in terms of improving dispersibility and dispersion stability, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl can be preferably used. (Meth)acrylamide. The structural unit represented by the general formula (I) may be composed of one type, or may include two or more types of structural units.

As a polymer having a structural unit represented by the general formula (I), it is preferable to further include a portion having solvent affinity in terms of improving dispersibility. As the solvent affinity site, it is preferable to appropriately select the monomer having an ethylenically unsaturated bond from the monomer having an ethylenically unsaturated bond that can be polymerized with the monomer that induces the constituent unit represented by the general formula (I) in a manner having solvent affinity. And use. As a standard, it is preferable to introduce the solvent affinity site so that the solubility of the polymer at 23° C. becomes 50 (g/100g solvent) or more with respect to the solvent used in combination. As the polymer used in the present invention, in terms of improving the dispersibility and dispersion stability of the color material and the heat resistance of the resin composition, thereby forming a high-brightness and high-contrast colored layer, among them, preferred It is a block copolymer or a graft copolymer, and is particularly preferably a block copolymer. Hereinafter, a particularly preferred block copolymer will be described in detail.

(Block copolymer)

If the block containing the structural unit represented by the above general formula (I) is referred to as the A block, the structural unit represented by the above general formula (I) of the A block has basicity and serves as a counter color material The adsorption part functions. On the other hand, the B block which does not contain the structural unit represented by the above general formula (I) functions as a block having solvent affinity. In the present invention, the arrangement of each block of the block copolymer is not particularly limited. For example, it can be an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like. Among them, in terms of excellent dispersibility, AB block copolymers or ABA block copolymers are preferred.

As the structural unit constituting the B block, a monomer having an unsaturated double bond that can be copolymerized with a monomer that induces the structural unit represented by the general formula (I) is exemplified. Among them, the following general formula (II) is preferred. ) Represents the constituent unit.

(In the general formula (II), A'is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is a hydrocarbyl 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, A monovalent group represented by -CHO, -CH ₂ CHO, or -CH ₂ COOR ^{9 , R 9} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; the above-mentioned hydrocarbon group may also have a substituent; x represents An integer of 1 or more and 18 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.)

As the divalent linking group A'of the general formula (II), it can be the same as A in the general formula (I). The direct bond means that A'does not have atoms, that is, C (carbon atom) and R ⁵ in the general formula (II) are bonded without other atoms. Among them, in terms of solubility in organic solvents, A'is preferably a direct bond, a divalent linking group including a -CONH- group or a -COO- group. In terms of the heat resistance of the obtained polymer or the solubility of propylene glycol monomethyl ether acetate (PGMEA), which can be suitably used as a solvent, and the relatively inexpensive material, A'is preferably -COO- base.

基、異

基、二環戊基、二環戊烯基、金剛烷基、低級烷基取代金剛烷基等。上述碳原子數2以上且18以下之烯基可為直鏈狀、支鏈狀、環狀之任一者。作為此種烯基，例如可列舉：乙烯基、烯丙基、丙烯基等。烯基之雙鍵之位置並無限定，就所獲得之聚合物之反應性之方面而言，較佳為於烯基之末端存在雙鍵。作為烷基或烯基等脂肪族烴之取代基，可列舉硝基、鹵素原子等。 As the hydrocarbon group in R ^5, preferably 1 or more carbon atoms and an alkyl group of 18 or less carbon atoms, 2 or more and 18 or less of the alkenyl group, an aralkyl group, or an aryl group. The above-mentioned alkyl group having 1 or more and 18 or less carbon atoms may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, and n-butyl. , 2-ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl,

Base, different

Group, dicyclopentyl, dicyclopentenyl, adamantyl, lower alkyl substituted adamantyl, etc. The above-mentioned alkenyl group having 2 or more and 18 or less carbon atoms may be linear, branched, or cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group, etc. are mentioned, for example. The position of the double bond of the alkenyl group is not limited. In terms of the reactivity of the obtained polymer, it is preferable that a double bond exists at the end of the alkenyl group. Examples of the substituent of aliphatic hydrocarbons such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

As an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less. Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less. As the substituent of an aromatic ring such as an aryl group or an aralkyl group, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, a halogen atom, and the like can also be mentioned. Furthermore, the above-mentioned preferred number of carbon atoms 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 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, and y is an integer of 1 or more and 5 or less, preferably It is 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, and more preferably an integer of 1 or more and 2 or less.

The hydrocarbon group in the above R ⁸ can be the same as that shown in the ^{above R 5.} R ⁹ is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, and may be linear, branched, or cyclic. ^{In addition, R 5} in the structural unit represented by the general formula (II) may be the same as or different from each other.

As the above-mentioned R ⁵ , among them, it is preferable to select so that the compatibility with the following solvent becomes excellent. Specifically, for the above-mentioned solvent, for example, the second solvent that is generally used as a colored resin composition for color filters is used. In the case of solvents such as alcohol ether acetate-based, ether-based, and ester-based solvents, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, etc. are preferred.

Furthermore, the above-mentioned R ⁵ may be substituted with substituents such as alkoxy, hydroxyl, epoxy, and isocyanate groups within a range that does not impair the dispersibility of the above-mentioned block copolymer, and it may also be used after the synthesis of the above-mentioned block copolymer. , React with the compound having the above-mentioned substituent to add the above-mentioned substituent.

In the present invention, the glass transition temperature (Tg) of the solvent-affinity block portion of the above-mentioned block copolymer may be appropriately selected. In terms of heat resistance, the glass transition temperature (Tg) of the solvent-compatible block portion is preferably 80°C or higher, more preferably 100°C or higher. The glass transition temperature (Tg) of the solvent affinity block part in the present invention can be calculated by the following formula. In addition, the glass transition temperature of the color material affinity block portion and the block copolymer can also be calculated in the same way.

1/Tg=Σ(Xi/Tgi)

Here, the solvent affinity block part is made by copolymerizing 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, Σ takes the sum of i=1 to n. Furthermore, the value of the homopolymer glass transition temperature (Tgi) of each monomer can be the value of the Polymer Handbook (3rd Edition) (by J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).

The number of structural units constituting the solvent-affinity block portion may be appropriately adjusted within the range of improving the dispersibility of the color material. Among them, in terms of allowing the solvent affinity site and the color material affinity site to effectively act to improve the dispersibility of the color material, the number of structural units constituting the solvent affinity block portion is preferably 10 or more and 200 or less , More preferably 10 or more and 100 or less, and still more preferably 10 or more and 70 or less.

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

Furthermore, in the present invention, it is preferable that the dispersing agent includes the structure represented by the above general formula (II) in terms of good dispersibility and no precipitation of foreign matter during coating film formation to improve brightness and contrast. And the amine value before salt formation is a polymer of 40 mgKOH/g or more and 120 mgKOH/g or less. By setting the amine value within the above range, the viscosity with time stability or heat resistance is excellent, and the alkali developability or solvent resolubility is also excellent. In the present invention, regarding the amine value of the dispersant, in terms of dispersibility and dispersion stability, the amine value before salt formation is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more. On the other hand, in terms of solvent resolubility, the amine value of the dispersant before salt formation is preferably 110 mgKOH/g or less, more preferably 105 mgKOH/g or less. The amine value refers to the mg number of potassium hydroxide equivalent to the amount of perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. In the case of measurement by this method, even if it is an amine group that forms a salt with the organic acid compound in the dispersant, usually because the organic acid compound is dissociated, it is also possible to measure the amount of the block copolymer itself used as the dispersant. Amine value.

Regarding the acid value of the dispersant used in the present invention, the lower limit is preferably 1 mgKOH/g or more in terms of the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2 mgKOH/g or more in terms of the more excellent effect of suppressing the development residue. On the other hand, in terms of dispersibility and dispersion stability, the acid value of the dispersant used in the present invention is preferably 0 mgKOH/g. Also, regarding the acid value of the dispersant used in the present invention, in terms of preventing deterioration of development adhesion or deterioration of solvent resolubility, the upper limit of the acid value of the dispersant is preferably 18 mgKOH/g or less . Among them, the acid value of the dispersant is more preferably 12 mgKOH/g or less, and even more preferably 8 mgKOH/g or less, in terms of good development adhesion 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, and more preferably 2 mgKOH/g or more. The reason is that the effect of suppressing development residue is improved. On the other hand, in terms of dispersibility and dispersion stability, the acid value of the block copolymer before salt formation is preferably 0 mgKOH/g. In addition, 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, and still more preferably 8 mgKOH/g or less. The reason is that the development adhesiveness and solvent resolubility become better.

Furthermore, in the present invention, the glass transition temperature of the dispersant is preferably 30°C or higher in terms of improvement in development adhesion. That is, the dispersant is a pre-salt-formed block copolymer or a salt-type block copolymer, and its glass transition temperature is preferably 30°C or higher. If the glass transition temperature of the dispersant is relatively low, it will be particularly close to the temperature of the developer (usually around 23°C), and the development adhesion may decrease. It is presumed that the reason is that if the glass transition temperature is close to the temperature of the developer, the movement of the dispersant during development becomes larger, and as a result, the development adhesion deteriorates. It is estimated that by setting the glass transition temperature to 30°C or higher, the molecular movement of the dispersant during development can be suppressed, and therefore the decrease in development adhesion can be suppressed. In terms of developing adhesiveness, the glass transition temperature of the dispersant is preferably 32°C or higher, and more preferably 35°C or higher. On the other hand, from the viewpoint of operability during use such as easy accurate weighing, it is preferably 200°C or lower. The glass transition temperature of the dispersant in the present invention can be determined by measuring by differential scanning calorimetry (DSC) in accordance with JIS K7121.

If the concentration of the color material is increased and the content of the dispersant is increased, the amount of binder will be relatively reduced. Therefore, the colored resin layer is likely to peel off from the base substrate during development. The dispersant contains a B block containing a structural unit derived from a carboxyl group-containing monomer, and has the above-mentioned specific acid value and glass transition temperature, thereby improving the development adhesion. It is estimated that if the acid value is too high, the developability is excellent, but if the polarity is too high, peeling easily occurs during development.

Based on the above, in the present invention, the dispersant is excellent in dispersion stability of the color material to improve contrast, excellent in solvent re-solubility when it is made into a colored resin composition, and higher developing adhesiveness. Preferably, it is a polymer comprising the structure represented by the general formula (I) and the amine value is 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 or 0 mgKOH/g , The glass transition temperature is above 30°C.

As the above-mentioned carboxyl group-containing monomer, a monomer which can be copolymerized with a monomer having a structural unit represented by the general formula (I) and which contains an unsaturated double bond and a carboxyl group can be used. Examples of such monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, and crotonic acid. , Cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride can also be used , Ω-carboxy-polycaprolactone mono(meth)acrylate, etc. In addition, as the precursor of the carboxyl group, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerization, cost, solubility, glass transition temperature, and the like.

In the block copolymer before salt formation, the content ratio of the constituent units derived from the carboxyl group-containing monomer can be appropriately set so that the acid value of the block copolymer falls within the range of the above-mentioned specific acid value. Particularly limited, with respect to the total mass of the total structural units of the block copolymer, it is preferably 0.05% by mass or more and 4.5% by mass or less, and more preferably 0.07% by mass or more and 3.7% by mass or less. By making the content ratio of the constitutional unit derived from the carboxyl group-containing monomer more than the above lower limit, the effect of suppressing development residues is exhibited, and by making it below the above upper limit, it is possible to prevent deterioration of development adhesion or Deterioration of solvent re-solubility. Furthermore, the structural unit derived from a carboxyl group-containing monomer should just have the said specific acid value, and it may be comprised by 1 type, and may contain 2 or more types of structural units.

In addition, in terms of setting the glass transition temperature of the dispersant used in the present invention to a specific value or higher to improve development adhesion, it is preferable to set the value of the glass transition temperature (Tgi) of the homopolymer of the monomer to The total amount of monomers at 10° C. or higher in the B block is 75% by mass or more, and more preferably 85% by mass or more.

In the block copolymer, the ratio m/n of the unit number m of the structural unit of the A block to the unit number n of the structural unit of the B block is preferably in the range of 0.05 or more and 1.5 or less, In terms of the 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. In terms of improving the dispersibility and dispersion stability of the color material, it is preferably 1,000 or more and 20,000 or less, more preferably 2,000 or more and 15,000 or less, and further Preferably it is 3000 or more and 12000 or less. Here, the weight average molecular weight (Mw) is calculated as a standard polystyrene conversion value by gel permeation chromatography (GPC). Furthermore, the macromonomers, salt-type block copolymers, and graft copolymers used as raw materials for the block copolymers are also carried out under the above-mentioned conditions.

The manufacturing method of the said block copolymer is not specifically limited. The block copolymer can be produced by a known method, and among them, it is preferably produced by a living polymerization method. The reason is that it can produce copolymers that are not prone to chain transfer or deactivation and have a uniform molecular weight, thereby improving dispersibility and the like. Examples of the living polymerization method include living anionic polymerization methods such as living radical polymerization methods and group transfer polymerization methods, living cationic polymerization methods, and the like. By using these methods to sequentially polymerize monomers, copolymers can be produced. For example, the A block is first produced, and the constituent units constituting the B block are polymerized into the A block, thereby producing a block copolymer. In addition, in the above-mentioned production method, the order of polymerization of the A block and the B block may be reversed. In addition, the A block and the B block may be produced separately, and thereafter, the A block and the B block may be coupled.

As a specific example of such a block copolymer having a block portion containing the structural unit represented by the above general formula (I) and a block portion having solvent affinity, for example, the one described in Japanese Patent No. 4911253 can be cited Block copolymers are preferred.

In the present invention, in terms of the dispersibility or dispersion stability of the color material, even if the general formula (I) is the same as the amine group in the polymer containing the structural unit represented by the general formula (I) It is also preferable to use as a dispersant as a dispersing agent at least a part of the nitrogen part of the terminal of the structural unit possessed by the organic acid compound or halogenated hydrocarbon. ). Among them, in terms of excellent developability, it is preferred that at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) forms a salt with an organic acid compound as a dispersion Agent. Among them, in terms of excellent dispersibility and dispersion stability of the color material and improved contrast, it is preferable that the polymer containing the repeating unit having a tertiary amine is a block copolymer, and the organic acid compound is a phenylphosphine Acidic organic phosphorus compounds such as acid or phenylphosphinic acid. As a specific example of the organic acid compound used for such a dispersing agent, the organic acid compound described in Unexamined-Japanese-Patent No. 2012-236882 etc. is mentioned as a preferable thing, for example. In addition, as the above-mentioned halogenated hydrocarbon, at least one of halogenated allyl groups such as brominated allyl group and chloride benzyl group and halogenated aralkyl group is preferable in terms of excellent dispersibility and dispersion stability of the color material. .

In addition, as the dispersant used in the present invention, it is preferable to have a structural unit represented by the general formula (I) in terms of dispersibility and dispersion stability, and in terms of suppressing the decrease in contrast caused by heating A part of the terminal nitrogen portion of the structural unit represented by the general formula (I) in the polymer forms a salt, and the nitrogen portion that does not form a salt remains. It is believed that the sulfonated derivative of the diketopyrrolopyrrole color material is easily adsorbed to the remaining nitrogen site, so that the dispersibility is more excellent and the contrast is improved. Among them, in terms of easily adsorbing the sulfonated derivative of the diketopyrrolopyrrole color material, it is preferable to compare the general formula (I) in the polymer having the structural unit represented by the general formula (I). The nitrogen part of the terminal of the structural unit represented by) is 1 mol and the organic acid compound is 0.2 mol equivalent or more and 0.8 mol equivalent or less to form a salt, more preferably 0.3 mol equivalent or more and 0.7 mol equivalent or less Form salt.

In the color material dispersion of the present invention, at least one polymer having the structural unit represented by the general formula (I) is used as a dispersant, and its content depends on the type of color material used, and the following color filter The solid content concentration in the colored resin composition for optical sheets, etc. is appropriately selected. In terms of dispersibility and dispersion stability, the content of the dispersant relative to 100 parts by mass of the total solid content in the color material dispersion is preferably 3 parts by mass or more and 45 parts by mass or less, more preferably 5 parts by mass. It is blended in a ratio of more than part by mass and less than 35 parts by mass. Especially in the case of forming a coating film or colored layer with a high color material concentration, the content of the dispersant is preferably 3 parts by mass or more and 25 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion. Hereinafter, it is more preferable to blend in a ratio of 5 parts by mass or more and 20 parts by mass or less. Furthermore, in the present invention, the solid content refers to all substances other than the above-mentioned solvents, and also includes monomers dissolved in the solvents and the like.

<Solvent>

The solvent is not particularly limited as long as it does not react with each component in the color material dispersion liquid and can dissolve or disperse these components. Specific examples of solvents include, for example, alcoholic solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxy Carbitol solvents such as ethyl alcohol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate , Ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, cyclohexanol acetate and other ester solvents; acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone, cyclohexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, Glycol ether acetate solvents such as 3-methoxybutyl acetate and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol Carbitol acetate solvents such as acetate (BCA); diacetate esters such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol mono Glycol ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; N, Aprotic amide solvents such as N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone-based solvents such as γ-butyrolactone; cyclic ether-based solvents such as tetrahydrofuran Solvents; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, in terms of solubility of other components, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents can be suitably used. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol ethyl in terms of solubility of other components or coating suitability. Acid ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate One or more of them.

Regarding the content ratio of the solid content in the solvent-containing color material dispersion liquid, when the entire color material dispersion liquid containing the solvent is 100 parts by mass, the solid content is preferably 0.1 parts by mass or more and 70 parts by mass or less, more preferably It is 1.0 part by mass or more and 50 parts by mass or less.

<Other ingredients>

As long as the effect of the present invention is not impaired, the dispersion auxiliary resin and other components may be further formulated in the color material dispersion liquid of the present invention as needed. Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the following colored resin composition for color filters. There are cases where the color material particles are not easily contacted with each other due to the steric hindrance of the alkali-soluble resin, thereby stabilizing the dispersion or having the effect of reducing the dispersant due to the dispersion stabilizing effect. In addition, as other components, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, defoaming agents, anti-shrinking agents, antioxidants, anti-aggregating agents, ultraviolet absorbers, etc. can be cited.

The color material dispersion of the present invention can be used as a ready-to-use preparation for preparing the following colored resin composition for color filters. In other words, the so-called color material dispersion liquid is prepared in advance in the stage of preparing the following colored resin composition for color filters (the quality of the color material in the composition)/(the solid form other than the color material in the composition) Parts mass) relatively high color material dispersion. Specifically, the ratio of (mass of color material components in the composition)/(mass of solid content other than the color material components in the composition) is usually 1.0 or more. The color material dispersion liquid can be mixed with the following components to prepare a colored resin composition for color filters with excellent dispersibility.

<Manufacturing Method of Color Material Dispersion Liquid for Color Filter>

The color material dispersion liquid for the color filter of the present invention can be prepared by adding at least a color material containing a diketopyrrolopyrrole color material, the above-mentioned pigment derivative, and the above-mentioned dispersing agent to the above-mentioned solvent, and performing a conventionally known dispersion. Obtained by processing. Examples of the dispersing machine for performing the dispersion treatment include: two-roll, three-roll, etc. roll mills, ball mills, vibrating ball mills, and other ball mills, paint conditioners, continuous disc type bead mills, continuous ring type bead mills, etc. Bead mill. As a preferable dispersion condition of the bead mill, the diameter of the beads used is preferably 0.03~2.00mm, more preferably 0.05~1.0mm.

The average dispersed particle size of the color material in the color material dispersion depends on the type of color material used, and is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. The average dispersed particle size of the color material in the color material dispersion liquid is the dispersed particle diameter of the color material particles dispersed in the color material dispersion liquid containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. As for the measurement of the particle size by the laser light scattering particle size distribution meter, the color material dispersion liquid can be appropriately diluted with the solvent used in the color material dispersion liquid to a concentration that can be measured by the laser light scattering particle size distribution meter (for example, 1000 times etc.), using a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.) and measuring by dynamic light scattering method at 23°C. The average dispersed particle diameter here is the volume average particle diameter.

II. Colored resin composition for color filter

The colored resin composition for a color filter of the present invention contains a color material, a pigment derivative, a dispersant, a binder component, and a solvent, and is characterized in that the color material includes a diketopyrrolopyrrole color material. The pigment derivative is a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material, and the mole of the monosulfonated derivative is relative to the above The ratio of the total molar ratio of the monosulfonated derivative and the disulfonated derivative {monosulfonated derivative/(monosulfonated derivative + disulfonated derivative)} is 0.10 or more and 0.90 or less, the above dispersant It is a polymer having a structural unit represented by the above general formula (I).

The colored resin composition for color filters of the present invention comprises a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material The combination of the above-mentioned dispersant and the color material containing the diketopyrrolopyrrole color material can suppress the decrease in contrast caused by heating during the formation of the coloring layer, so that a high-contrast coloring layer can be formed.

The colored resin composition for a color filter of the present invention contains at least a color material, a pigment derivative, 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. Hereinafter, each component contained in the colored resin composition for a color filter of the present invention will be described. The color material, pigment derivative, dispersant, and solvent are the same as those described in the above-mentioned color material dispersion of the present invention. Therefore, the description here is omitted.

<Adhesive Ingredients>

The colored resin composition for a color filter of the present invention contains a binder component for imparting film-forming properties or adhesion to the coated surface. In order to provide sufficient hardness to the coating film, it is preferable to contain a curable adhesive component. The curable adhesive component is not particularly limited, and conventionally known curable adhesive components for forming the colored layer of a color filter can be suitably used. As the curable adhesive component, for example, a photocurable adhesive component including a photocurable resin that can be polymerized and cured by visible light, ultraviolet rays, electron beams, etc., or a heat-curable resin that can be polymerized and cured by heating can be used. It is a thermosetting adhesive component of curable resin.

In the case of using the photolithography step when forming the coloring layer, a photosensitive adhesive component with alkali developability can be appropriately used. In addition, a thermosetting adhesive component may be further used in the photosensitive adhesive component. As the photosensitive binder component, a positive photosensitive binder component and a negative photosensitive binder component can be cited. Examples of the positive photosensitive binder component include a system containing an alkali-soluble resin and an o-quinonediazide group-containing compound as a photosensitive imparting component.

On the other hand, as a negative photosensitive adhesive component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator can be suitably used. In the colored resin composition for a color filter of the present invention, a negative photosensitive adhesive component is preferable in terms of a light lithography method and a simple pattern formation using an existing process. Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive adhesive component will be specifically described.

(Alkali-soluble resin)

The alkali-soluble resin in the present invention has an acidic group, functions as a binder resin, and can be appropriately selected and used from those that are soluble in the alkaline developer used for pattern formation. In the present invention, the so-called alkali-soluble resin may have an acid value of 40 mgKOH/g or more as a standard. Preferred alkali-soluble resins in the present invention are resins having acidic groups and usually carboxyl groups. Specifically, they include acrylic resins such as acrylic copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups. Carboxyl epoxy (meth)acrylate resin, etc. Among these, those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferable. The reason is that by containing a photopolymerizable functional group, the film strength of the formed cured film is improved. In addition, acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination of two or more types.

Acrylic resins such as acrylic copolymers having structural units containing carboxyl groups, and styrene-acrylic copolymers having carboxyl groups, for example, by known methods to make carboxyl-containing ethylenically unsaturated monomers, and if necessary A (co)polymer obtained by the (co)polymerization of other copolymerizable monomers. Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, and itaconic acid. Acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride can also be used , Ω-carboxy-polycaprolactone mono(meth)acrylate, etc. In addition, as the precursor of the carboxyl group, an acid anhydride-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerization, cost, solubility, glass transition temperature, and the like.

In terms of excellent adhesion of the colored layer, the alkali-soluble resin preferably further has a hydrocarbon ring. Since the alkali-soluble resin has a hydrocarbon ring as a bulky group, shrinkage during curing is suppressed, peeling between the substrates is relaxed, and the adhesion of the substrates is improved. In addition, the inventors of the present invention have obtained the knowledge that by using an alkali-soluble resin having a hydrocarbon ring, the solvent resistance of the obtained colored layer, especially the swelling of the colored layer, is suppressed. Although the effect is not clear, it is speculated that the movement of molecules in the colored layer is suppressed due to the large hydrocarbon ring contained in the colored layer. As a result, the strength of the coating film increases and the swelling caused by the solvent is suppressed. Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring that may have a substituent, an aromatic hydrocarbon ring that may have a substituent, and combinations of these. The hydrocarbon ring may have an alkyl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, and an amide group. Substituents such as hydroxy group, hydroxy group, nitro group, amine group, halogen atom, etc. The hydrocarbon ring may be contained in the form of a monovalent group, or may be contained in the form of a group having a valence of two or more.

烷、三環[5.2.1.0(2,6)]癸烷(二環戊烷)、金剛烷等脂肪族烴環；苯、萘、蒽、菲、茀等芳香族烴環；聯苯、三苯、二苯甲烷、三苯甲烷、茋等鏈狀多環或卡多(Cardo)結構(9,9-二芳基茀)等。 Specific examples of the hydrocarbon ring include: cyclopropane, cyclobutane, cyclopentane, cyclohexane,

Alkane, tricyclic [5.2.1.0(2,6)] decane (dicyclopentane), adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, sulphur and other aromatic hydrocarbon rings; biphenyl, tricyclic Benzene, diphenylmethane, triphenylmethane, stilbene and other chain polycyclic or Cardo structures (9,9-diaryl stilbene) etc.

In the case where an aliphatic hydrocarbon ring is included as the hydrocarbon ring, the heat resistance or adhesion of the colored layer is improved, and the brightness of the obtained colored layer is improved, which is preferable in this respect. In addition, when the above-mentioned Cardo structure is included, the curability of the colored layer is improved and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable in this respect.

烷、異

烷、金剛烷、三環[5.2.1.0(2,6)]癸烷、三環[5.2.1.0(2,6)]癸烯、三環戊烯、三環戊烷、三環戊二烯、二環戊二烯；該等基之一部分經取代基取代之基。作為上述取代基，可列舉：烷基、環烷基、烷基環烷基、羥基、羰基、硝基、胺基、鹵素原子等。 The alkali-soluble resin is preferably a cross-linked cyclic hydrocarbon ring having an aliphatic hydrocarbon ring having a structure having two or more rings sharing 2 or more atoms. As specific examples of cross-linked cyclic hydrocarbon rings, include:

Alkane, iso

Alkane, adamantane, tricyclo[5.2.1.0(2,6)]decane, tricyclo[5.2.1.0(2,6)]decene, tricyclopentene, tricyclopentane, tricyclopentadiene , Dicyclopentadiene; a part of these groups substituted by substituents. As said substituent, an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a halogen atom, etc. are mentioned.

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

In addition, 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 substituted hydrocarbon ring.)

When the alkali-soluble resin has the maleimide structure represented by the general formula (III), since the hydrocarbon ring has a nitrogen atom, it is a polymer having the structural unit represented by the general formula (I) The compatibility of the alkaline dispersant is very good, the development speed is faster, and the suppression effect of the development residue is improved.

^{As specific examples of the substituted hydrocarbon ring in R M} of the general formula (III), the same as the specific examples of the above-mentioned hydrocarbon ring can be cited. Examples include: aliphatic hydrocarbon rings such as cyclopentyl, cyclohexyl, and cyclooctyl, or phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, and methoxy Aromatic hydrocarbon rings such as phenyl, benzyl, hydroxyphenyl, and naphthyl, and groups in which a part of these groups is substituted with a substituent.

In the alkali-soluble resin used in the present invention, it is easy to adjust the amount of each structural unit, and it is easy to increase the amount of the structural unit having the above-mentioned hydrocarbon ring to improve the function of the structural unit. An acrylic copolymer having a structural unit having a carboxyl group and a structural unit having the above-mentioned hydrocarbon ring. The acrylic copolymer having a structural unit having a carboxyl group and the above-mentioned hydrocarbon ring can be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer".

基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯等，就於加熱處理中亦可維持顯影後之著色層之截面形狀之效果較大之方面而言，較佳為使用選自(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸苄酯、及苯乙烯中之至少1種。 Examples of ethylenically unsaturated monomers having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, and (meth)acrylic acid. different

Base ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., in terms of the effect of maintaining the cross-sectional shape of the colored layer after development during heat treatment , Preferably at least selected from cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene 1 kind.

In addition, the alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resin or the alkali-soluble resin and the polyfunctional monomer may form a crosslinked bond during the curing step of the resin composition during the color filter manufacturing. The film strength of the cured film is further improved, and the development resistance is improved. In addition, the thermal shrinkage of the cured film is suppressed, and the adhesion to the substrate becomes excellent. The method of introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a compound having an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth)acrylate and the like, is added to a carboxyl group of an alkali-soluble resin to introduce an ethylenic double bond into the side chain. The method, or a method in which a structural unit having a hydroxyl group is introduced into the copolymer in advance, a compound having an isocyanate group and an ethylenic double bond in the molecule is added, and an ethylenic double bond is introduced into the side chain.

The alkali-soluble resin of the present invention may further contain other structural units such as structural units having ester groups such as methyl (meth)acrylate and ethyl (meth)acrylate. The structural unit having an ester group not only functions as a component that inhibits the alkali solubility of the colored resin composition, but also functions as a component that improves the solubility to the solvent and further the solvent re-solubility.

The alkali-soluble resin in the present invention is preferably an acrylic resin having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, or an acrylic resin such as a styrene-acrylic copolymer, and more preferably has a structural unit having a carboxyl group , Acrylic resins such as acrylic copolymers and styrene-acrylic copolymers having structural units with hydrocarbon rings and structural units with ethylenic double bonds.

Alkali-soluble resins can be made into alkali-soluble resins with required properties by appropriately adjusting the addition amount of each constituent unit.

In terms of obtaining a good pattern, the addition amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5% by mass or more, and more preferably 10% by mass or more with respect to the total amount of monomers. On the other hand, in terms of suppressing film roughness on the pattern surface after development, the addition amount of the carboxyl group-containing ethylenically unsaturated monomer relative to the total amount of monomers is preferably 50% by mass or less, more preferably 40% by mass or less. If the ratio of the carboxyl group-containing ethylenically unsaturated monomer is more than the above lower limit, the obtained coating film has sufficient solubility in the alkaline developer, and if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is Below the above upper limit, when developing with an alkaline developer, the formed pattern tends to be less likely to fall off from the substrate or to produce film roughness on the surface of the pattern.

In addition, in acrylic resins such as acrylic copolymers and styrene-acrylic copolymers with structural units having ethylenic double bonds, which can be more preferably used as alkali-soluble resins, they have both epoxy and ethylenic properties. The addition amount of the double bond compound relative to the carboxyl group-containing ethylenically unsaturated monomer is 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, and more preferably 3,000 to 20,000. If it is less than 1,000, the adhesive function after curing may be significantly reduced, and if it exceeds 50,000, it may be difficult to form a pattern during development with an alkaline developer. Furthermore, the above-mentioned weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured by using polystyrene as a standard substance and tetrahydrofuran (THF, Tetrahydrofuran) as an eluent by Shodex GPC System-21H.

The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited. The epoxy (meth)acrylate compound is obtained by reacting the reactant of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride More suitable. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. The epoxy (meth)acrylate resin which has a carboxyl group may be used individually by 1 type, respectively, and may use 2 or more types together.

In terms of the developability (solubility) of the alkaline aqueous solution used in the developer, it is preferable to select and use an alkali-soluble resin having an acid value of 50 mgKOH/g or more. In terms of the developability (solubility) of the alkaline aqueous solution used in the developer and the adhesiveness to the substrate, the acid value of the alkali-soluble resin is preferably 70 mgKOH/g or more and 300 mgKOH/g or less, Among them, it is preferably 80 mgKOH/g or more and 280 mgKOH/g or less. Furthermore, in the present invention, the acid value can be measured in accordance with JIS K 0070.

In terms of obtaining the effects of improved film strength of the cured film, improved development resistance, and excellent adhesion to the substrate, the ethylenic unsaturated bond when the side chain of the alkali-soluble resin has an ethylenic unsaturated group The equivalent is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. If the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance or adhesiveness is excellent. Moreover, if it is 100 or more, the ratio of other structural units, such as the structural unit which has a carboxyl group, or the structural unit which has a hydrocarbon ring, can be relatively increased, and it is excellent in developability and heat resistance. Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight of the ethylenically unsaturated bond in the alkali-soluble resin per 1 mole, 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 number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W(g))

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

The alkali-soluble resin used in the colored resin composition for color filters can be used singly or in combination of two or more. The content is not particularly limited, and is relative to the solid form of the colored resin composition for color filters. As for the total amount, the alkali-soluble resin is preferably in the range of 5% by mass or more and 60% by mass or less, and more preferably in the range of 10% by mass or more and 40% by mass or less. If the content of the alkali-soluble resin is more than the above lower limit value, sufficient alkali developability is easily obtained, and if the content of the alkali-soluble resin is less than the above upper limit value, it is easy to suppress film roughness or pattern defects during development.

(Multifunctional monomer)

The polyfunctional monomer used in the colored resin composition for color filters is not particularly limited as long as it can be polymerized by the above-mentioned photoinitiator. Generally, those having two or more ethylenically unsaturated double bonds can be suitably used. The compound is particularly preferably a multifunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups. As such a polyfunctional (meth)acrylate, what is necessary is just to select it suitably from a well-known well-known thing, and to use it. As a specific example, for example, those described in JP 2013-029832 A, etc. can be cited.

These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when excellent photocurability (high sensitivity) is required for the colored resin composition for color filters of the present invention, the multifunctional monomer preferably has 3 (trifunctional) or more polymerizable double bonds Preferably, poly(meth)acrylates of polyhydric alcohols with three or more valences or these dicarboxylic acid modifiers are preferred. Specifically, trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, succinic acid modification product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Ester, dipentaerythritol penta(meth)acrylate modified by succinic acid, dipentaerythritol hexa(meth)acrylate, etc.

The content of the above-mentioned multifunctional monomer used in the colored resin composition for color filters is not particularly limited, and the multifunctional monomer is preferably 5 mass relative to the total solid content of the colored resin composition for color filters % Or more and 60% by mass or less, more preferably within the range of 10% by mass or more and 40% by mass or less. If the content of the multifunctional monomer is more than the above lower limit, the photocuring can be carried out sufficiently to suppress the elution of the exposed part during development, and if the content of the multifunctional monomer is less than the above upper limit, the alkali developability full.

(Photoinitiator)

二唑化合物、α-胺基酮、聯咪唑類、N,N-二甲胺基二苯甲酮、鹵甲基-S-三

系化合物、9-氧硫

等。作為起始劑之具體例，可列舉：二苯甲酮、4,4'-雙二乙胺基二苯甲酮、4-甲氧基-4'-二甲胺基二苯甲酮等芳香族酮類；安息香甲醚等安息香醚類；乙基安息香等安息香；2-(鄰氯苯基)-4,5-苯基咪唑二聚物等聯咪唑類；2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-

二唑等鹵甲基

二唑化合物；2-(4-丁氧基-萘并-1-基)-4,6-雙-三氯甲基-S-三

等鹵甲基-S-三

系化合物；2,2-二甲氧基-1,2-二苯乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-

啉基丙酮、1,2-苄基-2-二甲胺基-1-(4-

啉基苯基)-丁酮-1,1-羥基-環己基-苯基酮、二苯基乙二酮、苯甲醯苯甲酸、苯甲醯苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯硫醚、苄基甲基縮酮、二甲胺基酯苯甲酸、對二甲胺基苯甲酸異戊酯、2-正丁氧基乙基-4-二甲胺基苯甲酸酯、2-氯9-氧硫

、2,4-二乙基9-氧硫

、2,4-二甲基9-氧硫

、異丙基9-氧硫

、4-苯甲醯基-甲基二苯硫醚、1-羥基-環己基-苯基酮、2-苄基-2-(二甲胺基)-1-[4-(4-

啉基)苯基]-1-丁酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯 基]-1-丁酮、α-二甲氧基-α-苯基苯乙酮、苯基雙(2,4,6-三甲基苯甲醯基)氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-(4-

啉基)-1-丙酮等。其中，可較佳地使用2-甲基-1-[4-(甲硫基)苯基]-2-

啉基丙烷-1-酮、2-苄基-2-(二甲胺基)-1-(4-

啉基苯基)-1-丁酮、4,4'-雙(二乙胺基)二苯甲酮、二乙基9-氧硫

。就調整感度、抑制滲水，從而提高顯影耐受性之方面而言，進而較佳為將如2-甲基-1-[4-(甲硫基)苯基]-2-

啉基丙烷-1-酮般之α-胺基苯乙酮系起始劑與如二乙基9-氧硫

般之9-氧硫

系起始劑組合。使用α-胺基苯乙酮系起始劑與9-氧硫

系起始劑之情形時之該等之合計含量相對於著色樹脂組成物之固形份總量，較佳為5質量%以上且15質量%以下。若起始劑量為15質量%以下，則製造步驟中之昇華物減少，故而較佳。若起始劑量為5質量%以上，則滲水等顯影耐受性提高。 The initiator used in the colored resin composition for the color filter of the present invention is not particularly limited, and one kind or a combination of two or more kinds can be used from various known initiators. Examples of the initiator include: aromatic ketones, benzoin ethers, and halomethyl

Diazole compounds, α-amino ketones, biimidazoles, N,N-dimethylamino benzophenone, halomethyl-S-tri

Series compounds, 9-oxysulfur

Wait. Specific examples of the initiator include aromatics such as benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. Ketones; benzoin ethers such as methyl benzoin; benzoin such as ethyl benzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer; 2-trichloromethyl-5 -(P-methoxystyryl)-1,3,4-

Halomethyl

Diazole compound; 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-tri

Isohalomethyl-S-tri

Series compound; 2,2-Dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-

Alkylacetone, 1,2-benzyl-2-dimethylamino-1-(4-

(Hydroxyphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, diphenyl ethylenedione, benzyl benzoic acid, benzyl benzoic acid, methyl benzyl benzoate, 4-benzyl- 4'-Methyl diphenyl sulfide, benzyl methyl ketal, dimethylamino ester benzoic acid, isoamyl p-dimethylamino benzoate, 2-n-butoxyethyl-4-dimethylamine Base benzoate, 2-chloro-9-oxysulfur

, 2,4-Diethyl 9-oxysulfur

, 2,4-Dimethyl 9-oxysulfur

, Isopropyl 9-oxysulfur

, 4-Benzyl-methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-

Linyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

(Hydroxy)phenyl)-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzyl) phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4-

(Alpinyl)-1-acetone and the like. Among them, 2-methyl-1-[4-(methylthio)phenyl]-2-

Linylpropan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-

(Hydroxyphenyl)-1-butanone, 4,4'-bis(diethylamino)benzophenone, diethyl 9-oxysulfur

. In terms of adjusting sensitivity, suppressing water seepage, and improving development tolerance, it is more preferable to add 2-methyl-1-[4-(methylthio)phenyl]-2-

Alpha-aminoacetophenone-based starter and diethyl 9-oxysulfide like hydroxypropane-1-one

General 9-oxysulfur

Department of initiator combination. Using α-aminoacetophenone-based initiator and 9-oxysulfur

In the case of a starter, the total content of these is preferably 5% by mass or more and 15% by mass or less with respect to the total solid content of the colored resin composition. If the starting dose is 15% by mass or less, the sublimate in the manufacturing step is reduced, which is preferable. If the starting dose is 5% by mass or more, the development tolerance such as water seepage is improved.

In the present invention, from the viewpoint of improving sensitivity, among them, the initiator preferably includes an oxime ester-based photoinitiator. By using the oxime ester-based photoinitiator, it is easy to suppress the difference in the line width in the plane when the thin line pattern is formed. Furthermore, by using an oxime ester-based photoinitiator, there is a tendency that the development tolerance is improved and the effect of suppressing the occurrence of water seepage is improved. Furthermore, the term "water seepage" refers to a situation where water seepage marks are produced after alkaline development after washing with pure water if a component that improves alkaline developability is used. This kind of water seepage disappears after post-baking, so there is no problem as a product, but in the appearance inspection of the patterned surface after development, it will be detected as an uneven abnormality, so that it is impossible to distinguish between normal and abnormal products. The issue of distinction. Therefore, if the inspection sensitivity of the inspection device is lowered during the appearance inspection, it will result in a decrease in the yield of the final color filter product, which becomes a problem. As the oxime ester-based photoinitiator, in terms of reducing contamination of the colored resin composition for color filters or device contamination caused by decomposition products, among them, those having an aromatic ring are preferred, and those having an aromatic ring are more preferred. Those having a condensed ring containing an aromatic ring further preferably have a condensed ring containing a benzene ring and a heterocyclic ring. As the oxime ester-based photoinitiator, it can be selected from 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzyl oxime)], ethyl ketone, 1-[9 -Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl)-,1-(O-acetyloxime), Japanese Patent Laid-Open No. 2000-80068, Special The oxime ester-based photoinitiators described in Japanese Patent Publication No. 2001-233842, JP 2010-527339, JP 2010-527338, JP 2013-041153, etc. are appropriately selected. As a commercially available product, Irgacure OXE-01 (manufactured by BASF) with a carbazole skeleton, Adeka ARKLS NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka ARKLS NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (the above are manufactured by Changzhou Qiangli Electronic New Materials Co.), TR-PBG-365 (Changzhou) Manufactured by Qiangli Electronic New Materials Co., Ltd.) and so on. In terms of brightness, it is particularly preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a sulphur skeleton. Moreover, in terms of high sensitivity, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton. In addition, it is preferable to use two or more types of oxime ester-based photoinitiators in combination in terms of easy improvement in brightness and development tolerance, and a high water-bleeding generation suppression effect. In terms of higher brightness and higher heat resistance, it is particularly preferable to use a combination of two oxime ester photoinitiators with a diphenyl sulfide skeleton, or to use an oxime ester photoinitiator with a diphenyl sulfide skeleton. The starter is used in combination with the oxime ester-based photoinitiator with a citron skeleton. In addition, in terms of excellent sensitivity and brightness, it is preferable to combine an oxime ester-based photoinitiator having a carbazole skeleton and an oxime ester-based photoinitiator having a pyridine skeleton or an oxime ester-based photoinitiator having a diphenyl sulfide. The photoinitiator is used together.

啉基丙烷-1-酮(例如Irgacure 907，BASF公司製造)、2-苄基-2-(二甲胺基)-1-(4-

啉基苯基)-1-丁酮(例如Irgacure 369，BASF公司製造)、4,4'-雙(二乙胺基)二苯甲酮(例如Hicure ABP，川口藥品製造)等。又，就調整感度、抑制滲水而提高顯影耐受性之方面而言，較佳為將9-氧硫

系起始劑與肟酯系光起始劑進行組合，就亮度、顯影耐受性提高，容易調整感度、滲水產生抑制效果較高、顯影耐受性提高之方面而言，較佳為將2種以上之肟酯系光起始劑與9-氧硫

系起始劑進行組合。 Moreover, it is preferable to use a photoinitiator having a tertiary amine structure in combination with an oxime ester-based photoinitiator in terms of suppressing water seepage and improving sensitivity. The reason is that since the photoinitiator with a tertiary amine structure has a tertiary amine structure as an oxygen quencher in the molecule, the free radicals generated by the initiator are not easily deactivated by oxygen, so that the sensitivity can be improved. As a commercially available product of the photoinitiator having the tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2-

Alkylpropan-1-one (for example, Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-

(Alolinylphenyl)-1-butanone (for example, Irgacure 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)benzophenone (for example, Hicure ABP, manufactured by Kawaguchi Pharmaceutical), and the like. In addition, in terms of adjusting sensitivity, suppressing water seepage and improving development tolerance, it is preferable to add 9-oxysulfur

The combination of an oxime ester-based photoinitiator and an oxime ester-based photoinitiator is preferable in terms of improved brightness and development tolerance, easy adjustment of sensitivity, high water seepage suppression effect, and improved development tolerance. More than one kind of oxime ester photoinitiator and 9-oxysulfur

Department of initiators for combination.

The content of the photoinitiator used in the colored resin composition for color filters of the present invention is usually 0.01 parts by mass or more and 100 parts by mass or less, preferably 5 parts by mass, relative to 100 parts by mass of the above-mentioned polyfunctional monomer. Parts by mass or more and 60 parts by mass or less. If the content is more than the above lower limit, the photohardening is sufficiently performed to suppress the elution of the exposed part during development. On the other hand, if the content is less than the above upper limit, the yellowing of the obtained colored layer is weakened and can be suppressed The brightness decreases. In addition, as the photoinitiator used in the colored resin composition for the color filter of the present invention, in terms of fully exhibiting the effect of the combined use of the photoinitiators, the oxime ester-based photoinitiator 2 The total content of more than one species relative to the total solid content of the colored resin composition for color filters is preferably 0.1% by mass or more and 12.0% by mass or less, and more preferably in the range of 1.0% by mass or more and 8.0% by mass or less Inside.

In addition, the colored resin composition for a color filter of the present invention may further contain a thermal polymerization initiator as necessary when the binder component contains a thermosetting resin. The thermal polymerization initiator is not particularly limited, and one type or a combination of two or more types can be used from various thermal polymerization initiators such as conventionally known thermal free radical polymerization initiators and thermal cationic polymerization initiators. Examples of the thermal radical polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), and peroxides such as benzyl peroxide (BPO). Examples of the thermal cationic polymerization initiator include benzene sulfonate, alkyl sulfonate, and the like. When the colored resin composition for color filters of the present invention contains a thermal polymerization initiator, the total content of the various initiators relative to the total solid content of the colored resin composition for color filters is preferably 0.1% by mass or more and 15.0% by mass or less, more preferably 1.0% by mass or more and 10.0% by mass or less.

Regarding the binder components used in the colored resin composition for color filters of the present invention, the total content of these components relative to the total solid content of the colored resin composition for color filters is preferably 35% by mass Above and 97% by mass or less, more preferably 40% by mass or more and 96% by mass or less. If it is more than the above lower limit, a colored layer having excellent hardness and adhesion to the substrate can be obtained. Moreover, if it is the said upper limit or less, developability will be excellent, and it can also suppress that a micro wrinkle arises by thermal shrinkage.

(Optionally add ingredients)

The colored resin composition for color filters may also contain various additives as needed. Examples of additives include, in addition to antioxidants, mercapto compounds, polymerization stoppers, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, and adhesion promoters. Wait.

It is preferable that the colored resin composition for color filters of the present invention further contains an antioxidant in terms of improving heat resistance, suppressing the fading of the color material, and improving brightness. What is necessary is just to select an antioxidant suitably from a well-known thing. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc.; in terms of heat resistance, it is preferable to use Hindered phenolic antioxidants. It can also be a potential antioxidant as described in International Publication No. 2014/021023.

Examples of hindered phenol-based antioxidants include: pentaerythritol four [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation), 1 ,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-Tris (4- Hydroxy-3,5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methyl Phenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3 , Diethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF) and the like. Among them, in terms of heat resistance and light resistance, pentaerythritol four [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010, Made by BASF Corporation).

If the colored resin composition combination for a color filter of the present invention contains the above-mentioned oxime ester-based photoinitiator and an antioxidant, the brightness is improved due to a synergistic effect, which is preferable in this respect.

As the content of the antioxidant, relative to 100 parts by mass of the total solid content in the colored resin composition, the antioxidant is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 0.5 parts by mass or more and 5.0 parts by mass or less. If it is more than the said lower limit, it will be excellent in heat resistance and light resistance. On the other hand, if it is not more than the above upper limit, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

When an antioxidant is used in combination with the above-mentioned oxime ester-based photoinitiator, the content of the antioxidant is preferably 1 part by mass relative to 100 parts by mass of the total amount of the above-mentioned oxime-ester-based photoinitiator Above and 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and 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.

In terms of improving the effect of suppressing water seepage generation, the colored resin composition for a color filter of the present invention preferably further contains a mercapto compound. In addition, if the colored resin composition combination for a color filter of the present invention contains the above-mentioned oxime ester-based photoinitiator and a mercapto compound, the development resistance is improved, the effect of inhibiting the occurrence of water penetration is further improved, and when a fine line pattern is formed, The linearity is further improved, or the ability to form a thin line pattern like the design of the mask line width is improved, which is better in these respects. Furthermore, the term "improved linearity" means that the end of the colored layer formed in the development step after the application of the colored composition has less unevenness and is formed into a linear or slightly linear shape.

唑、2-巰基苯并咪唑、2-巰基-5-甲氧基苯并噻唑、2-巰基-5-甲氧基苯并咪唑、3-巰基丙酸、3-巰基丙酸甲酯、3-巰基丙酸乙酯、3-巰基丙酸辛酯、1,4-雙(3-巰基丁醯氧基)丁烷、1,3,5-叁(3-巰基丁基氧基乙基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷叁(3-巰基丙酸酯)、季戊四醇肆(3-巰基丁酸酯)、季戊四醇肆(3-巰基丙酸酯)、二季戊四醇陸(3-巰基丙酸酯)、及四乙二醇雙(3-巰基丙酸酯)等。作為巰基化合物，可單獨使用或將2種以上組合使用，其中，就交聯密度增高、滲水抑制效果提高之方面而言，較佳為使用選自由1分子中具有2個以上之巰基之多官能巰基化合物所構成之群組中之1種 以上。又，就於長期保存之情形時亦容易維持良好之滲水抑制效果之方面而言，較佳為巰基所鍵結之碳原子為二級碳原子之具有二級巰基之二級巰基化合物，進而更佳為1分子中具有2個以上之該二級巰基之多官能二級巰基化合物。 The sulfhydryl compound can function as a chain transfer agent, and has the property of taking free radicals from the slow-reacting free radicals to accelerate the reaction, thereby improving the hardenability. As the mercapto compound, for example, 2-mercaptobenzothiazole, 2-mercaptobenzo

Azole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl ester, 3 -Ethyl mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-Three

-2,4,6(1H,3H,5H)-triketone, trimethylolpropane three (3-mercaptopropionate), pentaerythritol four (3-mercaptobutyrate), pentaerythritol four (3-mercaptopropane) Acid ester), dipentaerythritol (3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate). As the mercapto compound, it can be used alone or in combination of two or more. Among them, in terms of increased crosslinking density and improved water penetration inhibitory effect, it is preferable to use a polyfunctional compound selected from the group having two or more mercapto groups in one molecule. One or more of the group consisting of mercapto compounds. In addition, in terms of maintaining a good water permeation inhibitory effect even during long-term storage, it is preferable that the carbon atom to which the sulfhydryl group is bonded is a secondary carbon atom with a secondary sulfhydryl group, and furthermore Preferably, it is a multifunctional secondary mercapto compound having two or more such secondary mercapto groups in one molecule.

The content of the mercapto compound used in the colored resin composition for color filters is not particularly limited. In terms of fully exerting the above effects, relative to the total solid content of the colored resin composition for color filters, The mercapto compound is preferably within a range of 0.2% by mass or more and 7% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less.

Moreover, as a specific example of a surfactant and a plasticizer, what is described in Unexamined-Japanese-Patent No. 2013-029832 can be mentioned, for example.

<The mixing ratio of the components in the colored resin composition for color filters>

The total content of the color material and the pigment derivative relative to the total solid content of the colored resin composition for color filters is preferably 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass. Proportion of less than mass% is deployed. If it is more than the above lower limit, the coloring layer has sufficient color density when the colored resin composition for color filters is applied to a predetermined film thickness (usually 1.0 to 5.0 μm). Moreover, if it is less than the said upper limit, the coloring layer which is excellent in storage stability, and has sufficient hardness, or adhesiveness with a board|substrate can be obtained. Especially in the case of forming a colored layer with a high color material concentration, the total content of the color material and the pigment derivative relative to the total solid content of the colored resin composition for color filters is preferably 15% by mass or more And 65% by mass or less, and more preferably 25% by mass or more and 60% by mass or less are blended. In the colored resin composition for a color filter of the present invention, the monosulfonated derivative of the diketopyrrolopyrrole color material and the diketopyrrolopyrrole in terms of suppressing the decrease in contrast caused by heating The total content of the two sulfonated derivatives of the color material, relative to 100 parts by mass of the diketopyrrolopyrrole color material, is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more On the other hand, in terms of further improving the brightness of the colored layer, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less. In the colored resin composition for color filters of the present invention, the total content of the above-mentioned diketopyrrolopyrrole-based color material monosulfonated derivative and the above-mentioned diketopyrrolopyrrole-based color material disulfonated derivative is determined in terms of color The total content (100% by mass) of the material and the pigment derivative is preferably 1% by mass or more and 20% by mass or less, more preferably 1.5% by mass or more and 15% by mass or less, still more preferably 2% by mass or more, and 10% by mass or less. By being more than the above-mentioned lower limit, it is possible to further suppress the decrease in contrast caused by heating, and by being less than the above-mentioned upper limit, the brightness of the colored layer can be further improved. In addition, when the colored resin composition for color filters of the present invention further contains the sulfonated derivative of PY138, the content of the sulfonated derivative of PY138 is equal to the total content of the color material and the pigment derivative (100% by mass) Among them, it is preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, and still more preferably 2% by mass or more and 7% by mass or less. By using this content, it is possible to produce a colored layer that meets the requirements of high brightness and high contrast without greatly changing the color tone. In addition, the content of the dispersant is not particularly limited as long as the color material can be uniformly dispersed. For example, it can be 1% by mass or more and 40% by mass relative to the total solid content of the colored resin composition for color filters. %the following. Furthermore, relative to the total solid content of the colored resin composition for color filters, it is preferably blended at a ratio of 2% by mass to 30% by mass, and particularly preferably 3% by mass to 25% by mass. Proportional deployment. If it is more than the above lower limit, the dispersibility and dispersion stability of the color material will be excellent, and the storage stability of the colored resin composition for color filters will be more excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially in the case of forming a colored layer with a high color material concentration, the content of the dispersant relative to the total solid content of the colored resin composition for color filters is preferably 2% by mass or more and 25% by mass or less , More preferably, it is blended in a ratio of 3% by mass or more and 20% by mass or less. Furthermore, in the case of the salt-type block copolymer, the mass of the dispersant is the total mass of the block copolymer and the organic acid compound, etc. before the salt is formed. In addition, the content of the solvent may be appropriately set within the range where the coloring layer can be formed with high accuracy. With respect to the total amount of the colored resin composition for color filters containing the solvent, it is usually preferably in the range of 55% by mass or more and 95% by mass or less, and more preferably 65% by mass or more and 88% by mass or less Within the range. By setting the content of the above-mentioned solvent within the above-mentioned range, it is possible to obtain an excellent coating property.

<Manufacturing Method of Colored Resin Composition for Color Filter>

The method for producing the colored resin composition for color filters of the present invention is not particularly limited, and examples include: (1) Adding alkali-soluble resin, polyfunctional monomer, and photoinitiator to the color material dispersion of the present invention. (2) Put the color material, the pigment derivative, the dispersant, the alkali-soluble resin, and the polyfunctional monofunctional resin into the solvent at the same time. (3) Add the alkali-soluble resin, the polyfunctional monomer, the photoinitiator, the photoinitiator, After mixing other components as needed, the method of adding and mixing the above-mentioned color material dispersion of the present invention.

III. Color filter

The color filter of the present invention has at least a substrate and a coloring layer provided on the substrate, and is characterized in that at least one layer of the coloring layer is the curing of the coloring resin composition for the color filter of the present invention Things.

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

<Colored layer>

At least one of the colored layers used in the color filter of the present invention is the colored layer of the cured product of the colored resin composition for the color filter of the present invention. The colored layer is usually formed in the opening of the light-shielding portion on the following substrate, and is usually composed of a colored pattern of more than three colors. In addition, the arrangement of the colored layers is not particularly limited, and it can be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type. In addition, the width, area, etc. of the colored layer can be arbitrarily set. The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration or viscosity of the colored resin composition for color filters, etc., and is usually preferably in the range of 1 to 5 μm.

This colored layer can be formed by the following method, for example. First, the above-mentioned colored resin composition for color filter of the present invention is applied by coating means such as spray coating method, dip coating method, bar coating method, roll coating method, spin coating method, and die coating method. Coated on the following substrates to form a wet coating film. Among them, the spin coating method and the die coating method can be preferably used. Then, after the wet coating film is dried using a hot plate, an oven, etc., it is exposed through a mask of a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, etc. are subjected to photopolymerization to form a cured coating film. As a light source used for exposure, ultraviolet rays, electron beams, etc., such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, are mentioned, for example. The amount of exposure is appropriately adjusted according to the light source used or the thickness of the coating film. In addition, in order to promote the polymerization reaction after exposure, heat treatment may be performed. The heating conditions are appropriately selected according to the blending ratio of the components in the colored resin composition for color filters used, the thickness of the coating film, and the like.

Then, a developing solution is used to perform a development process to dissolve and remove the unexposed part, thereby forming a coating film in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. It is also possible to add an appropriate amount of surfactants and the like to the alkaline solution. In addition, general methods can be used for the development method. After the development treatment, the developer is usually washed, and the cured coating film of the colored resin composition for color filters is dried to form a colored layer. In addition, after the development process, in order to fully harden the coating film, you may perform a heating process. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.

<Shading part>

The light-shielding part in the color filter of the present invention is formed in a pattern on the following substrate, and can be the same as that used as the light-shielding part in a general color filter. The pattern shape of the light-shielding portion is not particularly limited, and examples include shapes such as a stripe shape and a matrix shape. The light-shielding part may also be a metal thin film such as chromium formed by a sputtering method, a vacuum vapor deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of using a photosensitive resist and patterning by development, a method of using inkjet ink containing light-shielding particles, and a method of patterning the photosensitive resist Methods of thermal transfer, etc.

The film thickness of the light-shielding part is set at about 0.2~0.4 μm in the case of a metal thin film, and set at about 0.5~2 μm in the case of a black pigment dispersed or dissolved in a binder resin.

<Substrate>

As the substrate, the following transparent substrates, silicon substrates, and those having aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the transparent substrate or silicon substrate are used. Other color filter layers, resin layers, thin film transistors (TFT, Thin Film Transistor) and other transistors, circuits, etc. can also 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 a substrate transparent to visible light, and the transparent substrate used in general color filters can be used. Specifically, examples include: non-flexible and transparent rigid materials such as quartz glass, alkali-free glass, synthetic quartz plates, or transparent resin films, optical resin plates, flexible glass, and other flexible and transparent materials. Flexible material. The thickness of the transparent substrate is not particularly limited. According to the application of the color filter of the present invention, for example, a thickness of about 100 μm to 1 mm can be used. Furthermore, in addition to the above-mentioned substrate, light-shielding portion, and coloring layer, the color filter of the present invention may also be formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, or a columnar spacer.

IV. Display device

The display device of the present invention is characterized by having the above-mentioned color filter of the present invention. In the present invention, the structure of the display device is not particularly limited, and it can be appropriately selected from conventionally known display devices. For example, a liquid crystal display device or an organic light-emitting display device can be cited.

[Liquid crystal display device]

Examples of the liquid crystal display device of the present invention include a liquid crystal display device having the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. With reference to the drawings, the liquid crystal display device of the present invention will be described on the other. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As shown in FIG. 2, the liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and liquid crystal formed between the color filter 10 and the counter substrate 20. Layer 30. In addition, the liquid crystal display device of the present invention is not limited to the structure shown in FIG. 2, and may be a structure generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method commonly used in liquid crystal display devices can be adopted. As such a driving method, for example, a twisted nematic (TN, Twisted Nematic) method, an in-plane switching (IPS) method, an optically compensated bend (OCB, Optically Compensated Bend) method, and a multi-domain vertical alignment may be mentioned. (MVA, Multi-Domain Vertical Alignment) method, etc. In the present invention, any of these methods can be preferably used. In addition, as the counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention and the like. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies and mixtures thereof can be used according to 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, for example, a vacuum injection method or a liquid crystal dropping method can be cited. After the liquid crystal layer is formed by the above method, the liquid crystal cell is slowly cooled to normal temperature, thereby aligning the enclosed liquid crystal.

[Organic Light Emitting Display Device]

As the organic light-emitting display device of the present invention, for example, an organic light-emitting display device having the above-mentioned color filter and organic light-emitting body of the present invention can be cited. With reference to the drawings, the organic light emitting display device of the present invention will be described on the other. FIG. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention. As shown 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. It is also possible to have an organic protective layer 50 or an inorganic oxide film 60 between the color filter 10 and the organic light-emitting body 80.

Examples of the method of stacking the organic light-emitting body 80 include: successively forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of the color filter. The method, or the method of attaching the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60, etc. 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, and other configurations can be appropriately used known ones. The organic light emitting display device 100 fabricated in the above manner can also be applied to, for example, an organic electroluminescence (EL, Electroluminescence) display in a passive driving mode or an organic EL display in an active driving mode. Furthermore, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a configuration known as an organic light-emitting display device that generally uses color filters.

[Example]

Hereinafter, examples will be shown to specifically describe the present invention. The invention is not limited by these descriptions. Furthermore, the structure of the obtained pigment derivative, the number of introduced sulfonic acid groups, and the mixing ratio of the monosulfonated derivative and the disulfonated derivative can be achieved by using a nuclear magnetic resonance device (Bruker BioSpin, AVANCEIII HD500MHz) The measured 1H- and 13C-NMR spectra were confirmed by mass spectrometry (MS, mass spectrometry) spectra measured using a MALDI-TOF-MS device (manufactured by JEOL Ltd., model JMS-S3000).

(Manufacturing Examples 1~5: Preparation of R254 Sulfonates A~E)

30 parts by mass of diketopyrrolopyrrole color material (CI Pigment Red 254, trade name Hostaperm Red D2B-COFLV3781, manufactured by CLARIANT) was added to 300 parts by mass of 20% oleum, and thereafter, as shown in Table 1 below The reaction temperature (A°C) and reaction time (B hours) were used for the reaction. After cooling, the reaction mixture was precipitated in 3,000 parts by mass of ice water, and filtered and washed with water to obtain a water slurry. The water slurry was dried to obtain R254 sulfonates A to E in the yield (C parts by mass) shown in Table 1 below. The obtained R254 sulfonates A to E were analyzed by NMR, and the results were a mixture of the monosulfonate represented by the following chemical formula (1-m) and the disulfonate represented by the following chemical formula (1-d) Or the monosulfonate monomer represented by the following chemical formula (1-m). Table 1 shows the ratio (mol %) of monosulfonate (monomer) and disulfonate (dimer) in R254 sulfonates A to E.

(Manufacturing Example 6: Preparation of Azo Pigment 1)

Into 550g of distilled water, 23.1g of diazobarbituric acid and 19.2g of barbituric acid were introduced. Then, the potassium hydroxide aqueous solution was used to adjust so as to become azobarbituric acid (0.3 mol), and it was mixed with 750 g of distilled water. Add 5g of 30% hydrochloric acid by dripping. After that, 38.7 g of melamine was introduced. Then, 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution were mixed and added, and the mixture was stirred at a temperature of 80° C. for 8 hours. The pigment was separated by filtration, washed, dried at 120°C, and ground with a mortar to obtain Azo pigment 1 (Ni:Cu=95:5 (mole ratio) azo pigment).

(Manufacturing Example 7: Preparation of Azo Pigment 2)

In manufacturing example 6, 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution were used instead of 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution. Azo pigment 2 (Ni:Zn=65:35 (mole ratio) azo pigment) was obtained in the same manner as in Example 4.

(Synthesis example 1: Synthesis of salt type block copolymer A-1) (1) Synthesis of block copolymer A

After depressurizing and drying a 500ml four-neck separable flask, it was replaced with Ar (argon). While allowing Ar to flow, add 100g of dehydrated THF, 2.0g of methyltrimethylsilyldimethylketene acetal, 0.15ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), uniform 0.2g of trimethylbenzene. Use a dropping funnel to dropwise add 2-ethylhexyl methacrylate (EHMA) 13.4 parts by mass, n-butyl methacrylate (BMA) 14.3 parts by mass, and benzyl methacrylate (BzMA) 9.9 parts by mass into it for 45 minutes. Parts, 35.7 parts by mass of methyl methacrylate (MMA). As the reaction progresses, heat is generated, so the temperature is kept below 40°C by ice cooling. After 1 hour, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After reacting for 1 hour, 5 parts by mass of methanol was added to stop the reaction. The solvent was removed under reduced pressure, and a block copolymer A was obtained. The weight average molecular weight determined by GPC measurement (NMP LiBr10mM) was 8,350, and the amine value was 95mgKOH/g.

(2) Synthesis of salt type block copolymer A-1

In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer A was dissolved in 29.35 parts by mass of PGMEA, and 3.96 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry) was added (phenylphosphonic acid (PPA) relative to The DMMA unit 1 mol of block copolymer A is 0.25 mol, and PPA is binary, so it is 0.5 mol equivalent), stirred at a reaction temperature of 30°C for 20 hours, thereby obtaining salt type block copolymer A- 1 solution. The amine value after salt formation is specifically calculated as follows. Add 9 parts by mass of salt block copolymer A-1 (solid after reprecipitation) and 91 parts by mass of chloroform-D1NMR to the NMR sample tube and add 1g of the solution, using a nuclear magnetic resonance device (Manufactured by JEOL, FT NMR, JNM-AL400) The ¹³ C-NMR spectrum was measured under the conditions of room temperature and 10,000 times of accumulation. Calculate the formation based on the ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom that does not form a salt and the peak of the carbon atom adjacent to the nitrogen atom forming the salt in the obtained map data The ratio of the number of amine groups of the salt to the total number of amine groups was confirmed to be the same as the theoretical salt formation ratio (the two acidic groups of the total phenylphosphonic acid form a salt with the nitrogen site at the end of the DMMA of the block copolymer A). The amine value of 95 mgKOH/g before salt formation was subtracted from the 0.5 molar amine value of the DMMA unit (47.5 mgKOH/g), and the amine value after salt formation was calculated to be 47.5 mgKOH/g. The acid value of the salt type block copolymer A-1 after salt formation is the same as that of the block copolymer A before salt formation. Tables 2 and 3 show the acid value and amine value of the block copolymers obtained before and after the salt formation. Furthermore, in Tables 2 and 3, the amount of the salt-forming compound is represented by the number of moles of the salt-forming compound relative to 1 mole of the nitrogen site (DMMA) of the structural unit represented by the general formula (I).

(Synthesis example 2: Synthesis of salt type block copolymer A-2)

In (2) of Synthesis Example 1, p-toluenesulfonic acid was added in place of phenylphosphonic acid so as to be 0.5 mol relative to 1 mol of DMMA unit, and the salt form was obtained in the same manner as Synthesis Example 1 except that Block copolymer A-2 solution.

(Synthesis example 3: Synthesis of salt type block copolymer B-1) (1) Synthesis of block copolymer B

To a 500 mL round bottom four-neck separable flask equipped with a condenser, an addition funnel, a nitrogen 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 replacement was carried out sufficiently. After cooling the reaction flask to -60°C, 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. Using the addition funnel, dropwise add 3.3 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA), methyl 12.8 parts by mass of 2-ethylhexyl acrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) . After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a solid content 30% by mass solution. 32.5 parts by mass of water was added, the temperature was raised to 100° C. and reacted for 7 hours, and the structural unit derived from EEMA was deprotected to obtain a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain an A block containing the structural unit represented by the general formula (I) and containing Block copolymer B (acid value 8mgKOH/g) which is a constitutional unit of carboxyl monomer and has a solvent-philic B block. The block copolymer B obtained in this manner was confirmed by GPC (Gel Permeation Chromatography). As a result, the weight average molecular weight Mw was 7000. In addition, the amine value is 95 mgKOH/g.

(2) Synthesis of salt type block copolymer B-1

In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer B was dissolved in 29.35 parts by mass of PGMEA, and 3.98 parts by mass of phenylphosphonic acid (manufactured by Tokyo Chemical Industry) was added (phenylphosphonic acid (PPA) relative to block copolymerization). The DMMA unit 1 mol of the composite B is 0.25 mol, and the PPA is binary, so it is 0.5 mol equivalent), stirred at a reaction temperature of 30° C. for 20 hours, thereby obtaining a salt-type block copolymer B-1 solution. The amine value after salt formation was calculated in the same manner as in Synthesis Example 1. Table 2 shows the acid value and amine value of the block copolymers obtained before and after the salt formation.

(Synthesis Example 4: Preparation of Alkali-soluble Resin A Solution)

A mixed solution of 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 was added dropwise to a polymerization tank containing 150 parts by mass of PGMEA over 3 hours at 100°C under a nitrogen stream. After the dropwise addition, it was further heated at 100°C for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7,000. Then, 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. Air is introduced into the reaction solution. The obtained alkali-soluble resin A uses GMA to introduce the side chain with ethylenic double bond into the main chain formed by the copolymerization of BzMA, MMA and MAA. The solid content is 42.6% by mass and the acid value is 74mgKOH. /g, the weight average molecular weight is 12,000. Using polystyrene as a standard substance and THF as an eluent, the weight average molecular weight was measured by Shodex GPC System-21H. In addition, the acid value measurement method is based on JIS K 0070.

(Synthesis Example 5: Synthesis of Y138 Sulfonate)

374.76 parts by mass of 11% by mass oleum was cooled to 10° C. while stirring, and 74.96 parts by mass of PY138 was added. Then, it stirred at 90 degreeC for 6 hours. After adding the reaction liquid to 1,600 parts by mass of ice water and stirring for 15 minutes, the precipitate was filtered. The obtained wet cake was washed 3 times with 800 parts by mass of water. The wet cake was vacuum dried at 80°C to obtain Y138 sulfonate. The Y138 sulfonate is in the above general formula (S), Z"=SO ₃ H, w=1, and the molecular weight of the target is confirmed by TOF-MS (Time of Flight Mass Spectrometry).

(Example 1) (1) Manufacturing of color material dispersion R1

As a dispersant, 9.84 parts by mass of the salt-type block copolymer A-1 solution of Synthesis Example 1 and the diketopyrrolopyrrole color material (BrDPP, trade name "Irgaphor RED S 3621CF) represented by the following chemical formula (2) "Manufactured by BASF Corporation) 11.57 parts by mass, 0.65 parts by mass of R254 sulfonate A obtained in Manufacturing Example 1 (in the total content of pigment and pigment derivative 100% by mass, the proportion of R254 sulfonate A is 5% by mass), 0.78 parts by mass of the PY138 sulfonated derivative A obtained in Synthesis Example 5, 12.29 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 4, 64.87 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added to In the mayonnaise bottle, use a paint shaker (manufactured by Asada Iron Works Co., Ltd.) to shake for 1 hour as pre-crushing. Then, take out the zirconia beads with a diameter of 2.0 mm and add 200 parts by mass of zirconia beads with a diameter of 0.1 mm. In the same manner, dispersion was performed for 4 hours using a paint shaker as the main disintegration to obtain a color material dispersion liquid R1.

[化13]

(2) Manufacturing of colored resin composition R1 for color filters

啉基丙烷-1-酮(光起始劑：商品名Irgacure 907(IRG907)，BASF(股)製造)0.09質量份、2-苄基-2-二甲胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名Irgacure 369(IRG369)，BASF製造)0.04質量部、乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(光起始劑：商品名ADEKA ARKLS NCI-831(NCI831)，ADEKA公司製造)0.02質量份、氟系界面活性劑(商品名MEGAFAC F559，DIC(股)製造)0.07質量份、矽烷偶合劑(商品名KBM-503，信越矽利光製造)0.07質量份、巰基化合物(季戊四醇肆(3-巰基丁酸酯))0.05質量份、PGMEA 5.85質量份、乙酸3-甲氧基-3-甲基-1-丁酯3.92質量份，獲得彩色濾光片用著色樹脂 組成物R1。 Add 11.29 parts by mass of the color material dispersion R1 obtained in (1) above, 1.90 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 4, and a multifunctional monomer (trade name ARONIXM-403, Toagosei Co., Ltd.) Company manufacture) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-

Linylpropan-1-one (photoinitiator: trade name Irgacure 907 (IRG907), manufactured by BASF Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Alolinophenyl)-butanone-1 (photoinitiator: trade name Irgacure 369 (IRG369), manufactured by BASF) 0.04 mass part, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzene) (Formyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831 (NCI831), manufactured by ADEKA) 0.02 parts by mass , Fluorine-based surfactant (trade name MEGAFAC F559, manufactured by DIC Co., Ltd.) 0.07 parts by mass, silane coupling agent (trade name KBM-503, manufactured by Shin-Etsu Silicon Co., Ltd.) 0.07 parts by mass, mercapto compound (pentaerythritol 4 (3-mercapto) Butyrate)) 0.05 parts by mass, 5.85 parts by mass of PGMEA, and 3.92 parts by mass of 3-methoxy-3-methyl-1-butyl acetate to obtain a colored resin composition R1 for a color filter.

(3) Formation of colored layer

Use a spin coater to coat the colored resin composition R1 obtained in (2) above with a thickness of 0.7mm on a 100mm×100mm glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35"), and then use The heating plate was dried at 80°C for 3 minutes, and an ultra-high pressure mercury lamp was used to irradiate 60mJ/cm ² of ultraviolet rays, and then post-baked in a dust-free oven at 230°C for 30 minutes, so that the cured film thickness became 2.00μm. In this way, the film thickness is adjusted to form the colored layer R1.

(Examples 2 to 14, Comparative Examples 1 to 5) (1) Manufacturing of color material dispersion R2~R14, RC1~RC5

In (1) of Example 1, the types and blending ratios of color materials and pigment derivatives, and the types of dispersants were changed as shown in Tables 2 and 3, and the amount of dispersant used was changed to the solid content. The method of the same parts by mass was changed, and the amount of PGMEA was adjusted so that the total was 100 parts by mass, except that the color material dispersion liquids R2 to R14 and RC1 to RC5 were obtained in the same manner as in Example 1 (1). In addition, in Table 2 and Table 3, the blending ratio (mass %) of each color material and each pigment derivative when the total content of the color material and the pigment derivative is 100 parts by mass is shown. The total addition amount of the color material and the pigment derivative added to each color material dispersion liquid was 13 parts by mass.

(2) Manufacture of colored resin composition R2~R14, RC1~RC5 for color filters

In Example 1 (2), the color material dispersion liquid R2~R14, RC1~RC5 were used instead of the color material dispersion liquid R1, in order to set the film thickness of the color layer to 2.00μm, so that the P/V ratio became Table 2 The amount of alkali-soluble resin was adjusted according to the values shown in Table 3, except that the colored resin compositions R2 to R14 and RC1 to RC5 for color filters were obtained in the same manner as in Example 1 (2).

(3) Formation of colored layer

In Example 1 (3), the above colored resin composition R2~R14, RC1~R5 were used instead of the colored resin composition R1, except that the colored layer was obtained in the same manner as in Example 1 (3) R2~R14, RC1~RC5.

Here, the abbreviations in the table are as follows.

Br-DPP: Trade name Irgaphor RED S 3621CF, manufactured by BASF

R254: C.I. Pigment Red 254 (trade name Hostaperm Red D2B-COF LV3781, manufactured by CLARIANT)

Y150: C.I. Pigment Yellow 150 (G04, manufactured by Lanxess Co., Ltd.)

Byk2001: Trade name Disperbyk-2001, manufactured by BYK-Chemie

[Evaluation method] <Viscosity stability evaluation>

For the color material dispersions obtained in Examples 1 to 10 and Comparative Examples 1 to 4, the viscosity was measured immediately after preparation and after storage at 25°C for 30 days, and the viscosity change rate was calculated based on the viscosity before and after storage. Stability is evaluated. The viscosity measurement system uses a vibrating viscometer to measure the viscosity at 25.0±0.5°C. Viscosity change rate (%) is determined by {[Viscosity (mPa·s) after 30 days storage at 25°C-Viscosity immediately after preparation (mPa·s)]/Viscosity immediately after preparation (mPa·s)} ×100 and calculated. Table 2 shows the viscosity (initial viscosity) and viscosity change rate (%) immediately after preparation in Examples 1-10 and Comparative Examples 1-4. Here, the total mass of the solvent containing the color material dispersion liquid is a value when the total content of the color material and the pigment derivative is 13% by mass. If the viscosity change rate is less than 25%, the color material dispersion can be used in actual use. The smaller the viscosity change rate, the better the dispersion stability of the color material dispersion. Also, those with a viscosity change rate of 300% or more are set as "unmeasurable".

<Developability Evaluation>

The colored resin composition obtained in the examples and comparative examples was coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") using a spin coater, and then dried at 80°C using a hot plate 3 Min, use an ultra-high pressure mercury lamp to expose the ^{colored layer with 60mJ/cm 2} of ultraviolet rays through an independent thin-line pattern mask with a line width of 1 μm to 100 μm, thereby forming a coloring layer with a thickness of 2.0 μm on the glass substrate. Then, by rotating and developing 0.05 wt% potassium (KOH) as a developer, the developer was brought into contact with the developer for 60 seconds and then washed with pure water to perform a development process, pattern formation was performed, and developability was evaluated. In this development process, the time until the unexposed part is dissolved and removed is measured. Judge the end of development by visual inspection. The measurement results are shown in Tables 2 and 3. In Comparative Examples 1, 3, 4, and 5, the unexposed parts could not be dissolved or removed even if they were in contact with the developer for 60 seconds. In addition, if the time until the unexposed part is dissolved and removed is 45 seconds or less, it is evaluated as a practical level.

<Optical performance evaluation, contrast evaluation>

When forming the colored layer in the examples and comparative examples, the spectroscopic characteristic measuring device LCF-1500M made by Otsuka Electronics and the contrast measuring device CT-1B made by Kosaka Electric were used to measure the contrast of the colored layer after exposure, and after post-baking The contrast and chromaticity (x, y) of the colored layer. The measurement results are shown in Tables 2 and 3. In addition, as heat resistance evaluation, the contrast retention rate (%) calculated by (contrast after post-baking/contrast after exposure)×100 is shown in Tables 2 and 3. The higher the contrast retention rate, the more the reduction in contrast caused by heating can be suppressed, and the better the heat resistance.

[Summary of Results]

According to the results shown in Table 2 and Table 3, it is clearly shown that the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material will be mixed in a predetermined ratio. The color material dispersion liquid of Examples 1 to 14 formed by combining the dispersant of the polymer having the structural unit represented by the general formula (I) and the color material containing the diketopyrrolopyrrole color material and The colored resin composition suppresses the decrease in contrast caused by heating, thereby forming a colored layer with improved contrast. In addition, the color material dispersions of Examples 1 to 14 have good viscosity stability and excellent dispersion stability, and the coloring resin compositions of Examples 1 to 14 have good developability and less development residue. In addition, the color material dispersions of Examples 11 to 14 contain CI Pigment Yellow 150, or the anion of the azo compound represented by the above general formula (A) and the azo compound of its tautomeric structure, and two specific metals The Azo pigment, which is a composite molecule of a metal complex composed of ions and a compound represented by the general formula (B), is used as a yellow color material, so the contrast is further improved and the contrast retention rate is higher. Among them, Examples 12, 13, and 14 containing the above-mentioned Azo pigment have higher contrast retention rates, and higher contrast after post-baking.

Claims (12)

A color material dispersion liquid for color filters, which contains a color material, a pigment derivative, a dispersant, and a solvent, the color material system includes a diketopyrrolopyrrole color material, and the pigment derivative system includes pyrrolo A mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material, and the mole of the above-mentioned monosulfonated derivative is relative to the above-mentioned monosulfonated derivative and the above The ratio of the total moles of the disulfonated derivatives {monosulfonated derivative/(monosulfonated derivative + disulfonated derivative)} is 0.10 or more and 0.90 or less. Among the above-mentioned diketopyrrolopyrrole color materials The monosulfonated derivative is a monosulfonated derivative represented by the following general formula (1-m), and the disulfonated derivative of the diketopyrrolopyrrole color material is represented by the following general formula (1-d) Represents the two sulfonated derivatives, and the above-mentioned dispersant is a polymer having a structural unit represented by the following general formula (I),

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a heteroatom, R ² and R ³ may Bond each other to form a ring structure), [化2]

(In general formula (1-m) and general formula (1-d), Y ₁ and Y ₂ are each independently selected from a halogen atom, a cyano group, a benzyl group, a phenyl group that may be substituted with an alkyl group, and carbon Substituents in a group consisting of an alkyl group of 1-10, n and m each independently represent an integer of 0-5; when n and m are 2 or more, several Y ₁ and Y ₂ can be respectively The same or different; Z represents -OH). The color material dispersion liquid for color filters according to claim 1, wherein the dispersant is a salt-type polymer, and the salt-type polymer system has the general formula in the polymer having the structural unit represented by the general formula (I) A part of the nitrogen site at the terminal of the structural unit represented by (I) forms a salt. The color material dispersion liquid for color filters according to claim 1, wherein the ratio of the molar ratio of the above-mentioned monosulfonated derivative to the total molar ratio of the above-mentioned monosulfonated derivative and the above-mentioned disulfonated derivative {single The sulfonated derivative/(monosulfonated derivative+disulfonated derivative)} is 0.30 or more and 0.90 or less. The color material dispersion liquid for color filters of claim 1 or 2, wherein the total content of the monosulfonated derivative and the disulfonated derivative is relative to 100 parts by mass of the diketopyrrolopyrrole color material , Is 1 part by mass or more and 20 parts by mass or less. The color material dispersion liquid for color filter of claim 1 or 2, wherein the above-mentioned dispersion The acid value of the agent is 1 mgKOH/g or more and 18 mgKOH/g or less. A colored resin composition for a color filter, which contains a color material, a pigment derivative, a dispersant, a binder component, and a solvent. The color material system includes a diketopyrrolopyrrole color material, and the pigment derivative It is a mixture of the monosulfonated derivative of the diketopyrrolopyrrole color material and the disulfonated derivative of the diketopyrrolopyrrole color material, and the molar ratio of the above-mentioned monosulfonated derivative is relative to the above-mentioned monosulfonated The ratio {monosulfonated derivative/(monosulfonated derivative+disulfonated derivative)} of the total molar ratio of the derivative to the above-mentioned disulfonated derivative is 0.10 or more and 0.90 or less, and the above-mentioned diketopyrrolopyrrole The monosulfonated derivative of the color material is the monosulfonated derivative represented by the following general formula (1-m), and the di-sulfonated derivative of the diketopyrrolopyrrole color material is the following general formula (1 -d) The disulfonated derivative represented by the above-mentioned dispersant is a polymer having the structural unit represented by the following general formula (I),

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, R ² and R ³ Can be bonded to each other to form a ring structure), [化4]

(In general formula (1-m) and general formula (1-d), Y ₁ and Y ₂ are each independently selected from a halogen atom, a cyano group, a benzyl group, a phenyl group that may be substituted with an alkyl group, and carbon Substituents in a group consisting of an alkyl group of 1-10, n and m each independently represent an integer of 0-5; when n and m are 2 or more, several Y ₁ and Y ₂ can be respectively The same or different; Z represents -OH). The colored resin composition for a color filter according to claim 6, wherein the dispersant is a salt-type polymer, and the salt-type polymer system has the general formula in the polymer having the structural unit represented by the general formula (I) A part of the nitrogen site at the terminal of the structural unit represented by (I) forms a salt. The colored resin composition for a color filter according to claim 6, wherein the ratio of the molar ratio of the above-mentioned monosulfonated derivative to the total molar ratio of the above-mentioned monosulfonated derivative and the above-mentioned disulfonated derivative {single The sulfonated derivative/(monosulfonated derivative+disulfonated derivative)} is 0.30 or more and 0.90 or less. The colored resin composition for color filters according to claim 6 or 7, wherein the total content of the monosulfonated derivative and the disulfonated derivative is relative to 100 parts by mass of the diketopyrrolopyrrole color material , Is 1 part by mass or more and 20 parts by mass or less. Such as claim 6 or 7 of the colored resin composition for color filters, wherein the above The acid value of the dispersant is 1 mgKOH/g or more and 18 mgKOH/g or less. A color filter comprising at least a substrate and a coloring layer provided on the substrate, characterized in that: at least one layer of the coloring layer is used for the color filter of any one of claims 6 to 10 Cured material of colored resin composition. A display device characterized by having the color filter of Claim 11 above.

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