Process for the production of xanthene pigments

Abstract

Provided are a xanthene dye that exhibits a desired hue, a powder of the dye, a colored composition containing the dye, a color filter colorant containing the dye or the colored composition, a color filter using the colorant, and a method for producing the dye. The xanthene dye is represented by the following general formula (1), and in a diffraction pattern in powder X-ray diffraction using CuKα rays at a diffraction angle (2θ) = 5° to 34°, when the relative intensity of a diffraction peak present in the range of 2θ = 21.0° to 22.1° is taken as 1, the relative intensity of a diffraction peak present in the range of 2θ = 13.7° to 14.5° is 0.1 or less, and the relative intensity of a diffraction peak present in the range of 2θ = 8° to 10° is 0.03 or less. [In formula (1), R 1 and R 3 represent a hydrogen atom or an alkyl group, R 2 and R 4 represent an aromatic hydrocarbon group].

Description

[0001] This application is a divisional application of the invention patent application entitled "Xanton Pigment, Coloring Composition Containing the Pigment, Colorant for Filter and Filter and Method for Manufacturing the Pigment", filed on December 15, 2020, with application number "202011473191.5". Technical Field

[0002] This invention relates to a pigment, a coloring composition containing the pigment, a colorant for a filter containing the pigment or the coloring composition, a filter using the colorant, and a method for manufacturing the pigment. Background Technology

[0003] Color filters are used in liquid crystal display devices, electroluminescent (EL) display devices, and imaging elements such as CCD and CMOS. Color filters are manufactured by laminating pigment films, pigment-resin composite films, or other colored layers onto a light-transmitting substrate such as glass or transparent resin using methods such as dyeing, pigment dispersion, printing, or electrodeposition. As the pigment material constituting the color filter, compounds with a xanthan backbone (xanthan pigments) that possess excellent hue and heat resistance are often used (patent documents 1-4).

[0004] Xanthan pigments are generally widely used as water-soluble dyes. Some xanthan pigments have low solubility in organic solvents and are used as colorants for filters that use organic solvents as the primary solvent. They are often used as finely granulated pigments. Therefore, in manufacturing color filters that display the desired hue, it is necessary to control the hue (powder chromaticity) of the pigment in its solid powder (particle) state.

[0005] It is known that, for pigment compounds, even with the same molecular structure, the hue can change depending on its particle state (crystalline structure) (Non-Patent Document 1). In the reaction of synthesizing the target structure of xaton pigment in an organic solvent, in the case of insufficiently soluble xaton pigment, solid precipitation occurs from the pigment manufacturing reaction, making it difficult to control its particle state, and sometimes a solid (powder) that displays the desired hue cannot be obtained.

[0006] It has been taught that the crystalline structure of xaton pigment powder is related to the properties of color filters (Patent Document 5). However, it is believed that even xaton molecules with the same basic skeleton can vary not only in hue depending on the type of substituent, but also in crystalline structure depending on manufacturing conditions. Therefore, in order to obtain xaton pigment powder suitable for color characteristics (brightness, contrast, etc.) as a colorant for color filters, it is necessary to evaluate the solid properties, heat resistance, solubility, or dispersibility of samples prepared by various methods to determine the optimal manufacturing method.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2002-265834

[0010] Patent Document 2: Japanese Patent Application Publication No. 2012-207224

[0011] Patent Document 3: Japanese Patent Application Publication No. 2010-254964

[0012] Patent Document 4: Japanese Patent Application Publication No. 2014-12814

[0013] Patent Document 5: International Publication No. 2019 / 003915

[0014] Non-patent literature

[0015] Non-patent document 1: Edited by the Organic Synthesis Chemistry Association, "New Edition of Dye Handbook", Maruzen Co., Ltd., 1970, page 159. Summary of the Invention

[0016] The problem that the invention aims to solve

[0017] The present invention was made to solve the above-mentioned problems, and aims to provide: a pigment that displays a desired hue, a powder of the pigment, a coloring composition containing the pigment, a colorant for a filter containing the pigment or the coloring composition, a filter using the colorant, and a method for manufacturing the pigment.

[0018] Methods for solving problems

[0019] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by using the method described in this invention to recrystallize sulfadiazine pigment, a pigment powder displaying the desired hue can be obtained; and its properties can be analyzed by powder X-ray diffraction; thus, it is suitable as a colorant for color filters. In other words, the present invention is summarized as follows.

[0020] 1. A pyrochrome pigment, which is a pyrochrome pigment represented by the following general formula (1),

[0021] In powder X-ray diffraction of CuKα rays, in the diffraction pattern with a diffraction angle (2θ) of 5° to 34°, when the relative intensity of the diffraction peaks existing in the range of 2θ = 21.0° to 22.1° is set to 1, the relative intensity of the diffraction peaks existing in the range of 2θ = 13.7° to 14.5° is less than 0.1, and the relative intensity of the diffraction peaks existing in the range of 2θ = 8° to 10° is less than 0.03.

[0022]

Chemistry 1

[0023]

[0024] In equation (1), R 1 and R 3 Each of the following independently represents a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 8 carbon atoms and may have substituents: R 2 and R 4 Each can independently represent an aromatic hydrocarbon group with 6 to 20 carbon atoms and may have substituents. [Or]

[0025] In equation (1), R 1 and R 3 Each independently represents a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 8 carbon atoms and potentially substituents; R 2 and R 4 Each can independently represent an aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents.

[0026] 2. Xanthan pigment, wherein the chromaticity coordinates of the powder in the above-mentioned xanthan pigment are 0.460≤x≤0.500 and 0.285≤y≤0.305.

[0027] 3. Xanthan pigment, wherein, in the above-mentioned xanthan pigment, R 2 and R 4 It is a phenyl group with 6 to 10 carbon atoms, which may have substituents. Or

[0028] 3. Xanthan pigment, wherein, in the above-mentioned xanthan pigment, R 2 and R 4 It is a phenyl group with 6 to 10 carbon atoms that can have substituents.

[0029] 4. A coloring composition containing the above-mentioned pyrithione pigment.

[0030] 5. A colorant for a color filter, which contains the above-mentioned pyrithione pigment or coloring composition.

[0031] 6. A color filter that uses the colorant described above for color filters.

[0032] Alternatively, a color filter containing the aforementioned thallium pigment.

[0033] Alternatively, the use of the aforementioned pyrithione pigment, the aforementioned coloring composition, or the aforementioned colorant for filter manufacturing.

[0034] Alternatively, a method for manufacturing a color filter may use the aforementioned pyrithione pigment, the aforementioned coloring composition, or the aforementioned colorant for color filters.

[0035] 7. A manufacturing method, which is a method for manufacturing pyrithione pigment or the above-mentioned pyrithione pigment, characterized in that step 1 and step 2 are performed.

[0036] Step 1: React the compound represented by the following formula (2) with the compound represented by the following general formula (3).

[0037]

Chemistry 2

[0038]

[0039]

Transformation 3

[0040]

[0041] In equation (3), R 1 and R 2 This indicates a definition identical to the one defined in general formula (1) above.

[0042] Step 2: After dissolving the compound obtained in Step 1 using two or more organic solvents containing alcohol and an alkali, recrystallize it by mixing acid and / or water.

[0043] The effects of the invention

[0044] According to the present invention, a zeolite pigment displaying a desired hue and a powder of the pigment are obtained, and thus the coloring composition containing the pigment is useful as a colorant for color filters. Attached Figure Description

[0045] Figure 1 This is a powder X-ray diffraction (XRD) pattern of the pigments in the embodiments and comparative examples of the present invention.

[0046] Figure 2 for Figure 1 Enlarged views of the embodiments and comparative examples. Detailed Implementation

[0047] Hereinafter, embodiments of the present invention will be described in detail. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within its scope. First, the zeolite pigment represented by the above general formula (1) will be described. It should be noted that, in the following, when the functional group has substituents, not only the carbon atoms contained in the functional group, but also the carbon atoms contained in the substituents are included in the number of carbon atoms.

[0048] In general formula (1), as R 1 and R 3The phrase "straight-chain or branched alkyl groups with 1 to 8 carbon atoms and may have substituents" specifically includes straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isooctyl, and 2-ethylhexyl.

[0049] In general formula (1), R 2 and R 4 The "aromatic hydrocarbon group" in the phrase "aromatic hydrocarbon group with 6 to 20 carbon atoms and which may have substituents" includes aryl and fused polycyclic aromatic groups. Specifically, aromatic hydrocarbon groups such as phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, indene, pyrene, perylene, fluoranyl, and benzo[9,10]phenanthryl can be listed.

[0050] In general formula (1), as R 1 and R 3 The term "linear or branched alkyl group that may have substituents" or "composed of R" indicates that the alkyl group is a straight-chain or branched alkyl group that may have substituents. 2 and R 4 The "substituents" in "aromatic hydrocarbon groups that may have substituents" can specifically include, for example, the following:

[0051] Hydroxyl, cyano, trifluoromethyl, nitro; sulfonic acid or carboxylic acid groups (note that they can be formed by alkali metal M into -SO3M or -COOM);

[0052] Halogen atoms such as fluorine, chlorine, bromine, and iodine;

[0053] Alkyl groups with 1 to 20 carbon atoms, either straight-chain or branched;

[0054] Cycloalkyl groups having 3 to 20 carbon atoms;

[0055] Alkenes with 2 to 20 carbon atoms, either straight-chain or branched;

[0056] Alkyl groups with 1 to 20 carbon atoms, either straight-chain or branched;

[0057] Cycloalkoxy groups with 3 to 20 carbon atoms, or 1-adamantoxy and 2-adamantoxy groups;

[0058] Acyl groups with 1 to 20 carbon atoms;

[0059] Aromatic hydrocarbon groups or fused polycyclic aromatic groups with 6 to 20 carbon atoms;

[0060] Heterocyclic groups with 2 to 20 carbon atoms;

[0061] Aryloxy groups with 6 to 20 carbon atoms;

[0062] Unsubstituted amino groups; monosubstituted or disubstituted amino groups having 1 to 20 carbon atoms, etc. These "substituents" may be present in only one or multiple forms, and when multiple forms are present, they may be the same or different from each other. Furthermore, these "substituents" may further have the substituents exemplified above. To clarify, when a "substituent" contains a carbon atom, that carbon atom is included in the categories of "1 to 8 carbon atoms in a straight-chain or branched alkyl group that may have substituents" and "6 to 20 carbon atoms in an aromatic hydrocarbon group that may have substituents." Additionally, these substituents may form rings by bonding with each other via single bonds, double bonds, substituted or unsubstituted methylene groups, oxygen atoms, or sulfur atoms.

[0063] To clarify, in general formula (1), as in the case of R 1 ~R 4 Examples of "substituents" listed above, which are "groups" that represent "groups" and have "substituents", are listed below.

[0064] "Alkyl groups with 1 to 20 carbon atoms, either straight-chain or branched"

[0065] "Cycloalkyl groups with 3 to 20 carbon atoms"

[0066] "Alkenes with 2 to 20 carbon atoms, either straight-chain or branched"

[0067] "A straight-chain or branched alkoxy group with 1 to 20 carbon atoms"

[0068] "Cycloalkoxy groups with 3 to 20 carbon atoms"

[0069] Acyl groups with 1 to 20 carbon atoms

[0070] "Aromatic hydrocarbon groups or fused polycyclic aromatic groups with 6 to 20 carbon atoms"

[0071] "Heterocyclic groups with 2 to 20 carbon atoms"

[0072] "Aryloxy groups with 6 to 20 carbon atoms", and

[0073] "Monosubstituted or disubstituted amino groups with 1 to 20 carbon atoms," specifically, examples can be listed.

[0074] Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, etc., which are straight-chain or branched alkyl groups.

[0075] Cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, and other cycloalkyl groups;

[0076] Alkenes such as vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, etc., or straight-chain or branched alkenyl groups formed by multiple bonds;

[0077] Alkoxy groups, including methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, and isooctoxy, which are straight-chain or branched alkoxy groups.

[0078] Cycloalkoxy groups with 3 to 20 carbon atoms, such as cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexoxy, cyclononoxy, and cyclodecoxy.

[0079] Acyl groups such as formyl, acetyl, propionyl, acryloyl, and benzoyl;

[0080] Aromatic hydrocarbon groups or fused polycyclic aromatic groups such as phenyl, biphenyl, terphenyl, naphthyl, anthryl group, tetraphenyl, phenanthryl, fluorenyl, indene, pyrene, perylene, fluoranyl, benzo[9,10]phenanthryl;

[0081] Thiophene, furanyl, pyrrole, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothiophene, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzooxazolyl, benzoimidazolyl, benzotriazolyl, purinyl, carbazole, dibenzothiophene, dibenzofuranyl, pyridyl, pyrimidinyl, triazine, quinolinyl, isoquinolinyl, naphridinyl, acridineyl, phenanthrolinel, naphridinyl, carbolinyl, and other heterocyclic groups;

[0082] Aromatic oxy groups include phenoxy, toluoxy, biphenyloxy, naphthoxy, anthraceneoxy, and phenanthreneoxy.

[0083] Monosubstituted or disubstituted amino groups with straight-chain or branched alkyl or aromatic hydrocarbon groups, such as methylamino, dimethylamino, diethylamino, ethylmethylamino, dipropylamino, dibutylamino, di(2-ethylhexyl)amino, di-tert-butylamino, and diphenylamino.

[0084] In general formula (1), R is used as 1 and R 3 Preferably, it is a straight-chain or branched alkyl group with 1 to 6 carbon atoms, containing hydrogen atoms. 1 and R 3 Each can be the same or different independently, but the same is preferred.

[0085] In general formula (1), R is used as 2 and R 4 Preferably, it is a phenyl group with 6 to 12 carbon atoms and may have substituents. 2 and R 4Each can be the same or different independently, but the same is preferred.

[0086] Specific examples of preferred compounds of the present invention, represented by general formula (1), are shown in the following formulas (A-1) to (A-16), but the present invention is not limited to these compounds. It should be noted that some hydrogen atoms are omitted in the following structural formulas. Furthermore, even in the presence of stereoisomers, their planar structural formulas are described.

[0087]

Chemistry 4

[0088]

[0089]

Transformation 5

[0090]

[0091]

Transformation 6

[0092]

[0093]

Transformation 7

[0094]

[0095]

Transformation 8

[0096]

[0097]

Chemistry 9

[0098]

[0099]

Chemistry 10

[0100]

[0101]

Chemistry 11

[0102]

[0103] Regarding the saxanthin pigment represented by general formula (1) of the present invention, one type or a combination of two or more types with different molecular structures can be used (e.g., a mixture). In the coloring composition containing these saxanthin pigments, the weight concentration of the saxanthin pigment with the smallest occupancy in the total saxanthin pigment is 0.1 to 50% by weight. The type of saxanthin pigment is preferably one or two types.

[0104] Next, a method for manufacturing a compound of succinate pigment represented by general formula (1) (hereinafter sometimes referred to as "compound (1)") will be described. The succinate pigment of the present invention is synthesized by a manufacturing method characterized by performing the following steps 1 and 2.

[0105] Step 1 involves reacting a compound represented by formula (2) (hereinafter sometimes referred to as "compound (2)") with a compound represented by general formula (3) (hereinafter sometimes referred to as "compound (3)"), thereby obtaining a succinate pigment represented by general formula (1). These compounds (2) and (3) can be obtained from commercially available products or synthesized using any known method.

[0106]

Chemistry 12

[0107]

[0108]

Chemistry 13

[0109]

[0110] In equation (3), R 1 and R 2 This indicates the same meaning as the definition in general formula (1) above.

[0111] Specifically, in step 1, compound (2) and a compound having a corresponding group, namely R, are used. 1 and R 2 Compound (3) is mixed in an appropriate ratio in an appropriate solvent and reacted under appropriate reaction temperature, reaction time, and stirring conditions to obtain xatonine pigment or its intermediate, represented by the above general formula (1), and mixtures thereof. Step 1 can be repeated to synthesize the target xatonine pigment. In this case, the compound (3) used may be the same or different, and R may be used. 1 R 2 The part is replaced with R 3 R 4 Compounds.

[0112] In step 1, a solvent can be used. In addition, the reaction can be carried out even without a solvent. Considering convenience and efficiency, it is preferable to use a solvent to carry out the reaction.

[0113] As solvents in step 1, examples include aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; alcohols such as butanol, 2-ethoxyethanol, pentanol, and hexanol; diols such as ethylene glycol; amides such as 1-methyl-2-pyrrolidone (NMP) and dimethylformamide (DMF); sulfoxides such as dimethyl sulfoxide (DMSO); and sulfones such as sulfolane.

[0114] Regarding the solvent in step 1, only one type may be used, or two or more types may be mixed and used. The ratio (volume / mass) of the amount of solvent used (volume (mL)) to the amount of compound (2) used (mass (g)) is preferably 1 to 30, more preferably 1 to 10.

[0115] The reaction temperature in step 1 is preferably 60–200°C, and more preferably 100–160°C to suppress byproducts. It should be noted that the reaction temperature can be constant, or it can be appropriately varied within the above range.

[0116] Regarding the amount of compound used in step 1, relative to 1 mol of compound (2), it is preferred to use 2 to 20 mol of compound (3), and more preferably 2 to 10 mol.

[0117] There are no particular limitations on the atmosphere for the reaction in step 1. The reaction can be carried out in inert gases such as nitrogen or argon, or it can be carried out in the atmosphere.

[0118] The compound obtained in step 1 described above can be obtained in the form of a solution, a (tiny) solid (powder) dispersion in a reaction solution (in this invention, the dispersion is sometimes also referred to as a solution), or a powder precipitate. Generally, it can be obtained as a mixture containing the target xanthan pigment (other components in the mixture include products other than the target xanthan pigment, solvent, unreacted components, and other components). Next, the compound obtained in step 1 (or a mixture containing the compound) can be washed using the solvent used in the reaction or other solvents. Alternatively, the target compound can be removed as a solid (powder, etc.) using known methods such as filtration, concentration, extraction, and drying (heating, reduced pressure, etc.). Furthermore, it can be purified using various known methods. After step 1, it can be directly or after the aforementioned washing, drying, and purification processes, and then transferred to a manufacturing process as a colorant for color filters. In the manufacturing method of this invention, it is preferable to proceed with step 2 described below after step 1 to obtain the xanthan pigment or its powder.

[0119] Step 2 is characterized by the following step: "The compound obtained in Step 1 is dissolved in two or more organic solvents containing alcohol and an alkali, and then recrystallized by mixing with acid or water." Step 2 includes the step of obtaining a succinate pigment (hereinafter sometimes referred to as "compound (1)") represented by general formula (1) through this step 2. Hereinafter, an example of a specific method will be described, but it is not limited to this method.

[0120] In step 2, the so-called "compound obtained in step 1" can be a mixture containing compound (1) as the main component, or it can be the mixture obtained after the reaction in step 1.

[0121] The phrase "two or more organic solvents containing alcohols" means that there are two or more organic solvents, at least one of which is an alcohol. The phrase "dissolving with two or more organic solvents containing alcohols" means dissolving the compound obtained in step 1 above using an organic solvent that is an alcohol and an organic solvent other than an alcohol. The organic solvent that is an alcohol and the organic solvent other than an alcohol can be mixed in advance before dissolving (or dispersing) the compound obtained in step 1 above, or they can be mixed at the time of dissolving (or dispersing) it.

[0122] Additionally, as a dissolution (or dispersion) step, initially, the compound obtained in step 1 can be dissolved (or dispersed) in two or more organic solvents containing an alcohol, and then an alkali such as sodium hydroxide can be added to dissolve the compound obtained in step 1. Alternatively, the compound can be dissolved simultaneously in a liquid in which two or more organic solvents containing the alcohol are premixed with an alkali. Furthermore, the compound can be first dissolved in an alkali (or an aqueous solution containing an alkali), and then dissolved by mixing with the aforementioned organic solvent.

[0123] In step 2, as described above, the compound obtained in step 1 is dissolved using two or more organic solvents containing alcohol and an alkali. Then, acid or water is added and mixed, thereby allowing the target succinate pigment to be recrystallized (or crystallized). Step 2 can be repeated multiple times. In addition, during the addition process, washing and drying steps can be performed.

[0124] As for "two or more organic solvents containing alcohols" in step 2, commonly used solvents can be used. Examples of "alcohols" in step 2 include methanol, ethanol, propanol, and butanol. One alcohol can be used, or two or more can be mixed. Other organic solvents besides alcohols include ketones such as acetone and methyl ethyl ketone (MEK); aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane; halogenated hydrocarbons such as carbon tetrachloride; ester solvents such as ethyl acetate and butyl acetate; and ethers such as diethyl ether, tetrahydrofuran (THF), and dioxane. Only one of these organic solvents other than alcohols can be used, or two or more can be mixed. When using two or more organic solvents, including alcohols, any mixing ratio is acceptable.

[0125] The ratio (volume / mass) of the amount of solvent used (volume (mL)) to the theoretical yield (mass (g)) of compound (1) is preferably 2 to 20, more preferably 5 to 10.

[0126] The "alkali" in step 2 is not particularly limited, but generally, salts containing alkali metals such as sodium and potassium are preferred; salts containing alkaline earth metals such as calcium and magnesium are preferred, and sodium hydroxide or potassium hydroxide are even more preferred. In addition, regarding the amount of alkali used, relative to the theoretical yield of 1 mol of compound (1), the amount of alkali is preferably 0.5 to 5 mol, and more preferably 1 to 3 mol. It is even more preferable that the alkali is used as an aqueous solution.

[0127] In step 2, after mixing and dissolving using an organic solvent and an alkali, it is preferable to promote dissolution by heating. The dissolution temperature is preferably 60–200°C, more preferably 60–160°C. It should be noted that the temperature can be constant, or it can be appropriately varied within the above range.

[0128] The "acid" used in step 2 is not particularly limited, but examples include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, with hydrochloric acid being preferred. Furthermore, regarding the amount of acid used, relative to the theoretical yield of 1 mol of compound (1), 0.5 to 5 mol of acid is preferred, and more preferably 1 to 3 mol. It is even more preferable that the acid is used in an aqueous solution.

[0129] There are no special restrictions on the "water" used in step 2. It can be any kind of water, such as tap water, industrial water, ion-exchange water, distilled water, etc.

[0130] According to the method described above, a zeatin pigment represented by the above general formula (1), a powder of the pigment, and a coloring composition of the present invention containing at least one of the pigments are obtained. In the coloring composition of the present invention, components other than the zeatin pigment, such as solvents used in the above-described manufacturing method, may be included within a range that does not affect the manufacture of the color filter. Hereinafter, a method for obtaining a powder containing a form suitable as a colorant for a color filter, which is the problem to be solved by the present invention, will be described.

[0131] Regarding the shape of the powder of the succinate pigment of the present invention, it can be observed using an optical microscope, a scanning electron microscope (SEM), or the like. The powder of the present invention is generally used in the form of a solid powder having shapes such as crystalline, microcrystalline, micropowder, flake, needle-like crystals, or granules, but is not limited to these.

[0132] Regarding the succinate pigment powder of the present invention, detailed overall and average information about the shape of the powder is obtained by measuring particle size distribution (Coulter method, centrifugal sedimentation method, laser diffraction and scattering method, etc.), surface area, pore size distribution, powder density, etc. For the powder of the present invention, a particle size range of 0.1 μm to several mm is preferred. Since the shape of the particles varies depending on the manufacturing conditions and the method of recovering the dried powder, a specific particle size is not limited. For high solubility, a smaller particle size is preferred, and the central value of the particle size distribution is preferably in the range of 0.1 to 100 μm.

[0133] Regarding the powder of the succinate pigment of the present invention, elemental analysis, mass analysis, and crystal structure analysis using powder X-ray diffraction (XRD) can be performed, thereby allowing information related to the fine structure at the molecular and atomic levels to be deduced. As for other physical properties, methods for determining solubility, etc., can be the same known methods described in Patent Document 5, etc.

[0134] By performing thermogravimetric analysis-differential calorimetry (TG-DTA) on the pigment or coloring composition containing the pigment of the present invention, the decomposition onset temperature can be analyzed. The decomposition onset temperature is preferably 250°C or higher, more preferably 300°C or higher, and particularly preferably 360°C or higher. When applied to a color filter, a higher decomposition onset temperature is more preferred. Furthermore, as a temperature equivalent to the decomposition onset temperature, the temperature at which the weight of the sample decreases by a certain percentage (%) after heating can be used (e.g., the 5% weight reduction temperature).

[0135] By measuring the powder X-ray diffraction (XRD) of the zeolite pigment of the present invention, it is possible to analyze whether the powder is in a state suitable as a colorant for a color filter.

[0136] When the pigment powder has low solubility, it exists as a solid micro-powder in the color filter. The shape and size of the powder particles cause uneven coating during film formation, affecting lightfastness and heat resistance. In addition, the depolarization of transmitted light becomes complicated, affecting color development.

[0137] Furthermore, in the color filter, succinate forms aggregates with other pigments of different colors to achieve color matching. However, the charge movement between molecules of the light-excited pigment and succinate also presumably has a significant impact on the different crystal states of succinate.

[0138] Powder X-ray diffraction is suitable as a method for judging and inferring whether a powder of a certain pigment has a suitable crystalline structure, considering its dispersibility, thermal properties, and color properties. In powder X-ray diffraction, CuKα rays (hν = 8.048 keV (h is Planck's constant, ν is the frequency), wavelength λ = 0.15418 nm) or MoKα rays (hν = 17.5 keV, wavelength λ = 0.071073 nm) are typically used as the X-ray source, with CuKα ray powder X-ray diffraction being preferred. Furthermore, regarding the intensity of the X-rays used for irradiation, it is preferable to have a relative intensity of the diffraction peaks within the measurement range that does not change according to the X-ray intensity.

[0139] The measurement range of the diffraction angle (2θ) is preferably below 50°, and can be from 5° to 40°. In order to accurately obtain this information related to the crystal structure or the aggregation state of molecules, the measurement interval (scan step) of 2θ is preferably below 0.05°.

[0140] In the obtained diffraction pattern, peaks are observed at diffraction angles with high diffraction intensity. The presence of observed diffraction peaks (or shoulders near the peaks) indicates information about the periodic crystallization state of the powder, related to the intramolecular or intermolecular periodicity of the diffraction molecules. The position of the diffraction peaks contains information related to the characteristic lattice constant of the sample. The shape of the diffraction peaks can be symmetrical or asymmetrical.

[0141] The width of a diffraction peak can be expressed using the full width at half maximum (FWHM). Generally, the peak width tends to decrease as the grain diameter increases, thus providing information related to the size of the crystallites and the degree of crystallite deformation. Considering the powder preparation conditions and powder X-ray diffraction measurement conditions of the succinate pigment of this invention, it is preferable to observe peaks with a full width at half maximum (FWHM) of at least 0.2° to 0.5° among the peaks with the highest observed intensity.

[0142] In terms of peak intensity, it can be represented by the distance between the highest point of the peak and the baseline. Generally, diffraction patterns tend to have a gradual increase in diffraction intensity from the high diffraction angle side to the low diffraction angle side. In this invention, there is no particular limitation on the way the baseline is drawn. For example, within the range of diffraction angles containing the diffraction peak group being analyzed, a baseline can be drawn by connecting the valleys and flat areas between peaks located far from the diffraction peak positions using curves or straight lines. Peak intensity can be represented by the length between the baseline and the highest point of the peak. To observe the structure of the smallest intensity peak in the diffraction pattern, it is preferable that the SN ratio of the diffraction pattern is 3 or higher. In terms of the intensity ratio of the peaks of different sizes in the diffraction pattern, information related to the quantitative determination of the crystalline phase in the powder can be obtained.

[0143] In the powder X-ray diffraction pattern of the xatonium pigment in this invention, at least 10 to a maximum of 50 diffraction peaks and shoulders are sometimes observed in the range of 2θ = 5° to 40°, preferably 10 to 40 diffraction peaks (including shoulders). The presence of peaks in the range of 2θ = 5° to 40° in powder X-ray diffraction indicates the presence of atomic periodicity of approximately 0.2 nm to approximately 1.8 nm in the solid powder sample. For example, in a xatonium molecule such as Acid Red 52, a representative xatonium pigment, the shortest interatomic bonding distance is approximately 0.14 nm, and the distance between two nitrogen atoms is approximately 1 nm. The diffraction pattern observed within the aforementioned diffraction angle range contains information related to the periodicity between the atoms (C, O, N, etc.) within the xatonium molecule; these atoms can be directly bonded to each other, or other atoms can be interposed therein, with space between them. In terms of periodic length, a periodic length of at least the width of a 6-membered ring indicates information related to the arrangement of substituents within the xanthonium molecule, and even the arrangement of xanthonium molecules within the powder. For this reason, powder X-ray diffraction is an excellent method for analyzing the state of powders containing xanthonium pigments.

[0144] In this invention, the inventors discovered that the manufacturing method of xaton pigment powder is related to the resulting powder X-ray diffraction pattern and the hue of the pigment powder, particularly its suitability as a colorant for color filters. Specifically, for xaton pigment represented by general formula (1), the diffraction pattern in CuKα ray powder X-ray diffraction differs depending on the manufacturing method; for example, there are diffraction patterns with significant peak intensity at a specific diffraction angle (2θ) and diffraction patterns with insignificant peak intensity.

[0145] For example, regarding the high intensity peaks observed in the range of 2θ = 21° to 22.1° and the diffraction peak group observed in the range of 2θ = 17.5° to 34.0°, for the xanthon pigment represented by the general formula (1) obtained under certain manufacturing conditions, since the diffraction angles and intensities of the peak positions are observed in a roughly similar manner, it is believed that the characteristics are not affected by the condensation state of the molecules in the solid, such as the structure of “3H-xanthon” or the periodic structure of less than 0.5 nm contained in the atomic group including the nitrogen atoms bonded at the 3 and 6 positions.

[0146] On the other hand, within the range of 2θ = 5° to 17.5°, although several diffraction peaks were observed at approximately the same diffraction angle, differences in their intensity ratios, peak widths, etc., were also observed. The diffraction angles in this range exhibit a periodicity of more than 0.5 nm, suggesting that this is due to the presence of the substituent (phenyl) at position 9, the group bonded to it, or the substituent bonded to the nitrogen position within the xanthonite molecule. That is, it is taught that even xanthonite moleculees with the same basic skeleton of 3H-xanthonite, even with substituents of a certain structure and size, can sometimes have different crystal systems due to different manufacturing conditions of the solid (powder). For example, it is speculated that the molecular aggregation processes differ depending on whether the pigment is removed from a solution state by solid sublimation, recrystallization as a solid, or recrystallization as a solid. Furthermore, it is taught that even in the case of solvent recovery, different manufacturing conditions such as recrystallization result in products with different configurations of xanthonite molecules.

[0147] Thus, the different aggregation states in the powder also affect the magnitude and interaction of intermolecular forces between xanthannae molecules. As a result, it also has a significant impact on the solubility, dispersibility, hue, and interaction with other pigments and resin materials used in the color filter, directly affecting the various physical properties of the color filter. The xanthannae pigment of the present invention has the following characteristics: in a powder X-ray diffraction pattern with a diffraction angle (2θ) of 5° to 34° in CuKα ray diffraction, when the relative intensity of the diffraction peak existing in the range of 2θ = 21.0° to 22.1° is set to 1, the relative intensity of the diffraction peak existing in the range of 2θ = 13.7° to 14.5° is 0.1 or less, and the relative intensity of the diffraction peak existing in the range of 2θ = 8° to 10° is 0.03 or less. More preferably, no peak is observed in the range of 2θ = 13.7° to 14.5°, and even more preferably, no peak is observed in the range of 2θ = 8° to 10°.

[0148] Among them, as a method for determining relative intensity, the following method is preferred: for the peak with the highest intensity among all observed diffraction patterns, its height or peak area is used as a reference (e.g., 1) to determine the intensity of other peaks.

[0149] Regarding the zeolite pigment of the present invention, the visible light absorption spectrum or reflectance spectrum is measured in the form of solution, dispersion, film, or powder (solid); the chromaticity coordinates (x, y) and concentration (K / Sd) of the xy chromaticity diagram of the CIE 1931 color system using a spectrophotometer and colorimeter; and the hue (L) of the CIE 1976 color system is measured. ＊ a ＊ b ＊ ), color difference (ΔE) ＊Spectrophotometers and colorimeters can be used to evaluate the color characteristics (hue) of compounds. Even solutions, powders, and films of compounds with the same molecular structure can sometimes appear significantly different in color when viewed visually. In order to objectively quantify such color differences, spectrophotometers and colorimeters can be used for measurement.

[0150] Regarding the hue of the powder of the zeolite pigment of the present invention, the preferred chromaticity coordinates (x, y) are 0.460 ≤ x ≤ 0.500 and 0.285 ≤ y ≤ 0.305. Powders with this chromaticity exhibit a red to reddish-purple to purple color.

[0151] The colorant for color filters of the present invention comprises: a coloring composition containing at least one pyritin pigment represented by general formula (1), and components generally used in the manufacture of color filters. For a typical color filter, for example, in the case of a photolithography process, a liquid prepared by mixing a dye, pigment, or other pigment with a resin component (including monomers and oligomers) and a solvent is coated onto a substrate such as glass or resin, and photopolymerized using a photomask to create a color pattern of a pigment-resin composite film that is soluble / insoluble in the solvent. After cleaning, it is heated to obtain the filter. Furthermore, even in electrodeposition and printing methods, a product formed by mixing a pigment with a resin and other components is used to create the color pattern. Therefore, specific components of the colorant for color filters of the present invention include at least one pyritin pigment represented by general formula (1), other dyes, pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. Furthermore, these components can be selected from among them, and other components can be added as needed.

[0152] When using a coloring composition containing the pyrithione pigment of the present invention as a colorant for a filter, it can be used in various color filters, and is preferably used as a colorant for a red filter.

[0153] Regarding the colorant for filters containing the succinate pigment of the present invention, one or more succinate pigments may be used as pigments. To adjust the hue, other known pigments such as dyes or pigments may be mixed in. In the case of a colorant for a red filter, there are no particular limitations; examples include red pigments such as CI Pigment Red 177, 209, 242, 254, 255, 264, 269, CI Pigment Orange 38, 43, 71, etc.; other red lake pigments; yellow pigments such as CI Pigment Yellow 138, 139, 150, etc.; and red dyes such as CI Acid Red 88 and CI Basic Violet 10. When used as a colorant for cyan filters, there are no particular limitations, and examples include basic dyes such as Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, and 129; acid dyes such as Acid Blue 9 and 74; disperse dyes such as Disperse Blue 3, 7, and 377; spirocyclic ketone dyes; cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane, indanthrene, oxazine, dioxazine, azo, and xatonne (not included in this invention); and other cyan lake pigments and other cyan-based dyes or pigments.

[0154] Regarding the mixing ratio of other pigments in the colorant for filters containing the succinate pigment of the present invention, it is preferably 5 to 2000% by weight, more preferably 10 to 1000% by weight, relative to the succinate pigment (in the case of two or more). Regarding the mixing ratio of pigment components such as dyes in the liquid colorant for filters, it is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight, relative to the total colorant.

[0155] As the resin component in the colorant for color filters of the present invention, any known resin component can be used, provided that it has the manufacturing method for the color filter resin film formed by using it and the properties required for use. Examples include acrylic resins, olefin resins, styrene resins, polyimide resins, polyurethane resins, polyester resins, epoxy resins, vinyl ether resins, phenolic (varnish) resins, polycarbonate resins, cellulose resins, other transparent resins, photocurable resins, thermocurable resins, thermoplastic resins, and composites of these resins. These monomer or oligomer components can be appropriately combined for use. Furthermore, copolymers of these resins can also be used. Regarding the resin content in these colorant colorants for color filters, in the case of liquid colorants, it is preferably 5 to 95% by weight, more preferably 10 to 50% by weight.

[0156] Regarding the coloring composition of the present invention, in order to improve its performance as a colorant for color filters, surfactants, dispersants, defoamers, leveling agents, and other organic compounds mixed in the manufacture of colorants for color filters can be added as components other than compounds. However, it is preferable that the content of these additives in the coloring composition is appropriate, preferably a content that does not reduce or excessively increase the solubility of the coloring composition in the solvent of the present invention, and does not affect the effect of other additives of the same kind used in the manufacture of color filters. These additives can be added at any time during the preparation of the coloring composition.

[0157] Other additives in the colorant for color filters of the present invention include components required for the polymerization and curing of resins such as photopolymerization initiators and crosslinking agents. Additionally, surfactants, dispersants, etc., required to stabilize the properties of the components in the liquid colorant for color filters can also be included. These can all be well-known components used in color filter manufacturing, and there are no particular limitations. The mixing ratio of the total amount of these additives in the solid component of the colorant for color filters is preferably 5 to 60% by weight, more preferably 10 to 40% by weight.

[0158] Example

[0159] The embodiments of the present invention will be specifically described below through examples, but the present invention is not limited to the following examples. It should be noted that, regarding the identification of the compounds obtained in the examples, by... 1 The analysis was performed using H-NMR (Bluker Corporation nuclear magnetic resonance apparatus, model: Magnet System 300MHz / 54mm UltraShield), and the results are shown in the following examples.

[0160] [Example 1] Synthesis of Compound (A-1) Example 1

[0161] The following reaction was carried out under a nitrogen stream. 60.0 g of compound (2), 120 g of 2,6-dimethylaniline, and 300 mL of 1,2-dichlorobenzene were placed in a 1 L container and stirred at 130 °C for 78 hours to allow the reaction to proceed. After stirring, the reaction solution was cooled to below 40 °C, and the precipitated solid was filtered off. The filtered solid, 240 mL of toluene, and 240 mL of methanol were placed in a container and stirred under reflux (approximately 65 °C) for 1 hour. After cooling to below 40 °C, the solid was filtered off. The filtered solid, 60 mL of toluene, 300 mL of methanol, and 26.1 g of 24% sodium hydroxide aqueous solution were placed in a container and mixed. The mixture was heated at 65 °C to dissolve (disperse) the solid. The heated mixture was cooled to 50 °C, and 16.3 g of 35% hydrochloric acid aqueous solution was added dropwise. The mixture was cooled to below 40 °C, and the precipitated solid was filtered off. The filtered solid and 360 g of water were placed in a container and mixed. The mixture was stirred at room temperature for 2 hours. The stirred mixture was filtered, and the resulting solid was dried under reduced pressure at 80°C for 24 hours to obtain the following compound (A-1) (53.7 g, yield 63%) as a reddish-purple solid.

[0162] 1 H-NMR (300MHz, DMSO-d6): δ (ppm) = 9.89 (2H), 8.01 (1H), 7.62 (2H), 7.24-7.14 (11H), 5.94 (2H), 2.15 (12H).

[0163]

Chemistry 14

[0164]

[0165] [Example 2] Synthesis of Compound (A-1) Example 2

[0166] The following reaction was carried out under a nitrogen stream. 60.0 g of compound (2), 120 g of 2,6-dimethylaniline, and 300 mL of 2-ethoxyethanol were placed in a 1 L container and stirred at 130 °C for 43 hours to allow the reaction to proceed. After stirring, the reaction solution was cooled to below 40 °C, and the precipitated solid was filtered off. The filtered solid and 600 mL of methanol were placed in a container and stirred under reflux (approximately 65 °C) for 1 hour. After cooling to below 40 °C, the solid was filtered off. The filtered solid, 60 mL of toluene, 300 mL of methanol, and 26.1 g of 24% sodium hydroxide aqueous solution were placed in a container and mixed. The mixture was heated at 65 °C to dissolve (disperse) the solid. The heated mixture was cooled to 50 °C, and 16.3 g of 35% hydrochloric acid aqueous solution was added dropwise. After cooling the mixture to below 40 °C, the precipitated solid was filtered off. The filtered solid and 360 g of water were placed in a container and mixed. The mixture was stirred at room temperature for 2 hours. The stirred mixture was filtered, and the resulting solid was dried under reduced pressure at 80 °C for 24 hours to obtain compound (A-1) (58.6 g, yield 69%) as a reddish-purple solid.

[0167] [Example 3] Synthesis of Compound (A-1) Example 3

[0168] Except that the 2-ethoxyethanol used in the reaction of Example 2 was replaced with 1-methyl-2-pyrrolidone, the reaction was carried out in the same manner as in Example 2, and compound (A-1) (47.3 g, yield 56%) was obtained as a reddish-purple solid.

[0169] [Comparative Example 1]

[0170] The following reaction was carried out under a nitrogen stream. In a 1 L container, 60.0 g of compound (2), 120 g of 2,6-dimethylaniline, and 300 mL of 1,2-dichlorobenzene were stirred at 130 °C for 78 hours to allow the reaction to proceed. After stirring, the reaction mixture was cooled to below 40 °C, and the precipitated solid was filtered off. The filtered solid and 400 mL of methanol were added to the container and mixed. The mixture was stirred under reflux (approximately 65 °C) for 1 hour, then cooled to below 40 °C, and the solid was filtered off. The resulting solid was dried at 80 °C for 24 hours, yielding compound (A-1) (53.7 g, 70% yield) as a red solid.

[0171] [Powder X-ray Diffraction Measurement]

[0172] Powder X-ray diffraction (XRD) measurements were performed on the pigment powders of the compounds obtained in Examples 1-3 and Comparative Example 1 (PANalytical BV, multi-purpose X-ray diffractometer, model: Empyrean, X-ray source: CuKα rays (hν = 0.15418 nm, 40 kV, 30 mA), divergence slit: 1 / 2°, scattering slit: 1°, receiving slit: 7.5 mm, scanning step: 0.0131°, scanning speed: 0.034° / sec, scanning diffraction angle range: 2θ = 5° to 50°). The measurement results at diffraction angles (2θ) = 5° to 40° are shown below. Figure 1 and Figure 2 (Enlarged views of 2θ = 7°–10.5° and 13.0°–14.8°). For each diffraction pattern, a baseline is formed by connecting the flat portion of the valley between peaks at 2θ = 10° with the flat portion at 2θ = 34° using a straight line. In each diffraction pattern, the height of the peak with the highest observed intensity at 2θ = 21°–22.1° (distance from the baseline to the peak apex) is set as the reference value 1. Table 1 shows the range of diffraction angles 2θ (°) of the observed characteristic diffraction peaks and the relative intensities of the diffraction peaks observed within this range. Furthermore, the full width at half maximum (FWHM) (°) of each diffraction peak shown in Table 1 is shown in Table 2. Note that in Table 2, blank areas indicate peaks that could not be measured due to their absence or excessive smallness.

[0173] Table 1

[0174]

[0175] Table 2

[0176]

[0177] As can be seen from Tables 1 and 2, regarding the diffraction pattern of the embodiment, when the relative intensity of the diffraction peak existing in the range of 2θ = 21.0° to 22.1° is set to 1, the relative intensity of the diffraction peak existing in the range of 2θ = 13.7° to 14.5° is 0.1 or less, and the relative intensity of the diffraction peak existing in the range of 2θ = 8° to 10° is 0.03 or less and 0.02 or less, which has characteristics different from the comparative example.

[0178] [Colorimetry Measurement]

[0179] The chromaticity of the solid and powder pigment compounds obtained in Examples 1 to 3 and Comparative Example 1 was determined. The obtained pigment powders were placed seamlessly on a glass dish, and the chromaticity coordinates (x, y) were measured using a spectrophotometer (manufactured by Conicaminodes Co., Ltd., model: CM-5, light source: CIE standard light source D65). The results are shown in Table 3.

[0180] Table 3

[0181]

[0182] As shown in Table 3, according to the present invention, it is possible to obtain a zeolite pigment (powder) that displays the desired hue.

[0183] Industrial availability

[0184] With regard to the pigment and coloring composition containing the pigment of the present invention, it is useful as a colorant for color filters that display the desired hue in the manufacture of color filters used in imaging elements such as liquid crystal display devices, electroluminescent (EL) display devices, CCD, and CMOS.

Claims

1. A method for manufacturing a pyrithione pigment, comprising a method for manufacturing a pyrithione pigment represented by the following general formula (1), The chromaticity coordinates of the pyrithione pigment powder are 0.460≤x≤0.500 and 0.285≤y≤0.

305. Perform process 1 and process 2. Step 1: React the compound represented by formula (2) below with the compound represented by general formula (3) below. Step 2: Dissolve the compound obtained in Step 1 using a mixed solvent containing methanol and toluene and sodium hydroxide, then mix with hydrochloric acid or water to perform recrystallization. In equation (1), R 1 and R 3 R represents a hydrogen atom. 2 and R 4 It represents 2,6-dimethylphenyl. In equation (3), R 1 and R 2 This means the same as the definition of the general formula (1) above.

2. The method for manufacturing pyrithione pigment according to claim 1, wherein, In the powder X-ray diffraction of CuKα rays of the thallium pigment, in the diffraction pattern with a diffraction angle (2θ) of 5° to 34°, when the relative intensity of the diffraction peak existing in the range of 2θ = 21.0° to 22.1° is set to 1, the relative intensity of the diffraction peak existing in the range of 2θ = 13.7° to 14.5° is 0.1 or less, and the relative intensity of the diffraction peak existing in the range of 2θ = 8° to 10° is 0.03 or less.

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