CN112980213A - Xanthene dye, coloring composition containing the dye, coloring agent for color filter, and method for producing the dye - Google Patents
Xanthene dye, coloring composition containing the dye, coloring agent for color filter, and method for producing the dye Download PDFInfo
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- CN112980213A CN112980213A CN202011473191.5A CN202011473191A CN112980213A CN 112980213 A CN112980213 A CN 112980213A CN 202011473191 A CN202011473191 A CN 202011473191A CN 112980213 A CN112980213 A CN 112980213A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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Abstract
Disclosed are a xanthene dye exhibiting a desired hue, a powder of the dye, a coloring composition containing the dye, a colorant for a color filter containing the dye or the coloring 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 which the diffraction angle (2 theta) in powder X-ray diffraction of CuK alpha rays is 5 DEG to 34 DEG, the relative intensity of a diffraction peak existing in the range of 21.0 DEG to 22.1 DEG is set asIn the case of 1, the relative intensity of the diffraction peak present in the range of 13.7 ° to 14.5 ° 2 θ is 0.1 or less, and the relative intensity of the diffraction peak present in the range of 8 ° to 10 ° 2 θ is 0.03 or less.
[ in the formula (1), R1And R3Represents a hydrogen atom or an alkyl group, R2And R4Represents an aromatic hydrocarbon group.]。
Description
Technical Field
The present invention relates to a xanthene dye, a coloring composition containing the dye, a colorant for a color filter containing the dye or the coloring composition, a color filter using the colorant, and a method for producing the dye.
Background
Color filters are used in liquid crystal display devices, Electroluminescence (EL) display devices, and image sensors such as CCDs and CMOSs. Color filters are produced by laminating a colored layer such as a pigment film or a pigment-resin composite film on a light-transmissive substrate such as glass or a transparent resin by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. As a dye material constituting a color filter, a compound having a xanthene skeleton (xanthene dye) excellent in hue and heat resistance is often used (patent documents 1 to 4).
Xanthene dyes are widely used as water-soluble dyes, and among them, xanthene dyes having low solubility in organic solvents are used as colorants for color filters, which use organic solvents as the main solvents, and are often used as fine particulate colorants. Therefore, when a color filter exhibiting a desired hue is to be manufactured, it is necessary to control the hue (powder chromaticity) of the solid powder (particle) state of the coloring material.
It is known that: even if the dye compound has the same molecular structure, the color changes depending on the state of the particles (crystal structure) (non-patent document 1). In the reaction for synthesizing a xanthene dye of a target structure in an organic solvent, in the case of a xanthene dye having insufficient solubility, precipitation of a solid occurs in the reaction for producing the dye, and it is difficult to control the particle state thereof, and a solid (powder) showing a desired hue may not be obtained.
Teaching out: the crystal structure of xanthene dye powder has a correlation with color filter characteristics (patent document 5). However, it is believed that: even a xanthene molecule having the same basic skeleton has a crystal structure that varies greatly depending on the production conditions, as well as the hue of the molecule varies depending on the type of substituent. Therefore, in order to obtain a powder of xanthene dye suitable as a colorant for color filters exhibiting desired color characteristics (brightness, contrast, etc.), it is necessary to evaluate solid properties, heat resistance, solubility, and dispersibility of samples prepared by various methods and determine an optimum production method.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2002-265834
Patent document 2: japanese patent laid-open publication No. 2012-207224
Patent document 3: japanese laid-open patent publication No. 2010-254964
Patent document 4: japanese patent laid-open No. 2014-12814
Patent document 5: international publication No. 2019/003915
Non-patent document
Non-patent document 1: editions of society, society of organic Synthesis chemistry, New dye Exchequer, Wanshan Kabushiki Kaisha, 1970, page 159
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide: xanthene dye exhibiting a desired hue, powder of the dye, coloring composition containing the dye, colorant for color filter containing the dye or the coloring composition, color filter using the colorant, and method for producing the dye.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, have found that: obtaining a powder of a dye exhibiting a desired hue by recrystallizing a xanthene dye by the method described in the present invention; and its properties can be analyzed by powder X-ray diffraction; further, the composition is suitable as a colorant for color filters. That is, the present invention is summarized as follows.
1. A xanthene dye represented by the following general formula (1),
in a diffraction pattern in which the diffraction angle (2 theta) in powder X-ray diffraction of CuK alpha rays is 5 DEG to 34 DEG, when the relative intensity of a diffraction peak present in the range of 21.0 DEG to 22.1 DEG to 2 theta is 1, the relative intensity of a diffraction peak present in the range of 13.7 DEG to 14.5 DEG to 2 theta is 0.1 or less, and the relative intensity of a diffraction peak present in the range of 8 DEG to 10 DEG to 2 theta is 0.03 or less.
[ CHEM 1]
[ in the formula (1), R1And R3Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms and optionally having a substituent, R2And R4Each independently represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms.]Or is or
[ in the formula (1), R1And R3Each independently represents a hydrogen atom, or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, R2And R4Each independently represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms.]
2. Xanthene dye, wherein the chromaticity coordinate of the powder is 0.460. ltoreq. x.ltoreq.0.500, and 0.285. ltoreq. y.ltoreq.0.305.
3. Xanthene dye, wherein, in the xanthene dye, R is2And R4Is a phenyl group having 6 to 10 carbon atoms and optionally having a substituent. Or
3. Xanthene dye, wherein, in the xanthene dye, R is2And R4Is a phenyl group having 6 to 10 carbon atoms which may have a substituent.
4. A coloring composition comprising the xanthene dye.
5. A colorant for color filters, which contains the above xanthene dye or coloring composition.
6. And a color filter using the colorant for color filters.
Alternatively, a color filter containing the xanthene dye.
Or a use of the xanthene dye, the coloring composition, or the colorant for color filters for producing color filters.
Alternatively, a method for producing a color filter using the xanthene dye, the coloring composition, or the colorant for color filters.
7. The method for producing a xanthene dye or the xanthene dye is characterized by performing step 1 and step 2.
Step 1: a compound represented by the following formula (2) is reacted with a compound represented by the following general formula (3).
[ CHEM 2]
[ CHEM 3]
[ in the formula (3), R1And R2Represents the same definition as that of the above general formula (1).]
And a step 2: the compound obtained in step 1 is dissolved using 2 or more organic solvents containing an alcohol and a base, and then mixed with an acid and/or water to be recrystallized.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a xanthene dye exhibiting a desired hue and a powder of the dye are obtained, and therefore a coloring composition containing the dye is useful as a colorant for color filters.
Drawings
FIG. 1 is a powder X-ray diffraction (XRD) pattern of a dye according to an example of the present invention and a dye according to a comparative example.
Fig. 2 is an enlarged view of the embodiment and the comparative example of fig. 1.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention. First, the xanthene dye represented by the above general formula (1) will be described. In the following, when the functional group has a substituent, not only carbon atoms contained in the functional group but also carbon atoms contained in the substituent are included in the number of carbon atoms.
In the general formula (1), as represented by R1And R3The "linear or branched alkyl group" in the "linear or branched alkyl group having 1 to 8 carbon atoms and may have a substituent(s)" may specifically include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group; and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isooctyl, and 2-ethylhexyl.
In the general formula (1), by R2And R4The "aromatic hydrocarbon group" in the "aromatic hydrocarbon group having 6 to 20 carbon atoms and which may have a substituent(s)" includes an aryl group and a condensed polycyclic aromatic group, and specific examples thereof include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylene group, a fluoranthyl group, a benzo [9,10] group]And aromatic hydrocarbon groups such as phenanthryl.
In the general formula (1), as represented by R1And R3The "alkyl group which may have a linear or branched substituent" represented by the formula (I) or R2And R4The "substituent" in the "optionally substituted aromatic hydrocarbon group" may specifically be mentioned
Hydroxy, cyano, trifluoromethyl, nitro; sulfonic acid group or carboxylic acid group (it is explained that-SO can be formed by alkali metal M)3M or-COOM. ) (ii) a
Halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom;
a straight-chain or branched alkyl group having 1 to 20 carbon atoms;
a cycloalkyl group having 3 to 20 carbon atoms;
a linear or branched alkenyl group having 2 to 20 carbon atoms;
a linear or branched alkoxy group having 1 to 20 carbon atoms;
a C3-20 cycloalkoxy group, a 1-adamantyloxy group, or a 2-adamantyloxy group;
an acyl group having 1 to 20 carbon atoms;
an aromatic hydrocarbon group or a condensed polycyclic aromatic group having 6 to 20 carbon atoms;
a heterocyclic group having 2 to 20 carbon atoms;
an aryloxy group having 6 to 20 carbon atoms;
an unsubstituted amino group; a C1-20 mono-or di-substituted amino group, and the like. These "substituents" may include only 1 or a plurality thereof, and when a plurality thereof is included, they may be the same or different from each other. These "substituents" may further have the substituents exemplified above. When the "substituent" includes a carbon atom, the carbon atom is counted as 1 to 8 carbon atoms in the "linear or branched alkyl group which may have 1 to 8 carbon atoms" and 6 to 20 carbon atoms in the "aromatic hydrocarbon group which may have 6 to 20 carbon atoms" described above. These substituents may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.
In the general formula (1), R is defined as1～R4Examples of the "substituent" of the various "groups" having the "substituent" and the "group" shown above,
A straight-chain or branched alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 20 carbon atoms,
A straight-chain or branched alkenyl group having 2 to 20 carbon atoms,
A straight-chain or branched alkoxy group having 1 to 20 carbon atoms,
A cycloalkoxy group having 3 to 20 carbon atoms,
An acyl group having 1 to 20 carbon atoms,
An aromatic hydrocarbon group or condensed polycyclic aromatic group having 6 to 20 carbon atoms,
A heterocyclic group having 2 to 20 carbon atoms,
An aryloxy group having 6 to 20 carbon atoms, and
"C1-20 monosubstituted or disubstituted amino group", specifically, there may be mentioned
A straight-chain or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, a 2-ethylhexyl group, a heptyl group, an octyl group, an isooctyl group, a nonyl group, and a decyl group;
cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl;
an alkenyl group such as a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 1-hexenyl group, an isopropenyl group, an isobutenyl group, or a straight-chain or branched alkenyl group formed by bonding a plurality of alkenyl groups;
a straight-chain or branched alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, or an isooctyloxy group;
a C3-20 cycloalkoxy group such as a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cyclononyloxy group, a cyclodecyloxy group, etc.;
acyl groups such as formyl, acetyl, propionyl, acryloyl, and benzoyl;
aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl, biphenyl, terphenyl, naphthyl, anthryl (anthryl group), tetracenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, benzo [9,10] phenanthryl, and the like;
a heterocyclic group such as a thienyl group, furyl group, pyrrolyl group, thiazolyl group, oxazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, benzothienyl group, benzofuryl group, indolyl group, isoindolyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzotriazolyl group, purinyl group, carbazolyl group, dibenzothienyl group, dibenzofuryl group, pyridyl group, pyrimidyl group, triazinyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, acridinyl group, phenanthrolinyl group, naphthyridinyl group, and carbolinyl group;
aryloxy groups such as phenoxy, tolyloxy, biphenyloxy, naphthyloxy, anthracenyloxy, phenanthrenyloxy and the like;
and a mono-or di-substituted amino group having a linear or branched alkyl group or an aromatic hydrocarbon group, such as a methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, dibutylamino group, di (2-ethylhexyl) amino group, di-tert-butylamino group, or diphenylamino group.
In the general formula (1), as R1And R3Preferably a hydrogen atom or a C1-6 linear or branched alkyl group. R1And R3Independently of one another, may be the same or different, preferably the same.
In the general formula (1), as R2And R4Preferably a phenyl group having 6 to 12 carbon atoms which may have a substituent. R2And R4Independently of one another, may be the same or different, preferably the same.
Specific examples of the compounds preferred as the xanthene dye of the present invention represented by the general formula (1) are shown in the following formulae (A-1) to (A-16), but the present invention is not limited to these compounds. In the following structural formula, a part of hydrogen atoms is omitted. In addition, even in the case where a stereoisomer exists, its planar structural formula is described.
[ CHEM 4 ]
[ CHEM 5 ]
[ CHEM 6 ]
[ CHEM 7 ]
[ CHEM 8 ]
[ CHEM 9 ]
[ CHEM 10]
[ CHEM 11 ]
The xanthene dye represented by the general formula (1) of the present invention may be used in combination (e.g., mixed) of 1 type or 2 or more types having different molecular structures, and in a coloring composition containing these xanthene dyes, the weight concentration ratio of the 1 type of xanthene dye having the smallest occupancy rate in the total xanthene dye is 0.1 to 50% by weight. The kinds of xanthene pigments are preferably 1 or 2.
Next, a method for producing a compound (hereinafter, sometimes referred to as "compound (1)") which is a xanthene dye represented by general formula (1) will be described. The xanthene dye of the present invention is synthesized by a production method characterized by performing the following steps 1 and 2.
The step 1 is a step comprising reacting a compound represented by the following formula (2) (hereinafter, sometimes referred to as "compound (2)") with a compound represented by the following formula (3) (hereinafter, sometimes referred to as "compound (3)"), and the xanthene dye represented by the formula (1) can be obtained by the step 1. These compounds (2) and (3) can be obtained by using commercially available products or can be synthesized by any known method.
[ CHEM 12 ]
[ CHEM 13 ]
[ in the formula (3), R1And R2Represents the same meaning as defined in the above general formula (1).]
In step 1, specifically, the compound (2) and R having a corresponding group1And R2The compound (3) of (a) can be mixed in an appropriate solvent at an appropriate ratio and reacted under appropriate reaction temperature and reaction time, appropriate stirring conditions, or the like, thereby obtaining the xanthene dye represented by the general formula (1) or an intermediate thereof, and a mixture containing the same. The process 1 can be further repeated to synthesize the desired xanthene dye. In this case, the compounds (3) used may be the same or different, and R may be used1、R2Is replaced by R3、R4The compound of (1).
In step 1, a solvent may be used, and the reaction can be carried out even without a solvent, and it is preferable to use a solvent for the reaction in terms of convenience, efficiency, and the like.
Examples of the solvent in step 1 include aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; alcohols such as butanol, 2-ethoxyethanol, pentanol, hexanol and the like; glycols such as ethylene glycol; amides such as 1-methyl-2-pyrrolidone (NMP) and Dimethylformamide (DMF); sulfoxides such as dimethyl sulfoxide (DMSO); sulfones such as sulfolane, and the like.
The solvent used in step 1 may be used alone in 1 kind, or 2 or more kinds may be mixed and used. The ratio (volume/mass) of the amount of the solvent used (volume (mL)) to the amount of the compound (2) used (mass (g)) is preferably 1 to 30, and more preferably 1 to 10.
The reaction temperature in step 1 is preferably 60 to 200 ℃ and more preferably 100 to 160 ℃ from the viewpoint of suppressing by-products. The reaction temperature may be constant, or may be appropriately changed within the above range.
The amount of the compound used in the step 1 is preferably 2 to 20mol, more preferably 2 to 10mol of the compound (3) to 1mol of the compound (2).
The atmosphere in which the reaction in step 1 is carried out is not particularly limited. The reaction may be carried out in an inert gas such as nitrogen or argon, or in the atmosphere.
The compound obtained in the above step 1 can be obtained in a state of a solution, a state in which a (fine) solid (powder) is dispersed in a reaction solution (this dispersion liquid is sometimes referred to as a solution in the present invention), a state in which a powder is precipitated, or the like. Usually, the xanthene dye is obtained in the form of a mixture containing the desired xanthene dye (as other components in the mixture, products other than the desired xanthene dye, solvents, unreacted components, and other components). Next, the compound obtained in the above step 1 (or a mixture containing the compound) may be washed with a solvent used in the reaction or another solvent. The target compound may be extracted as a solid (powder or the like) by a known method such as filtration, concentration, extraction, and drying (heating, reduced pressure or the like). Further, purification can be carried out by various known methods. After step 1, the process may be transferred to a process for producing a colorant for color filters as it is or after the above-mentioned washing, drying, purification, etc., and in the production method of the present invention, it is preferable to obtain xanthene dye or a powder of the dye by performing the following step 2 following step 1.
In the step 2, the "compound obtained in the step 1" may be a mixture containing the compound (1) as a main component, or may be the mixture obtained after the reaction in the step 1.
The phrase "2 or more organic solvents containing an alcohol" means that the organic solvents are 2 or more organic solvents, and at least 1 of the organic solvents is an alcohol. The phrase "dissolving with 2 or more organic solvents containing an alcohol" means that the compound obtained in the above step 1 is dissolved with an organic solvent that is an alcohol and an organic solvent other than an alcohol, and the organic solvent that is an alcohol and the organic solvent other than an alcohol may be mixed in advance before dissolving (or dispersing) the compound obtained in the above step 1, or may be mixed at the time of dissolving (or dispersing) the compound.
In addition, as a step of dissolving (or dispersing), the compound obtained in the above step 1 may be dissolved (or dispersed) in 2 or more kinds of organic solvents including alcohol at first, and then the compound obtained in the above step 1 may be dissolved by adding an alkali (alkal i) such as sodium hydroxide. Alternatively, the compounds may be dissolved simultaneously in a liquid obtained by mixing 2 or more kinds of organic solvents containing the alcohol with a base in advance. Further, the compound may be dissolved by dissolving the compound in a base (or an aqueous solution containing a base) and then mixing the organic solvent.
In step 2, as described above, the target xanthene dye can be obtained by recrystallization (or crystallization) by adding and mixing an acid or water in a state of "dissolving the compound obtained in step 1 in 2 or more organic solvents containing alcohol and an alkali". The above step 2 may be repeated a plurality of times, and the step of washing and drying may be performed during the addition.
As the "2 or more organic solvents containing alcohol" in the step 2, a commonly used solvent can be used. Examples of the "alcohol" in step 2 include alcohols such as methanol, ethanol, propanol, and butanol. The alcohol may be 1 kind or 2 or more kinds may be mixed and used. As the organic solvent other than the alcohol, 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; ethers such as diethyl ether, Tetrahydrofuran (THF), and dioxane. The organic solvent other than these alcohols may be used alone in 1 kind, or 2 or more kinds may be mixed and used. When 2 or more organic solvents including alcohol are used, the mixing ratio can be arbitrarily set.
The ratio (volume/mass) of the amount of the solvent used (volume (mL)) to the theoretical yield (mass (g)) of the compound (1) is preferably 2 to 20, and more preferably 5 to 10.
The "alkali" (alkali) in step 2 is not particularly limited, but generally, a salt containing an alkali metal such as sodium or potassium; salts containing alkaline earth metals such as calcium and magnesium, and sodium hydroxide or potassium hydroxide are more preferable. The amount of the base used is preferably 0.5 to 5mol, more preferably 1 to 3mol, based on 1mol of the theoretical yield of the compound (1). Further preferably, the base is used as an aqueous solution.
In step 2, after mixing and dissolving the mixture using an organic solvent and an alkali, the dissolution is preferably accelerated by heating. The temperature during dissolution is preferably 60 to 200 ℃, more preferably 60 to 160 ℃. The temperature may be constant, or may be appropriately changed within the above range.
The "acid" in step 2 is not particularly limited, and specific examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like, and hydrochloric acid is preferred. The amount of the acid used is preferably 0.5 to 5mol, more preferably 1 to 3mol, based on 1mol of the theoretical yield of the compound (1). It is more preferable to use the acid as an aqueous solution.
The "water" in the step 2 is not particularly limited, and may be ordinary water, and specific examples thereof include tap water, industrial water, ion-exchanged water, and distilled water.
The xanthene dye represented by the above general formula (1), the powder of the dye, and the colored composition of the present invention containing at least 1 of the dyes were obtained according to the methods described above. The colored composition of the present invention may contain components such as a solvent used in the above-described production process, other than xanthene dye, within a range that does not affect the production of the color filter. Hereinafter, a method for obtaining a powder having a form suitable as a colorant for color filters, which is an object to be solved by the present invention, will be described.
The shape of the powder of the xanthene dye of the present invention can be observed using an optical microscope, a Scanning Electron Microscope (SEM), or the like. The powder of the present invention is usually used in the form of a solid powder having a shape such as a crystal, a microcrystalline, a fine powder, a flake, a needle crystal, or a granule, but is not limited thereto.
The xanthene dye powder of the present invention is subjected to measurement of particle size distribution (coulter method, centrifugal sedimentation method, laser diffraction/scattering method, etc.), surface area, pore size distribution, powder density, etc., to obtain detailed information on the overall and average shape of the powder. The powder of the present invention is preferably in the range of 0.1 μm to several mm in particle diameter, and the particle shape is changed depending on the production conditions and the method of recovering the dried powder, and therefore, the particle diameter is not limited to a specific one. For high solubility, the particle size is preferably smaller, and the median value of the particle size distribution is preferably in the range of 0.1 to 100. mu.m.
The xanthene dye powder of the present invention can be used for estimating information on a molecular-level and atomic-level fine structure by performing elemental analysis, mass analysis, and crystal structure analysis by powder X-ray diffraction (XRD). As other physical properties, a known method similar to the method described in patent document 5 and the like can be used for measuring solubility and the like.
The decomposition initiation temperature can be analyzed by thermogravimetric analysis-differential thermal analysis (TG-DTA) of the xanthene dye of the present invention or a colored composition containing the dye. The decomposition initiation temperature is preferably 250 ℃ or higher, more preferably 300 ℃ or higher, and particularly preferably 360 ℃ or higher. In the case of application to a color filter, the higher the decomposition start temperature is, the more preferable. As the temperature corresponding to the decomposition starting temperature, a temperature at the time when the weight of the sample is reduced by a certain percentage (%) after heating (for example, 5% weight reduction temperature) can be used.
By measuring the powder X-ray diffraction (XRD) of the xanthene dye of the present invention, it can be analyzed whether or not the powder is a powder suitable as a colorant for color filters.
When the xanthene dye powder has low solubility, the color filter colorant is present as a solid fine powder. The shape and size of the powder particles cause uneven coating during film formation, which affects light resistance and heat resistance, and the depolarization effect of transmitted light is complicated, which affects color developability.
Further, in the color filter, the xanthene dye and the pigment of another color form an aggregate to perform color toning, but it is also assumed that the difference in the crystal state of the xanthene dye does not affect the charge transfer between the molecules between the pigment excited by light and the xanthene dye to a small extent.
As a method for determining and estimating whether or not the powder has an appropriate crystal structure for the dispersibility, thermal characteristics, color characteristics, and the like of the xanthene dye powder, powder X-ray diffraction is suitable. Among the powder X-ray diffraction, in general, CuK α rays (h ν 8.048keV (h is a planck constant, ν is a frequency), a wavelength λ 0.15418 nm), MoK α rays (h ν 17.5keV, wavelength λ 0.071073nm) and preferably powder X-ray diffraction using CuK α rays are used as an X-ray source. In addition, the X-ray intensity to be irradiated is preferably: the relative intensity ratio of the diffraction peaks in the measurement range does not have an intensity that varies depending on the X-ray intensity.
The measurement range of the diffraction angle (2 θ) is preferably 50 ° or less, and may be 5 ° to 40 °. In order to accurately obtain the information on the crystal structure or the aggregation state of the molecule, the measurement interval (scanning step) of 2 θ is preferably 0.05 ° or less.
In the obtained diffraction pattern, a peak was observed at a diffraction angle with a large diffraction intensity. The presence of the observed diffraction peak (or shoulder near the peak) indicates information on the crystal state of the xanthene intramolecular or intermolecular period in the powder. The position of the diffraction peak has information about the lattice constant of the features in the sample. The shape of the diffraction peak may be symmetrical or asymmetrical.
The width of the diffraction peak can be expressed using the full width at half maximum (FWHM). Since the diffraction peak width generally tends to become larger as the crystal grain diameter becomes larger and smaller, information on the size of the crystallites and information on the degree of deformation of the crystallites are obtained. In view of the conditions for producing the xanthene dye powder of the present invention and the conditions for measuring powder X-ray diffraction, it is preferable that at least a full width at half maximum of 0.2 ° to 0.5 ° is observed among the peaks having the highest observed intensity.
The intensity of the peak can be expressed by the distance between the highest portion of the peak and the base line. Generally, diffraction patterns have the following tendency: the diffraction intensity increases gently from the high diffraction angle side to the low diffraction angle side. In the present invention, the form of drawing the base line is not particularly limited, and for example, the base line in which a portion of a valley between peaks located at a position distant from the diffraction peak position and a flat portion are connected by using a curve or a straight line can be drawn in a range including the diffraction angle of the diffraction peak group to be analyzed. The peak intensity may be represented by the length between the baseline and the highest point of the peak. In order to observe the structure of the peak of the minimum intensity in the diffraction pattern, the SN ratio of the diffraction pattern is preferably 3 or more. Information on the quantification of the crystalline phase in the powder is obtained in terms of the intensity ratio of the size peaks in the diffraction pattern.
In the diffraction pattern of the powder X-ray diffraction of the xanthene dye of the present invention, at least about 10 to at most 50 diffraction peaks and shoulders may be observed in the range of 5 ° to 40 ° 2 θ, and 10 to 40 diffraction peaks (including shoulders) are preferably observed. In the case where a peak appears in the range of 5 ° to 40 ° in the powder X-ray diffraction, this indicates that a periodicity of atoms of about 0.2nm to about 1.8nm is present in the solid powder sample. For example, in a xanthene molecule such as acid red 52, which is a typical xanthene dye, the shortest interatomic bonding distance is about 0.14nm, and the distance of 2 nitrogen atoms is about 1 nm. The diffraction pattern observed in the above-mentioned range of diffraction angles has information on the periodicity between the atoms (C, O, N, etc.) in the xanthene molecule, and they may be directly bonded to each other or may have a space between them with other atoms interposed therebetween. The periodic length represents information on the arrangement of the substituents in the xanthene molecule, and further information on the length of the arrangement of the xanthene molecules in the powder, from a periodic length of at least about 6-membered rings in width. For this reason, powder X-ray diffraction is excellent as a method for analyzing the state in a powder containing a xanthene dye.
In the invention, the inventor finds that: the method for producing xanthene dye powder, the resulting powder X-ray diffraction pattern, and the hue of the dye powder thereof, particularly the characteristics suitable as a colorant for color filters, have a correlation. Specifically, in the xanthene dye represented by the general formula (1), the characteristics of the diffraction pattern in the powder X-ray diffraction of CuK α rays differ depending on the production method, and for example, there are a diffraction pattern in which the intensity of the peak at a specific diffraction angle (2 θ) is significant and a diffraction pattern in which the peak is insignificant.
For example, in the case of a group including a peak having a large intensity observed in a range of 2 θ of 21 ° to 22.1 ° and a diffraction peak group observed in a range of 2 θ of 17.5 ° to 34.0 °, the xanthene dye represented by the general formula (1) obtained under a specific production condition is considered to have a cycle of 0.5nm or less due to a characteristic not affected by the aggregation state of molecules in a solid, for example, "3H-xanthene" or a structure including a nitrogen atom bonded to the 3-and 6-positions thereof, because the diffraction angle and the intensity at the peak position are observed in common in the same manner.
On the other hand, in the range of 5 ° to 17.5 °, although several diffraction peaks are observed at substantially the same diffraction angle, it is observed that there are differences in the intensity ratio, peak width, and the like. The diffraction angle in this range has a periodicity of 0.5nm or more, and it is estimated that: the xanthene dye is caused by the presence of a substituent (phenyl group) at the 9-position, a group bonded thereto, or a substituent bonded to the nitrogen position in the molecule. Namely, the teaching is: even in the case of xanthene dyes having the same basic skeleton 3H-xanthene, when the dyes have a substituent having a certain structure and size, the crystal system may be different depending on the production conditions of the solid (powder). For example, when a solid is sublimated and recrystallized again as a solid, or when a dye is extracted as a solid by recrystallization from a solution state, the aggregation processes of the molecules are supposed to be different from each other. Further, the teaching is: even when the xanthene is recovered from the solvent, the xanthene molecules are arranged differently depending on the production conditions such as recrystallization.
In this way, the difference in aggregation state among the powders also affects the magnitude of intermolecular force and interaction between xanthene molecules, and as a result, the difference greatly affects solubility in a solvent, dispersibility, hue, and interaction with other pigments for color filters, resin materials, and the like, and directly affects the respective physical properties of the color filter. The xanthene dye of the present invention is a xanthene dye having the following characteristics: in a diffraction pattern in which the diffraction angle (2 theta) in powder X-ray diffraction of CuK alpha rays is 5 DEG to 34 DEG, when the relative intensity of a diffraction peak present in the range of 21.0 DEG to 22.1 DEG to 2 theta is 1, the relative intensity of a diffraction peak present in the range of 13.7 DEG to 14.5 DEG to 2 theta is 0.1 or less, and the relative intensity of a diffraction peak present in the range of 8 DEG to 10 DEG to 2 theta is 0.03 or less. More preferably, no peak is observed in the range of 13.7 ° to 14.5 ° 2 θ, and preferably no peak is observed in the range of 8 ° to 10 ° 2 θ.
Among them, as a method for measuring the relative intensity, for example, the following method is preferable: the intensity of the other peaks is determined with reference to the height or peak area of the peak having the highest intensity among all observed diffraction patterns (for example, 1).
The xanthene dye of the present invention is obtained by measuring the visible light absorption spectrum or reflection spectrum in the form of a solution, dispersion, film or powder (solid), the chromaticity coordinates (x, y) and concentration (K/Sd) of the xy chromaticity diagram of CIE 1931 color system using a spectrocolorimeter or a colorimeter, and the color tone (L) of CIE 1976 color system using a CIE 1976 color system＊、a＊、b＊) Color difference (Δ E)＊) And the color characteristics (hue) thereof can be evaluated. Even solutions, powders, and films of compounds having the same molecular structure may have a distinct color by visual observation, and measurement can be performed using a spectrocolorimeter or a colorimeter in order to objectively quantify such a color difference.
The hue of the xanthene dye powder of the present invention preferably has chromaticity coordinates (x, y) of 0.460. ltoreq. x.ltoreq.0.500 and 0.285. ltoreq. y.ltoreq.0.305. The powder with this hue shows red to magenta to purple.
The colorant for color filters of the present invention comprises: a coloring composition containing at least 1 xanthene pigment represented by the general formula (1) and a component generally used in the production of color filters. In a general color filter, for example, in the case of a method using a photolithography process, a liquid prepared by mixing a dye such as a dye or a pigment with a resin component (including a monomer or an oligomer) and a solvent is applied onto a substrate such as glass or resin, and is photopolymerized using a photomask to form a colored pattern of a dye-resin composite film soluble/insoluble in the solvent, followed by cleaning and heating. In addition, in the electrodeposition method and the printing method, a colored pattern is produced by using a mixture of a pigment, a resin, and other components. Therefore, specific components in the colorant for color filters of the present invention include at least 1 type of xanthene dye represented by the general formula (1), other dyes, pigments such as pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. Further, these components may be selected from them, and other components may be added as necessary.
When the coloring composition containing the xanthene dye of the present invention is used as a colorant for color filters, it can be used for color filters of various colors, and is preferably used as a colorant for red color filters.
The color filter colorant containing the xanthene dye of the present invention may be one using only 1 or 2 or more xanthene dyes as the dye, and other known dyes such as dyes and pigments may be mixed for color adjustment. When the colorant is used for a red color filter, the colorant is not particularly limited, and examples thereof include red pigments such as c.i. pigment red 177, 209, 242, 254, 255, 264, 269, c.i. pigment orange 38, 43, 71 and the like; other red lake pigments; yellow pigments such as c.i. pigment yellow 138, 139, and 150; red dyes such as c.i. acid red 88 and c.i. basic violet 10. When the colorant is used for a cyan color filter, the colorant is not particularly limited, and examples thereof include basic dyes such as c.i. basic blue 3, 7, 9, 54, 65, 75, 77, 99, 129; acid dyes such as c.i. acid blue 9 and 74; disperse dyes such as disperse blue 3, 7, 377, etc.; a spirocyclic ketone dye; cyanine series, indigo series, phthalocyanine series, anthraquinone series, methine series, triarylmethane series, indanthrene series, oxazine series, dioxazine series, azo series, xanthene series not belonging to the present invention; other cyan dyes or pigments such as cyan lake pigments.
The mixing ratio of the other pigments in the colorant for color filters containing the xanthene dye of the present invention is preferably 5 to 2000% by weight, and more preferably 10 to 1000% by weight, based on the xanthene dye (in the case of 2 or more types, the total of them). The mixing ratio of the pigment component such as dye in the liquid colorant for color filter is preferably 0.5 to 70 wt%, more preferably 1 to 50 wt% with respect to the entire colorant.
As the resin component in the colorant for color filters of the present invention, a known resin component can be used as long as it has properties required in the production method and use of a color filter resin film formed using the colorant. Examples thereof include acrylic resins, olefin resins, styrene resins, polyimide resins, polyurethane resins, polyester resins, epoxy resins, vinyl ether resins, phenol (novolak) resins, polycarbonate resins, cellulose resins, other transparent resins, photocurable resins, thermosetting resins, thermoplastic resins, and composites of these resins, and these monomer or oligomer components can be used in combination as appropriate. In addition, copolymers of these resins may be used in combination. The content of the resin in the colorant for color filters is preferably 5 to 95% by weight, more preferably 10 to 50% by weight, in the case of a liquid colorant.
In order to improve the performance as a coloring agent for color filters, the coloring composition of the present invention may contain, as components other than the compound, organic compounds such as a surfactant, a dispersant, an antifoaming agent, a leveling agent, and other additives mixed during the production of the coloring agent for color filters. However, the content of these additives in the coloring composition is preferably an appropriate amount, and is preferably a content within a range in which the solubility in the solvent of the coloring composition of the present invention is not reduced or excessively improved, and the effect of other additives of the same kind used in the production of color filters is not affected. These additives can be added at any timing in the preparation of the coloring composition.
As other additives in the colorant for color filters of the present invention, components necessary for polymerization and curing of resins such as photopolymerization initiators and crosslinking agents can be cited, and surfactants, dispersants, and the like necessary for stabilizing the properties of components in liquid colorants for color filters can be cited. Any of these can be used with known components for color filter production, and is not particularly limited. The mixing ratio of the total amount of these additives in the entire solid content of the colorant for color filters is preferably 5 to 60% by weight, and more preferably 10 to 40% by weight.
Examples
The embodiments of the present invention will be described specifically below with reference to examples, but the present invention is not limited to the examples below. It should be noted that, in terms of the identification of the compounds obtained in the examples, the compounds were obtained by1H-NMR analysis (Nuclear magnetic resonance apparatus manufactured by ブルカー Co.)And the model is as follows: magnet System 300MHz/54mm UltraShield), and the measurement results are shown in the following examples.
EXAMPLE 1 Synthesis of Compound (A-1) EXAMPLE 1
The following reaction was carried out under a nitrogen stream. In a 1L vessel, 60.0g of compound (2), 120g of 2, 6-dimethylaniline and 300mL of 1, 2-dichlorobenzene were placed and reacted with stirring at 130 ℃ for 78 hours. After stirring, the reaction mixture was cooled to 40 ℃ or lower, and the precipitated solid was collected by filtration. The collected solid, 240mL of toluene and 240mL of methanol were placed in a vessel, and the mixture was stirred under reflux (about 65 ℃) for 1 hour, cooled to 40 ℃ or lower, and the solid was collected by filtration. The solid obtained by filtration, 60mL of toluene, 300mL of methanol, and 26.1g of a 24% aqueous solution of sodium hydroxide were placed in a container, and mixed, and the mixture was heated at 65 ℃ to dissolve (disperse) the solid. The heated mixture was cooled to 50 ℃ and 16.3g of a 35% aqueous hydrochloric acid solution was added dropwise thereto. The mixture was cooled to 40 ℃ or lower, the precipitated solid was collected by filtration, and the collected solid and 360g of water were placed in a container and mixed, followed by stirring at room temperature for 2 hours. The stirred mixture was filtered, and the obtained solid was dried under reduced pressure at 80 ℃ for 24 hours to obtain the following compound (A-1) (53.7g, yield 63%) as a reddish purple solid.
1H-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)。
[ CHEM 14 ]
EXAMPLE 2 Synthesis of Compound (A-1) EXAMPLE 2
The following reaction was carried out under a nitrogen stream. A1L vessel was charged with 60.0g of Compound (2), 120g of 2, 6-dimethylaniline and 300mL of 2-ethoxyethanol, and the mixture was stirred at 130 ℃ for 43 hours to effect a reaction. After stirring, the reaction mixture was cooled to 40 ℃ or lower, and the precipitated solid was collected by filtration. The collected solid and 600mL of methanol were placed in a vessel, and after stirring under reflux (about 65 ℃ C.) for 1 hour, the mixture was cooled to 40 ℃ or lower, and the solid was collected by filtration. The solid obtained by filtration, 60mL of toluene, 300mL of methanol, and 26.1g of a 24% aqueous solution of sodium hydroxide were placed in a container, and mixed, and the mixture was heated at 65 ℃ to dissolve (disperse) the solid. The heated mixture was cooled to 50 ℃ and 16.3g of a 35% aqueous hydrochloric acid solution was added dropwise thereto. The mixture was cooled to 40 ℃ or lower, the precipitated solid was collected by filtration, and the collected solid and 360g of water were placed in a container and mixed, followed by stirring at room temperature for 2 hours. The stirred mixture was filtered, and the obtained solid was dried under reduced pressure at 80 ℃ for 24 hours to obtain compound (A-1) (58.6g, yield 69%) as a reddish purple solid.
EXAMPLE 3 Synthesis of Compound (A-1) EXAMPLE 3
The procedure of example 2 was carried out in the same manner as in example 2 except that 2-ethoxyethanol used in the reaction of example 2 was changed to 1-methyl-2-pyrrolidone to obtain compound (a-1) (47.3g, yield 56%) as a reddish purple solid.
Comparative example 1
The following reaction was carried out under a nitrogen stream. In a 1L vessel, 60.0g of compound (2), 120g of 2, 6-dimethylaniline and 300mL of 1, 2-dichlorobenzene were stirred at 130 ℃ for 78 hours to react. After stirring, the reaction mixture was cooled to 40 ℃ or lower, and the precipitated solid was collected by filtration. The collected solid and 400mL of methanol were put into a vessel, mixed, stirred under reflux (about 65 ℃) for 1 hour, then cooled to 40 ℃ or lower, and the solid was collected by filtration. The obtained solid was dried at 80 ℃ for 24 hours to obtain compound (A-1) (53.7g, yield 70%) as a red solid.
[ powder X-ray diffraction measurement ]
The pigment powders of the compounds obtained in examples 1 to 3 and comparative example 1 were subjected to powder X-ray diffraction (XRD) measurement (manufactured by PANalytical b.v., a multipurpose X-ray diffraction apparatus, model: Empyrean, X-ray source: CuK α ray (h v 0.15418nm, 40kV, 30mA), divergence slit: 1/2 °, scattering slit: 1 °, light receiving slit: 7.5mm, scanning step: 0.0131 °, scanning speed: 0.034 °/sec, and scanning diffraction angle range: 2 θ 5 ° to 50 °). The results of measurement at a diffraction angle (2 θ) of 5 ° to 40 ° are shown in fig. 1 and fig. 2 (enlarged views of 2 θ of 7 ° to 10.5 ° and 13.0 ° to 14.8 °). Each diffraction pattern is formed as a base line by connecting a flat portion of a valley between peaks at 2 θ of 10 ° and a flat portion at 2 θ of 34 ° by a straight line. In each diffraction pattern, the height of the peak with the maximum intensity observed at 21 ° to 22.1 ° 2 θ (distance from the base line to the peak top) is set as a reference value 1. Table 1 shows the range of diffraction angles 2 θ (°) of characteristic diffraction peaks observed and the relative intensities of the diffraction peaks observed in this range. Table 2 shows the full widths at half maximum (FWHM) (°) of each diffraction peak shown in table 1. In table 2, the blank part indicates that the measurement cannot be performed because the peak is absent or too small.
[ TABLE 1]
[ TABLE 2]
As is clear from tables 1 and 2, the diffraction patterns of the examples have different characteristics from those of the comparative examples, in which the relative intensity of the diffraction peak present in the range of 2 θ of 21.0 ° to 22.1 ° is 1, the relative intensity of the diffraction peak present in the range of 2 θ of 13.7 ° to 14.5 ° is 0.1 or less, and the relative intensity of the diffraction peak present in the range of 2 θ of 8 ° to 10 ° is 0.03 or less and 0.02 or less.
[ measurement of color ]
The chromaticity of the solid powder of the dye compound obtained in examples 1 to 3 and comparative example 1 was measured. The obtained pigment powder was placed on a glass dish without a gap, and the chromaticity coordinates (x, y) were measured using a spectrophotometer (model CM-5, manufactured by コニカミノルタ, CIE standard illuminant D65). The results are shown in Table 3.
[ TABLE 3]
As shown in table 3, according to the present invention, xanthene dye (powder) exhibiting a desired hue can be obtained.
Industrial applicability
The xanthene dye of the present invention and the coloring composition containing the dye are useful as a colorant for color filters that displays a desired hue in the production of color filters used in liquid crystal display devices, Electroluminescence (EL) display devices, and image sensors such as CCDs and CMOSs.
Claims (7)
1. A kind of
Xanthene dye represented by the following general formula (1)
One ton of pigment is added into the mixture,
in a diffraction pattern in which the diffraction angle (2 theta) in powder X-ray diffraction of CuK alpha rays is 5 DEG to 34 DEG, when the relative intensity of a diffraction peak existing in the range of 21.0 DEG to 22.1 DEG to 2 theta is 1, the relative intensity of a diffraction peak existing in the range of 13.7 DEG to 14.5 DEG is 0.1 or less, the relative intensity of a diffraction peak existing in the range of 8 DEG to 10 DEG is 0.03 or less,
in the formula (1), R1And R3Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms and optionally having a substituent, R2And R4Each independently represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms.
2. The method of claim 1
Xanthene dye, wherein
In the ton of pigment, the chromaticity coordinate of the powder is more than or equal to 0.460 and less than or equal to 0.500, and the chromaticity coordinate of the powder is more than or equal to 0.285 and less than or equal to 0.305.
3. The method of claim 1 or 2
Xanthene dye, wherein
In ton of pigment, R2And R4Is a phenyl group having 6 to 10 carbon atoms and optionally having a substituent.
4. A coloring composition comprising the compound according to any one of claims 1 to 3
Ton pigment.
5. A colorant for color filters, comprising the compound according to any one of claims 1 to 3
A xanthene colorant or the coloring composition of claim 4.
6. A color filter using the colorant for color filters according to claim 5.
7. A method of manufacture which comprises
A process for producing a xanthene dye, characterized in thatThen, the step 1 and the step 2 are performed,
step 1: reacting a compound represented by the following formula (2) with a compound represented by the following general formula (3),
in the formula (3), R1And R2Represents the same meaning as defined in the above general formula (1),
and a step 2: the compound obtained in step 1 is dissolved in 2 or more organic solvents containing an alcohol and a base, and then mixed with an acid or water to be recrystallized.
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| TW202132475A (en) | 2021-09-01 |
| KR20210077592A (en) | 2021-06-25 |
| JP2021095561A (en) | 2021-06-24 |
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