Fluorescent coloring composition, ink, toner, sheet for thermal transfer recording, and resist composition for color filter

Abstract

Provided is a fluorescent coloring composition with which it is possible to prepare an ink or the like that is capable of recording an image having excellent fluorescence persistence and light resistance. The fluorescent coloring composition contains a fluorescent dye and a compound represented by general formula (1). (In the general formula (1), R1 represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group; R2 represents a hydrogen atom, a hydroxy group, or a hydroxyalkyl group; R3 represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxy group, or an aryl group; R4 represents a hydrogen atom or an alkyl group; at least one of R1 to R3 is a hydroxy group or a group that contains a hydroxy group; and R1 and R2 may be bonded to form a 1,3-dioxane ring.)

Description

Fluorescent coloring compositions, inks, toners, thermal transfer recording sheets, and resist compositions for color filters

[0001] This disclosure relates to fluorescent coloring compositions, inks, toners, thermal transfer recording sheets, and resist compositions for color filters.

[0002] In recent years, there has been a growing demand for a wider range of colors in many fields, including eye-catching, vibrant colors in documents, posters and point-of-purchase (POP) displays, and packaging for food and beverage products. Expanding the color gamut requires high-luminosity special colors and fluorescent colors in addition to the basic colors of yellow, magenta, and cyan. However, it is generally known that fluorescent dyes used to create fluorescent colors do not have good lightfastness.

[0003] Dilute solutions of fluorescent dyes emit vivid fluorescent colors, but beyond a certain concentration, the fluorescence intensity decreases (concentration quenching, self-quenching). Furthermore, unlike general organic pigments, organic fluorescent pigments are powdered solid solutions of fluorescent dyes and resins. Fluorescent dyes used in organic fluorescent pigments include acid dyes, dispersible dyes, and basic dyes. Therefore, the properties of organic fluorescent pigments, such as color development, lightfastness, solvent resistance, and heat resistance, are considered to depend on the properties of the resin.

[0004] Examples of fluorescent dyes include xanthene dyes and triphenylmethane dyes. However, when the molecules of these fluorescent dyes are exposed to light (ultraviolet light) or ozone, singlet oxygen is generated, and this generated singlet oxygen attacks adjacent molecules, leading to decomposition. Various studies have been conducted to suppress such decomposition. For example, ink compositions containing polyvinyl butyral resin and salt-forming dyes made from diazo acid dyes and basic dyes have been proposed (Patent Documents 1 and 2). In addition, inks in which carbon nanotubes are added to improve the gas barrier properties of the resin have been proposed (Patent Document 3).

[0005] Japanese Patent Publication No. 2016-147477, Japanese Patent Publication No. 2018-9172, Japanese Patent Publication No. 2004-075705

[0006] However, the lightfastness of images recorded with the ink compositions proposed in Patent Documents 1 to 3 was not necessarily sufficient, and there was room for further improvement. In addition, these ink compositions had the problem of being prone to fading due to the presence of excess dye.

[0007] Therefore, this disclosure aims to provide a fluorescent coloring composition that can prepare inks and the like that can record images with excellent fluorescence persistence and lightfastness. Furthermore, this disclosure aims to provide inks, toners, thermal transfer recording sheets, and color filter resist compositions using this fluorescent coloring composition.

[0008] In other words, the present disclosure provides a fluorescent coloring composition containing a fluorescent dye and a compound represented by the following general formula (1).

[0009] (In the above general formula (1), R １ R represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group. ２ R represents a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group. ３ R represents a hydrogen atom, alkyl group, hydroxyalkyl group, alkoxy group, or aryl group. ４ R represents a hydrogen atom or an alkyl group. １ ~R ３ At least one of them is a hydroxyl group or a group containing a hydroxyl group, R １ and R ２ (These may bond to form a 1,3-dioxane ring.)

[0010] This disclosure provides a fluorescent coloring composition that can be used to prepare inks and the like that can record images with excellent fluorescence persistence and lightfastness. Furthermore, this disclosure provides inks, toners, thermal transfer recording sheets, and color filter resist compositions using this fluorescent coloring composition.

[0011] The present disclosure will be further described below with reference to preferred embodiments. Unless otherwise specified, the physical properties are given at room temperature (25°C), normal pressure (1 atmosphere = 101,325 Pa), and normal humidity (50% relative humidity).

[0012] Fluorescent dyes are generally known to have poor lightfastness. Fluorescent dyes are dyes that absorb energy from excitation light, entering a highly unstable excited state (hereinafter also referred to as "excited dye"), and emit fluorescence (fluorescence energy) when the energy returns to the ground state. In contrast, non-fluorescent dyes release thermal energy when the excited dye returns to the ground state, so no fluorescence is observed. In other words, there is a trade-off between fluorescence and lightfastness.

[0013] One known method for improving the lightfastness of dyes involves designing the molecular structure of the dye so that when the excited dye returns to its ground state, thermal energy, rather than fluorescent energy, is released (e.g., Japanese Patent Publication No. 5451556). However, this method improves the lightfastness of the dye, but it completely eliminates fluorescence. It is also known that dispersing the dye in a resin or coating the dye with a resin improves the lightfastness of the dye. However, fluorescent dyes often have hydrogen-bonding substituents, making them very prone to aggregation in resins. Furthermore, fluorescent dyes can generate singlet oxygen (reactive oxygen species) that function as photosensitizers. As a result, the generated singlet oxygen can attack the aggregated fluorescent dye, causing oxidative decomposition and fading of the fluorescent dye. Therefore, it has been extremely difficult to improve lightfastness while maintaining fluorescence.

[0014] As a result of their investigations, the inventors have found that by incorporating a fluorescent dye and a compound represented by general formula (1), it is possible to obtain a composition that can be used to prepare an ink or the like that can record images with excellent fluorescence persistence and lightfastness, leading to this disclosure. The inventors speculate that the mechanism by which the combined use of a fluorescent dye and a compound represented by general formula (1) enables the recording of images with excellent fluorescence persistence and lightfastness is as follows.

[0015] Since the compound represented by the general formula (1) has one or more hydroxy groups in the molecule, it has high compatibility with a fluorescent dye. Further, it has a 1,3-dioxane ring in the molecule, and the active oxygen (singlet oxygen) trapped at the 2-position of this 1,3-dioxane ring is deactivated. Thus, it is considered that a composition capable of preparing an ink or the like capable of recording an image excellent in fluorescence persistence and light resistance can be obtained.

[0016] In the fluorescent coloring composition of the present disclosure, the fluorescent dye is not substantially aggregated and is dispersed in a good state. Therefore, the fluorescence spectrum of the fluorescent coloring composition of the present disclosure is shifted to the longer wavelength side than the absorption spectrum of the fluorescent dye.

[0017] <Fluorescent coloring composition> The fluorescent coloring composition of the present disclosure is a composition suitable as an ink, a toner, a sheet for thermal transfer recording, a resist composition for a color filter, and a writing instrument, containing a fluorescent dye and a compound represented by the following general formula (1). Hereinafter, the details of the fluorescent coloring composition of the present disclosure will be described.

[0018] (In the general formula (1), R １ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group, R ２ represents a hydrogen atom, a hydroxy group, or a hydroxyalkyl group, R ３ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxy group, or an aryl group, R ４ represents a hydrogen atom or an alkyl group, R １ to R ３ at least one of which is a hydroxy group or a group containing a hydroxy group, and R １ and R ２ may combine to form a 1,3-dioxane ring)

[0019] (Compound represented by general formula (1)) The compound represented by the following general formula (1) has one or more hydroxy groups and a 1,3-dioxane ring in its molecule.

[0020] (In the general formula (1), R １ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group, R２ R represents a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group. ３ R represents a hydrogen atom, alkyl group, hydroxyalkyl group, alkoxy group, or aryl group. ４ R represents a hydrogen atom or an alkyl group. １ ~R ３ At least one of them is a hydroxyl group or a group containing a hydroxyl group, R １ and R ２ (These may bond to form a 1,3-dioxane ring.)

[0021] In general formula (1), R １ Examples of alkyl groups represented by include saturated or unsaturated linear, branched, or cyclic alkyl groups such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, octyl group, dodecyl group, nonadecyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, 2-ethylpropyl, 2-ethylhexyl group, and cyclohexenylethyl group. The alkyl group may also be a primary to tertiary alkyl group having 1 to 20 carbon atoms.

[0022] In general formula (1), R ２ Examples of hydroxyalkyl groups represented by this formula include those in which a hydroxyl group has been introduced to the above-mentioned alkyl group.

[0023] In general formula (1), R ３ Examples of alkyl groups represented by include saturated or unsaturated linear, branched, or cyclic alkyl groups such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, octyl group, dodecyl group, nonadecyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, 2-ethylpropyl, 2-ethylhexyl group, and cyclohexenylethyl group. The alkyl group may also be a primary to tertiary alkyl group having 1 to 20 carbon atoms.

[0024] In general formula (1), R ３Examples of hydroxyalkyl groups represented by this formula include those in which a hydroxyl group has been introduced to the above-mentioned alkyl group.

[0025] In general formula (1), R ３ Examples of alkoxy groups represented by include methoxy groups, ethoxy groups, propyl groups, and butoxy groups.

[0026] In general formula (1), R ３ Examples of aryl groups represented by this symbol include phenyl groups, methylphenyl groups, and methoxyphenyl groups.

[0027] Compounds represented by general formula (1) can be synthesized by referring to known methods. Alternatively, commercially available compounds can be used as compounds represented by general formula (1).

[0028] In general formula (1), R ３ or R ４ It is preferable that is a hydrogen atom. Specific examples of compounds represented by general formula (1) include the compounds represented by formulas (1-1) to (1-15) shown below (compounds (1-1) to (1-15)).

[0029]

[0030]

[0031] The compounds represented by general formula (1) may be used individually or in combination of two or more depending on the application. In particular, among the compounds represented by general formula (1), compounds represented by formulas (1-1) to (1-5) (compounds (1-1) to (1-5)) are preferred, and compounds represented by formulas (1-1) to (1-3) (compounds (1-1) to (1-3)) are more preferred. By using these compounds, it is possible to prepare a fluorescent coloring composition that can record inks and the like with superior fluorescence persistence and lightfastness.

[0032] (Fluorescent dyes) It is preferable to use dyes that are easily faded by singlet oxygen as fluorescent dyes. It is preferable to use at least one selected from the group consisting of xanthene (rhodamine) dyes, triphenylmethane dyes, cyanine dyes, azo dyes, quinophthalone dyes, and stilbene dyes as fluorescent dyes. Near-infrared fluorescent dyes such as cyanine are also included in fluorescent dyes.

[0033] The xanthene dye is preferably a compound represented by the following general formula (2).

[0034] (In the above general formula (2), R ５ and R ６ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ７ R represents a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid amide group, a sulfonic acid group, a sulfonic acid ester group, or a sulfonic acid amide group. ８ R represents a hydrogen atom, a sulfonic acid ester group, a sulfonic acid amide group, or a metal salt of sulfonic acid. ９ and R １１ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R １０ and R １２ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, X － represents a counter anion, R ７ If R is a carboxylic acid group or a sulfonic acid group, these groups may form an anion. However, R ７ If it is an anion of a carboxylic acid group or an anion of a sulfonic acid group, then X － (There is no counter anion represented by this.)

[0035] In general formula (2), R ９ and R １１Examples of C1-C8 alkyl groups represented by include linear, branched, or cyclic C1-C8 alkyl groups. Examples of such C1-C8 alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexacyl, and 2-ethylhexyl groups. Among these, methyl, ethyl, n-propyl, n-butyl, or 2-ethylhexyl groups are preferred because they enable the preparation of inks that can record images with superior fluorescence persistence and lightfastness.

[0036] In general formula (2), R １０ and R １２ Examples of C1-C8 alkyl groups represented by include linear, branched, or cyclic C1-C8 alkyl groups. Examples of such C1-C8 alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexacyl, and 2-ethylhexyl groups. Among these, methyl, ethyl, n-propyl, n-butyl, or 2-ethylhexyl groups are preferred because they enable the preparation of inks that can record images with superior fluorescence persistence and lightfastness.

[0037] Also, R ９ and R １１ is a hydrogen atom, R ２ and R ４ R is the same alkyl group having 1 to 8 carbon atoms. ９ ~R １２ It is preferable that the alkyl groups have the same number of carbon atoms (1 to 8). In particular, alkyl groups with 1 to 4 carbon atoms are preferred because it is possible to prepare inks that can record images with superior fluorescence persistence and lightfastness.

[0038] In general formula (2), R ５ and R ６Examples of C1-C4 alkyl groups represented by include methyl, ethyl, n-propyl, and n-butyl groups. Among these, methyl or ethyl groups are preferred because they enable the preparation of inks that can record images with superior fluorescence persistence and lightfastness.

[0039] In general formula (2), R ７ Examples of carboxylic acid ester groups represented by this symbol include methyl carboxylate, ethyl carboxylate, propyl carboxylate, and butyl carboxylate.

[0040] In general formula (2), R ７ Examples of carboxylic acid amide groups represented by this formula include monomethyl carboxylic acid amide group, monoethyl carboxylic acid amide group, monopropyl carboxylic acid amide group, monobutyl carboxylic acid amide group, dimethyl carboxylic acid amide group, diethyl carboxylic acid amide group, dipropyl carboxylic acid amide group, and dibutyl carboxylic acid amide group.

[0041] In general formula (2), R ７ Examples of sulfonic acid ester groups represented by this symbol include methyl sulfonate ester group, ethyl sulfonate ester group, propyl sulfonate ester group, and butyl sulfonate ester group.

[0042] In general formula (2), R ７ Examples of sulfonic acid amide groups represented by this symbol include sulfonic acid monomethylamide group, sulfonic acid monoethylamide group, sulfonic acid monopropylamide group, sulfonic acid monobutylamide group, sulfonic acid dimethylamide group, sulfonic acid diethylamide group, sulfonic acid dipropylamide group, and sulfonic acid dibutylamide group.

[0043] In general formula (2), R ８ Examples of sulfonic acid ester groups represented by this symbol include methyl sulfonate ester group, ethyl sulfonate ester group, propyl sulfonate ester group, and butyl sulfonate ester group.

[0044] In general formula (2), R８ Examples of sulfonic acid amide groups represented by this symbol include sulfonic acid monomethylamide group, sulfonic acid monoethylamide group, sulfonic acid monopropylamide group, sulfonic acid monobutylamide group, sulfonic acid dimethylamide group, sulfonic acid diethylamide group, sulfonic acid dipropylamide group, and sulfonic acid dibutylamide group.

[0045] In general formula (2), R ８ Examples of metal salts of sulfonic acid represented by include lithium salts, sodium salts, and potassium salts of sulfonic acid.

[0046] In general formula (2), X － Examples of counter anions represented by include halogen ions such as chloride ions, bromide ions, and iodide ions; sulfate ions, perchlorate ions (ClO2). ４ － ), phosphate ions, and ZnCl ４ － Examples include inorganic acid ions such as acetate ions; organic acid ions such as acetate ions; and so on.

[0047] The fluorescent dye (xanthene dye) represented by general formula (2) is a compound that has a high affinity for alcohols and emits fluorescence. In general formula (2), R ９ ~R １２ Compounds having a structure in which an aromatic ring such as a phenyl group is attached to any of these structures will no longer emit fluorescence.

[0048] Compounds represented by general formula (2) (xanthene dyes) can be synthesized by referring to known methods. Alternatively, commercially available products can be used as compounds represented by general formula (2).

[0049] The compound represented by general formula (2) may be a mixture of tautomers. Specific examples of compounds represented by general formula (2) include the compounds represented by formulas (2-1) to (2-11) shown below (compounds (2-1) to (2-11)).

[0050]

[0051]

[0052] The compounds represented by general formula (2) may be used individually, or two or more may be used in combination depending on the application or to adjust the color tone, etc. Furthermore, they may be used in combination with known pigments and dyes as needed, to the extent that the effects of this disclosure are not impaired. In particular, among the compounds represented by general formula (2), the compounds represented by formulas (2-1) to (2-3), (2-5), (2-6), (2-8), and (2-9) (compounds (2-1) to (2-3), (2-5), (2-6), (2-8), and (2-9)) are preferred, and the compounds represented by formulas (2-2), (2-3), (2-5), (2-6), (2-8), and (2-9) (compounds (2-2), (2-3), (2-5), (2-6), (2-8), and (2-9)) are more preferred. By using these compounds, it is possible to prepare fluorescent coloring compositions that can record inks and the like that have superior fluorescence persistence and lightfastness.

[0053] The triphenylmethane-based dye is preferably a compound represented by the following general formula (3).

[0054] (In the above general formula (3), R １３ and R １５ Each of these independently represents a hydrogen atom, a benzyl group, or an alkyl group having 1 to 8 carbon atoms, R １４ and R １６ Each of these independently represents a benzyl group or an alkyl group having 1 to 8 carbon atoms, R １７ and R １８ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R １９ R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid amide group, a sulfonic acid group, a sulfonic acid ester group, or a sulfonic acid amide group. ２０ Y represents a hydrogen atom, a sulfonic acid ester group, a sulfonic acid amide group, a metal salt of sulfonic acid, a monoalkylamino group, or a dialkylamino group. － represents a counter anion, R １９When it is a carboxylic acid group or a sulfonic acid group, these groups may form anions. However, R １９ When it is an anion of a carboxylic acid group or an anion of a sulfonic acid group, Y － The counter anion represented by does not exist)

[0055] In the general formula (3), R １３ and R １５ Examples of the alkyl group having 1 to 8 carbon atoms represented by include linear, branched, or cyclic alkyl groups having 1 to 8 carbon atoms. Examples of such an alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a 2-ethylhexyl group. Among them, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 2-ethylhexyl group is preferable in that it enables preparation of an ink capable of recording an image excellent in fluorescence persistence and light resistance.

[0056] In the general formula (3), R １４ and R １６ Examples of the alkyl group having 1 to 8 carbon atoms represented by include linear, branched, or cyclic alkyl groups having 1 to 8 carbon atoms. Examples of such an alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a 2-ethylhexyl group. Among them, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 2-ethylhexyl group is preferable in that it enables preparation of an ink capable of recording an image excellent in fluorescence persistence and light resistance.

[0057] Further, R １３ and R １５ are hydrogen atoms, R １４ and R １６ are the same alkyl group having 1 to 8 carbon atoms, and R １３ to R １６is preferably an alkyl group having 1 to 8 carbon atoms and being the same. Among them, an alkyl group having 1 to 4 carbon atoms is preferable in that it enables preparation of an ink or the like capable of recording an image with excellent fluorescence persistence and light resistance.

[0058] In the general formula (3), R １７ and R １８ Examples of the alkyl group having 1 to 4 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Among them, a methyl group or an ethyl group is preferable in that it enables preparation of an ink or the like capable of recording an image with excellent fluorescence persistence and light resistance.

[0059] In the general formula (3), R １９ Examples of the alkyl group having 1 to 8 carbon atoms represented by include linear, branched, or cyclic alkyl groups having 1 to 8 carbon atoms. Examples of such an alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a 2-ethylhexyl group. Among them, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 2-ethylhexyl group is preferable in that it enables preparation of an ink or the like capable of recording an image with excellent fluorescence persistence and light resistance.

[0060] In the general formula (3), R １９ Examples of the halogen atom represented by include a chlorine atom, a bromine atom, and a fluorine atom. Among them, a chlorine atom is preferable in that it enables preparation of an ink or the like capable of recording an image with excellent fluorescence persistence and light resistance.

[0061] In the general formula (3), R １９ Examples of the carboxylic acid ester group represented by include a methyl carboxylic acid ester group, an ethyl carboxylic acid ester group, a propyl carboxylic acid ester group, and a butyl carboxylic acid ester group.

[0062] In the general formula (3), R １９Examples of carboxylic acid amide groups represented by this formula include monomethyl carboxylic acid amide group, monoethyl carboxylic acid amide group, monopropyl carboxylic acid amide group, monobutyl carboxylic acid amide group, dimethyl carboxylic acid amide group, diethyl carboxylic acid amide group, dipropyl carboxylic acid amide group, and dibutyl carboxylic acid amide group.

[0063] In general formula (3), R １９ Examples of sulfonic acid ester groups represented by this symbol include methyl sulfonate ester group, ethyl sulfonate ester group, propyl sulfonate ester group, and butyl sulfonate ester group.

[0064] In general formula (3), R １９ Examples of sulfonic acid amide groups represented by this symbol include sulfonic acid monomethylamide group, sulfonic acid monoethylamide group, sulfonic acid monopropylamide group, sulfonic acid monobutylamide group, sulfonic acid dimethylamide group, sulfonic acid diethylamide group, sulfonic acid dipropylamide group, and sulfonic acid dibutylamide group.

[0065] In general formula (3), R ２０ Examples of sulfonic acid ester groups represented by this symbol include methyl sulfonate ester group, ethyl sulfonate ester group, propyl sulfonate ester group, and butyl sulfonate ester group.

[0066] In general formula (3), R ２０ Examples of sulfonic acid amide groups represented by this symbol include sulfonic acid monomethylamide group, sulfonic acid monoethylamide group, sulfonic acid monopropylamide group, sulfonic acid monobutylamide group, sulfonic acid dimethylamide group, sulfonic acid diethylamide group, sulfonic acid dipropylamide group, and sulfonic acid dibutylamide group.

[0067] In general formula (3), R ２０ Examples of metal salts of sulfonic acid in this context include lithium salts, sodium salts, and potassium salts of sulfonic acid.

[0068] In general formula (3), R ２０Examples of monoalkylamino groups represented by include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, and 2-ethylhexylamino group.

[0069] In general formula (3), R ２０ Examples of dialkylamino groups represented by include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, and dihexylamino group.

[0070] In general formula (3), Y － Examples of counter anions represented by include halogen ions such as chloride ions, bromide ions, and iodide ions; sulfate ions, perchlorate ions (ClO2). ４ － ), phosphate ions, and ZnCl ４ － Examples include inorganic acid ions such as acetate ions; organic acid ions such as acetate ions; and so on.

[0071] The fluorescent dye (triphenylmethane-based dye) represented by general formula (3) is a compound that has a high affinity for alcohols and emits fluorescence. In general formula (3), R １３ ~R １６ Compounds having a structure in which an aromatic ring such as a phenyl group is attached to any of these structures will no longer emit fluorescence.

[0072] The compound represented by general formula (3) (triphenylmethane-based dye) can be synthesized by referring to known methods. Alternatively, commercially available products can be used as the compound represented by general formula (3).

[0073] The compound represented by general formula (3) may be a mixture of tautomers. Specific examples of compounds represented by general formula (3) include the compounds represented by formulas (3-1) to (3-10) shown below (compounds (3-1) to (3-10)).

[0074]

[0075]

[0076] The compounds represented by general formula (3) may be used individually, or two or more may be used in combination depending on the application or to adjust the color tone, etc. Furthermore, they may be used in combination with known pigments and dyes as needed, to the extent that the effects of this disclosure are not impaired. In particular, among the compounds represented by general formula (3), the compounds represented by formulas (3-1) and (3-2) to (3-7) (compounds (3-1) and (3-2) to (3-7)) are preferred, and the compounds represented by formulas (3-1) and (3-5) (compounds (3-1) and (3-5)) are more preferred. By using these compounds, it is possible to prepare fluorescent coloring compositions that can record inks and the like that have superior fluorescence persistence and lightfastness.

[0077] Other suitable fluorescent dyes besides the xanthene and triphenylmethane dyes mentioned above include the compounds represented by the following formulas (4-1) to (4-5) (compounds (4-1) to (4-5)).

[0078]

[0079] The amount of the compound represented by general formula (1) in the fluorescent coloring composition can be appropriately set depending on the application. For example, the content (mass%) of the compound represented by general formula (1) in the fluorescent coloring composition is preferably 1 to 1,000 times the content (mass%) of the fluorescent dye, more preferably 5 to 500 times, and particularly preferably 10 to 200 times.

[0080] The fluorescent colored composition of this disclosure makes it possible to prepare inks and the like that can record images with excellent fluorescence persistence and lightfastness. For this reason, the fluorescent colored composition of this disclosure is suitable as a material for inks, toners, thermal transfer recording sheets, color filter resist compositions, and writing instruments.

[0081] <Ink, Writing Instruments> The ink of this disclosure contains the aforementioned fluorescent coloring composition and is suitable as an inkjet ink, printing ink, paint, and writing instrument ink. Furthermore, it is suitable as an ink for color filters and an ink for thermal transfer recording sheets. The writing instrument of this disclosure is equipped with an ink containing the aforementioned fluorescent coloring composition. Because the ink of this disclosure contains the aforementioned fluorescent coloring composition, it can record images with excellent fluorescence persistence and lightfastness.

[0082] The ink further contains, for example, a liquid medium. Components other than the fluorescent coloring composition and the liquid medium are appropriately designed according to the intended use of the ink and may contain various additives.

[0083] As a liquid medium, water, organic solvents, and mixed solvents containing water and organic solvents can be used. Examples of organic solvents include alcohols such as methanol, ethanol, denatured ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 2-methyl-2-butanol, 3-pentanol, octanol, benzyl alcohol, and cyclohexanol; glycols such as methyl cellosolve, ethyl cellosolve, diethylene glycol, and diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, ethyl propionate, and cellosolve acetate; hexane, oc... Examples include aliphatic hydrocarbons such as tan, petroleum ether, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, and tetrabromoethane; ethers such as diethyl ether, dimethyl glycol, trioxane, and tetrahydrofuran; acetals such as methylal and diethyl acetal; organic acids such as formic acid, acetic acid, and propionic acid; and organic compounds containing sulfur or nitrogen such as nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethyl sulfoxide, and dimethylformamide.

[0084] Furthermore, polymerizable monomers can also be used as organic solvents. Polymerizable monomers include addition-polymerizable monomers and condensation-polymerizable monomers, and it is preferable to use addition-polymerizable monomers. Examples of polymerizable monomers include styrene monomers such as styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene; acrylate monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acrylonitrile, and acrylamide; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, and methacrylate. Examples include methacrylate monomers such as behenyl acid, 2-ethylhexyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylonitrile, and methacrylate amide; olefin monomers such as ethylene, propylene, butylene, butadiene, isoprene, isobutylene, and cyclohexene; halogenated vinyl monomers such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl iodide; vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl benzoate; vinyl ether monomers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; and vinyl ketone monomers such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone.

[0085] The ink may further contain colorants other than the fluorescent coloring composition (other colorants) as needed. The ink may also further contain a resin. Examples of resins include polystyrene resin, styrene copolymer, polyacrylic acid resin, polymethacrylic acid resin, polyacrylate resin, polymethacrylate resin, acrylic acid copolymer, methacrylic acid copolymer, polyester resin, polyvinyl ether resin, polyvinyl methyl ether resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyurethane resin, and polypeptide resin.

[0086] The ink can be manufactured, for example, by following these steps: While stirring the liquid medium, the fluorescent coloring composition is gradually added together with other colorants, emulsifiers, and resins used as needed, and thoroughly mixed. Furthermore, by applying mechanical shear force using a disperser, the components are stably dissolved or finely dispersed to obtain the desired ink. As dispersers, media-type dispersers such as rotary shear homogenizers, ball mills, sand mills, and attritors; high-pressure opposing impact dispersers; and the like can be used.

[0087] <Toner> The toner of this disclosure contains the aforementioned fluorescent coloring composition. Because the toner of this disclosure contains the aforementioned fluorescent coloring composition, it can record images with excellent fluorescence persistence and lightfastness.

[0088] There are no particular limitations on the method for producing the toner particles that make up the toner, but examples include grinding, suspension polymerization, suspension granulation, emulsion polymerization, and emulsion agglutination. The toner can also be used as a developer used in liquid development (hereinafter also referred to as "liquid developer"). Magnetic materials, waxes, charge control agents, and other additives may be added to the toner as needed. Furthermore, it can be used in combination with known pigments and dyes to adjust the color tone, etc.

[0089] Examples of waxes include polyethylene wax, paraffin wax, and fatty acid ester wax.

[0090] Examples of charge control agents that control the toner to a negative charge include polymers and copolymers having sulfonic acid groups, sulfonic acid bases, or sulfonic acid ester groups, salicylic acid derivatives and their metal complexes, monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids, their metal salts, anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarenes, and resin-based charge control agents.

[0091] Examples of charge control agents that control the positive charge of toner include nigrosine, nigrosine modified by fatty acid metal salts, guanidine compounds, imidazole compounds, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof, and their lake pigments, triphenylmethane dyes and their lake pigments (lake agents include phosphotungstic acid, phosphomolybdic acid, phosphotungstenmolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, and ferrocyanide), metal salts of higher fatty acids, diorganostin oxides such as dibutyltin oxide, dioctyltin oxide, and dicyclohexyltin oxide, diorganostin borates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate, and resin-based charge control agents. These charge control agents may be used individually or in combination of two or more types.

[0092] <Thermal Transfer Recording Sheet> The thermal transfer recording sheet of this disclosure (hereinafter also simply referred to as the "recording sheet") comprises a substrate and a color material layer formed by the aforementioned fluorescent coloring composition, provided on the substrate. Because the recording sheet of this disclosure comprises a color material layer formed by the aforementioned fluorescent coloring composition, it is possible to record images with excellent fluorescence persistence and lightfastness.

[0093] A thermal transfer recording sheet can be manufactured, for example, by following the procedure below. While stirring a liquid medium, a fluorescent coloring composition and a binder resin are gradually added together with surfactants and waxes as needed, and thoroughly mixed. Furthermore, an ink is prepared by applying mechanical shear force using a disperser to stably dissolve or finely disperse each component. Next, the prepared ink is applied to a substrate (base film), and then dried to form a colorant layer, thereby obtaining a thermal transfer recording sheet. As for the disperser, media-type dispersers such as rotary shear homogenizers, ball mills, sand mills, and attritors; high-pressure opposing impact dispersers; etc. can be used.

[0094] Methods for applying ink to a substrate include using a bar coater, gravure coater, reverse roll coater, rod coater, and air doctor coater. In terms of transferability, it is preferable to apply the ink in such a way that the thickness of the colorant layer after drying is in the range of 0.1 to 5 μm.

[0095] Suitable binder resins include water-soluble resins such as cellulose resin, polyacrylic acid resin, starch resin, and epoxy resin; and organic solvent-soluble resins such as polyacrylate resin, polymethacrylate resin, polystyrene resin, polycarbonate resin, polyethersulfone resin, polyvinyl butyral resin, ethylcellulose resin, acetylcellulose resin, polyester resin, AS resin, and phenoxy resin.

[0096] As the liquid medium, the same liquid medium as that used to constitute the ink can be used. That is, as the liquid medium, water, organic solvents, and mixed solvents containing water and organic solvents can be used. Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, and isobutanol; cellosolves such as methyl cellosolve and ethyl cellosolve; aromatic hydrocarbons such as toluene, xylene, and chlorobenzene; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; halogenated hydrocarbons such as methylene chloride, chloroform, and trichloroethylene; ethers such as tetrahydrofuran and dioxane; N,N-dimethylformamide; N-methylpyrrolidone; and others.

[0097] The ink used to form the colorant layer may further contain colorants other than the fluorescent colorant composition (other colorants) to impart desired spectral characteristics. From the viewpoint of improving transferability, the ratio of binder resin to fluorescent colorant composition (binder resin:fluorescent colorant composition) is preferably in the range of 1:2 to 2:1 by mass. A surfactant may be added to the ink used to form the colorant layer to provide sufficient lubricity when the thermal head is heated (during printing). Examples of surfactants include cationic surfactants, anionic surfactants, and nonionic surfactants.

[0098] Examples of cationic surfactants include dodecylammonium chloride, dodecylammonium bromide, dodecyltrimethylammonium bromide, dodecylpyridinium chloride, dodecylpyridinium bromide, and hexadecyltrimethylammonium bromide.

[0099] The ink used to form the colorant layer may contain wax to provide sufficient lubricity when the thermal head is not heated. Examples of waxes include polyethylene wax, paraffin wax, and fatty acid ester wax. The ink used to form the colorant layer may also contain, if necessary, additional components such as UV absorbers, preservatives, antioxidants, antistatic agents, and viscosity modifiers.

[0100] Examples of substrates (base films) include thin papers such as condenser paper and glassine paper; and plastic films such as polyester, polycarbonate, polyamide, polyimide, and polyaramid. From the viewpoint of heat resistance and other factors, it is preferable to use a plastic film as the substrate. Furthermore, from the viewpoint of mechanical strength, solvent resistance, and cost-effectiveness, it is even more preferable to use polyethylene terephthalate film as the substrate. From the viewpoint of transferability and other factors, the thickness of the substrate is preferably 3 to 50 μm.

[0101] To improve heat resistance and thermal head movement, it is preferable to provide a resin layer containing a lubricant, highly lubricated heat-resistant fine particles, and a binder on the surface of the substrate opposite to the surface on which the colorant layer is provided. Examples of lubricants include amino-modified silicone compounds and carboxy-modified silicone compounds. Examples of heat-resistant fine particles include silica and other fine particles. Examples of binders include acrylic resins.

[0102] When recording an image on the thermal transfer recording sheet of this disclosure, heating means such as a thermal head, infrared light, and laser light can be used. Furthermore, by using an electrically conductive heat-generating film that generates heat when electricity is passed through it as a base material, an electrically conductive dye transfer sheet can also be made.

[0103] <Resist Composition for Color Filters> The resist composition for color filters of this disclosure (hereinafter also simply referred to as "resist composition") contains the fluorescent coloring composition described above. Because the resist composition of this disclosure contains the fluorescent coloring composition described above, it is possible to manufacture color filters with excellent fluorescence persistence and light resistance.

[0104] The resist composition further contains, for example, a binder resin and a liquid medium. The binder resin can be any resin that is soluble in an organic solvent, an alkaline aqueous solution, water, or a commercially available developer in either the light-irradiated area or the light-shielding area during the exposure process. In particular, from the viewpoint of workability and post-resist formation processing, it is preferable to use a binder resin that can be developed with water or an alkaline aqueous solution.

[0105] As the binder resin, a resin can be used that is copolymerized by known methods in an appropriate mixing ratio between hydrophilic polymerizable monomers such as acrylic acid, methacrylic acid, N-(2-hydroxyethyl)acrylamide, N-vinylpyrrolidone, and polymerizable monomers having ammonium salts, and lipophilic polymerizable monomers such as acrylic acid esters, methacrylic acid esters, vinyl acetate, styrene, and N-vinylcarbazole. Such a binder resin is used in combination with radical polymerizable monomers having ethylenically unsaturated groups, cationic polymerizable monomers having oxirane rings or oxetane rings, radical generators, acid generators, and base generators. Since the solubility of such a binder resin in the exposed area in the developer is reduced, it can be used as a binder resin for negative-type resists in which only the light-shielded area is removed by development.

[0106] Furthermore, a combination of a binder resin having acid-cleavable groups, such as a resin having a quinone diazide group that cleaves upon light to generate a carboxylic acid group, tert-butyl carbonate of polyhydroxystyrene, and tetrahydropyranyl ether, and an acid generator that generates acid upon exposure can also be used. Since such a binder resin improves the solubility of the exposed area in the developer, it can be used as a binder resin for positive-type resists in which only the exposed area is removed by development.

[0107] When the resist composition is of the negative type, it is preferable to use a polymerizable monomer that undergoes addition polymerization by exposure (hereinafter also referred to as "photopolymerizable monomer"). The photopolymerizable monomer is preferably a compound having one or more ethylenically unsaturated double bonds that can be added polymerized in the molecule, and having a boiling point of 100°C or higher at normal pressure. Examples of such photopolymerizable monomers include monofunctional acrylates such as polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, phenoxyethyl acrylate, and phenoxyethyl methacrylate; polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetraacrylate. Examples include polyfunctional acrylates and methacrylates such as methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, tri(acryloyloxyethyl) cyanurate, glycerin triacrylate, and glycerin trimethacrylate; and polyfunctional acrylates and methacrylates obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane or glycerin, followed by acrylate or methacrylate formation.Furthermore, examples include urethane acrylates, polyester acrylates, and polyfunctional epoxy acrylates and epoxy methacrylates which are reaction products of epoxy resin with acrylic acid or methacrylic acid. Among these, it is preferable to use trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate.

[0108] In the resist composition, the content (mass%) of photopolymerizable monomers is preferably 5% to 50% by mass, and more preferably 10% to 40% by mass, based on the total solid content in the resist composition. By keeping the photopolymerizable monomer content within the above range, exposure sensitivity and pixel intensity can be improved, and the adhesiveness of the resist composition can be made appropriate.

[0109] If the resist composition is negative, a photopolymerization initiator may be further included. Examples of photopolymerization initiators include bicinal polyketoaldonyl compounds, α-carbonyl compounds, acioin ethers, polyquinone compounds, combinations of triallylimidazole dimer and p-aminophenyl ketone, and trioxadiazole compounds. Among these, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (trade name "Irgacure 369", manufactured by BASF) is preferred. Note that when using an electron beam, it is not necessary to include a photopolymerization initiator.

[0110] If the resist composition is of the positive type, a photoacid generator may be further included. Known photoacid generators such as salts of onium ions (such as sulfonium, iodonium, selenium, ammonium, and phosphonium) with anions can be used as photoacid generators.

[0111] As the liquid medium, water, organic solvents, and mixed solvents containing water and organic solvents can be used. Examples of organic solvents include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, 1,2,4-trichlorobenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropanol, butanol, methyl isobutyl ketone, and petroleum-based solvents. The liquid medium may be the same as or different from the liquid medium used in the fluorescent coloring composition, as long as it does not inhibit the dispersibility of the fluorescent dye.

[0112] The resist composition may further contain, as needed, an ultraviolet absorber or a silane coupling agent to improve adhesion to the glass substrate during the manufacture of the color filter.

[0113] In a color filter in which two or more pixels exhibiting different spectral characteristics are arranged adjacent to each other, at least one pixel of one of the multiple pixel colors (e.g., red, green, and blue) is formed with the resist composition of this disclosure. This makes it possible to obtain a color filter with excellent fluorescence persistence and lightfastness. In addition, other dyes may be used in combination to achieve the desired spectral characteristics.

[0114] A resist composition for color filters can be manufactured, for example, by following the procedure below. While stirring a liquid medium, a fluorescent coloring composition and a binder resin are gradually added together with polymerizable monomers, polymerization initiators, and photoacid generators as needed. Then, by applying mechanical shear force using a disperser to stably dissolve or finely disperse each component, the desired resist composition can be obtained. As dispersers, media-type dispersers such as rotary shear homogenizers, ball mills, sand mills, and attritors; high-pressure opposing impact dispersers; and the like can be used.

[0115] The present disclosure will be described in more detail below with reference to examples and comparative examples, but the present disclosure is not limited in any way by the following examples unless it exceeds the gist of the disclosure. Unless otherwise specified, amounts of components expressed in "parts" and "%" are based on mass. The structure of the obtained compound is: １ H nuclear magnetic resonance spectroscopy ( １ Identification was achieved by analysis using a 1H-NMR instrument and a MALDI-TOF / MS instrument. １ For the H-NMR system, we used the "AVANCE NEO 500 (500MHz)" (manufactured by BRUKER). For the MALDI-TOF / MS system, we used the "JMS-S3000" (manufactured by JEOL).

[0116] <Ink Production> (Examples 1-11, Comparative Examples 1-8) Inks (1) to (19) were obtained by mixing the compound represented by general formula (1), a fluorescent dye, 350 parts of toluene, 350 parts of ethyl acetate, and 300 parts of 2-butanone in the types and amounts (parts) shown in Table 1.

[0117] <Preparation of Image Samples> Ink manufactured by the bar coating method (Bar No. 10) was applied to opacity measurement paper, and then air-dried overnight to prepare image samples.

[0118] <Evaluation (1)> The prepared image sample was placed in a xenon test apparatus (product name "AtlasCi4000", manufactured by Toyo Seiki Seisakusho Co., Ltd.) and illuminated at 340 nm and 0.28 W / m². ２ An exposure test was conducted in which the black panel was exposed for 10 hours under conditions of a temperature of 40°C and a relative humidity of 50%.

[0119] (Sustainability of fluorescence intensity) The fluorescence intensity of image samples before and after exposure was measured using a spectrofluorometer (product name "F4500", manufactured by Hitachi, Ltd.). Below, the fluorescence intensity before exposure (initial) is given by I ０ The fluorescence intensity after 10 hours of exposure was measured as I(10) and I ０ Let X1 be the ratio of I(10) to X. X1 = I(10) / I ０It is calculated as follows. The closer the value of X1 is to 1, the closer the fluorescence intensity after 10 hours of exposure is to the initial fluorescence intensity, meaning that the fluorescence intensity persistence is excellent. Fluorescence intensity before exposure (I ０ The persistence of fluorescence intensity was evaluated according to the following evaluation criteria based on the ratio (X1) of the fluorescence intensity (I(10)) after 10 hours of exposure to (10). The results are shown in Table 1. A: 0.70 ≤ X1 B: 0.25 ≤ X1 < 0.70 C: X1 < 0.25

[0120] (Lightfastness) A reflectance densitometer (product name "FD-7", manufactured by Konica Minolta) was used to measure the reflectance (OD) of image samples before and after exposure. Below, the reflectance before exposure (initial) is referred to as OD. ０ The reflectance after 10 hours of exposure is OD(10), OD ０ Let Y1 be the ratio of OD(10) to . Y1 = OD(10) / OD ０ The value of Y1 is calculated as follows. The closer the Y1 value is to 1, the closer the reflectance after 10 hours of exposure is to the initial reflectance, indicating excellent lightfastness. Based on the Y1 value calculated as described above, the lightfastness of the fluorescent colored resin composition was evaluated according to the evaluation criteria shown below. The results are shown in Table 1. [Evaluation Criteria for Lightfastness] A: 0.80 ≤ Y1 B: 0.50 ≤ Y1 < 0.80 C: Y1 < 0.50

[0121]

[0122] <Manufacturing of inkjet ink> (Example 12) 2.8 parts of compound (1-2), 2.8 parts of compound (2-8), 10 parts of glycerin, 10 parts of triethylene glycol, 1 part of nonionic surfactant, and 35 parts of water were mixed. As the nonionic surfactant, the product name "Acetylenel E100" (manufactured by Kawaken Fine Chemicals) was used. After stirring, the mixture was pressure filtered through a 3.0 μm pore size microfilter (manufactured by Fujifilm) to prepare the ink. The pH of the prepared ink was in the range of 8.5 to 9.0.

[0123] The prepared ink was filled into an ink cartridge and mounted in an inkjet recording device (product name "PIXUS Pro-10", manufactured by Canon). Using this inkjet recording device, a magenta image sample was created. The created image sample was subjected to the same exposure test as described in "Evaluation (1)" above. The fluorescence intensity (I) before exposure was then measured. ０ The ratio (X1) of the fluorescence intensity (I(10)) after 10 hours of exposure to (OD) and the reflectance concentration (OD) before exposure. ０ The ratio (Y1) of the reflectance concentration (OD(10)) after 10 hours of exposure to X1 was calculated. As a result, X1 was "0.86" and Y1 was "0.83".

[0124] <Toner Production> (Example 13) A mixture of 12 parts of compound (1-2), 12 parts of compound (2-8), and 120 parts of styrene was dispersed for 3 hours using an attritor (manufactured by Mitsui Mining Co., Ltd.) to obtain a dye dispersion (1). In addition, 710 parts of deionized water and 450 parts of 0.1 mol / L trisodium phosphate aqueous solution were placed in a four-necked flask equipped with a high-speed stirring device (product name "T.K. Homomixer", manufactured by Primix Co., Ltd.), and stirred at a rotation speed of 12,000 rpm while being heated to 60°C. 68 parts of 1.0 mol / L calcium chloride aqueous solution were gradually added to prepare an aqueous dispersion medium containing minute amounts of poorly water-soluble dispersion stabilizer calcium phosphate.

[0125] A mixture of the following compositions was heated to 60°C and stirred at 5,000 rpm using a high-speed stirrer to dissolve and disperse uniformly. Ten parts of a polymerization initiator (2,2'-azobis(2,4-dimethylvaleronitrile)) were added and dissolved to prepare a polymerizable monomer composition. • Dye dispersion (1): 133.2 parts • Styrene: 46.0 parts • n-butyl acrylate: 34.0 parts • Aluminum salicylate compound (trade name "Bontron E-88", manufactured by Orient Chemical Industry): 2.0 parts • Polar resin (polycondensate of propylene oxide-modified bisphenol A and isophthalic acid, Tg = 65°C, Mw = 10,000, Mn = 6,000): 10.0 parts • Ester wax (peak temperature of maximum endothermic peak in DSC measurement = 70°C, Mn = 704): 25.0 parts • Divinylbenzene: 0.10 parts

[0126] A polymerizable monomer composition was added to an aqueous dispersion medium and granulated by stirring at 12,000 rpm for 15 minutes. The high-speed stirring device was changed to a propeller stirring blade, and polymerization was carried out at a liquid temperature of 60°C for 5 hours, then the temperature was raised to 80°C and polymerization was carried out for 8 hours. After the polymerization reaction was completed, the remaining monomers were removed by distillation at 80°C under reduced pressure. Then, the liquid temperature was cooled to 30°C to obtain a polymer fine particle dispersion.

[0127] The obtained polymer microparticle dispersion was transferred to a washing container, and dilute hydrochloric acid was added while stirring to adjust the pH to 1.5, and the mixture was stirred for a further 2 hours. Solid-liquid separation was performed using a filter to obtain polymer microparticles. The polymer microparticles were redispersed in water and solid-liquid separated, and this process was repeated until the phosphate and calcium compounds containing calcium phosphate were sufficiently removed. Finally, the polymer microparticles that had undergone solid-liquid separation were thoroughly dried using a dryer to obtain toner matrix particles.

[0128] A mixture was obtained by mixing 100 parts of toner mother particles, 1.00 part of hydrophobic silica fine powder (number average primary particle size 7 nm), 0.15 parts of rutile-type titanium dioxide fine powder (number average primary particle size 45 nm), and 0.50 parts of rutile-type titanium dioxide fine powder (number average primary particle size 200 nm). The hydrophobic silica fine powder used was surface-treated with hexamethyldisilazane. The mixture obtained was dry-mixed for 5 minutes using a Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd.) to obtain toner (1).

[0129] (Example 14) 100 parts of binder resin, 6 parts of compound (1-2), 6 parts of compound (2-8), 0.5 parts of 1,4-di-t-butylsalicylate aluminum compound, and 5 parts of paraffin wax (maximum endothermic peak temperature 78°C) were blended. A polyester resin (Tg 55°C, acid value 20 mg KOH / g, hydroxyl value 16 mg KOH / g, molecular weight: Mp 4,500, Mn 2,300, Mw 38,000) was used as the binder resin. The mixture was obtained by mixing using a Henschel mixer (product name "FM-75J type", manufactured by Mitsui Mining). The mixture was kneaded using a twin-screw kneader (product name "PCM-45 type", manufactured by Ikegai Steel) set to a temperature of 130°C at a feed rate of 60 kg / hr to obtain a kneaded product. The temperature of the kneaded product at discharge was approximately 150°C. The resulting mixture was cooled, coarsely crushed in a hammer mill, and then finely ground at a feed rate of 20 kg / hr using a mechanical pulverizer (product name "T-250", manufactured by Turbo Industries) to obtain toner pulverized material.

[0130] The obtained toner pulverized material was classified using a multi-segment classifier utilizing the Coanda effect to obtain toner matrix particles. 100 parts of the obtained toner matrix particles were divided into two sections, and the specific surface area measured by the BET method was 200 m². ２ 1.8 parts of hydrophobized silica fine powder at a concentration of / g were added and dry-mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain toner (2).

[0131] (Comparative Example 9) Toner (3) was obtained in the same manner as in Example 13 described above, except that compound (1-2) was not used.

[0132] (Comparative Example 10) Toner (4) was obtained in the same manner as in Example 14 described above, except that compound (1-2) was not used.

[0133] <Preparation and Evaluation of Image Samples> Image samples were prepared using toners (1) to (4), and their image characteristics were compared and evaluated. For the comparison and evaluation of image characteristics, a modified version of the image forming machine (LBP) "LBP-5300" (manufactured by Canon) was used for paper feeding endurance testing. The modifications to the LBP are as follows: - The developing blade in the process cartridge (CRG) was replaced with an 8 μm thick SUS blade. - The LBP was modified to allow the application of a -200V blade bias to the developing bias applied to the developing roller, which is the toner carrier.

[0134] For the evaluation of image characteristics, CRGs (Camera Regulators) filled with each toner were prepared for each evaluation item. Each CRG filled with each toner was then set up in the LBP (Laser Printer) and evaluated for the items listed below.

[0135] (Exposure Test) The prepared image sample was placed in a xenon test apparatus (product name "AtlasCi4000", manufactured by Toyo Seiki Seisakusho Co., Ltd.) and exposed to 0.28 W / m² at 340 nm. ２ An exposure test was conducted in which the black panel was exposed for 10 hours under conditions of a temperature of 40°C and a relative humidity of 50%.

[0136] (Sustainability of fluorescence intensity) Under normal conditions (temperature 25°C / humidity 60% RH), the maximum toner load was 0.45 mg / cm². ２ A 16-level grayscale image sample was created using a modified color copier (product name "CLC-1100," manufactured by Canon, with the fixing oil application mechanism omitted). "CLC Color Copy Paper" (manufactured by Canon) was used as the base paper for the image samples.

[0137] The fluorescence intensity of image samples before and after exposure was measured using a spectrofluorometer (product name "F4500", manufactured by Hitachi, Ltd.). Below, the fluorescence intensity before exposure (initial) is given by I ０ The fluorescence intensity after 10 hours of exposure was measured as I(50) and I ０ Let X² be the ratio of I(50) to I. X² = I(50) / I ０ It is calculated as follows: Fluorescence intensity before exposure (I ０The persistence of fluorescence intensity was evaluated based on the ratio (X²) of the fluorescence intensity (I(50)) after 50 hours of exposure to (I(50)) according to the evaluation criteria shown below. The results are shown in Table 2. [Evaluation Criteria for Fluorescence Intensity Persistence] A: 0.70 ≤ X² B: 0.25 ≤ X² < 0.70 C: X² < 0.25

[0138] (Lightfastness) The reflectance density (OD) of the image sample was measured using a reflectance densitometer (product name "FD-7", manufactured by Konica Minolta). Below, the reflectance density before exposure (initial) is referred to as OD. ０ The reflectance after 50 hours of exposure is OD(50), OD ０ Let Y2 be the ratio of OD(50) to . Y2 = OD(50) / OD ０ The value of Y2 is calculated as follows. Based on the Y2 value calculated as described above, the lightfastness was evaluated according to the evaluation criteria shown below. The results are shown in Table 2. [Evaluation Criteria for Lightfastness] A: 0.80 ≤ Y2 B: 0.50 ≤ Y2 < 0.80 C: Y2 < 0.50

[0139]

[0140] <Preparation of Resist Composition and Image Sample for Color Filters> (Example 15) 12 parts of compound (1-2), 12 parts of compound (2-8), and 120 parts of cyclohexanone were mixed and dispersed for 1 hour using an attritor (manufactured by Mitsui Mining Co., Ltd.) to obtain an ink for preparing the resist composition. As the acrylic copolymer, a copolymer with a monomer ratio of 40% n-butyl methacrylate, 30% acrylic acid, and 30% hydroxyethyl methacrylate, with an Mw of 10,000, was used. 22 parts of the ink for preparing the resist composition were slowly added to a solution containing 6.7 parts of the acrylic copolymer, 1.3 parts of dipentaerythritol pentaacrylate, 0.4 parts of a photopolymerization initiator, and 96 parts of cyclohexanone, and the mixture was stirred at room temperature for 3 hours. 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone was used as the photopolymerization initiator. The mixture was filtered through a 1.5 μm filter to obtain resist composition (1). The resist composition (1) obtained was spin-coated onto a glass substrate to obtain an image sample.

[0141] (Comparative Example 11) A resist composition (2) was obtained in the same manner as in Example 15, except that compounds (1-2) were not used. An image sample was obtained in the same manner as in Example 15, except that the obtained resist composition (2) was used instead of resist composition (1).

[0142] <Evaluation (2)> The same exposure test as in "Evaluation (1)" above was performed on the image samples, and the rate of change in fluorescence intensity (△I(10)) and the remaining OD (△E) were calculated. As a result, it was found that the image sample obtained in Example 15 had a △I(10) that was 0.61 higher and a △E that was 0.60 higher than the image sample obtained in Comparative Example 11.

[0143] <Manufacturing of Thermal Transfer Recording Sheet and Image Sample> (Example 16) Five parts of polyvinyl butyral resin (product name "Denka 3000-K", manufactured by Denki Kagaku Kogyo Co., Ltd.) were gradually added to a mixed solution of 45 parts methyl ethyl ketone and 45 parts toluene and dissolved. Five parts of compound (1-2) and five parts of compound (2-8) were further added and dissolved to obtain an ink. The ink was applied to a polyethylene terephthalate film (product name "Lumirror", manufactured by Toray Industries, Ltd.) with a thickness of 4.5 μm so that the thickness after drying was 1 μm, and then dried to obtain a thermal transfer recording sheet (1). An image sample was obtained by using the obtained thermal transfer recording sheet (1) and transferring it to photographic paper using a Selphy modified machine.

[0144] (Comparative Example 12) An ink was obtained in the same manner as in Example 16, except that compound (1-2) was not used. A thermal transfer recording sheet (2) was obtained in the same manner as in Example 16, except that the obtained ink was used. Furthermore, an image sample was obtained in the same manner as in Example 16, except that the obtained thermal transfer recording sheet (2) was used.

[0145] <Evaluation (3)> The same exposure test as in "Evaluation (1)" above was performed on the image samples. The fluorescence intensity before exposure (I ０ The ratio (X1) of the fluorescence intensity (I(10)) after 10 hours of exposure to (OD) and the reflectance concentration (OD) before exposure. ０The ratio (Y1) of the reflectance density (OD(10)) after 10 hours of exposure to the given image was calculated. As a result, it was found that the image sample obtained in Example 16 had a higher X1 of 0.68 and a higher Y1 of 0.66 compared to the image sample obtained in Comparative Example 12.

[0146] <Manufacturing of Writing Instruments and Image Samples> (Example 17) To a mixed solution of 78 parts 1-phenoxy-2-propanol and 22 parts benzyl alcohol, 9 parts resin and 1 part polyvinylpyrrolidone resin were added, and the mixture was heated to 70°C to dissolve, then cooled to room temperature. The resin used was "Elec BL-1" (manufactured by Sekisui Chemical Co., Ltd.). The polyvinylpyrrolidone resin used was "K-90" (manufactured by Nippon Shokubai Co., Ltd.). 12 parts of compound (1-2), 15 parts of compound (2-8), and 3 parts of ester phosphate type anionic surfactant (product name "Prysurf A208N", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were added. The mixture was dispersed for 3 hours using an attritor (manufactured by Mitsui Mining Co., Ltd.) to obtain an oil-based ink composition for writing instruments. The obtained oil-based ink composition was filled into an ink container made of polypropylene tubing with an inner diameter of 1.2 mm and a length of 140 mm. A writing instrument (1) was fabricated, which is a ballpoint pen (ball diameter 0.7 mm) equipped with an ink reservoir tube and a phosphor bronze tip. Using the fabricated writing instrument (1), a 2 cm square image sample was obtained with a constant writing pressure.

[0147] (Comparative Example 13) An oil-based ink composition for a writing instrument was obtained in the same manner as in Example 17, except that compound (1-2) was not used. A writing instrument (2) was then prepared in the same manner as in Example 17, except that the obtained oil-based ink composition was used. An image sample was then obtained in the same manner as in Example 17, except that the prepared writing instrument (2) was used.

[0148] <Evaluation (4)> For the image samples, the same exposure test as in "Evaluation (1)" above was performed. The fluorescence intensity before exposure (I ０ The ratio (X1) of the fluorescence intensity (I(10)) after 10 hours of exposure to (OD) and the reflectance concentration (OD) before exposure. ０The ratio (Y1) of the reflectance density (OD(10)) after 10 hours of exposure to the given value was calculated. As a result, it was found that the image sample obtained in Example 17 had a higher X1 of 0.65 and a higher Y1 of 0.68 compared to the image sample obtained in Comparative Example 13.

[0149] This disclosure is not limited to the embodiments described above, and various modifications and alterations are possible without departing from the spirit and scope of this disclosure. Accordingly, the following claims are attached to make the scope of this disclosure public.

[0150] This application claims priority based on Japanese Patent Application No. 2025-013039 filed on 29 January 2025 and Japanese Patent Application No. 2026-001887 filed on 8 January 2026, and all of the contents of those applications are incorporated herein by reference.

Claims

1. A fluorescent coloring composition containing a fluorescent dye and a compound represented by the following general formula (1). (In the above general formula (1), R １ R represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group. ２ R represents a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group. ３ R represents a hydrogen atom, alkyl group, hydroxyalkyl group, alkoxy group, or aryl group. ４ R represents a hydrogen atom or an alkyl group. １ ~R ３ At least one of them is a hydroxyl group or a group containing a hydroxyl group, R １ and R ２ (These may bond to form a 1,3-dioxane ring.) 2. In the general formula (1), R ３ or R ４ The fluorescent coloring composition according to claim 1, wherein is a hydrogen atom.

3. The fluorescent coloring composition according to claim 1 or 2, wherein the fluorescent dye is at least one selected from the group consisting of xanthene dyes, triphenylmethane dyes, cyanine dyes, azo dyes, quinophthalone dyes, and stilbene dyes.

4. The fluorescent coloring composition according to claim 3, wherein the xanthene dye is a compound represented by the following general formula (2). (In the above general formula (2), R ５ and R ６ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ７ R represents a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid amide group, a sulfonic acid group, a sulfonic acid ester group, or a sulfonic acid amide group. ８ R represents a hydrogen atom, a sulfonic acid ester group, a sulfonic acid amide group, or a metal salt of sulfonic acid. ９ and R １１ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R １０ and R １２ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, X － represents a counter anion, R ７ If R is a carboxylic acid group or a sulfonic acid group, these groups may form an anion. However, R ７ If it is an anion of a carboxylic acid group or an anion of a sulfonic acid group, then X － (There is no counter anion represented by this.) 5. The fluorescent coloring composition according to claim 3, wherein the triphenylmethane-based dye is a compound represented by the following general formula (3). (In the above general formula (3), R １３ and R １５ Each of these independently represents a hydrogen atom, a benzyl group, or an alkyl group having 1 to 8 carbon atoms, R １４ and R １６ Each of these independently represents a benzyl group or an alkyl group having 1 to 8 carbon atoms, R １７ and R １８ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R １９ R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid amide group, a sulfonic acid group, a sulfonic acid ester group, or a sulfonic acid amide group. ２０ Y represents a hydrogen atom, a sulfonic acid ester group, a sulfonic acid amide group, a metal salt of sulfonic acid, a monoalkylamino group, or a dialkylamino group. － represents a counter anion, R １９ If R is a carboxylic acid group or a sulfonic acid group, these groups may form an anion. However, R １９ If it is an anion of a carboxylic acid group or an anion of a sulfonic acid group, Y － (There is no counter anion represented by this.) 6. An ink containing the fluorescent coloring composition according to any one of claims 1 to 5.

7. A toner containing the fluorescent coloring composition according to any one of claims 1 to 5.

8. A thermal transfer recording sheet comprising a base material and a colorant layer provided on the base material, which is formed from a fluorescent coloring composition according to any one of claims 1 to 5.

9. A resist composition for color filters containing the fluorescent coloring composition according to any one of claims 1 to 5.

Images