WO2018052022A1 - 着色樹脂組成物、硬化物及び画像表示装置 - Google Patents

着色樹脂組成物、硬化物及び画像表示装置 Download PDF

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WO2018052022A1
WO2018052022A1 PCT/JP2017/033031 JP2017033031W WO2018052022A1 WO 2018052022 A1 WO2018052022 A1 WO 2018052022A1 JP 2017033031 W JP2017033031 W JP 2017033031W WO 2018052022 A1 WO2018052022 A1 WO 2018052022A1
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group
mass
ring
substituent
preferable
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PCT/JP2017/033031
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English (en)
French (fr)
Japanese (ja)
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紫陽 平岡
裕子 ▲高▼橋
智子 門脇
夕起 鈴木
美佳 岡松
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三菱ケミカル株式会社
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Priority to JP2018539750A priority Critical patent/JP6897685B2/ja
Priority to CN201780054610.1A priority patent/CN109689697B/zh
Publication of WO2018052022A1 publication Critical patent/WO2018052022A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Definitions

  • the present invention relates to a colored resin composition, a cured product, and an image display device.
  • Non-Patent Document 1 discloses pigment particles. A method is disclosed in which the particle size is reduced to 1/2 or less of the coloration wavelength.
  • Japanese Unexamined Patent Publication No. 2014-153570 Japanese Unexamined Patent Publication No. 2014-219663 Japanese Unexamined Patent Publication No. 2013-064096 Japanese Unexamined Patent Publication No. 2013-050693 Japanese Unexamined Patent Publication No. 2013-253168 Japanese Unexamined Patent Publication No. 2013-061619
  • Non-Patent Document 1 the blue pigment has a shorter coloration wavelength than other red and green pigments, requires further fine dispersion, and increases costs and stability after dispersion. Become. Further, as a result of investigations by the present inventors, when a color filter is produced using a colored resin composition containing a conventional xanthene dye as a colorant as described in Patent Documents 1 to 5, the contrast is practical. It was not enough.
  • the present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a colored resin composition containing a xanthene dye having high luminance and high contrast and low solubility in water.
  • the gist of the present invention is as follows.
  • a colored resin composition comprising a xanthene dye represented by the following general formula (I), a solvent, a dispersant, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator.
  • R 1 and R 2 each independently represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 3 and R 4 each independently represents a divalent hydrocarbon group which may have a substituent.
  • R 5 and R 6 each independently represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 7 represents a monovalent group having at least one selected from the group consisting of —SO 2 — and —COO—.
  • m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R 7 may be the same or different.
  • X ⁇ represents a monovalent anion.
  • l represents an integer of 0 or 1.
  • —CH 2 — contained in the alkyl group, aromatic ring group and hydrocarbon group is —O—, —CO—, —COO—, —CONH—, —CONR 8 —, —NH—, —NR It may be substituted with at least one selected from the group consisting of 8 —, —SO 2 —, —SO 2 NH—, —SO 2 NR 8 — and —S—.
  • R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • the xanthene dye represented by the general formula (I) is a xanthene dye represented by the following general formula (I-1), according to any one of [1] to [3] Colored resin composition.
  • R 1 and R 2 are as defined above for formula (I).
  • R 3a and R 4a each independently represents an alkylene group.
  • R 5, R 6, R 7 , m, X - and l have the same meanings as in the formula (I).
  • R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 1 and R 2 each independently represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 3 and R 4 each independently represents a divalent hydrocarbon group which may have a substituent.
  • R 5 and R 6 each independently represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 7 represents a monovalent group having at least one selected from the group consisting of —SO 2 — and —COO—.
  • m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R 7 may be the same or different.
  • X ⁇ represents a monovalent anion.
  • l represents an integer of 0 or 1.
  • —CH 2 — contained in the alkyl group, aromatic ring group and hydrocarbon group is —O—, —CO—, —COO—, —CONH—, —CONR 8 —, —NH—, —NR It may be substituted with at least one selected from the group consisting of 8 —, —SO 2 —, —SO 2 NH—, —SO 2 NR 8 — and —S—.
  • R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • the xanthene dye represented by the general formula (I) is a xanthene dye represented by the following general formula (I-1), according to any one of [9] to [11] Xanthene dyes.
  • R 1 and R 2 are as defined above for formula (I).
  • R 3a and R 4a each independently represents an alkylene group.
  • R 5, R 6, R 7 , m, X - and l have the same meanings as in the formula (I).
  • R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element having the color filter of the present invention.
  • (meth) acryl means “at least one of acrylic and methacryl”, “at least one of acrylate and methacrylate”, and the like, for example, “( “Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.
  • total solid content means all components of the colored resin composition of the present invention other than the solvent components described later.
  • aromatic ring means both “aromatic hydrocarbon ring” and “aromatic heterocycle”.
  • a term such as “CI Pigment Green” means a color material name included in the color index (CI).
  • the colored resin composition of the present invention contains a xanthene dye represented by the following general formula (I), a solvent, a dispersant, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator. If necessary, it may further contain other coloring materials, dispersion aids, quenchers, etc., and each component is usually used in a state dissolved or dispersed in a solvent.
  • the xanthene dye which is a characteristic component in the colored resin composition of the present invention
  • each component of the dye dispersion containing the xanthene dye, and each component of the colored resin composition will be described in detail in this order.
  • Xanthene dyes (Xanthene dye represented by the general formula (I))
  • the xanthene dye of the present invention is represented by the following general formula (I).
  • R 1 and R 2 each independently represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 3 and R 4 each independently represents a divalent hydrocarbon group which may have a substituent.
  • R 5 and R 6 each independently represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 7 represents a monovalent group having at least one selected from the group consisting of —SO 2 — and —COO—.
  • m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R 7 may be the same or different.
  • X ⁇ represents a monovalent anion.
  • l represents an integer of 0 or 1.
  • —CH 2 — contained in the alkyl group, aromatic ring group and hydrocarbon group is —O—, —CO—, —COO—, —CONH—, —CONR 8 —, —NH—, —NR It may be substituted with at least one selected from the group consisting of 8 —, —SO 2 —, —SO 2 NH—, —SO 2 NR 8 — and —S—.
  • R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • the xanthene dye of the present invention has two substituents on the nitrogen atom as in the general formula (I), it is considered that the molar extinction coefficient is increased and the luminance becomes high.
  • the hydrogen bond between molecules causes aggregation and the solubility is lowered, so that the solubility in water is lowered, and since it exists in a particle state in a solvent, fluorescence is suppressed and high Contrast is considered.
  • R 1 and R 2 each independently represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • alkyl group for R 1 and R 2 include a linear, branched or cyclic alkyl group.
  • the number of carbon atoms is usually 1 or more, preferably 2 or more, preferably 12 or less, more preferably 6 or less. When the number of carbon atoms of the alkyl group is at least the lower limit, the durability tends to be high, and when the number is less than the upper limit, the solubility tends to be low with respect to the organic solvent.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3- A methylbutyl group etc. are mentioned. Among these, an ethyl group is preferable from the viewpoint of synthesis.
  • Examples of the substituent that the alkyl group may have include those described in the substituent group W1 described later.
  • Specific examples of the alkyl group having a substituent include phenethyl group, 2-ethoxyethyl group, 4,4,4-trifluorobutyl group and the like.
  • Examples of the aromatic ring group in R 1 and R 2 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the number of carbon atoms in the aromatic ring group is at least the lower limit, the durability tends to be high, and when the number is less than the upper limit, the synthesis tends to be easy.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
  • Examples of the substituent that the aromatic ring group may have include those described in the substituent group W2 described later.
  • R 1 and R 2 are preferably each independently an aromatic ring group which may have a substituent, and are a benzene ring group substituted with an alkyl group. Is more preferable, and it is more preferable that both of the two ortho positions are benzene ring groups substituted with an alkyl group.
  • R 3 and R 4 each independently represents a divalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group include linear, branched, cyclic, or combinations thereof. Examples thereof include an alkylene group, an arylene group, and a group in which an alkylene group and an arylene group are linked.
  • the carbon number of the divalent hydrocarbon group is usually 1 or more, preferably 3 or more, more preferably 6 or more, further preferably 8 or more, preferably 20 or less, more preferably 16 or less, and further 14 or less. Preferably, 12 or less is more preferable, 11 or less is particularly preferable, and 9 or less is most preferable.
  • the number of carbon atoms of the divalent hydrocarbon group is not less than the lower limit, the durability tends to be high, and when it is not more than the upper limit, synthesis is facilitated and the solubility in an organic solvent is reduced. Tend to.
  • alkylene group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, a cyclopentylene group, an n-hexylene group, a cyclohexylene group, and an n-heptylene group. It is done. Among these, an n-propylene group is preferable from the viewpoint of durability and solubility.
  • Specific examples of the arylene group include ortho-, meta-, or para-phenylene group, naphthylene group, fluorene group, indylene group, anthracene group, furan group, thiophene group and the like.
  • a phenylene group is preferable from the viewpoint of synthesis.
  • Specific examples of the group in which an alkylene group and an arylene group are linked include a combination of the above alkylene group and the above phenylene group.
  • a combination of propylene group and para-phenylene group is preferable from the viewpoint of durability and solubility.
  • Examples of the substituent that the divalent hydrocarbon group may have include those described in the substituent group W3 described later.
  • R 3 and R 4 are each independently a group in which an alkylene group which may have a substituent and an arylene group which may have a substituent are linked. It is preferable that a propylene group and a para-phenylene group be combined.
  • R 5 and R 6 each independently represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • alkyl group for R 5 and R 6 include a linear, branched or cyclic alkyl group.
  • the carbon number is usually 1 or more, preferably 12 or less, more preferably 6 or less, and even more preferably 2 or less. There exists a tendency for it to become low solubility with respect to the organic solvent by making carbon number of an alkyl group below the said upper limit.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexyl.
  • examples thereof include an ethyl group and a 3-methylbutyl group.
  • a methyl group is preferable from the viewpoint of solubility.
  • Examples of the substituent that the alkyl group may have include those described in the substituent group W1 described later.
  • Specific examples of the alkyl group having a substituent include phenethyl group, 2-ethoxyethyl group, 4,4,4-trifluorobutyl group and the like.
  • Examples of the aromatic ring group for R 5 and R 6 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less. When the number of carbon atoms in the aromatic ring group is at least the lower limit, the durability tends to be high, and when the number is less than the upper limit, the synthesis tends to be easy.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
  • Examples of the substituent that the aromatic ring group may have include those described in the substituent group W2 described later.
  • R 5 and R 6 are each independently preferably an alkyl group which may have a substituent, and more preferably a methyl group.
  • R 7 represents a monovalent group having at least one selected from the group consisting of —SO 2 — and —COO—.
  • Examples of the monovalent group having —SO 2 — include —SO 3 — , —SO 3 H, —SO 3 M, —SO 3 R 8 , —SO 2 NHR 9 and —SO 2 NR 9 R 10.
  • —SO 3 ⁇ , —SO 2 NHR 9 and —SO 2 NR 9 R 10 are preferable, and —SO 3 — is more preferable.
  • M includes a lithium atom, a sodium atom, or a potassium atom, and among these, a sodium atom is preferable from the viewpoint of synthesis.
  • R 8 examples include an alkyl group which may have a substituent and an aromatic ring group which may have a substituent. Among these, an alkyl group which may have a substituent is preferable from the viewpoint of synthesis.
  • Examples of the alkyl group for R 8 include linear, branched or cyclic alkyl groups.
  • the carbon number is usually 1 or more, preferably 2 or more, preferably 12 or less, more preferably 6 or less, and still more preferably 3 or less. When the number of carbon atoms of the alkyl group is at least the lower limit, the durability tends to be high, and when the number is less than the upper limit, the organic solvent has a low solubility.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexyl.
  • Examples thereof include an ethyl group and a 3-methylbutyl group. Among these, an ethyl group is preferable from the viewpoint of durability and synthesis.
  • the alkyl group may be substituted with a substituent described in the substituent group W1 described later.
  • Examples of the aromatic ring group for R 8 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less. When the number of carbon atoms in the aromatic ring group is at least the lower limit, the durability tends to be high, and when the number is less than the upper limit, the synthesis tends to be easy.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
  • Examples of the substituent that the aromatic ring group may have include those described in the substituent group W2 described later.
  • R 9 and R 10 each independently include an alkyl group which may have a substituent and an aromatic ring group which may have a substituent.
  • an alkyl group which may have a substituent is preferable, and a branched alkyl group which may have a substituent is more preferable.
  • Examples of the alkyl group in R 9 and R 10 include a linear, branched or cyclic alkyl group.
  • the number of carbon atoms is usually 1 or more, preferably 2 or more, more preferably 6 or more, and preferably 12 or less.
  • the number of carbon atoms of the alkyl group is at least the above lower limit value, it tends to be insoluble in water, and when it is at most the above upper limit value, the organic solvent has a low solubility.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexyl. Examples thereof include an ethyl group and a 3-methylbutyl group. Among these, a 2-ethylhexyl group is preferable from the viewpoint of solubility.
  • the alkyl group may be substituted with a substituent described in the substituent group W1 described later.
  • the methylene group contained in the alkyl group may be substituted with an oxygen atom, a carbonyl group or —NR 8 —.
  • R 8 is the same as described above.
  • Examples of the aromatic ring group in R 9 and R 10 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less. When the number of carbon atoms in the aromatic ring group is at least the lower limit, the durability tends to be high, and when the number is less than the upper limit, the synthesis tends to be easy.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
  • a benzene ring or naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.
  • the substituent that the aromatic ring group may have include those described in the substituent group W2 described later.
  • examples of the monovalent group having —COO— include —CO 2 ⁇ , —CO 2 H, and —CO 2 R 8.
  • —CO 2 — is preferable from the viewpoint of solubility.
  • R 8 is the same as described above.
  • R 7 represents a monovalent group having at least one selected from the group consisting of —SO 2 — and —COO—, and among these, water and organic solvents From the viewpoint of insolubility in water, —SO 3 — is preferable.
  • m represents an integer of 0 to 5.
  • the plurality of R 7 may be the same or different.
  • m is preferably selected so that the charge in general formula (I) is zero.
  • R 7 is a monovalent anion
  • m may be 1 and l may be 0.
  • R 7 is not an anion
  • m can be freely selected within the range of 0-5.
  • 4 or less is preferable, 3 or less is more preferable, 2 or less is more preferable, and 1 is most preferable.
  • X ⁇ represents a monovalent anion.
  • the monovalent anion include a sulfonate anion, a sulfonylimide anion, and a halogen anion.
  • a halogen anion is preferable from the viewpoint of synthesis.
  • the halogen anion include F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ and the like.
  • Cl ⁇ is preferable from the viewpoint of synthesis.
  • l represents an integer of 0 or 1. From the viewpoint of insolubility in water, l is preferably selected so that the charge in general formula (I) is zero.
  • R 7 is a monovalent anion and m is 1, l may be 0, and when R 7 has no unpaired electron, l may be 1.
  • R 7 is a monovalent anion, m is 1, and l is 0.
  • —CH 2 — contained in the alkyl group, aromatic ring group and hydrocarbon group is —O—, —CO—, —COO—, —CONH—.
  • R 8 is the same as described above.
  • —O— and —COO— are desirable from the viewpoint of durability and synthesis. Examples of the divalent group substituted with these groups include —CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 OCO—, and the like.
  • Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkenyl group having 2 to 8 carbon atoms; alkoxyl group having 1 to 8 carbon atoms; aromatic carbonization such as phenyl group, mesityl group, tolyl group and naphthyl group A hydrogen ring group; a cyano group; a carboxyl group; an acetyloxy group; an alkylcarbonyloxy group having 2 to 9 carbon atoms; a sulfamoyl group; an alkylsulfamoyl group having 2 to 9 carbon atoms; an alkylcarbonyl group having 2 to 9 carbon atoms; Phenethyl group; hydroxyethyl group; acetylamide group; dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms; trifluoromethyl group; trialkyls
  • an alkoxyl group having 1 to 8 carbon atoms preferred are an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom. .
  • Halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; alkyl group having 1 to 8 carbon atoms; alkenyl group having 2 to 8 carbon atoms; hydroxyl group; alkoxyl group having 1 to 8 carbon atoms: phenyl group, mesityl Group, tolyl group, naphthyl group and other aromatic hydrocarbon ring groups; cyano group; carboxyl group; acetyloxy group; alkylcarbonyloxy group having 2 to 9 carbon atoms; sulfonic acid group; sulfamoyl group; An alkylsulfamoyl group; a carbonyl group; an alkylcarbonyl group having 2 to 9 carbon atoms; a hydroxyethyl group; an acetylamide group; a dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms;
  • an alkyl group having 1 to 12 carbon atoms preferably an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, and an alkyl group having 2 to 9 carbon atoms.
  • Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl group having 1 to 8 carbon atoms; alkenyl group having 2 to 8 carbon atoms; alkoxyl group having 1 to 8 carbon atoms; phenyl group, mesityl group and tolyl Group, aromatic hydrocarbon ring group such as naphthyl group; cyano group; carboxyl group; acetyloxy group; alkylcarbonyloxy group having 2 to 9 carbon atoms; sulfamoyl group; alkylsulfamoyl group having 2 to 9 carbon atoms; carbon An alkylcarbonyl group having 2 to 9 carbon atoms; a phenethyl group; a hydroxyethyl group; an acetylamide group; a dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms;
  • an alkoxyl group having 1 to 8 carbon atoms preferred are an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom. .
  • xanthene dye represented by the general formula (I-1) Among the xanthene dyes represented by the general formula (I), those represented by the following general formula (I-1) are preferable from the viewpoint of insolubility in water and organic solvents.
  • R 1 and R 2 have the same meaning as in the formula (I).
  • R 3a and R 4a each independently represents an alkylene group.
  • R 5, R 6, R 7 , m, X - and l have the same meanings as in the formula (I).
  • R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 3a and R 4a each independently represents an alkylene group.
  • the alkylene group usually has 1 or more carbon atoms, preferably 2 or more, more preferably 3 or more, and preferably 12 or less, more preferably 6 or less, and still more preferably 4 or less.
  • the number of carbon atoms of the alkylene group is at least the lower limit, the durability tends to be high, and when the number is less than the upper limit, the solubility tends to be low.
  • alkylene group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, a cyclopentylene group, an n-hexylene group, a cyclohexylene group, and an n-heptylene group. It is done. Among these, n-propylene group is preferable from the viewpoint of durability and solubility.
  • —CH 2 — contained in the alkylene group is —O—, —CO—, —COO—, —CONH—, —CONR 8 —, —NH—, —NR 8 —, —SO 2 —, —SO 2 NH It may be substituted with at least one selected from the group consisting of —, —SO 2 NR 8 — and —S—.
  • R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. Examples of the alkylene group in which at least one of —CH 2 — is substituted with these groups include —CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 OCO— and the like.
  • the aromatic ring group which may have a substituted alkyl group or even substituent in R 8 applying those mentioned as R 8 in the general formula (I) Can do.
  • xanthene dye represented by the general formula (I) and the xanthene dye represented by the general formula (I-1) include the following.
  • the xanthene dye of the present invention may be synthesized with reference to Japanese Patent Application Laid-Open No. 2013-253168 using a commercially available xanthene dye (for example, “DCSF” manufactured by Chugai Kasei Co., Ltd.) as a starting material. it can.
  • a commercially available xanthene dye for example, “DCSF” manufactured by Chugai Kasei Co., Ltd.
  • the xanthene dye of the present invention can be suitably used as a dye for a dye dispersion. Particularly, since it has low solubility in water, it is used as a dye dispersion that is one of the raw materials of a colored resin composition for a color filter. It is more preferable.
  • the dye dispersion may contain, for example, the above-mentioned xanthene dye, a solvent, and a dispersant. Furthermore, it can also contain arbitrary components, such as another coloring material, a dispersion aid, and a quencher.
  • the xanthene dye in the dye dispersion liquid of the present invention, as the xanthene dye, those represented by the general formula (I) can be preferably used.
  • the content of the xanthene dye represented by the general formula (I) is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, based on the total solid content. % By mass or more is more preferred, 30% by mass or more is more preferred, 50% by mass or more is particularly preferred, 70% by mass or more is most preferred, 99% by mass or less is preferred, 95% by mass or less is more preferred, 90% The mass% or less is further preferable, and 85 mass% or less is particularly preferable.
  • the content ratio of the xanthene dye represented by the general formula (I) is set to the lower limit value or more, the brightness tends to be high, and when the content ratio is set to the upper limit value or less, the contrast tends to be high.
  • the solvent is not particularly limited as long as it can dissolve or disperse each component contained therein and adjust the viscosity, but from the viewpoint of improving contrast, the xanthene dye of the present invention can be dispersed. Those are preferred.
  • the boiling point of the solvent at 1013.25 hPa is not particularly limited, but is preferably 100 ° C or higher, more preferably 120 ° C or higher, preferably 200 ° C or lower, and more preferably 170 ° C or lower.
  • the boiling point of the solvent By setting the boiling point of the solvent to be equal to or higher than the lower limit value, bumping at the time of vacuum drying tends to be prevented, and by setting the boiling point to be equal to or lower than the upper limit value, the residual solvent at the time of vacuum drying tends to be reduced.
  • solvents include the following. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;
  • Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;
  • Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone; Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin
  • Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, cyclohexyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, isobutyric acid Methyl, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3- Linear or cyclic esters such as butyl methoxypropionate, ⁇ -butyrolactone; Al
  • glycol monoalkyl ethers from the viewpoint of adhesion between the substrate and the coating film, and the coating film can form a uniform film thickness.
  • propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
  • the glycol alkyl ether is further used as a solvent from the viewpoint of relatively high solubility of the constituent components in the colored resin composition. It is more preferable to use a mixture of acetates.
  • glycol monoalkyl ethers are highly polar and tend to aggregate the pigment, which may reduce storage stability, such as increasing the viscosity of the colored resin composition. Therefore, it is preferable that the amount of glycol monoalkyl ether used is not excessively large, and the proportion of glycol monoalkyl ether in the solvent is preferably 0 to 50% by mass, more preferably 0 to 30% by mass.
  • a solvent having a boiling point of 150 ° C. or higher it is also preferable to use a solvent having a boiling point of 150 ° C. or higher.
  • the content of such a high-boiling solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass with respect to the whole solvent.
  • the solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .
  • the content of the solvent is not particularly limited, but is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 75% by mass or more, and particularly preferably 80% by mass or more, Moreover, 95 mass% or less is preferable, and 90 mass% or less is more preferable.
  • the content of the solvent is not less than the lower limit, there is a tendency to become a stable dispersion, and when the content is not more than the upper limit, the degree of freedom in blending the components of the colored resin composition tends to increase. .
  • the dispersant in the dye dispersion of the present invention is not particularly limited as long as it can disperse dyes and other colorants and can maintain stability, but when mixed with a pigment dispersion, the dispersion becomes unstable. In order to prevent this, it is preferable to use the same dispersant as the pigment dispersion.
  • cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers.
  • block copolymers polyurethanes, and cationic comb graft polymers are preferred.
  • a block copolymer is preferable from the viewpoint of luminance, and among these, a block copolymer composed of an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom is preferable.
  • the B block having a nitrogen atom-containing functional group includes a unit structure having at least one of a quaternary ammonium base and an amino group in the side chain, while the solvophilic A block is a quaternary.
  • a unit structure having no ammonium base and amino group can be mentioned.
  • the B block constituting the acrylic block copolymer has a unit structure having at least one of a quaternary ammonium base and an amino group, and has a coloring material (dye, pigment) adsorption function.
  • the quaternary ammonium base may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group.
  • Examples of such a block copolymer include those described in Japanese Patent Application Laid-Open No. 2009-025813.
  • the content of the dispersant in the dye dispersion liquid of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more, and more preferably 10% by mass or more in the total solid content.
  • 15% by mass or more is particularly preferable, 20% by mass or more is most preferable, 40% by mass or less is preferable, 30% by mass or less is more preferable, and 25% by mass or less is more preferable.
  • Dispersion stability tends to be improved by setting the content ratio of the dispersant to the lower limit value or more, and pattern forming properties during development tend to be improved by setting the content ratio of the dispersant to the upper limit value or less.
  • the dye dispersion of the present invention may contain other color materials, dispersion aids, dispersion resins, quenchers, and the like as optional components in addition to the dye, the dispersant, and the solvent.
  • other color materials include a dye other than the xanthene dye represented by the general formula (I) (hereinafter, abbreviated as “other dye”). ) And pigments.
  • Other dyes include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, triarylmethane dyes, Preferred examples include dipyrromethene dyes.
  • azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.
  • anthraquinone dyes examples include C.I. I. Bat Blue 4, C.I. I. Acid Blue 25, C.I. I. Acid Blue 40, C.I. I. Acid Blue 80, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
  • phthalocyanine dyes include C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Bat Blue 5, those described in Japanese Patent Laid-Open No. 2002-14222, Japanese Patent Laid-Open No. 2005-134759, Japanese Patent Laid-Open No. 2010-191358, Japanese Patent Laid-Open No. 2011-148950, etc.
  • quinoneimine dyes include C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
  • triarylmethane dyes examples include C.I. I. Acid Blue 86, C.I. I. Acid Blue 88, C.I. I. Acid Blue 108, International Publication No. 2009/107734, International Publication No. 2011/162217, International Publication No. 2015/080217, and the like.
  • examples of the cyanine dye include those described in International Publication No. 2011/162217, and the preferred embodiments are also the same.
  • dipyrromethene-based dye examples include, for example, Japanese Unexamined Patent Publication No. 2008-292970, Japanese Unexamined Patent Publication No. 2010-84009, Japanese Unexamined Patent Publication No. 2010-84141, Japanese Unexamined Patent Publication No. 2010-85454, JP 2011-158654 A, JP 2012-158739 A, JP 2012-224852 A, JP 2012-224849 A, JP 2012-224847 A Japan, The thing as described in Unexamined-Japanese-Patent No. 2012-224846 etc. is mentioned.
  • the dye dispersion liquid of the present invention only one kind of other dyes may be contained, or two or more kinds thereof may be contained.
  • pigments of various colors such as blue and purple can be used.
  • examples of the chemical structure include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, and perylene.
  • various inorganic pigments can be used.
  • specific examples of usable pigments are indicated by pigment numbers.
  • blue pigments examples include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.
  • a phthalocyanine pigment having a central metal is preferable, and a blue copper phthalocyanine pigment is particularly preferable.
  • the copper phthalocyanine pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and the like are preferable, and C.I. I. Pigment Blue 15: 6.
  • the dye dispersion liquid of the present invention contains a blue pigment, it is 80% by mass or more, particularly 90% by mass or more, especially 95 to 100% by mass with respect to the total content of the blue pigment.
  • I. Pigment Blue 15: 6 is preferable.
  • purple pigments examples include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.
  • a purple dioxazine pigment is preferable, and as the dioxazine pigment, C.I. I. Pigment Violet 19 and 23 are preferable, and C.I. I. Pigment Violet 23.
  • the dye dispersion of the present invention contains a violet pigment, it is 80% by mass or more, particularly 90% by mass or more, particularly 95 to 100% by mass, based on the total content of the violet pigment.
  • I. Pigment Violet 23 is preferable. These may be used alone or in a combination of two or more in any combination and ratio.
  • the pigment that can be used in the dye dispersion liquid of the present invention is preferably a pigment having a small average primary particle diameter from the viewpoint of forming a high-contrast pixel.
  • the average primary particle diameter is 40 nm or less.
  • it is 35 nm or less.
  • the average primary particle size is preferably 40 nm or less, more preferably 35 nm or less, and still more preferably 20 to 30 nm.
  • the average primary particle size is preferably 40 nm or less, more preferably 25 to 35 nm. From the viewpoint that the pigment is less likely to aggregate in the colored resin composition, it is preferable that the average primary particle size is not too small.
  • the average primary particle diameter of the pigment can be a value measured and calculated by the following method.
  • the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). From this image, the particle diameter of each pigment particle is determined for a plurality of (usually about 200 to 300) pigment particles, where the diameter of each pigment particle is equivalent to an area circle equivalent diameter converted to the diameter of a circle having the same area. Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.
  • TEM transmission electron microscope
  • Particle size of individual pigment particles X 1 , X 2 , X 3 , X 4 , ..., X i , ..., X m (m is the number of particles)
  • a pigment from the viewpoint of improving heat resistance and light resistance and from the viewpoint of improving heat resistance and light resistance due to the blue color material, it is more preferable to include a blue pigment, From the viewpoint of improving heat resistance and light resistance resulting from the purple color material, it is more preferable to include a purple pigment. Further, from the viewpoint of improving the luminance, it is preferable to include other dyes, and from the viewpoint of improving the luminance caused by the blue color material, it is more preferable to include a triarylmethane dye.
  • Examples of other colorants include blue pigments alone, blue dyes alone, combinations of blue pigments and blue dyes, combinations of blue pigments and purple pigments, combinations of blue pigments, blue dyes and purple pigments, blue pigments and blue dyes, Combinations of purple dyes, combinations of blue pigments, purple pigments and purple dyes, and the like can be given.
  • the content ratio of the other colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and 30% by mass in the total solid content. % Or more is more preferable, 50% or more is particularly preferable, 90% or less is preferable, 80% or less is more preferable, and 70% or less is more preferable.
  • the content ratio of the other coloring material is set to the lower limit value or more, there is a tendency to increase the contrast, and when the content ratio is set to the upper limit value or less, the degree of freedom in blending the components of the colored resin composition tends to increase. is there.
  • the content of other dyes is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and 30% by mass in the total solid content.
  • the above is more preferable, 50% by mass or more is particularly preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is more preferable.
  • the content ratio of other dyes is set to the lower limit value or more, the brightness tends to be high, and when the content ratio is set to the upper limit value or less, the degree of freedom in blending the components of the colored resin composition tends to increase. .
  • the content ratio of the pigment is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content, 30 mass% or more is further more preferable, 50 mass% or more is especially preferable, 90 mass% or less is preferable, 80 mass% or less is more preferable, and 70 mass% or less is further more preferable.
  • the content ratio of the xanthene dye represented by the general formula (I) is not particularly limited, but is preferably 0.5% by mass or more in the total solid content, 1% by mass or more is more preferable, 5% by mass or more is further preferable, 10% by mass or more is more preferable, 12% by mass or more is particularly preferable, 50% by mass or less is preferable, and 40% by mass or less is more preferable. 30 mass% or less is further more preferable, and 20 mass% or less is especially preferable.
  • the content ratio of the xanthene dye represented by the general formula (I) is set to the lower limit value or more, the brightness tends to be high, and when the content ratio is set to the upper limit value or less, the contrast tends to be high.
  • a pigment derivative is preferably exemplified.
  • the pigment derivative include Japanese Unexamined Patent Publication No. 2001-220520, Japanese Unexamined Patent Publication No. 2001-271004, Japanese Unexamined Patent Publication No. 2002-179976, Japanese Unexamined Patent Publication No. 2007-113000, and Japanese Specialties.
  • Various compounds described in JP 2007-186861 A can be used.
  • the content of the dispersion aid is not particularly limited, but is preferably 0.01% by mass or more, preferably 6% by mass or less, based on the total solid content. More preferably, it is more preferably 1% by mass or less. Moreover, 0.1 mass part or more is preferable with respect to 100 mass parts of xanthene dye represented by general formula (I), 30 mass parts or less are preferable, 10 mass parts or less are more preferable, and 5 mass parts or less are 5 mass parts or less. Further preferred. By controlling the content ratio within the above range, a stable dispersion tends to be obtained.
  • the dispersion resin is not limited in any way as long as it contributes to the dispersion stability of the xanthene dyes and pigments by a synergistic effect with the dispersant, and as a result, the addition amount of the dispersant can be reduced. From the viewpoint of forming a pattern, an alkali-soluble resin is preferable. As alkali-soluble resin, what was mentioned as binder resin in the below-mentioned [colored resin composition] can be used preferably.
  • the content ratio of the dispersion resin is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 40% by mass in the total solid content. % Or less is preferable, 20 mass% or less is more preferable, and 10 mass% or less is further more preferable.
  • the dispersion resin is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 200 parts by mass or less, and 100 parts by mass or less, based on 100 parts by mass of the xanthene dye represented by the general formula (I). Is more preferable, and 40 parts by mass or less is even more preferable.
  • the quencher is not particularly limited as long as it has absorption in the vicinity of the wavelength of fluorescence emitted by the xanthene dye.
  • anthraquinone dyes phthalocyanine dyes
  • tetraazaporphyrin dyes Preferable examples include triarylmethane dyes.
  • anthraquinone dyes examples include C.I. I. Bat Blue 4, C.I. I. Acid Blue 23, C.I. I. Acid Blue 25, C.I. I. Acid Blue 27, C.I. I. Acid Blue 40, C.I. I. Acid Blue 41, C.I. I. Acid Blue 43, C.I. I. Acid Blue 45, C.I. I. Acid Blue 62, C.I. I. Acid Blue 78, C.I. I. Acid Blue 80, C.I. I. Acid Blue 112, C.I. I. Acid Blue 138, C.I. I. Acid Blue 182, C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 35, C.I. I.
  • Solvent Blue 36 C.I. I. Solvent Blue 45, C.I. I. Solvent Blue 59, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 78, C.I. I. Solvent Blue 94, C.I. I. Solvent Blue 97, C.I. I. Solvent Blue 101, C.I. I. Solvent Blue 104, C.I. I. Solvent Blue 122, C.I. I. Reactive Blue 4, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60, those described in International Publication No. 2014/012814, Japanese Patent Application Laid-Open No. 2017-2257, and the like.
  • phthalocyanine dyes examples include C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Bat Blue 5 etc. are mentioned.
  • tetraazaporphyrin-based dyes examples include those described in International Publication No. 2014/012814.
  • triarylmethane dyes for example, C.I. I. Acid Blue 86, C.I. I. Acid Blue 88, C.I. I. Acid Blue 108, International Publication No. 2009/107734, International Publication No. 2011/162217, International Publication No. 2015/080217, and the like.
  • anthraquinone dyes are preferable from the viewpoint of heat resistance, luminance, and availability or ease of synthesis.
  • anthraquinone dyes C.I. I. Solvent blue 122 or one represented by the following general formula (II) is preferable.
  • each R a independently represents an alkyl group which may have a substituent.
  • Each R b independently represents an alkyl group containing an ether structure.
  • a independently represents an integer of 0 to 3;
  • Examples of the alkyl group for R a include a linear, branched, or cyclic alkyl group.
  • the number of carbon atoms is usually 1 or more, preferably 12 or less, more preferably 6 or less, further preferably 3 or less, and particularly preferably 2 or less.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3- A methylbutyl group etc. are mentioned. Among these, a methyl group or an ethyl group is preferable from the viewpoint of heat resistance.
  • Examples of the substituent that the alkyl group may have include those described in the aforementioned substituent group W1.
  • A represents an integer of 0 to 3, preferably 1 or more, more preferably 2 or more, and further preferably 3 from the viewpoint of heat resistance.
  • alkyl group containing an ether structure in Rb examples include an alkoxyalkyl group and an alkyl group containing a cyclic ether structure.
  • the alkoxyalkyl group may be linear or branched.
  • the number of carbon atoms of the alkoxyalkyl group is not particularly limited, but is usually 2 or more, preferably 3 or more, more preferably 4 or more, and usually 15 or less, preferably 10 or less, and more preferably 6 or less.
  • solubility to improve by making carbon number of an alkoxyalkyl group more than the said lower limit, and there exists a tendency for a synthesis
  • alkoxyalkyl group examples include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, an isopropoxypropyl group, and a butoxypropyl group.
  • a methoxymethyl group a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, an isopropoxypropyl group, and a butoxypropyl group.
  • the carbon number of the alkyl group containing a cyclic ether structure is not particularly limited, but is usually 5 or more, preferably 15 or less, more preferably 10 or less, and further preferably 6 or less. There exists a tendency for a synthesis
  • Examples of the cyclic ether structure include 5- to 8-membered ring ether structures such as a tetrahydrofuran structure, a tetrahydropyran structure, a dioxane structure, and a dioxolane structure.
  • a tetrahydrofuran structure is preferable from the viewpoint of heat resistance, acid resistance, and ease of synthesis.
  • alkyl group having a cyclic ether structure examples include a tetrahydrofuranylmethyl group, a 2- (1,3-dioxolan-2-yl) ethyl group, and the like.
  • the content of the quencher is not particularly limited, but is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on the total solid content. 5 mass% or more is further more preferable, 7 mass% or less is preferable, 3 mass% or less is more preferable, and 1 mass% or less is further more preferable. Further, the content of the quencher is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and preferably 50 parts by mass or less, based on 100 parts by mass of the xanthene dye. The amount is more preferably at most 20 parts by mass, and still more preferably at most 20 parts by mass. When the content ratio of the quencher is set to the lower limit value or more, high contrast tends to be obtained, and when the content rate is set to the upper limit value or less, high brightness tends to be obtained.
  • the colored resin composition of the present invention contains the xanthene dye of the present invention, a solvent, a dispersant, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator.
  • the colored resin composition of the present invention may contain a dispersion aid, a quencher and the like as optional components.
  • the xanthene dye of the present invention has low solubility in water, it is preferable to use the colored resin composition of the present invention as a colored resin composition for a color filter.
  • the dye dispersion liquid of the present invention may be used.
  • the dye dispersion liquid of the present invention, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator may be contained.
  • the xanthene dye in the colored resin composition of the present invention, as the xanthene dye, those represented by the general formula (I) can be suitably used.
  • the content ratio of the xanthene dye represented by the general formula (I) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more in the total solid content.
  • 2% by mass or more is more preferable, 3% by mass or more is more preferable, 4% by mass or more is particularly preferable, 15% by mass or less is preferable, 10% by mass or less is more preferable, and 6% by mass or less is further more preferable.
  • the content ratio of the xanthene dye represented by the general formula (I) is set to the lower limit value or more, the brightness tends to be high, and when the content ratio is set to the upper limit value or less, the contrast tends to be high.
  • the same solvent as that used for the dye dispersion can be preferably used.
  • the content of the solvent is not particularly limited, but is preferably 70% by mass or more, more preferably 75% by mass or more, further preferably 80% by mass or more, and preferably 99% by mass or less. 95 mass% or less is more preferable, and 90 mass% or less is still more preferable.
  • the viscosity is suitable for the formation of a coating film by setting the content of the solvent to the above lower limit value or more, and the colored resin composition of the present invention required for forming the coating film by setting it to the upper limit value or less. There is a tendency to reduce the amount of objects.
  • the same dispersant as that used in the dye dispersion can be suitably used as the dispersant.
  • the content of the dispersant is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more based on the total solid content. More preferably, it is more preferably 6% by mass or more, more preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 15% by mass or less, and particularly preferably 10% by mass or less.
  • Dispersion stability tends to be improved by setting the content ratio of the dispersant to the lower limit value or more, and pattern forming properties during development tend to be improved by setting the content ratio of the dispersant to the upper limit value or less.
  • the other color materials the same color materials as the other color materials used in the dye dispersion can be suitably used.
  • the content of other colorants is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more, based on the total solid content. It is particularly preferably at least mass%, more preferably at most 30 mass%, more preferably at most 25 mass%, further preferably at most 20 mass%.
  • the content ratio is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more in the total solid content. 30 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
  • the content ratio of other dyes is equal to or higher than the lower limit value, the contrast tends to be high, and when the content ratio is equal to or lower than the upper limit value, the degree of freedom in blending the components of the colored resin composition tends to increase. .
  • the content ratio is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and more preferably 15% by mass or more in the total solid content. Is particularly preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.
  • the content ratio of the pigment is set to the lower limit value or more, high contrast tends to be obtained, and when the pigment content ratio is set to the upper limit value or less, the degree of freedom in blending the components of the colored resin composition tends to increase.
  • the pigment may or may not be contained in the dye dispersion, but is preferably contained in the dye dispersion from the viewpoint of contrast and is stable over time. From the viewpoint of properties, it is desirable that the dye is not contained in the dye dispersion.
  • the binder resin is not limited in any way as long as it is soluble in the above-mentioned solvent and can form a cured film having a sufficient degree of curing, but it is said that a pattern is formed by alkali development.
  • an alkali-soluble resin is preferable.
  • Japanese Patent Application Laid-Open No. 7-207211, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-140144, Japanese Patent Application Laid-Open No. 11-174224 The polymer compounds described in JP-A No. 2000-56118, JP-A No. 2003-233179, and the like can be used. Among them, the following (C-1) is preferable. To (C-5) resins.
  • (C-1) An unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer with respect to the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer.
  • An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction or the resin formed by the addition reaction hereinafter sometimes referred to as “resin (C-1)”).
  • (C-2) Carboxyl group-containing linear alkali-soluble resin (hereinafter sometimes referred to as “resin (C-2)”)
  • C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
  • C-4) (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
  • C-5) Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
  • the resin (C-1) is particularly preferable, which will be described in detail below.
  • the resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. This is the same as that described as the same item in Japanese Patent Laid-Open No. 2009-025813. The preferred embodiment is also the same.
  • the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group
  • examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.
  • epoxy group-containing (meth) acrylate examples include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.
  • the other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired.
  • vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (III) Acrylate is preferred.
  • the repeating unit derived from a mono (meth) acrylate having a structure represented by the following formula (III) contains 5 to 90 mol% of repeating units derived from “another radical polymerizable monomer”. Those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable.
  • R 89 represents a hydrogen atom or a methyl group
  • R 90 represents a structure represented by the following formula (IV).
  • R 91 to R 98 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 96 and R 98 may be connected to each other to form a ring.
  • the ring formed by connecting R 96 and R 98 is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
  • a structure represented by the following structural formula (IVa), (IVb), or (IVc) is particularly preferable.
  • the mono (meth) acrylate which has a structure represented by said Formula (IV) may be used individually by 1 type, and may use 2 or more types together.
  • “Other radical polymerizable monomers” other than the mono (meth) acrylate having the structure represented by the formula (IV) can improve heat resistance and strength excellent in the colored resin composition.
  • the content of the repeating unit derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
  • a known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.
  • the copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer may include 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and the like.
  • the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and the strength of the film are sufficient, which is preferable.
  • the epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
  • an unsaturated monobasic acid added to an epoxy group a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.
  • (meth) acrylic acid crotonic acid, o-, m- or p-vinylbenzoic acid; the ⁇ -position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group or a cyano group
  • monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These may be used alone or in combination of two or more.
  • unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time.
  • a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.
  • a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
  • dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone
  • examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride.
  • succinic anhydride and tetrahydrophthalic anhydride are preferred.
  • These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.
  • alkali solubility can be imparted to the binder resin used in the present invention.
  • These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.
  • a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.
  • glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be.
  • the structure of such a resin is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.
  • the above-mentioned binder resin has a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography), preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more. Moreover, 100,000 or less is preferable, 50,000 or less is more preferable, 30,000 or less is further more preferable, 15,000 or less is further more preferable, and 13,000 or less is especially preferable. When the weight average molecular weight (Mw) is within the above range, heat resistance, film strength, and solubility in a developing solution are preferable. Further, as a measure of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.
  • the acid value of the binder resin is usually 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably 25 mgKOH / g or more, more preferably 50 mgKOH / g or more, and usually 200 mgKOH / g or less, preferably 150 mgKOH / g. g or less, more preferably 100 mgKOH / g or less.
  • the acid value is at least the lower limit, the solubility in the developer tends to be good, and when the acid value is at most the upper limit, the occurrence of film roughness tends to be suppressed.
  • the content ratio of the binder resin is not particularly limited, but is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and 25% by mass in the total solid content.
  • the above is particularly preferable, 80% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, and 40% by mass or less is particularly preferable.
  • the photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic”). It is sometimes referred to as “compound”.).
  • the ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiator described later when the colored resin composition of the present invention is irradiated with actinic rays.
  • the photopolymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.
  • a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule is particularly desirable.
  • the number of ethylenically unsaturated bonds that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15 or less, more preferably 10 It is as follows. By setting it as the said lower limit or more, there exists a tendency for polymerizability to improve and to become high sensitivity, and there exists a tendency for developability to become more favorable by setting it as the said upper limit or less.
  • Examples of the ethylenic compound in the photopolymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids.
  • unsaturated carboxylic acids such as (meth) acrylic acid
  • esters of monohydroxy compounds and unsaturated carboxylic acids esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids.
  • An ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid by an esterification reaction of the unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound;
  • the obtained ester an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;
  • Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate.
  • the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.
  • ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid examples include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
  • the ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may be a single substance or a mixture.
  • condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol
  • condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol
  • condensates of (meth) acrylic acid, maleic acid, and diethylene glycol condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol
  • a condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol
  • Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate.
  • Formula diisocyanates aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane
  • aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate
  • (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane
  • examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.
  • the ethylenic compound may be a monomer having an acid value.
  • the monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol.
  • the acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 100 mg-KOH / g, and particularly preferably 5 to 80 mg-KOH / g.
  • the acid value is within the above range, the development and dissolution characteristics are not easily lowered, and the production and handling are easy.
  • a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.
  • the content ratio of the photopolymerizable monomer is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more, based on the total solid content. More preferably, it is more preferably 30% by mass or more, more preferably 80% by mass or less, more preferably 60% by mass or less, and further preferably 40% by mass or less.
  • the content ratio of the photopolymerizable monomer is set to the lower limit value or more, the curing degree tends to increase, and when the photopolymerizable monomer content is set to the upper limit value or less, the adhesion to the substrate tends to be improved.
  • the colored resin composition of the present invention contains a photopolymerization initiator for the purpose of curing the coating film.
  • the curing method may be other than those using these initiators.
  • the colored resin composition of the present invention contains a resin having an ethylenic double bond as the binder resin, or contains an ethylenic compound as the photopolymerizable monomer, it directly absorbs light or increases the photosensitivity.
  • a photopolymerization initiator that has a function of generating a polymerization active radical by causing a decomposition reaction or a hydrogen abstraction reaction.
  • An optional additive such as a polymerization accelerator and a sensitizing dye may be used in combination with the photopolymerization initiator.
  • the photopolymerization initiator in the present invention is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.
  • Examples of the photopolymerization initiator include titanocene derivatives described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197; Japanese Patent Application Laid-Open No.
  • photopolymerization initiators described in International Publication No. 2009/107734.
  • photopolymerization initiators ⁇ -aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.
  • oxime ester derivatives examples include 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, O-acetyl-1- [6- (2-methylbenzoyl) -9. -Ethyl-9H-carbazol-3-yl] ethanone oxime and a compound represented by the following formula (V).
  • R 101 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkyl having 4 to 25 carbon atoms. Group, any of which may have a substituent. Alternatively, R 101 may be bonded to X or Z to form a ring.
  • R 102 represents an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms.
  • X represents at least one of a divalent aromatic hydrocarbon ring group and an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
  • Z represents an aromatic ring group which may have a substituent.
  • compounds in which X is a carbazole ring which may have a substituent are preferred, and specifically, compounds represented by the following formula (VI), etc. Among them, the compound represented by the following formula (VII) is particularly preferable.
  • R 101 , R 102 and Z have the same definitions as in formula (V).
  • R 103 to R 109 each independently represents a hydrogen atom or an arbitrary substituent.
  • R 101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (VIIa).
  • R 102a represents an alkanoyl group having 2 to 4 carbon atoms
  • X a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms.
  • Z a represents an even better naphthyl group optionally substituted by also a phenyl group or a morpholino group substituted with an alkyl group.
  • R 110 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkyl having 4 to 25 carbon atoms. Indicates a group. * Represents a binding site.
  • oxime ester derivatives Commercial products may be used as the oxime ester derivatives. Examples of commercially available products are OXE-01, OXE-02 (BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (Changzhou Powerful Electronic New Materials Co., Ltd.) Examples include public corporations (Changzhou TRONLY NEW ELECTRONIC MATERIALS CO., LTD), NCI-831, and NCI-930 (ADEKA).
  • OXE-01, OXE-02 BASF
  • TRONLYTR-PBG-304 TRONLYTR-PBG-309
  • TRONLYTR-PBG-305 TRONLYTR-PBG-314
  • Examples include public corporations (Changzhou TRONLY NEW ELECTRONIC MATERIALS CO., LTD), NCI-831, and NCI-930 (ADEKA).
  • photopolymerization initiators include benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone, benzoic acid ester derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like. Commercial products may be used as these initiators.
  • Examples of commercially available products include IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, RECICRURE TPO, and IRGACURE 8PO Is a registered trademark).
  • ⁇ -aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable.
  • oxime ester derivatives are preferable.
  • the polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, Examples include mercapto compounds having a heterocyclic ring such as 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.
  • Each of these photopolymerization initiators and polymerization accelerators may be used alone or in combination of two or more. Further, a sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used depending on the wavelength of the image exposure light source. For example, xanthene dyes described in Japanese Patent Laid-Open Nos.
  • a sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.
  • the content ratio of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass or more in the total solid content. More preferably, 2% by mass or more is more preferable, 3% by mass or more is particularly preferable, 20% by mass or less is preferable, 10% by mass or less is more preferable, and 5% by mass or less is more preferable.
  • the content ratio of the photopolymerization initiator is set to the lower limit value or more, the curing degree tends to increase, and when the photopolymerization initiator content is set to the upper limit value or less, the brightness tends to increase.
  • the content is not particularly limited, but is preferably 0.03% by mass or more, more preferably 0.1% by mass or more, based on the total solid content. 2 mass% or more is especially preferable, 1 mass% or less is preferable, 0.6 mass% or less is more preferable, and 0.4 mass% or less is especially preferable.
  • the content ratio of the polymerization accelerator is set to the lower limit value or more, the degree of curing tends to increase, and when the polymerization accelerator content is set to the upper limit value or less, the temporal stability tends to be improved.
  • a content rate of the polymerization accelerator with respect to 100 mass parts of photoinitiators 1 mass part or more is preferable, 3 mass parts or more are more preferable, 5 mass parts or more are especially preferable, and 30 mass parts or less are preferable. 20 parts by mass or less is more preferable, and 15 parts by mass or less is particularly preferable.
  • Dispersion aid In the colored resin composition of the present invention, as the dispersion aid, the same dispersion aid as that used in the dye dispersion can be suitably used.
  • the content of the dispersion aid is not particularly limited, but is preferably 0.01% by mass or more, preferably 6% by mass or less, more preferably 2% by mass or less in the total solid content. 1% by mass or less is more preferable. Further, the dispersion aid is preferably 0.1 parts by mass or more, preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less with respect to 100 parts by mass of the xanthene dye. Dispersion stability tends to be good by controlling the addition amount within the above range.
  • the same quencher as that used for the dye dispersion can be suitably used.
  • the content of the quencher is not particularly limited, but is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and more preferably 0.2% by mass or more in the total solid content. More preferably, 0.3 mass% or more is further more preferable, 0.5 mass% or more is particularly preferable, 7 mass% or less is preferable, 3 mass% or less is more preferable, and 1 mass% or less is further preferable. Further, the quencher is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, more preferably 50 parts by mass or less, and preferably 30 parts by mass or less with respect to 100 parts by mass of the xanthene dye. More preferred is 20 parts by mass or less. When the content ratio of the quencher is set to the lower limit value or more, high contrast tends to be obtained, and when the content rate is set to the upper limit value or less, high brightness tends to be obtained.
  • the colored resin composition of the present invention includes, in addition to the above components, at least one of a surfactant, an antioxidant, an organic carboxylic acid and an organic carboxylic anhydride, a thermosetting compound, a plasticizer, and a thermal polymerization inhibitor. Further, it may contain a storage stabilizer, a surface protective agent, an adhesion improver, a development improver and the like. As these optional components, for example, various compounds described in Japanese Patent Application Laid-Open No. 2007-113000 can be used.
  • the dye dispersion can be prepared by an appropriate method.
  • a dye dispersion is optionally dispersed in the presence of a dispersant and, if necessary, a dispersion aid.
  • a paint shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like are used to mix and disperse while pulverizing to prepare a dye dispersion.
  • the colored resin composition can be prepared by an appropriate method.
  • the dye dispersion described above is prepared, and a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and an optional component are prepared therein. It can be prepared by mixing together.
  • a cured product can be obtained by curing the colored resin composition of the present invention.
  • a cured product obtained by curing the colored resin composition can be suitably used as a color filter.
  • the colored resin composition of the present invention application as a pixel of a color filter, and an image display device using them, specifically, a liquid crystal display device (panel) and an organic EL display device will be described. To do.
  • the color filter of the present invention has a pixel formed from the colored resin composition of the present invention.
  • the method for forming the color filter of the present invention will be described below.
  • the pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.
  • a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed.
  • the solvent is evaporated to form a coating film.
  • each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.
  • the pixel formed using the colored resin composition of the present invention is a blue pixel.
  • the substrate used for forming the pixels is not particularly limited as long as it is transparent and has an appropriate strength.
  • these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.
  • pretreatment such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.
  • a spinner method When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.
  • the thickness of the coating film is usually 0.2 to 20 ⁇ m, preferably 0.5 to 10 ⁇ m, particularly preferably 0.8 to 5.0 ⁇ m as the film thickness after drying. Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
  • the radiation used in the exposure for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.
  • the light source used for image exposure for using radiation having a wavelength of 190 to 450 nm is not particularly limited.
  • An optical filter can also be used when used by irradiating light of a specific wavelength.
  • the exposure dose of radiation is preferably 10 to 10,000 J / m 2 .
  • the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-ethanolamine, di-ethanolamine, tri-ethanolamine, mono-methylamine, Di-methylamine, tri-methylamine, mono-ethylamine, di-ethylamine, tri-ethylamine, mono-isopropylamine, di-isopropylamine, n-butylamine, mono-isopropanolamine, di-isopropanol Amines, tri - isopropanolamine, ethyleneimine, ethylene diimine, te
  • a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
  • a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like
  • the development processing method any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used.
  • the development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).
  • the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower.
  • the developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.
  • the substrate after the development treatment may be subjected to additional exposure by a method similar to the above exposure method, or may be subjected to a thermosetting treatment.
  • the thermosetting treatment conditions at this time are selected in the range of 100 ° C. to 280 ° C., preferably in the range of 150 ° C. to 250 ° C., and in the range of 5 to 60 minutes.
  • a transparent electrode such as ITO is formed on the image as it is and used as a part of a component such as a color display or a liquid crystal display device.
  • a top coat layer such as polyamide or polyimide can be provided on the image as necessary.
  • the transparent electrode may not be formed.
  • ribs may be formed.
  • a column structure (photo spacer) by a photolithography method may be formed instead of the bead dispersion type spacer.
  • the image display device of the present invention contains a cured product obtained by curing a colored resin composition.
  • the image display device is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display device described later.
  • ⁇ Liquid crystal display device> The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction
  • the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).
  • Organic EL display device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, on a blue color filter in which pixels 20 are formed on the transparent support substrate 10 by the colored resin composition of the present invention.
  • a multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.
  • a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter.
  • a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used.
  • the organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.
  • N-acetamidophenol (12.0 g, 79.4 mmol) and 1,5-dibromopentane (32.2 mL, 238.2 mmol) were dissolved in acetone (150 mL), and potassium carbonate (22.0 g, 159 mmol) was added and stirred at reflux for 15 hours.
  • the reaction solution was cooled to room temperature, potassium carbonate was filtered off, and hexane (200 mL) was added. The obtained solid was collected by filtration and dried to obtain Compound 4 (25.5 g).
  • the inside of the reaction vessel was changed to air substitution, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours.
  • THPA tetrahydrophthalic anhydride
  • the weight average molecular weight Mw measured by GPC of the resin A thus obtained was about 8,400, and the acid value in terms of solid content was 80 mgKOH / g.
  • PGMEA was added to this resin solution so that solid content might be 44 mass%, and it was used as resin A.
  • the inside of the reaction vessel was changed to air substitution, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 18.7 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours.
  • THPA tetrahydrophthalic anhydride
  • the weight average molecular weight Mw measured by GPC of the resin B thus obtained was about 8,200, and the acid value was 32 mgKOH / g in terms of solid content.
  • PGMEA was added to this resin solution so that the solid content was 44% by mass and used as Resin B.
  • ⁇ Preparation of pigment dispersion> (Preparation of blue pigment dispersion A)
  • C.I. I. Pigment Blue 15: 6 is 11.36 parts by mass, 57.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and “Dispervic 2000” (manufactured by BYK Chemie) as a dispersant is 3.02 parts by mass in terms of solid content
  • a stainless steel container was filled with 215.7 parts by weight of 0.5 mm zirconia beads and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion A.
  • ⁇ Preparation of pigment / dye co-dispersion> (Preparation of blue pigment / dye co-dispersion A)
  • a blue pigment C.I. I. 9.6 parts by mass of Pigment Blue 15: 6, 2.4 parts by mass of Dye A, 56 parts by mass of propylene glycol monomethyl ether acetate as a solvent, 24 parts by mass of propylene glycol monomethyl ether, and “Dispervic 2000” (Bic Chemie) as a dispersant 4 parts by mass in terms of solid content
  • the prepared liquid is a zirconia bead having a diameter of 0.3 mm as a first dispersion, a peripheral speed of 12 m / s, a residence time of 3 hours, and a diameter of 0 as a second dispersion.
  • Blue pigment / dye co-dispersions A to D and blue pigment dispersion A are used for the colored resin compositions of Examples 1 to 4, and the dye dispersion A and blue pigment are used for the colored resin compositions of Examples 5 to 9.
  • Dispersion B was used, and blue pigment dispersion A and comparative dye 1 were used for the colored resin composition of Comparative Example 1.
  • Dye F The following compound synthesized by the method described in Japanese Patent Application Laid-Open No. 2017-2257
  • Dye G The following compound synthesized by the method described in Japanese Patent Application Laid-Open No. 2017-2257
  • Dye H C.I. I. Solvent Blue 122
  • each of the colored resin compositions of Examples 1 to 9 and Comparative Example 1 prepared in the above [Preparation of colored resin composition] has a y value of 0 after firing by spin coating. After applying to 0.075 and drying under reduced pressure, it was pre-baked on a hot plate at 80 ° C. for 3 minutes. Thereafter, the entire surface was exposed at an exposure amount of 40 mJ / cm 2 and then baked at 230 ° C. for 30 minutes in a clean oven to obtain a substrate with a colored resin film.
  • the spectral transmittance was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) and luminance in the XYZ color system were calculated. The results are shown in Table 2, Table 4 and Table 5.
  • the dye solution 2 was left standing. At this time, the dye may not be completely dissolved but may be undissolved.
  • the absorbance of the dye solution 3 was measured by a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), the absorbance at the maximum absorption wavelength at this time is set as a 3.
  • the solubility of the dye is represented by the concentration of the supernatant of the dye solution 2 and is calculated by [0.1 ⁇ (a 3 / a 1 )] mass%.
  • the maximum concentration of the dye solution 2 is 10% by mass
  • the upper limit of the solubility that can be evaluated is 10% by mass. Therefore, when the calculated value is 10% by mass, it is expressed as “10% or more”.
  • Table 3 The results are shown in Table 3.
  • the xanthene dyes of the present invention had high brightness and high contrast and low solubility in water.
  • Dyes (dyes A to D) contained in the colored resin compositions of Examples 1 to 4 have low solubility in water. This is presumably because the dyes A to D satisfy the general formula (I) and have an amide group, so that the solubility is reduced by agglomeration between molecules due to hydrogen bonding. As described above, it was suggested that the xanthene dye of the present invention has low solubility in water, and can easily treat waste liquid such as developer and washing water discharged during the production of the color filter.
  • the colored resin compositions of Examples 1 to 4 have a higher contrast ratio than the colored resin composition of Comparative Example 1. Further, when the colored resin films of Examples 1 to 4 and Comparative Example 1 were irradiated with ultraviolet rays, it was confirmed that Comparative Example 1 emitted fluorescence, while Examples 1 to 4 showed weak fluorescence. Was confirmed. From this, the colored resin film of Comparative Example 1 emits fluorescence due to the presence of the dye in the molecular state, and the contrast ratio is low, whereas in the colored resin films of Examples 1 to 4, the dye resin Since the solubility in propylene glycol monomethyl ether acetate is low, it has been clarified that the presence of the dye in the particle state sufficiently suppresses fluorescence and increases the contrast ratio.
  • the contrast ratio could be further improved by adding an anthraquinone dye as a quencher to the xanthene dye of the present invention.
  • an anthraquinone dye as a quencher
  • the maximum wavelength of weak fluorescence emitted by the xanthene dye of the present invention is in the vicinity of 580 nm, and it is considered that it absorbs fluorescence by using an anthraquinone dye having an absorption band in that region. It is done.
  • the anthraquinone dye from the excited xanthene dye of the present invention is an anthraquinone dye.
  • each colored resin composition of Examples 6 to 9 prepared in the above [Preparation of colored resin composition] has a y value of 0.075 after firing by spin coating. After being applied and dried under reduced pressure, it was pre-baked on a hot plate at 80 ° C. for 3 minutes. Then, after exposure at an exposure amount of 40 mJ / cm 2 through a photomask, development was performed at a development pressure of 0.25 MPa for 60 seconds using a potassium hydroxide aqueous solution adjusted to have a conductivity of 2.46 S / m. Thereafter, it was washed with water. At this time, the time from the start of development until the pattern was observed (development omission time) was visually observed, and this was defined as BT (seconds). The results are shown in Table 5.
  • the affinity with the developer was increased by using an anthraquinone dye having a functional group capable of interacting with water or alkali as in Examples 7 to 9.
  • Development omission time was shortened.
  • the sulfonamide group of the anthraquinone dye of Example 6 contains an oxygen atom and a nitrogen atom that can interact with water, but the anthraquinone dyes of Examples 7 to 8 have side chains in addition thereto. Since it contains more oxygen atoms that have an ether bond and can interact with water, it is considered that the affinity with the developer is high.
  • the anthraquinone dye of Example 9 has a small number of sulfonamide groups, it contains an acidic phenol group, and thus is considered to be more easily dissolved in an alkaline developer.
  • the present invention it is possible to provide a colored resin composition containing a xanthene dye having high brightness and high contrast and low solubility in water. Further, according to the present invention, it is possible to provide a color filter having high brightness and high contrast, and a high-quality image display device. Therefore, the present invention is useful in applications to color filters and image display devices.

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020012921A (ja) * 2018-07-17 2020-01-23 三菱ケミカル株式会社 着色樹脂組成物、カラーフィルタ及び画像表示装置
KR20200032446A (ko) * 2018-09-18 2020-03-26 주식회사 엘지화학 화합물, 색재 조성물, 감광성 수지 조성물, 감광재, 컬러필터 및 디스플레이 장치
KR20200039356A (ko) * 2018-10-05 2020-04-16 주식회사 엘지화학 화합물, 색재 조성물, 감광성 수지 조성물, 감광재, 컬러필터 및 디스플레이 장치
WO2022039224A1 (ja) * 2020-08-20 2022-02-24 三菱ケミカル株式会社 着色樹脂組成物、カラーフィルタ、及び画像表示装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021095561A (ja) * 2019-12-17 2021-06-24 保土谷化学工業株式会社 キサンテン色素、該色素を含有する着色組成物、カラーフィルター用着色剤およびカラーフィルター、ならびに該色素の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014219663A (ja) * 2013-04-09 2014-11-20 Jsr株式会社 着色組成物、着色硬化膜及び表示素子
WO2015115416A1 (ja) * 2014-01-31 2015-08-06 富士フイルム株式会社 着色組成物、硬化膜、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子および画像表示装置
JP2016102187A (ja) * 2014-11-28 2016-06-02 キヤノン株式会社 化合物、インク、インクカートリッジ、及びインクジェット記録方法
JP2017039890A (ja) * 2015-08-21 2017-02-23 キヤノン株式会社 インク、インクカートリッジ、及びインクジェット記録方法
JP2017132835A (ja) * 2016-01-25 2017-08-03 日本化薬株式会社 キサンテン化合物

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4873750B2 (ja) * 2007-05-01 2012-02-08 キヤノン株式会社 インクジェット用インク、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置
TWI542644B (zh) * 2011-02-09 2016-07-21 Sumitomo Chemical Co Coloring the photosensitive resin composition
JP5760584B2 (ja) * 2011-03-29 2015-08-12 住友化学株式会社 着色硬化性樹脂組成物
TWI624726B (zh) * 2011-05-23 2018-05-21 Sumitomo Chemical Co Colored curable resin composition
KR101632461B1 (ko) * 2011-08-05 2016-06-21 스미또모 가가꾸 가부시키가이샤 착색 경화성 수지 조성물
JP5647279B2 (ja) * 2013-02-08 2014-12-24 大日本印刷株式会社 着色剤分散液、着色剤分散液の製造方法、カラーフィルタ用着色樹脂組成物、カラーフィルタ、液晶表示装置、及び有機発光表示装置
KR101653865B1 (ko) * 2013-06-18 2016-09-02 주식회사 엘지화학 염료 및 이를 포함하는 컬러필터
CN104672198B (zh) * 2013-11-26 2018-11-16 东友精细化工有限公司 化合物及着色固化性树脂组合物
TWI559084B (zh) * 2014-03-24 2016-11-21 奇美實業股份有限公司 彩色濾光片用藍色感光性樹脂組成物及其應用
CN105589297B (zh) * 2014-11-11 2021-02-19 住友化学株式会社 着色固化性树脂组合物
CN105929636A (zh) * 2015-02-26 2016-09-07 东友精细化工有限公司 着色固化性树脂组合物、滤色器及显示装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014219663A (ja) * 2013-04-09 2014-11-20 Jsr株式会社 着色組成物、着色硬化膜及び表示素子
WO2015115416A1 (ja) * 2014-01-31 2015-08-06 富士フイルム株式会社 着色組成物、硬化膜、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子および画像表示装置
JP2016102187A (ja) * 2014-11-28 2016-06-02 キヤノン株式会社 化合物、インク、インクカートリッジ、及びインクジェット記録方法
JP2017039890A (ja) * 2015-08-21 2017-02-23 キヤノン株式会社 インク、インクカートリッジ、及びインクジェット記録方法
JP2017132835A (ja) * 2016-01-25 2017-08-03 日本化薬株式会社 キサンテン化合物

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020012921A (ja) * 2018-07-17 2020-01-23 三菱ケミカル株式会社 着色樹脂組成物、カラーフィルタ及び画像表示装置
KR20200032446A (ko) * 2018-09-18 2020-03-26 주식회사 엘지화학 화합물, 색재 조성물, 감광성 수지 조성물, 감광재, 컬러필터 및 디스플레이 장치
KR102268234B1 (ko) 2018-09-18 2021-06-22 주식회사 엘지화학 화합물, 색재 조성물, 감광성 수지 조성물, 감광재, 컬러필터 및 디스플레이 장치
KR20200039356A (ko) * 2018-10-05 2020-04-16 주식회사 엘지화학 화합물, 색재 조성물, 감광성 수지 조성물, 감광재, 컬러필터 및 디스플레이 장치
KR102301360B1 (ko) 2018-10-05 2021-09-10 주식회사 엘지화학 화합물, 색재 조성물, 감광성 수지 조성물, 감광재, 컬러필터 및 디스플레이 장치
WO2022039224A1 (ja) * 2020-08-20 2022-02-24 三菱ケミカル株式会社 着色樹脂組成物、カラーフィルタ、及び画像表示装置
KR20230052272A (ko) 2020-08-20 2023-04-19 미쯔비시 케미컬 주식회사 착색 수지 조성물, 컬러 필터 및 화상 표시 장치

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