WO2017082226A1 - 着色組成物、カラーフィルタ、パターン形成方法、固体撮像素子、および、画像表示装置 - Google Patents
着色組成物、カラーフィルタ、パターン形成方法、固体撮像素子、および、画像表示装置 Download PDFInfo
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- WO2017082226A1 WO2017082226A1 PCT/JP2016/083023 JP2016083023W WO2017082226A1 WO 2017082226 A1 WO2017082226 A1 WO 2017082226A1 JP 2016083023 W JP2016083023 W JP 2016083023W WO 2017082226 A1 WO2017082226 A1 WO 2017082226A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B25/00—Quinophthalones
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0041—Blends of pigments; Mixtured crystals; Solid solutions mixtures containing one azo dye
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
Definitions
- the present invention relates to a coloring composition.
- the present invention relates to a color filter, a pattern forming method, a solid-state imaging device, and an image display device using a colored composition.
- CCD charge-coupled device
- yellow colorants include quinophthalone compounds, azo compounds, thiazole compounds, methine compounds, and the like.
- Patent Documents 1 to 6 describe a colored composition using a yellow colorant.
- Patent Documents 7 to 9 describe that a green color filter is produced using a coloring composition containing a halogenated phthalocyanine pigment and tetrabromophthalimide.
- a coloring composition containing a resin, a colorant and a solvent as described above may be used after being stored for a long period of time.
- the coloring composition may be stored under conditions in which temperature control is performed, or may be stored in an environment with temperature fluctuation that is not temperature controlled. According to the study by the present inventors, it was found that when a film was produced after storing a colored composition containing a heterocyclic ring-containing colorant containing a nitrogen atom for a long period of time, defects were likely to occur in the film. In particular, it has been found that defects are likely to occur when the colored composition is stored for a long period of time in an environment with temperature fluctuations.
- Patent Documents 1 to 9 do not discuss defects in the case of using a colored composition after long-term storage.
- an object of the present invention is to provide a coloring composition, a color filter, and a pattern that can produce a film in which the occurrence of defects is suppressed even when the coloring composition is stored for a long period of time in an environment with temperature fluctuations.
- a forming method, a solid-state imaging device, and an image display device are provided.
- the present invention provides the following. ⁇ 1> A heterocyclic ring-containing colorant containing a nitrogen atom, a phthalimide compound, a solvent, and a resin, wherein the heterocyclic ring-containing colorant is at least one selected from the following formulas (1) to (4).
- R 1 to R 13 each independently represents a hydrogen atom or a substituent, and adjacent groups of R 1 to R 8 may be bonded to form a ring; , At least one pair of two adjacent groups of R 1 to R 8 is bonded to form an aromatic ring;
- R 205 and R 208 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R 201 to R 204 , R 206 and R 207 each independently represent a hydrogen atom.
- Y 1 represents a nitrogen atom or —CR Y1 —
- Y 2 represents a sulfur atom or —NR Y2 —
- R Y1 and R Y2 each independently represent a hydrogen atom, an alkyl group or a substituent.
- R 301 , R 311 and R 310 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R 302 to R 305 and R 306 to R 309 are each independently And X represents a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, or an anion having a boron atom;
- R 401 and R 402 each independently represents SO 2 R 403 or COR 403 ;
- R 403 represents an alkyl group, an aryl group or a heteroaryl group.
- phthalimide compound is a compound represented by the following formula (PI);
- a 1 to A 4 each independently represents a hydrogen atom, a halogen atom, or an alkyl group.
- the phthalimide compound is such that at least one of A 1 to A 4 in the formula (PI) is a bromine atom.
- the phthalimide compound is contained in an amount of 0.001 to 6.0 parts by mass with respect to a total of 100 parts by mass of the compounds represented by the formulas (1) to (4).
- ⁇ 5> The colored composition according to any one of ⁇ 1> to ⁇ 4>, further comprising a curable compound.
- ⁇ 6> The colored composition according to ⁇ 5>, wherein the curable compound contains a radically polymerizable compound and further contains a photopolymerization initiator.
- ⁇ 7> A color filter using the colored composition according to any one of ⁇ 1> to ⁇ 6>.
- ⁇ 8> A step of forming a colored composition layer on a support using the colored composition according to any one of ⁇ 1> to ⁇ 6>, and a colored composition layer by a photolithography method or a dry etching method. Forming a pattern with respect to the pattern.
- ⁇ 9> A solid-state imaging device having the color filter according to ⁇ 7>.
- ⁇ 10> An image display device having the color filter according to ⁇ 7>.
- a coloring composition, a color filter, and a pattern forming method capable of producing a film or the like in which generation of defects is suppressed even when the coloring composition is stored for a long period of time in an environment with temperature fluctuations. It has become possible to provide a solid-state imaging device and an image display device.
- the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- light means actinic rays or radiation.
- Actinic light or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
- exposure means not only exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also drawing with electron beams, ion beams, etc. unless otherwise specified. Include in exposure.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the total solid content refers to the total mass of components obtained by removing the solvent from all components of the colored composition.
- “(meth) acrylate” represents both and / or acrylate and methacrylate
- “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”.
- Allyl represents both and / or allyl and methallyl
- “(meth) acryloyl” represents both and / or acryloyl and methacryloyl.
- the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
- a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement.
- the pigment means an insoluble compound that is difficult to dissolve in a specific solvent. Typically, it means a compound that exists in a dispersed state as particles in the composition.
- a solvent the solvent illustrated in the column of the solvent mentioned later, for example is mentioned.
- the colored composition of the present invention contains at least one compound selected from formulas (1) to (4) described later, a phthalimide compound, a solvent, and a resin. If a colored composition containing a compound represented by the formulas (1) to (4) described later, a solvent, and a resin and not containing a phthalimide compound is stored for a long time in an environment with temperature fluctuation, However, by further containing a phthalimide compound, even when the colored composition is stored for a long period of time in an environment with temperature fluctuation, it is possible to produce a film in which the occurrence of defects is suppressed. . It is assumed that the mechanism for obtaining such an effect is as follows.
- the compounds represented by the formulas (1) to (4) are pigments having low solubility in a solvent
- the compounds when the temperature of the colored composition is lowered during storage (low temperature state), the compounds are aggregated. It is thought that it precipitates.
- the temperature of the colored composition rises from a low temperature state, a part of the precipitated compound returns to the dispersed state, but the precipitate remaining without being dispersed serves as a nucleus to induce precipitation of the compound at a low temperature state.
- the nucleus will grow.
- the solvent is removed and eliminated during drying, so that these nuclei promote crystallization of the compound and defects may occur in the film.
- the colored composition of the present invention further contains a phthalimide compound in addition to the compounds represented by the formulas (1) to (4).
- the phthalimide compound is considered to easily interact with the compounds represented by the formulas (1) to (4), and the phthalimide compound is adsorbed on the surface of the compounds represented by the formulas (1) to (4), It is presumed that a film or the like in which the occurrence of defects is suppressed as a result of suppressing the precipitation of the compound accompanying the temperature fluctuation during storage can be produced.
- the compounds represented by formulas (1) to (4) are dyes or the like that tend to have high solubility in a solvent
- the solubility may decrease, and nuclei derived from the compounds represented by the formulas (1) to (4) may be generated.
- this nucleus dissolves in the solvent in the colored composition, but a part thereof may remain as a nucleus without dissolving. It is considered that the nuclei remaining undissolved induce precipitation of the compound at a low temperature, and the nuclei grow.
- the solvent is removed during drying, and thus the above compound is precipitated (crystallized) around the nuclei. As a result, the obtained film is formed. Defects may occur.
- the colored composition of the present invention further contains a phthalimide compound in addition to the compounds represented by the formulas (1) to (4), the compound represented by the formulas (1) to (4), the phthalimide compound, Interact with each other to suppress crystallization of the compounds represented by the formulas (1) to (4), and as a result, it is presumed that a film or the like in which generation of defects is suppressed can be manufactured.
- the colored composition of the present invention contains at least one compound (heterocyclic-containing colorant) selected from the following formulas (1) to (4).
- Compounds of the formulas (1) to (4) can be preferably used as a yellow colorant.
- the heterocyclic ring-containing colorant is preferably a compound represented by the formula (1). According to this aspect, it is easier to manufacture a film in which defects are suppressed.
- the compound represented by Formula (1), the compound represented by Formula (2), the compound represented by Formula (3), and the compound represented by Formula (4) are respectively represented by Compound (1), Also referred to as compound (2), compound (3), and compound (4).
- R 1 to R 13 each independently represents a hydrogen atom or a substituent, and adjacent groups of R 1 to R 8 may be bonded to form a ring. However, at least one set of two adjacent groups of R 1 to R 8 is bonded to form an aromatic ring.
- R 205 and R 208 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R 201 to R 204 , R 206 and R 207 each independently represent a hydrogen atom.
- Y 1 represents a nitrogen atom or —CR Y1 —
- Y 2 represents a sulfur atom or —NR Y2 —
- R Y1 and R Y2 each independently represent a hydrogen atom, an alkyl group or a substituent.
- X represents a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion or an anion having a boron atom.
- R 301 , R 311 and R 310 each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group
- R 302 to R 305 and R 306 to R 309 are each independently Represents a hydrogen atom or a substituent
- X represents a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, or an anion having a boron atom.
- R 401 and R 402 each independently represents SO 2 R 403 or COR 403 ;
- R 403 represents an alkyl group, an aryl group or a heteroaryl group.
- R 1 to R 13 each independently represents a hydrogen atom or a substituent.
- substituent include the groups described in Substituent group T described later.
- a metal salt, an alkyl ammonium salt of a sulfo group, an alkyl ammonium salt of a carboxyl group, a phthalimidomethyl group, or a sulfamoyl group is preferable, and a halogen atom is more preferable.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferable.
- R 9 to R 13 are preferably hydrogen atoms.
- R 1 to R 8 are preferably a hydrogen atom or a substituent. Further, it is preferable that at least one of R 1 ⁇ R 8 is a halogen atom.
- adjacent groups among R 1 to R 8 may be bonded to form a ring. However, at least one set of two adjacent groups of R 1 to R 8 is bonded to form an aromatic ring.
- the ring formed by combining adjacent groups among R 1 to R 8 include alicyclic rings (non-aromatic hydrocarbon rings), aromatic rings, and heterocyclic rings.
- the ring may be monocyclic or polycyclic.
- the ring is preferably an aromatic ring.
- the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring.
- the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.
- Heteroaromatic rings include pyridine ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, carbazole A ring etc. are mentioned.
- the aromatic ring is preferably a hydrocarbon aromatic ring, and more preferably a benzene ring.
- the compound (1) is preferably a compound represented by any one of the following formulas (1a) to (1c).
- R 1 to R 13 and R 101 to R 108 each independently represent a hydrogen atom or a substituent.
- Examples of the substituent represented by R 1 to R 13 and R 101 to R 108 in the formulas (1a) to (1c) include groups described in the substituent group T described later.
- a halogen atom, an alkyl group, an alkoxy group , Aryl group, heteroaryl group, sulfo group, carboxyl group, metal salt of sulfo group, metal salt of carboxyl group, alkyl ammonium salt of sulfo group, alkyl ammonium salt of carboxyl group, phthalimidomethyl group, or sulfamoyl group is preferable
- a halogen atom is more preferable.
- At least one of R 9 to R 13 in the formulas (1a) to (1c) is preferably a hydrogen atom, and more preferably all of R 9 to R 13 are hydrogen atoms.
- R 1 to R 8 and R 101 to R 108 are preferably each independently a hydrogen atom or a halogen atom.
- Preferred embodiments of compound (1) include the following ⁇ 1> to ⁇ 3>.
- ⁇ 1> In the formula (1a), at least one of R 9 to R 13 is a hydrogen atom, at least one of R 1 , R 4 , R 101 to R 104 is a hydrogen atom, and at least one of R 5 to R 8 An embodiment in which one is a halogen atom. More preferably, R 9 to R 13 are hydrogen atoms, R 1 , R 4 and R 101 to R 104 are hydrogen atoms, and R 5 to R 8 are halogen atoms.
- At least one of R 9 to R 13 is a hydrogen atom
- at least one of R 1 to R 4 is a halogen atom
- at least one of R 5 , R 8 , R 105 to R 108 An embodiment in which one is a hydrogen atom. More preferably, R 9 to R 13 are hydrogen atoms, R 1 to R 4 are halogen atoms, and R 5 , R 8 , and R 105 to R 108 are hydrogen atoms.
- At least one of R 9 to R 13 is a hydrogen atom
- at least one of R 1 , R 4 , and R 101 to R 104 is a hydrogen atom
- the compound (1) include the following compounds.
- compounds described in paragraphs 0033 to 0034 of JP2013-54339A and compounds described in paragraphs 0049 to 0051 of JP2014-26228A are also included. These contents are incorporated herein.
- R 205 and R 208 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group.
- the alkyl group, aryl group and heteroaryl group may be an unsubstituted alkyl group, an unsubstituted aryl group or an unsubstituted heteroaryl group, and may further have a substituent. Examples of the substituent include groups described in the substituent group T described later.
- the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 3 carbon atoms.
- the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
- the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
- the aryl group is preferably a phenyl group.
- the heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
- the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
- the hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
- the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.
- R 201 to R 204 , R 206 and R 207 each independently represent a hydrogen atom or a substituent.
- substituent include groups described in the substituent group T described later.
- R 201 to R 204 are each independently preferably a hydrogen atom, an alkyl group or a halogen atom, more preferably a hydrogen atom.
- the alkyl groups include alkyl groups described in R 205 and R 208 described above.
- R 206 is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom, an alkyl group or an aryl group, and further preferably an aryl group.
- alkyl group, aryl group, and heteroaryl group examples include the alkyl group, aryl group, and heteroaryl group described above for R 205 and R 208 .
- R 207 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
- the alkyl groups include alkyl groups described in R 205 and R 208 described above.
- Y 1 represents a nitrogen atom or —CR Y1 —
- Y 2 represents a sulfur atom or —NR Y2 —
- R Y1 and R Y2 each independently represent a hydrogen atom or an alkyl group Represents an aryl group or a heteroaryl group.
- R Y1 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
- R Y2 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and still more preferably an alkyl group.
- Examples of the alkyl group, aryl group, and heteroaryl group represented by R Y1 and R Y2 include the alkyl group, aryl group, and heteroaryl group described above for R 205 and R 208 .
- Y 1 and Y 2 the following ⁇ 1> and ⁇ 2> are mentioned as preferred embodiments.
- ⁇ 2> A combination in which Y 1 is —CR Y1 — and Y 2 is a sulfur atom.
- X represents a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, or an anion having a boron atom.
- the bis (sulfonyl) imide anion include anions represented by the following (AN-1), and a bis (trifluoromethanesulfonyl) imide anion is more preferable.
- the tris (sulfonyl) methide anion include anions represented by the following (AN-2), and a tris (trifluoromethanesulfonyl) methide anion is more preferable.
- the anion having a boron atom include a tetrafluoroborate anion, a tetraphenylborate anion, and a tetraperfluorophenylborate anion.
- X 1 and X 2 each independently represent a halogen atom or an alkyl group. X 1 and X 2 may be bonded to each other to form a ring.
- Halogen atoms X 1 and X 2 represents a fluorine atom is preferable.
- the number of carbon atoms of the alkyl group represented by X 1 and X 2 is preferably 1 to 10, and more preferably 1 to 4.
- the alkyl group may be an unsubstituted alkyl group or may have a substituent.
- a halogen atom is preferable, and a fluorine atom is more preferable.
- X 1 and X 2 are each independently preferably a fluorine atom or an alkyl group having a fluorine atom, and more preferably an alkyl group having a fluorine atom.
- the alkyl group having a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and a perfluoroalkyl group having 1 to 4 carbon atoms. Is more preferable, and a trifluoromethyl group is particularly preferable.
- X 3 , X 4 and X 5 each independently represent a halogen atom or an alkyl group.
- the number of carbon atoms of the alkyl group represented by X 3 , X 4 and X 5 is preferably 1 to 10, and more preferably 1 to 4.
- the alkyl group may be an unsubstituted alkyl group or may have a substituent.
- a halogen atom is preferable, and a fluorine atom is more preferable.
- X 3 , X 4 and X 5 are each independently preferably a fluorine atom or an alkyl group having a fluorine atom, more preferably an alkyl group having a fluorine atom.
- the alkyl group having a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and a perfluoroalkyl group having 1 to 4 carbon atoms. Is more preferable, and a trifluoromethyl group is particularly preferable.
- the mass per molecule of the anion represented by X is preferably from 100 to 1,000, more preferably from 200 to 500. Although the specific example of an anion is shown below, this invention is not limited to these.
- Specific examples of the compound (2) include the following compounds.
- X represents a bis (trifluoromethanesulfonyl) imide anion, a tris (trifluoromethanesulfonyl) methide anion, a tetrafluoroborate anion, a tetraphenylborate anion, or a tetraperfluorophenylborate anion.
- specific examples of the compound (2) include compounds described in paragraph 0025 of JP2011-184493A, the contents of which are incorporated herein.
- R 301 , R 311 and R 310 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group.
- the alkyl group, aryl group and heteroaryl group may be an unsubstituted alkyl group, an unsubstituted aryl group or an unsubstituted heteroaryl group, and may further have a substituent. Examples of the substituent include groups described in the substituent group T described later.
- the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 3 carbon atoms.
- the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
- the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
- the aryl group is preferably a phenyl group.
- the heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
- the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
- the hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
- the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.
- R 302 to R 305 and R 306 to R 309 each independently represent a hydrogen atom or a substituent.
- substituent include groups described in the substituent group T described later. Examples include a halogen atom, an alkyl group, an alkoxy group, an amino group, an acylamino group, a nitro group, an aryl group, and a hydroxyl group, and an alkyl group or an alkoxy group is preferable.
- R 302 and R 305 are preferably hydrogen atoms.
- R 303 and R 304 are preferably a hydrogen atom or a substituent.
- R 306 to R 309 are preferably hydrogen atoms.
- X represents a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, or an anion having a boron atom.
- Specific examples of the compound (3) include the following compounds.
- X represents a bis (trifluoromethanesulfonyl) imide anion, a tris (trifluoromethanesulfonyl) methide anion, a tetrafluoroborate anion, a tetraphenylborate anion, or a tetraperfluorophenylborate anion.
- Specific examples of the compound (3) include the compounds described in paragraph 0019 of JP2012-158649A, the contents of which are incorporated herein.
- R 401 and R 402 each independently represents SO 2 R 403 or COR 403
- R 403 represents an alkyl group, an aryl group, or a heteroaryl group.
- R 403 is preferably an alkyl group or an aryl group, and more preferably an alkyl group.
- the alkyl group, aryl group and heteroaryl group represented by R 403 may be an unsubstituted alkyl group, an unsubstituted aryl group or an unsubstituted heteroaryl group, and may further have a substituent. Examples of the substituent include the groups described in the substituent group T described later.
- alkyl group preferably has 4 to 18 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 12 carbon atoms.
- the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
- alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, 3-heptyl group, octyl group, 2-ethylhexyl group.
- the aryl group preferably has 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms.
- the aryl group include a phenyl group, a 2-methylphenyl group, a 4-ethoxycarbonylphenyl group, a 4-chlorophenyl group, and a 3- (2-ethylhexyloxycarbonyl) phenyl group.
- the heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
- the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
- the hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
- the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and more preferably 3 to 12.
- R 401 and R 402 are preferably a compound represented by SO 2 R 403, and more preferably both a compound represented by SO 2 R 403.
- R 403 is preferably an alkyl group having 4 to 18 carbon atoms.
- R 401 and R 402 are preferably the same group.
- the compound (4) include the following compounds.
- compounds described in paragraphs 0030 to 0032 of JP-A-2014-25010 are also exemplified, the contents of which are incorporated herein.
- the following compounds can be synthesized, for example, according to the method described in JP-A-2014-25010, paragraphs 0036 to 0044.
- a halogen atom for example, fluorine atom, chlorine atom, bromine atom, iodine atom
- a linear or branched alkyl group a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl
- a cycloalkyl group preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl and cyclopentyl, and a multicycloalkyl group such as a bicycloalkyl group (preferably having 5 to 30 carbon atoms).
- Substituted or unsubstituted bicycloalkyl groups such as, for example, polycyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octan-3-yl) and tricycloalkyl groups
- a linear or branched alkenyl group a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl
- a cycloalkenyl group preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl
- An alkynyl group preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group
- An aryl group preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl
- a heteroaryl group preferably a 5- to 7-membered substituted or unsubstituted, monocyclic or condensed heteroaryl group, more preferably a ring-constituting atom selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom
- amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms is an arylamino group, a heteroarylamino group having 0 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazine-2- Ilamino);
- An acylamino group preferably a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, Lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino
- 2-benzothiazolyl Luthio, 1-phenyltetrazol-5-ylthio Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl); Sulfo group (hydrogen atom may be dissociated (that is, sulfonate group), salt state (metal salt (for example, sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, aluminum salt, etc.), alkyl ammonium) Salts (eg, ammonium salts of long
- a colorant (other colorant) other than the above-described compounds (1) to (4) can be further used.
- the colored composition of the present invention preferably contains another colorant.
- the other colorant may be either a dye or a pigment, or a combination of both. Pigments are preferred.
- the pigment include conventionally known various inorganic pigments or organic pigments. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having an average particle size as small as possible, and considering the handling properties, the average particle size of the pigment is 0.01 to 0.1 ⁇ m is preferable, and 0.01 to 0.05 ⁇ m is more preferable.
- inorganic pigments include metal compounds such as metal oxides and metal complex salts.
- black pigments such as carbon black and titanium black, iron, cobalt, aluminum, cadmium, lead, copper, titanium,
- oxides of metals such as magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.
- Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Japanese Patent No. 2592207, and US Pat. No. 4,808,501. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used.
- pyrazole azo compounds When classified as a chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used.
- a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP 2011-213925 A, JP 2013-041097 A, JP 2015-028144 A, and JP 2015-030742 A.
- a green colorant is preferable, a green pigment is more preferable, a halogenated phthalocyanine pigment is further preferable, and a halogenated zinc phthalocyanine pigment is particularly preferable.
- the halogenated zinc phthalocyanine pigment is a halogenated phthalocyanine pigment having zinc as a central metal, and as represented by the following formula (A1), the central metal zinc is surrounded by four nitrogens of an isoindole ring. It takes a planar structure located in the area.
- any 8 to 16 of X 1 to X 16 represent a halogen atom, and the rest represent a hydrogen atom or a substituent.
- substituent include the groups described in the substituent group T described above.
- halogenated zinc phthalocyanine pigment examples include, for example, the embodiments shown in the following ⁇ 1> to ⁇ 3> as preferable examples.
- ⁇ 1> A zinc halide phthalocyanine pigment having an average number of halogen atoms in one molecule of phthalocyanine of 8 to 12.
- X 1 to X 16 preferably contain one or more chlorine atoms, bromine atoms, and hydrogen atoms.
- X 1 to X 16 are preferably 0 to 4 chlorine atoms, 8 to 12 bromine atoms, and 0 to 4 hydrogen atoms.
- a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in one molecule of phthalocyanine of 14 to 16.
- the average number of halogen atoms in one phthalocyanine molecule is more preferably 15-16.
- the average number of bromine atoms in one molecule of phthalocyanine is preferably 0 to 12, more preferably 1 to 8, still more preferably 1 to 7, and still more preferably 2 to 7.
- Specific examples include the compounds described in WO2015 / 118720.
- halogenated zinc phthalocyanine pigment examples include C.I. as a compound classified as a pigment in the color index (CI; issued by The Society of Dyers and Colorists). I. And CI pigment green 58 and 59.
- the content of the other colorant is preferably 100 to 300 parts by mass with respect to 100 parts by mass in total of the compounds (1) to (4).
- the upper limit is preferably 250 parts by mass or less, and more preferably 230 parts by mass or less.
- the lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. 1 type may be sufficient as another colorant, and 2 or more types may be sufficient as it. When 2 or more types are included, the total is preferably within the above range.
- the coloring composition of the present invention contains a phthalimide compound.
- the phthalimide compound interacts with the above compounds (1) to (4), and even when the colored composition is stored for a long time in an environment with temperature fluctuation, a film in which generation of defects is suppressed Can be manufactured.
- the phthalimide compound used in the present invention is preferably a compound represented by the following general formula (PI).
- PI general formula
- a 1 to A 4 each independently represents a hydrogen atom, a halogen atom, or an alkyl group.
- the halogen atom include a chlorine atom, a bromine atom, and a fluorine atom, and a chlorine atom or a fluorine atom is preferable.
- the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
- the alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
- At least one of A 1 to A 4 is preferably selected from a chlorine atom and a bromine atom, and more preferably a bromine atom.
- all of the A 1 ⁇ A 4 is a chlorine atom and, more preferably selected from a bromine atom, all of A 1 ⁇ A 4 is more preferably a bromine atom.
- the content of the phthalimide compound is preferably 0.001 to 6.0 parts by mass with respect to 100 parts by mass in total of the compounds represented by the above formulas (1) to (4).
- the lower limit is preferably 0.1 parts by mass or more, and more preferably 1.0 parts by mass or more.
- the upper limit is preferably 5.0 parts by mass or less, and more preferably 3.0 parts by mass or less.
- the content of the phthalimide compound is preferably 0.001 to 5% by mass with respect to the total solid content in the colored composition.
- the lower limit is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.15% by mass or more.
- the upper limit is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.9% by mass or less, and particularly preferably 0.8% by mass or less. If content of a phthalimide compound is the said range, the effect of this invention will be easy to be acquired more notably.
- the phthalimide compound may be one type or two or more types. When 2 or more types are included, the total is preferably within the above range.
- the coloring composition of the present invention contains a resin.
- the resin is blended, for example, for the purpose of dispersing the colorant in the composition or the purpose of the binder.
- a resin used mainly for dispersing a colorant such as a pigment is also referred to as a dispersant.
- such use of the resin is an example, and the resin can be used for purposes other than such use.
- the resin content is preferably 10 to 80% by mass with respect to the total solid content of the colorable composition.
- the lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more.
- the upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
- the coloring composition of this invention contains a dispersing agent as resin.
- a dispersant examples include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
- the dispersant preferably includes at least an acidic dispersant, and more preferably only an acidic dispersant.
- the dispersant contains at least an acidic dispersant, the dispersibility of the colorant is improved and luminance unevenness is less likely to occur. Furthermore, since excellent developability can be obtained, pattern formation can be suitably performed by photolithography.
- content of an acidic dispersing agent is 99 mass% or more in the total mass of a dispersing agent, for example that a dispersing agent is only an acidic dispersing agent, and shall be 99.9 mass% or more. You can also.
- the acidic dispersant represents a resin in which the amount of acid groups is larger than the amount of basic groups.
- the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of groups is more preferred.
- the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group.
- the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups.
- the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups accounts for 50 mol% or more when the total amount of acid groups and basic groups is 100 mol%.
- the basic group possessed by the basic dispersant is preferably an amine.
- the acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.
- the dispersant examples include a polymer dispersant [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth). Acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.
- a polymer dispersant for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth).
- Acrylic copolymer, naphthalenesulfonic acid formalin condensate] polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.
- Polymer dispersants can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
- the polymer dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
- a graft copolymer containing a repeating unit represented by any one of the following formulas (1) to (4) can also be used.
- W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH
- X 1 , X 2 , X 3 , X 4 , and X 5 each independently represents a hydrogen atom or a monovalent organic group
- Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group
- Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a monovalent organic group
- R 3 represents an alkylene group
- R 4 represents a hydrogen atom or a monovalent organic group
- n, m, p, and q each independently represents 1 to Represents an integer of 500
- j and k each independently represent an integer of 2 to 8
- a plurality of R 3 may be the same or different from each other.
- may, in the formula (4), when q is 2 ⁇ 500, X 5 and R 4 existing in plural numbers may be different
- W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
- X 1 , X 2 , X 3 , X 4 , and X 5 are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably each independently a hydrogen atom or a methyl group, A methyl group is particularly preferred.
- Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
- the structure of the monovalent organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 is not particularly limited.
- an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group examples thereof include an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group.
- the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
- a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable.
- the alkyl group contained in the alkoxy group may be linear, branched or cyclic.
- n, m, p, and q are each independently an integer of 1 to 500.
- j and k each independently represent an integer of 2 to 8.
- J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
- R 3 represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms.
- p is 2 to 500, a plurality of R 3 may be the same or different.
- R 4 represents a hydrogen atom or a monovalent organic group.
- the monovalent organic group is not particularly limited in terms of structure.
- R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group.
- R 4 is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and 1 to 20 carbon atoms is preferable.
- linear alkyl groups having 1 to 6 carbon atoms are particularly preferable.
- q is 2 to 500
- a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
- the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the above contents are incorporated in this specification.
- Specific examples of the graft copolymer include the following resins. Further, there are resins described in JP-A-2012-255128, paragraphs 0072 to 0094, the contents of which are incorporated herein.
- an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain can be used.
- the oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less and a side chain containing a side chain Y having 40 to 10,000 atoms, and has a main chain and a side chain.
- a resin having at least one basic nitrogen atom is preferred.
- the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
- oligoimine-based dispersant the description in paragraphs 0102 to 0174 of JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification.
- resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.
- the dispersant is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid).
- Ester 110 (copolymer containing an acid group), 111 (phosphate dispersing agent), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), BYK -P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA 4047, 4050-4165 (polyurethane type), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (manufactured by EFKA) Polyester amide), 5765 (high molecular weight polycarboxylate), 6220 Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajispur PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer), Polyflow No.
- Acrybase FFS-6752 Acrybase FFS-187 (manufactured by Fujikura Kasei Co., Ltd.), Acryure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), and Cyclomer P (manufactured by Daicel Corporation) are used. You can also.
- the resin described as the dispersant can be used for purposes other than the dispersant. For example, it can be used as a binder.
- the coloring composition of this invention can contain alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formation are improved.
- the alkali-soluble resin can also be used as a dispersant or a binder.
- the molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably 5000 to 100,000.
- the number average molecular weight (Mn) is preferably 1000 to 20,000.
- the alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having groups to promote.
- the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance.
- Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
- Examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What can be developed is preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
- a known radical polymerization method can be applied.
- Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.
- the alkali-soluble resin is preferably a polymer having a carboxyl group in the side chain, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified malein.
- a methacrylic acid copolymer such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified malein.
- Examples include an acid copolymer, an alkali-soluble phenol resin such as a novolak resin, an acidic cellulose derivative having a carboxyl group in the side chain, and a polymer having a hydroxyl group added with an acid anhydride.
- a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
- examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
- alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate,
- vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfury
- N-substituted maleimide monomers described in JP-A-10-300922 can be used as the other monomers.
- N-substituted maleimide monomers include N-phenylmaleimide and N-cyclohexylmaleimide.
- only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.
- Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used.
- an alkali-soluble resin having a polymerizable group may be used as the alkali-soluble resin.
- the polymerizable group include a (meth) allyl group and a (meth) acryloyl group.
- the alkali-soluble resin having a polymerizable group an alkali-soluble resin containing a polymerizable group in a side chain is useful.
- the alkali-soluble resin containing a polymerizable group include Dianar NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer.
- Diamond Shamrock Co., Ltd. Biscote R-264, KS resist 106 ( All are manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Corporation), Acrycure RD-F8 ( Nippon Shokubai Co., Ltd.).
- the alkali-soluble resin is a compound represented by the following general formula (ED1) and / or a compound represented by the general formula (1) of JP 2010-168539 A (hereinafter, these compounds are referred to as “ether dimers”). It is also preferable to include a polymer obtained by polymerizing a monomer component including
- R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
- ether dimer for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.
- the alkali-soluble resin may contain a repeating unit derived from a compound represented by the following formula (X).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkylene group having 2 to 10 carbon atoms
- R 3 represents a hydrogen atom or a benzene ring that may contain a benzene ring.
- n represents an integer of 1 to 15.
- the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
- the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R 3 may contain a benzene ring.
- Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
- alkali-soluble resin examples include the following resins.
- Me is a methyl group.
- the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
- the lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.
- the upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and still more preferably 120 mgKOH / g or less.
- the content of the alkali-soluble resin is preferably 1 to 80% by mass with respect to the total solid content of the coloring composition.
- the lower limit is preferably 2% by mass or more, and more preferably 3% by mass or more.
- the upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
- the colored composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.
- the coloring composition of the present invention preferably contains a solvent.
- the solvent is preferably an organic solvent.
- the solvent is not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied.
- organic solvents include the following.
- esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyloxyalkyl acetate (Eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- Organic solvents may be used alone or in combination of two or more.
- the organic solvent preferably contains 2-methoxy-1-propyl acetate.
- the content of 2-methoxy-1-propyl acetate is preferably 0.001 to 5% by mass with respect to the mass of the coloring composition.
- the upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less.
- the content of 2-methoxy-1-propyl acetate is preferably 0.01 to 0.5% by mass with respect to the mass of the solvent.
- the lower limit is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more.
- the upper limit is preferably 0.4% by mass or less, and more preferably 0.2% by mass or less.
- the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
- the content of the solvent is preferably such that the total solid content of the colored composition is 5 to 80% by mass.
- the lower limit is preferably 10% by mass or more.
- the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.
- the colored composition of the present invention preferably contains a curable compound.
- a curable compound known compounds that can be cross-linked by radicals, acids, and heat can be used.
- a compound having a group having an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane) group, a methylol group and the like can be mentioned.
- the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the curable compound is preferably a polymerizable compound, and more preferably a radical polymerizable compound.
- the content of the curable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the coloring composition.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less.
- One curable compound may be used alone, or two or more curable compounds may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the polymerizable compound may be in a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof.
- a monomer is preferable.
- the molecular weight of the polymerizable compound is preferably 100 to 3000.
- the upper limit is preferably 2000 or less, and more preferably 1500 or less.
- the lower limit is preferably 150 or more, and more preferably 250 or more.
- the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound. Specific examples of these compounds are described in paragraph Nos. 0095 to 0108 in JP-A-2009-288705, paragraph No. 0227 in JP-A-2013-29760, and paragraph numbers 0254 to 0257 in JP-A-2008-292970. And the contents of which are incorporated herein.
- the polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.).
- Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, manufactured as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
- A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues (for example, commercially available from Sartomer) , SR454, SR499) Is preferred.
- These oligomer types can also be used.
- KAYARAD RP-1040 and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used.
- the following compounds can also be used.
- the polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
- an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
- Examples of commercially available products include M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
- the polymerizable compound is also preferably a compound having a caprolactone structure.
- examples of the polymerizable compound having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.
- a polymerizable compound having an alkyleneoxy group can also be used.
- the polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups.
- a hexafunctional (meth) acrylate compound is more preferable.
- polymerizable compound having an alkyleneoxy group examples include the following compounds.
- Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy groups.
- Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Is also preferable.
- urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA -306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
- the content of the polymerizable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the composition.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less.
- One curable compound may be used alone, or two or more curable compounds may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the content of the polymerizable compound is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, based on the total mass of the curable compound.
- a compound having an epoxy group can also be used as the curable compound.
- a compound having two or more epoxy groups in one molecule is preferable. It is preferable to have 2 to 100 epoxy groups in one molecule.
- the upper limit may be 10 or less, and may be 5 or less.
- the compound having an epoxy group preferably has a structure having an aromatic ring and / or an aliphatic ring, and more preferably has a structure having an aliphatic ring.
- the epoxy group is preferably bonded to the aromatic ring and / or the aliphatic ring via a single bond or a linking group.
- the linking group include an alkylene group, an arylene group, —O—, —NR ′ — (R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
- the epoxy group is preferably a compound formed by directly bonding (single bond) to the aliphatic ring.
- the epoxy group is preferably a compound formed by bonding to an aromatic ring via a linking group.
- the linking group is preferably an alkylene group or a group comprising a combination of an alkylene group and —O—.
- the compound which has an epoxy group can also use the compound which has a structure which two or more aromatic rings connected with the hydrocarbon group.
- the hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. It is preferable that the epoxy group is connected via the connecting group.
- the compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or even a molecular weight of less than 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more).
- the weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
- the upper limit of the weight average molecular weight is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less.
- bisphenol A type epoxy resin jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050 , EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc.
- bisphenol F-type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, Mitsubishi Chemical Corporation), EPICLON830, EPICLON835.
- Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (or more DIC Co., Ltd.), EOCN-1020 (Nippon Kayaku Co., Ltd.), etc., and aliphatic epoxy resins are ADEKA RESIN EP-4080S, EP-4085.
- EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, Daicel Corporation), Denacol EX-212L EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation) and the like.
- ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), and the like.
- the content of the compound having an epoxy group is preferably 0.1 to 40% by mass with respect to the total solid content of the colored composition.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
- the compound which has an epoxy group may be single 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the content of the compound having an epoxy group is preferably 1 to 80% by mass and more preferably 1 to 50% by mass with respect to the total mass of the curable compound.
- a curing accelerator may be added for the purpose of promoting the reaction of the polymerizable compound or lowering the curing temperature.
- the curing accelerator include polyfunctional thiol compounds having two or more mercapto groups in the molecule.
- the polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
- the polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).
- T1 In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.
- the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
- Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable. These polyfunctional thiol compounds can be used alone or in combination.
- Curing accelerators include methylol compounds (for example, compounds exemplified as a crosslinking agent in paragraph 0246 of JP-A-2015-34963), amines, phosphonium salts, amidine salts, amide compounds (above, for example, special No. 2013-41165, curing agent described in paragraph 0186), base generator (for example, ionic compound described in JP-A-2014-55114), cyanate compound (for example, JP-A-2012-150180) A compound described in paragraph 0071), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP2011-255304A), an onium salt compound (for example, paragraph 0216 in JP2015-34963A).
- Compounds exemplified as acid generators, JP2009 Compounds described in JP-180949 can also be used.
- the content of the curing accelerator is preferably 0.3 to 8.9% by mass, and preferably 0.8 to 6% based on the total solid content of the colored composition. More preferably, 4% by mass.
- the colored composition of the present invention preferably further contains a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light in the ultraviolet region to the visible region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
- the photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
- the photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives.
- Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
- photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, Selected from the group consisting of triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds Are preferred.
- hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
- hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a light source of 365 nm or 405 nm can also be used.
- acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
- the colored composition of the present invention when used for the production of a color filter of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it be developed. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator.
- an oxime compound as the photopolymerization initiator.
- a stepper exposure machine is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device.
- oxime compound can improve the color transfer.
- paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
- photopolymerization initiator examples include oxime compounds.
- oxime compounds compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166 can be used.
- oxime compounds examples include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
- IRGACURE-OXE01 manufactured by BASF
- IRGACURE-OXE02 manufactured by BASF
- TRONLY TR-PBG-304 TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcles 30 (Made by ADEKA) can also be used.
- oxime compounds other than those described above compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of the carbazole ring, and those described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety
- the oxime compound is preferably a compound represented by the following formula (OX-1).
- the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
- R and B each independently represent a monovalent substituent
- A represents a divalent organic group
- Ar represents an aryl group.
- the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
- the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
- these groups may have one or more substituents.
- the substituent mentioned above may be further substituted by another substituent.
- the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
- the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- an oxime compound having a fluorene ring can also be used as a photopolymerization initiator.
- Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A No. 2014-137466. This content is incorporated herein.
- an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.
- an oxime compound having a nitro group can be used as a photopolymerization initiator.
- Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, ADEKA Acruz NCI-831 (made by ADEKA) is mentioned.
- oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
- the oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably a compound having an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a compound having high absorbance at 365 nm and 405 nm.
- the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200,000 from the viewpoint of sensitivity. 000 is particularly preferred.
- a known method can be used. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is used and an ethyl acetate solvent is used. It is preferable to measure at a concentration of 0.01 g / L. You may use a photoinitiator in combination of 2 or more type as needed.
- the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5%, based on the total solid content of the colored composition. -30% by mass, more preferably 1-20% by mass. Within this range, better sensitivity and pattern formability can be obtained.
- the colored composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
- the colored composition of the present invention preferably contains a pigment derivative.
- the pigment derivative include compounds having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group, or a phthalimidomethyl group.
- the pigment derivative is preferably a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability. Particularly preferred are pigment derivatives having a basic group.
- a combination in which the resin is an acidic resin having an acid group and the pigment derivative has a basic group is preferable.
- organic pigment for constituting the pigment derivative examples include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
- a sulfonic acid group As an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its quaternary ammonium base are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable.
- the basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
- the description in paragraphs 0162 to 0183 of JP2011-252065 A can be referred to, the contents of which are incorporated herein.
- the content of the pigment derivative in the colored composition of the present invention is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the total mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
- the colored composition of the present invention may contain various surfactants from the viewpoint of further improving coatability.
- various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
- the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid-saving properties are further improved. can do. That is, when a film is formed using a coating liquid to which a coloring composition containing a fluorosurfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is reduced. Is improved, and the coating property to the coated surface is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
- the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
- fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (above, the product made by OMNOVA) etc.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
- the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
- As the fluorosurfactant a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples thereof include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, such as MegaFac RS-101, RS-102, and RS-718K manufactured by DIC.
- nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
- NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. NCW-101,
- cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
- phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
- organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
- (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
- W001 manufactured by Yusho Co., Ltd.
- anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei Co., Ltd.), and the like.
- silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.
- the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the coloring composition.
- the coloring composition of the present invention can contain a silane coupling agent.
- silane coupling agent silane compounds having at least two types of functional groups having different reactivity in one molecule are also preferable, and those having an amino group and an alkoxy group as functional groups are particularly preferable.
- silane coupling agents include N- ⁇ -aminoethyl- ⁇ -aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -amino.
- Propyl-trimethoxysilane (trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-triethoxysilane (trade name KBE-602, manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl -Trimethoxysilane (trade name KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-triethoxysilane (trade name KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Company brand name KBM-503).
- the silane coupling agent the description of paragraph numbers 0155 to 0158 in JP2013-254047A can be referred to, the contents of which are incorporated herein.
- the content of the silane coupling agent is preferably 0.001 to 20% by mass with respect to the total solid content of the coloring composition, 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable.
- the coloring composition of the present invention may contain only one type of silane coupling agent or two or more types. When two or more types are included, the total amount is preferably within the above range.
- the coloring composition of the present invention preferably contains a polymerization inhibitor.
- Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.) and the like.
- the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the colored composition.
- the coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
- additives for example, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like can be blended with the colored composition of the present invention as necessary.
- additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
- the antioxidant for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph No. 0042 of JP2011-90147A), a thioether compound, or the like can be used.
- the coloring composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the same publication.
- the colored composition may contain a metal element.
- the content of the Group 2 elements (calcium, magnesium, etc.) in the colored composition is 50 ppm or less. It is preferable that the content be controlled to 0.01 to 10 ppm.
- the total amount of the inorganic metal salt in the coloring composition is preferably 100 ppm or less, and more preferably controlled to 0.5 to 50 ppm.
- the coloring composition of the present invention can be prepared by mixing the aforementioned components. There are no particular restrictions on the order of injection and working conditions when blending.
- the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be prepared by mixing them.
- any filter can be used without particular limitation as long as it has been conventionally used for filtration.
- fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight)
- PP polypropylene
- polypropylene including high density polypropylene
- nylon are preferable.
- the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, more preferably about 0.05 to 0.5 ⁇ m. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of a uniform and smooth composition in a post process. Further, it is also preferable to use a fiber-shaped filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. , TPR005, etc.) and SHPX type series (SHPX003 etc.) filter cartridges can be used.
- the filtering by the first filter may be performed only once or may be performed twice or more.
- the pore diameter here can refer to the nominal value of the filter manufacturer.
- a commercially available filter for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) can do.
- the second filter a filter formed of the same material as the first filter described above can be used.
- the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.
- the color filter of the present invention is formed using the above-described colored composition of the present invention.
- the film thickness of the color filter of the present invention can be appropriately adjusted according to the purpose.
- the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
- the color filter of the present invention can be used for solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), image display devices, and the like.
- the pattern forming method of the present invention includes a step of forming a colored composition layer on a support using the colored composition of the present invention, and a pattern is formed on the colored composition layer by a photolithography method or a dry etching method. And a step of performing.
- Pattern formation by the photolithography method includes a step of forming a colored composition layer on a support using a colored composition, a step of exposing the colored composition layer in a pattern, and developing and removing an unexposed portion. Forming the step. As needed, you may provide the process (prebaking process) of baking a coloring composition layer, and the process (post-baking process) of baking the pattern formed by image development.
- pattern formation by the dry etching method includes forming a colored composition layer on a support using a colored composition and curing to form a cured product layer, and forming a photoresist layer on the cured product layer.
- a step of patterning the photoresist layer by exposure and development to obtain a resist pattern and a step of forming a pattern by dry etching the cured product layer using the resist pattern as an etching mask.
- Step of Forming Colored Composition Layer In the step of forming the curable composition layer, the colored composition layer is formed on the support using the colored composition.
- a solid-state image sensor substrate in which a solid-state image sensor (light receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
- the pattern in the present invention may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface).
- an undercoat layer may be provided on the support to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the substrate surface.
- various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be used.
- the colored composition layer formed on the support may be dried (prebaked).
- pre-baking may not be performed.
- the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.
- the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher.
- the prebake time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Drying can be performed with a hot plate, oven, or the like.
- Exposure process When forming a pattern by photolithography, ⁇ Exposure process >> Next, the colored composition layer is exposed in a pattern (exposure process).
- pattern exposure can be performed by exposing the coloring composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
- radiation (light) that can be used for exposure ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line).
- Irradiation dose (exposure dose) for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
- the oxygen concentration at the time of exposure can be appropriately selected.
- the exposure illuminance can be set as appropriate, and can usually be selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , 35000 W / m 2 ). .
- Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
- the unexposed portion is developed and removed to form a pattern.
- the development removal of the unexposed portion can be performed using a developer.
- the coloring composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
- the developer an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable.
- the temperature of the developer is preferably 20 to 30 ° C., for example.
- the development time is preferably 20 to 180 seconds.
- the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
- alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide.
- organic alkaline compounds such as dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene.
- an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used.
- the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
- the inorganic alkali for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.
- a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described curable composition, and a nonionic surfactant is preferable.
- clean (rinse) with a pure water after image development.
- Post-baking is a heat treatment after development for complete film curing.
- the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable.
- the post-bake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower. Preferably, 100 ° C. or lower is more preferable, and 90 ° C. or lower is particularly preferable.
- the lower limit can be, for example, 50 ° C. or higher.
- Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. . Further, when a pattern is formed by a low temperature process, post baking is not necessary.
- the pattern formation by the dry etching method is performed by curing the composition layer formed on the support to form a cured product layer, and then using the patterned photoresist layer as a mask to etch the obtained cured product layer.
- a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable.
- the descriptions in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and the contents thereof are incorporated in this specification.
- the solid-state imaging device of the present invention has the above-described color filter of the present invention.
- the configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration that includes the color filter of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.
- CCD charge coupled device
- CMOS complementary metal oxide semiconductor
- Device protection consisting of silicon nitride, etc., which has a light-shielding film that opens only on the photodiode and the transfer electrode on the photodiode and the transfer electrode, and is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part It has a film, and has a color filter on the device protective film.
- a configuration having a light condensing means for example, a micro lens, etc., the same applies hereinafter
- a structure having the light condensing means on the color filter, etc. may be.
- the color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device.
- an image display device such as a liquid crystal display device or an organic electroluminescence display device.
- display devices and details of each display device refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year).
- the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”.
- the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
- Example 101 A mixed solution composed of 30.72 parts of compound a11, 10.8 parts of resin A and 120 parts of propylene glycol methyl ether acetate (PGMEA) was mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm diameter), A pigment dispersion was prepared. To the obtained pigment dispersion, 0.60 part of phthalimide compound (FE-1) was added to produce a colored composition of Example 101.
- PGMEA propylene glycol methyl ether acetate
- Example 101 the colored compositions of Examples 102 to 104 were produced in the same manner as in Example 101, except that compounds a12 to 14 were used instead of compound a11, respectively.
- Example 105 A colored composition of Example 105 was prepared by adding 0.60 part of phthalimide compound (FE-1) to a mixed solution of 30.72 parts of compound a21, 10.8 parts of resin A and 120 parts of PGMEA. Manufactured.
- Example 105 the colored compositions of Examples 106 to 108 were produced in the same manner as in Example 105, except that compounds a31, a41, and a51 were used instead of compound a21, respectively.
- Example 201 -Production of Dispersion Y1 A mixture comprising 30.72 parts of compound a11, 10.8 parts of resin A and 120 parts of PGMEA was mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm diameter) to obtain a dispersion. Y1 was produced. -Manufacture of dispersion G1 A mixture of 30.72 parts of green pigment G1, 10.8 parts of resin A and 120 parts of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm diameter) to disperse. Liquid G1 was produced. -Manufacture of coloring composition The following component was mixed and the coloring composition of Example 201 was manufactured.
- Dispersion Y1 51 parts Dispersion G1: 110 parts Resin B: 36 parts Curable compound (M-1): 33 parts Photopolymerization initiator (I-1): 9.92 parts p-methoxyphenol: 0.04 Parts PGMEA: 160 parts Phthalimide compound (FE-1): 0.2 parts
- Example 201 dispersions Y2 to Y4 were produced in the same manner as dispersion Y1, except that compounds a12 to a14 were used instead of compound a11.
- Example 201 the colored compositions of Examples 202 to 204 were produced in the same manner as Example 201, except that dispersions Y2 to Y4 were used instead of dispersion Y1.
- Example 205 -Production of liquid mixture 1 30.72 parts of compound a21, 10.8 parts of resin A, and 120 parts of PGMEA were mixed to produce liquid mixture 1. -Manufacture of coloring composition The following component was mixed and the coloring composition of Example 205 was manufactured.
- Liquid mixture 1 51 parts Dispersion G1: 110 parts Resin B: 36 parts Curing compound (M-1): 33 parts Photopolymerization initiator (I-1): 9.92 parts p-methoxyphenol: 0.04 Parts PGMEA: 160 parts Phthalimide compound (FE-1): 0.2 parts
- Example 206 to 208 mixtures 2 to 4 were produced in the same manner as in the mixture 1, except that the compound a31, a41 or a51 was used instead of the compound a21.
- Example 205 the colored compositions of Examples 206 to 208 were produced in the same manner as in Example 205, except that the mixed liquids 2 to 4 were used instead of the mixed liquid 1.
- Examples 301 to 308 were prepared in the same manner as in Examples 201 to 208 except that 2-methoxy-1-propyl acetate was contained in an amount of 0.1% by mass with respect to the mass of the colored composition. 308 colored compositions were produced.
- Example 309 In Example 301, the coloring composition of Example 309 was changed in the same manner as in Example 301 except that the photopolymerization initiator (I-1) was changed to the same amount of photopolymerization initiator (I-2). Manufactured.
- Examples 401 to 404 A mixed solution composed of 30.72 parts of green pigment G2, 10.8 parts of resin A, and 120 parts of PGMEA was mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm diameter) to prepare dispersion G2.
- a bead mill zirconia beads 0.3 mm diameter
- colored compositions of Examples 401 to 404 were produced in the same manner as Examples 201 to 204, except that the dispersion G2 was used instead of the dispersion G1.
- Example 405 In Example 401, the coloring composition of Example 405 was changed in the same manner as in Example 401 except that the photopolymerization initiator (I-1) was changed to the same amount of photopolymerization initiator (I-2). Manufactured.
- Example 201 coloring of Examples 502 to 508 was performed in the same manner as Example 201 except that phthalimide compounds (FE-2) to (FE-8) were used instead of phthalimide compound (FE-1). A composition was prepared.
- Example 602 to 607 the colored compositions of Examples 602 to 608 were produced in the same manner as in Example 201 except that the blending amount of the phthalimide compound (FE-1) was changed to the blending amounts shown in the following table, respectively. .
- Example 702 to 707 the colored compositions of Examples 702 to 707 were produced in the same manner as Example 301 except that the content of 2-methoxy-1-propyl acetate was changed to the ratio shown in the following table. .
- Comparative Example 1, 9-15 In Examples 101 to 108, colored compositions of Comparative Examples 1 and 9 to 15 were produced in the same manner as in Examples 101 to 108, except that no phthalimide compound was used.
- Example 101 colored compositions of Comparative Examples 2 to 5 were produced in the same manner as in Example 101, except that compounds b11 to b14 were used instead of compound a11, respectively.
- Comparative Examples 6 to 8 In Examples 105 to 107, the colored compositions of Comparative Examples 6 to 8 were prepared in the same manner as in Examples 105 to 107, except that compounds b21, b31, and b41 were used instead of compounds a21, a31, and a41, respectively. Manufactured.
- Each colored composition is put in a sealed container and subjected to a temperature cycle test at 5 ° C. for 4 hours and at 25 ° C. for 2 hours for 150 days. Then, the colored composition is taken out from the sealed container, and the colored composition is placed on a glass wafer. The film was dried using a spin coater so that the film thickness after drying was 0.5 ⁇ m, and heat-treated (prebaked) for 180 seconds using a hot plate at 100 ° C. to produce a coating film for evaluation. The coating film on the glass wafer was visually observed by enlarging a 0.5 mm square area 100 times with an optical microscope, the number of defects on the film surface was counted, and the defects were evaluated according to the following criteria.
- the colored compositions of the examples were able to produce a film in which the occurrence of defects was suppressed even when the colored composition was stored for a long time in an environment with temperature fluctuations.
- the film using the coloring composition of the comparative example had many defects.
- the 0.5 mm square area was magnified 100 times with an optical microscope. The number of defects on the film surface was counted and the number of defects on the film surface was counted, and the defects after placement were evaluated. As a result, the number of defects in the sample of Comparative Example 1 was further increased as compared with the case where the samples were not placed. .
- the samples of Examples 101, 201, 301, and 401 showed no increase in defects even after placement, and it was found that the so-called “placement” performance was improved.
- Compounds b11 to b14, b21, b31, b41 the following structures.
- M in b11 is Na.
- Compound b13 is C.I. I. Pigment Yellow 150 and Compound b14 is C.I. I. Pigment Yellow 185.
- Green pigment A compound having an average number of bromine atoms of 12 and an average number of chlorine atoms of 4 among X 1 to X 16 in formula A1.
- G2 A compound in which the average number of bromine atoms is 9, the average number of chlorine atoms is 3, and the average number of hydrogen atoms is 4 among X 1 to X 16 in formula A1.
- FE-1 Compound in which A 1 to A 4 of formula PI are all bromine atoms
- FE-2 Compound in which A 1 to A 4 of formula PI are all chlorine atoms
- FE-3 A 1 to A 4 of formula PI
- Compound FE-4 in which two of them are bromine atoms and two are chlorine atoms:
- Compound FE- 5 in which two of A 1 to A 4 of formula PI are bromine atoms and two are hydrogen atoms:
- a of formula PI Compound FE-6 in which two of 1 to A 4 are bromine atoms, one is a chlorine atom and one is a hydrogen atom:
- Compound FE-7 in which all of A 1 to A 4 in formula PI are hydrogen atoms
- Formula PI Compound FE-8 in which A 1 to A 4 are all methyl groups: Compound in which A 1 to A 4 of formula PI are all n-butyl groups
- I-1 The following structure I-2: IRGACURE-OXE01 (manufactured by BASF)
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Abstract
Description
<1> 窒素原子を含む複素環含有着色剤と、フタルイミド化合物と、溶剤と、樹脂とを含み、複素環含有着色剤が下記式(1)~(4)から選ばれる少なくとも1種である、着色組成物;
式(2)において、R205およびR208は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、R201~R204、R206およびR207は、それぞれ独立に、水素原子または置換基を表し、Y1は、窒素原子または-CRY1-を表し、Y2は、硫黄原子または-NRY2-を表し、RY1およびRY2は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、Xは、ビス(スルホニル)イミドアニオン、トリス(スルホニル)メチドアニオンまたはホウ素原子を有するアニオンを表す;
式(3)において、R301、R311およびR310は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、R302~R305、R306~R309は、それぞれ独立に、水素原子または置換基を表し、Xは、ビス(スルホニル)イミドアニオン、トリス(スルホニル)メチドアニオンまたはホウ素原子を有するアニオンを表す;
式(4)において、R401およびR402は、それぞれ独立に、SO2R403またはCOR403を表す;R403は、アルキル基、アリール基またはヘテロアリール基を表す。
<2> フタルイミド化合物が、下記式(PI)で表される化合物である、<1>に記載の着色組成物;
<3> フタルイミド化合物は、式(PI)のA1~A4の少なくとも一つが、臭素原子である、<2>に記載の着色組成物。
<4> 式(1)~(4)で表される化合物の合計100質量部に対し、フタルイミド化合物を0.001~6.0質量部含有する、<1>~<3>のいずれかに記載の着色組成物。
<5> さらに、硬化性化合物を含有する、<1>~<4>のいずれかに記載の着色組成物。
<6> 硬化性化合物が、ラジカル重合性化合物を含み、さらに、光重合開始剤を含有する、<5>に記載の着色組成物。
<7> <1>~<6>のいずれかに記載の着色組成物を用いたカラーフィルタ。
<8> <1>~<6>のいずれかに記載の着色組成物を用いて支持体上に着色組成物層を形成する工程と、フォトリソグラフィ法またはドライエッチング法により、着色組成物層に対してパターンを形成する工程と、を有するパターン形成方法。
<9> <7>に記載のカラーフィルタを有する固体撮像素子。
<10> <7>に記載のカラーフィルタを有する画像表示装置。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書において光とは、活性光線または放射線を意味する。また、「活性光線」または「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等を意味する。
本明細書において「露光」とは、特に断らない限り、水銀灯、エキシマレーザーに代表される遠紫外線、X線、EUV光などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も露光に含める。
本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本明細書において、全固形分とは、着色組成物の全成分から溶剤を除いた成分の総質量をいう。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「(メタ)アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「(メタ)アリル」は、アリルおよびメタリルの双方、または、いずれかを表し、「(メタ)アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィ(GPC)測定によるポリスチレン換算値として定義される。
本発明において、顔料は、特定の溶剤に対し溶解しにくい不溶性の化合物を意味する。典型的には、組成物中に粒子として分散された状態で存在する化合物を意味する。ここで、溶剤とは、例えば後述する溶剤の欄で例示する溶剤が挙げられる。
本発明の着色組成物は、後述する式(1)~(4)から選ばれる少なくとも1種の化合物と、フタルイミド化合物と、溶剤と、樹脂とを含む。
後述する式(1)~(4)で表される化合物と、溶剤と、樹脂とを含み、かつ、フタルイミド化合物を含まない着色組成物を、温度変動のある環境下で長期間保管すると、欠陥が生じることがあったが、さらにフタルイミド化合物を含有させることにより、着色組成物を温度変動のある環境下で長期間保管した場合であっても、欠陥の発生が抑制された膜などを製造できる。このような効果が得られるメカニズムは、次によるものであると推測する。
本発明の着色組成物は、式(1)~(4)で表される化合物に加えて、さらに、フタルイミド化合物を含む。フタルイミド化合物は、式(1)~(4)で表される化合物と相互作用しやすいと考えられ、フタルイミド化合物が、式(1)~(4)で表される化合物の表面に吸着して、保管時の温度変動に伴う上記化合物の析出を抑制し、その結果、欠陥の発生が抑制された膜などを製造できると推定される。
本発明の着色組成物は、式(1)~(4)で表される化合物に加えて、さらに、フタルイミド化合物を含むので、式(1)~(4)で表される化合物とフタルイミド化合物とが相互作用して、式(1)~(4)で表される化合物の結晶化を抑制でき、その結果、欠陥の発生が抑制された膜などを製造できると推定する。
以下、本発明の着色組成物について詳細に説明する。
本発明の着色組成物は、下記式(1)~(4)から選ばれる少なくとも1種の化合物(複素環含有着色剤)を含む。式(1)~(4)の化合物は、黄色着色剤として好ましく用いることができる。本発明において、複素環含有着色剤は、式(1)で表される化合物が好ましい。この態様によれば、欠陥の抑制された膜をより製造しやすい。以下、式(1)で表される化合物、式(2)で表される化合物、式(3)で表される化合物および式(4)で表される化合物を、それぞれ、化合物(1)、化合物(2)、化合物(3)、化合物(4)ともいう。
式(2)において、R205およびR208は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、R201~R204、R206およびR207は、それぞれ独立に、水素原子または置換基を表し、Y1は、窒素原子または-CRY1-を表し、Y2は、硫黄原子または-NRY2-を表し、RY1およびRY2は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、Xは、ビス(スルホニル)イミドアニオン、トリス(スルホニル)メチドアニオンまたはホウ素原子を有するアニオンを表す。
式(3)において、R301、R311およびR310は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、R302~R305、R306~R309は、それぞれ独立に、水素原子または置換基を表し、Xは、ビス(スルホニル)イミドアニオン、トリス(スルホニル)メチドアニオンまたはホウ素原子を有するアニオンを表す。
式(4)において、R401およびR402は、それぞれ独立に、SO2R403またはCOR403を表す;R403は、アルキル基、アリール基またはヘテロアリール基を表す。
式(1)において、R1~R13は、それぞれ独立に、水素原子または置換基を表す。置換基としては、後述する置換基T群で説明した基が挙げられ、ハロゲン原子、アルキル基、アルコキシ基、アリール基、ヘテロアリール基、スルホ基、カルボキシル基、スルホ基の金属塩、カルボキシル基の金属塩、スルホ基のアルキルアンモニウム塩、カルボキシル基のアルキルアンモニウム塩、フタルイミドメチル基、または、スルファモイル基が好ましく、ハロゲン原子がより好ましい。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、塩素原子または臭素原子が好ましい。
式(1a)~(1c)のR9~R13の少なくとも一つは、水素原子であることが好ましく、R9~R13のすべてが水素原子であることがより好ましい。
式(1a)~(1c)のR1~R8、および、R101~R108が、それぞれ独立に、水素原子またはハロゲン原子が好ましい。
<1> 式(1a)において、R9~R13の少なくとも一つが水素原子であり、R1、R4、R101~R104の少なくとも一つが水素原子であり、R5~R8の少なくとも一つがハロゲン原子である態様。さらに好ましくは、R9~R13が水素原子であり、R1、R4、R101~R104が水素原子であり、R5~R8がハロゲン原子である態様。
<2> 式(1b)において、R9~R13の少なくとも一つが水素原子であり、R1~R4の少なくとも一つがハロゲン原子であり、R5、R8、R105~R108の少なくとも一つが水素原子である態様。さらに好ましくは、R9~R13が水素原子であり、R1~R4がハロゲン原子であり、R5、R8、R105~R108が水素原子である態様。
<3> 式(1c)において、R9~R13の少なくとも一つが水素原子であり、R1、R4、R101~R104の少なくとも一つが水素原子であり、R5、R8、R105~R108の少なくとも一つが水素原子である態様。さらに好ましくは、R1~R13およびR101~R108が水素原子である態様。
式(2)において、R205およびR208は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、水素原子またはアルキル基が好ましく、アルキル基がより好ましい。アルキル基、アリール基およびヘテロアリール基は、無置換のアルキル基、無置換のアリール基および無置換のヘテロアリール基であってもよく、置換基をさらに有していてもよい。置換基としては、後述する置換基T群で説明する基が挙げられる。
アルキル基の炭素数は、1~20が好ましく、1~10がより好ましく、1~3が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。
アリール基の炭素数は、6~30が好ましく、6~20がより好ましく、6~12が更に好ましい。アリール基は、フェニル基が好ましい。
ヘテロアリール基は、単環または縮合環が好ましく、単環または縮合数が2~8の縮合環が好ましく、単環または縮合数が2~4の縮合環がより好ましい。ヘテロアリール基の環を構成するヘテロ原子の数は1~3が好ましい。ヘテロアリール基の環を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。ヘテロアリール基は、5員環または6員環が好ましい。ヘテロアリール基の環を構成する炭素原子の数は3~30が好ましく、3~18がより好ましく、3~12が更に好ましい。
R201~R204は、それぞれ独立に、水素原子、アルキル基またはハロゲン原子が好ましく、水素原子がより好ましい。アルキル基としては、上述したR205およびR208で説明したアルキル基が挙げられる。
R206は、水素原子、アルキル基、アリール基またはヘテロアリール基が好ましく、水素原子、アルキル基またはアリール基がより好ましく、アリール基がさらに好ましい。アルキル基、アリール基およびヘテロアリール基としては、上述したR205およびR208で説明したアルキル基、アリール基およびヘテロアリール基が挙げられる。
R207は、水素原子またはアルキル基が好ましく、水素原子がより好ましい。アルキル基としては、上述したR205およびR208で説明したアルキル基が挙げられる。
<1>Y1が窒素原子で、Y2が-NRY2-である組み合わせ。
<2>Y1が-CRY1-で、Y2が硫黄原子である組み合わせ。
X1およびX2は、それぞれ独立に、フッ素原子またはフッ素原子を有するアルキル基が好ましく、フッ素原子を有するアルキル基がより好ましい。フッ素原子を有するアルキル基は、フッ素原子を有する炭素数1~10のアルキル基が好ましく、炭素数1~10のペルフルオロアルキル基であることがより好ましく、炭素数1~4のペルフルオロアルキル基であることがさらに好ましく、トリフルオロメチル基が特に好ましい。
X3、X4およびX5は、それぞれ独立に、フッ素原子またはフッ素原子を有するアルキル基が好ましく、フッ素原子を有するアルキル基がより好ましい。フッ素原子を有するアルキル基は、フッ素原子を有する炭素数1~10のアルキル基が好ましく、炭素数1~10のペルフルオロアルキル基であることがより好ましく、炭素数1~4のペルフルオロアルキル基であることがさらに好ましく、トリフルオロメチル基が特に好ましい。
以下に、アニオンの具体例を示すが本発明はこれらに限定されるものではない。
式(3)において、R301、R311およびR310は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、水素原子またはアルキル基が好ましく、アルキル基がより好ましい。アルキル基、アリール基およびヘテロアリール基は、無置換のアルキル基、無置換のアリール基および無置換のヘテロアリール基であってもよく、置換基をさらに有していてもよい。置換基としては、後述する置換基T群で説明する基が挙げられる。
アルキル基の炭素数は、1~20が好ましく、1~10がより好ましく、1~3が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。
アリール基の炭素数は、6~30が好ましく、6~20がより好ましく、6~12が更に好ましい。アリール基は、フェニル基が好ましい。
ヘテロアリール基は、単環または縮合環が好ましく、単環または縮合数が2~8の縮合環が好ましく、単環または縮合数が2~4の縮合環がより好ましい。ヘテロアリール基の環を構成するヘテロ原子の数は1~3が好ましい。ヘテロアリール基の環を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。ヘテロアリール基は、5員環または6員環が好ましい。ヘテロアリール基の環を構成する炭素原子の数は3~30が好ましく、3~18がより好ましく、3~12が更に好ましい。
式(3)において、R302およびR305は水素原子であることが好ましい。また、R303およびR304は、水素原子または置換基であることが好ましい。また、R306~R309は、水素原子であることが好ましい。
式(4)において、R401およびR402は、それぞれ独立に、SO2R403またはCOR403を表し、R403は、アルキル基、アリール基またはヘテロアリール基を表す。R403は、アルキル基またはアリール基が好ましく、アルキル基がより好ましい。R403が表すアルキル基、アリール基およびヘテロアリール基は、無置換のアルキル基、無置換のアリール基および無置換のヘテロアリール基であってもよく、置換基をさらに有していてもよい。置換基としては、後述する置換基T群で説明した基が挙げられる。例えば、ハロゲン原子、アルキル基、アリール基、アルコキシ基、アシル基、アルキルカルボニルオキシ基、アリールカルボニルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アルキルスルホニル基、アリールスルホニル基、アルキルスルフィニル基、アリールスルフィニル基などが挙げられる。
アルキル基の炭素数は、4~18が好ましく、6~18がより好ましく、6~12が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、3-ヘプチル基、オクチル基、2-エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、メトキシエトキシエチル基、エトキシカルボニルエチル基等が挙げられる。
アリール基の炭素数は、6~18が好ましく、6~12がより好ましい。アリール基の具体例としては、フェニル基、2-メチルフェニル基、4-エトキシカルボニルフェニル基、4-クロロフェニル基、3-(2-エチルヘキシルオキシカルボニル)フェニル基が挙げられる。
ヘテロアリール基は、単環または縮合環が好ましく、単環または縮合数が2~8の縮合環が好ましく、単環または縮合数が2~4の縮合環がより好ましい。ヘテロアリール基の環を構成するヘテロ原子の数は1~3が好ましい。ヘテロアリール基の環を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。ヘテロアリール基は、5員環または6員環が好ましい。ヘテロアリール基の環を構成する炭素原子の数は3~30が好ましく、3~18がより好ましく、3~12がより好ましい。
ハロゲン原子(例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子);
直鎖もしくは分岐のアルキル基(直鎖または分岐の置換もしくは無置換のアルキル基で、好ましくは炭素数1~30のアルキル基であり、例えばメチル、エチル、n-プロピル、イソプロピル、tert-ブチル、n-オクチル、2-クロロエチル、2-シアノエチル、2-エチルヘキシル);
シクロアルキル基(好ましくは、炭素数3~30の置換または無置換のシクロアルキル基、例えば、シクロヘキシル、シクロペンチルが挙げられ、多シクロアルキル基、例えば、ビシクロアルキル基(好ましくは、炭素数5~30の置換もしくは無置換のビシクロアルキル基で、例えば、ビシクロ[1,2,2]ヘプタン-2-イル、ビシクロ[2,2,2]オクタン-3-イル)やトリシクロアルキル基等の多環構造の基が挙げられる。好ましくは単環のシクロアルキル基、ビシクロアルキル基であり、単環のシクロアルキル基が特に好ましい);
直鎖もしくは分岐のアルケニル基(直鎖または分岐の置換もしくは無置換のアルケニル基で、好ましくは炭素数2~30のアルケニル基であり、例えば、ビニル、アリル、プレニル、ゲラニル、オレイル);
シクロアルケニル基(好ましくは、炭素数3~30の置換もしくは無置換のシクロアルケニル基で、例えば、2-シクロペンテン-1-イル、2-シクロヘキセン-1-イルが挙げられ、多シクロアルケニル基、例えば、ビシクロアルケニル基(好ましくは、炭素数5~30の置換もしくは無置換のビシクロアルケニル基で、例えば、ビシクロ[2,2,1]ヘプト-2-エン-1-イル、ビシクロ[2,2,2]オクト-2-エン-4-イル)やトリシクロアルケニル基であり、単環のシクロアルケニル基が特に好ましい。);
アルキニル基(好ましくは、炭素数2~30の置換または無置換のアルキニル基、例えば、エチニル、プロパルギル、トリメチルシリルエチニル基);
アリール基(好ましくは炭素数6~30の置換もしくは無置換のアリール基で、例えばフェニル、p-トリル、ナフチル、m-クロロフェニル、o-ヘキサデカノイルアミノフェニル);
ヘテロアリール基(好ましくは5~7員の置換もしくは無置換、単環もしくは縮環のヘテロアリール基であり、より好ましくは、環構成原子が炭素原子と、酸素原子、窒素原子および硫黄原子から選択されるヘテロ原子を少なくとも一個有するヘテロアリール基であり、更に好ましくは、炭素数3~30の5もしくは6員のヘテロアリール基である。);
シアノ基;
ヒドロキシル基;
ニトロ基;
カルボキシル基(水素原子が解離していてもよく(すなわち、カルボネート基)、塩の状態(金属塩(例えば、ナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩、鉄塩、アルミニウム塩等)、アルキルアンモニウム塩(例えば、オクチルアミン、ラウリルアミン、ステアリルアミン等の長鎖モノアルキルアミンのアンモニウム塩、パルミチルトリメチルアンモニウム塩、ジラウリルジメチルアンモニウム塩、ジステアリルジメチルアンモニウム塩等の4級アルキルアンモニウム塩)など)であってもよい);
アルコキシ基(好ましくは、炭素数1~30の置換もしくは無置換のアルコキシ基で、例えば、メトキシ、エトキシ、イソプロポキシ、tert-ブトキシ、n-オクチルオキシ、2-メトキシエトキシ);
アリールオキシ基(好ましくは、炭素数6~30の置換もしくは無置換のアリールオキシ基で、例えば、フェノキシ、2-メチルフェノキシ、2,4-ジ-tert-アミルフェノキシ、4-tert-ブチルフェノキシ、3-ニトロフェノキシ、2-テトラデカノイルアミノフェノキシ);
シリルオキシ基(好ましくは、炭素数3~20のシリルオキシ基で、例えば、トリメチルシリルオキシ、tert-ブチルジメチルシリルオキシ);
ヘテロアリールオキシ基(好ましくは、炭素数2~30の置換もしくは無置換のヘテロアリールオキシ基で、ヘテロアリール部は前述のヘテロアリール基で説明されたヘテロアリール部が好ましく、例えば、1-フェニルテトラゾール-5-オキシ、2-テトラヒドロピラニルオキシ);
アシルオキシ基(好ましくは、炭素数2~30の置換もしくは無置換のアルキルカルボニルオキシ基、炭素数6~30の置換もしくは無置換のアリールカルボニルオキシ基であり、例えば、ホルミルオキシ、アセチルオキシ、ピバロイルオキシ、ステアロイルオキシ、ベンゾイルオキシ、p-メトキシフェニルカルボニルオキシ);
カルバモイルオキシ基(好ましくは、炭素数1~30の置換もしくは無置換のカルバモイルオキシ基で、例えば、N,N-ジメチルカルバモイルオキシ、N,N-ジエチルカルバモイルオキシ、モルホリノカルボニルオキシ、N,N-ジ-n-オクチルアミノカルボニルオキシ、N-n-オクチルカルバモイルオキシ);
アルコキシカルボニルオキシ基(好ましくは、炭素数2~30の置換もしくは無置換のアルコキシカルボニルオキシ基で、例えばメトキシカルボニルオキシ、エトキシカルボニルオキシ、tert-ブトキシカルボニルオキシ、n-オクチルカルボニルオキシ);
アリールオキシカルボニルオキシ基(好ましくは、炭素数7~30の置換もしくは無置換のアリールオキシカルボニルオキシ基で、例えば、フェノキシカルボニルオキシ、p-メトキシフェノキシカルボニルオキシ、p-n-ヘキサデシルオキシフェノキシカルボニルオキシ);
アミノ基(アルキルアミノ基、アリールアミノ基およびヘテロアリールアミノ基を含む。好ましくは、アミノ基、炭素数1~30の置換もしくは無置換のアルキルアミノ基、炭素数6~30の置換もしくは無置換のアリールアミノ基、炭素数0~30のヘテロアリールアミノ基であり、例えば、アミノ、メチルアミノ、ジメチルアミノ、アニリノ、N-メチル-アニリノ、ジフェニルアミノ、N-1,3,5-トリアジン-2-イルアミノ);
アシルアミノ基(好ましくは、炭素数1~30の置換もしくは無置換のアルキルカルボニルアミノ基、炭素数6~30の置換もしくは無置換のアリールカルボニルアミノ基であり、例えば、ホルミルアミノ、アセチルアミノ、ピバロイルアミノ、ラウロイルアミノ、ベンゾイルアミノ、3,4,5-トリ-n-オクチルオキシフェニルカルボニルアミノ);
アミノカルボニルアミノ基(好ましくは、炭素数1~30の置換もしくは無置換のアミノカルボニルアミノ基、例えば、カルバモイルアミノ、N,N-ジメチルアミノカルボニルアミノ、N,N-ジエチルアミノカルボニルアミノ、モルホリノカルボニルアミノ);
アルコキシカルボニルアミノ基(好ましくは、炭素数2~30の置換もしくは無置換のアルコキシカルボニルアミノ基で、例えば、メトキシカルボニルアミノ、エトキシカルボニルアミノ、tert-ブトキシカルボニルアミノ、n-オクタデシルオキシカルボニルアミノ、N-メチル-メトキシカルボニルアミノ);
アリールオキシカルボニルアミノ基(好ましくは、炭素数7~30の置換もしくは無置換のアリールオキシカルボニルアミノ基で、例えば、フェノキシカルボニルアミノ、p-クロロフェノキシカルボニルアミノ、m-n-オクチルオキシフェノキシカルボニルアミノ);
スルファモイルアミノ基(好ましくは、炭素数0~30の置換もしくは無置換のスルファモイルアミノ基で、例えば、スルファモイルアミノ、N,N-ジメチルアミノスルホニルアミノ、N-n-オクチルアミノスルホニルアミノ);
アルキル又はアリールスルホニルアミノ基(好ましくは炭素数1~30の置換もしくは無置換のアルキルスルホニルアミノ基、炭素数6~30の置換もしくは無置換のアリールスルホニルアミノ基であり、例えば、メチルスルホニルアミノ、ブチルスルホニルアミノ、フェニルスルホニルアミノ、2,3,5-トリクロロフェニルスルホニルアミノ、p-メチルフェニルスルホニルアミノ);
メルカプト基;
アルキルチオ基(好ましくは、炭素数1~30の置換もしくは無置換のアルキルチオ基で、例えばメチルチオ、エチルチオ、n-ヘキサデシルチオ);
アリールチオ基(好ましくは炭素数6~30の置換もしくは無置換のアリールチオ基で、例えば、フェニルチオ、p-クロロフェニルチオ、m-メトキシフェニルチオ);
ヘテロアリールチオ基(好ましくは、炭素数2~30の置換または無置換のヘテロアリールチオ基で、ヘテロアリール部は前述のヘテロアリール基で説明したヘテロアリール部が好ましく、例えば、2-ベンゾチアゾリルチオ、1-フェニルテトラゾール-5-イルチオ);
スルファモイル基(好ましくは、炭素数0~30の置換もしくは無置換のスルファモイル基で、例えば、N-エチルスルファモイル、N-(3-ドデシルオキシプロピル)スルファモイル、N,N-ジメチルスルファモイル、N-アセチルスルファモイル、N-ベンゾイルスルファモイル、N-(N’-フェニルカルバモイル)スルファモイル);
スルホ基(水素原子が解離していてもよく(すなわち、スルホネート基)、塩の状態(金属塩(例えば、ナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩、鉄塩、アルミニウム塩等)、アルキルアンモニウム塩(例えば、オクチルアミン、ラウリルアミン、ステアリルアミン等の長鎖モノアルキルアミンのアンモニウム塩、パルミチルトリメチルアンモニウム塩、ジラウリルジメチルアンモニウム塩、ジステアリルジメチルアンモニウム塩等の4級アルキルアンモニウム塩)など)であってもよい);
アルキル又はアリールスルフィニル基(好ましくは、炭素数1~30の置換または無置換のアルキルスルフィニル基、炭素数6~30の置換または無置換のアリールスルフィニル基であり、例えば、メチルスルフィニル、エチルスルフィニル、フェニルスルフィニル、p-メチルフェニルスルフィニル);
アルキル又はアリールスルホニル基(好ましくは、炭素数1~30の置換または無置換のアルキルスルホニル基、炭素数6~30の置換または無置換のアリールスルホニル基であり、例えば、メチルスルホニル、エチルスルホニル、フェニルスルホニル、p-メチルフェニルスルホニル);
アシル基(好ましくはホルミル基、炭素数2~30の置換または無置換のアルキルカルボニル基、炭素数7~30の置換もしくは無置換のアリールカルボニル基であり、例えば、アセチル、ピバロイル、2-クロロアセチル、ステアロイル、ベンゾイル、p-n-オクチルオキシフェニルカルボニル);
アリールオキシカルボニル基(好ましくは、炭素数7~30の置換もしくは無置換のアリールオキシカルボニル基で、例えば、フェノキシカルボニル、o-クロロフェノキシカルボニル、m-ニトロフェノキシカルボニル、p-tert-ブチルフェノキシカルボニル);
アルコキシカルボニル基(好ましくは、炭素数2~30の置換もしくは無置換のアルコキシカルボニル基で、例えば、メトキシカルボニル、エトキシカルボニル、tert-ブトキシカルボニル、n-オクタデシルオキシカルボニル);
カルバモイル基(好ましくは、炭素数1~30の置換もしくは無置換のカルバモイル基、例えば、カルバモイル、N-メチルカルバモイル、N,N-ジメチルカルバモイル、N,N-ジ-n-オクチルカルバモイル、N-(メチルスルホニル)カルバモイル);
アリール又はヘテロアリールアゾ基(好ましくは炭素数6~30の置換もしくは無置換のアリールアゾ基、炭素数3~30の置換もしくは無置換のヘテロアリールアゾ基(ヘテロアリール部は前述のヘテロアリール基で説明したヘテロアリール部が好ましい)、例えば、フェニルアゾ、p-クロロフェニルアゾ、5-エチルチオ-1,3,4-チアジアゾール-2-イルアゾ);
イミド基(好ましくは、炭素数2~30の置換もしくは無置換のイミド基で、例えばN-スクシンイミド、メチルフタルイミド);
ホスフィノ基(好ましくは、炭素数2~30の置換もしくは無置換のホスフィノ基、例えば、ジメチルホスフィノ、ジフェニルホスフィノ、メチルフェノキシホスフィノ);
ホスフィニル基(好ましくは、炭素数2~30の置換もしくは無置換のホスフィニル基で、例えば、ホスフィニル、ジオクチルオキシホスフィニル、ジエトキシホスフィニル);
ホスフィニルオキシ基(好ましくは、炭素数2~30の置換もしくは無置換のホスフィニルオキシ基で、例えば、ジフェノキシホスフィニルオキシ、ジオクチルオキシホスフィニルオキシ);
ホスフィニルアミノ基(好ましくは、炭素数2~30の置換もしくは無置換のホスフィニルアミノ基で、例えば、ジメトキシホスフィニルアミノ、ジメチルアミノホスフィニルアミノ);
シリル基(好ましくは、炭素数3~30の置換もしくは無置換のシリル基で、例えば、トリメチルシリル、tert-ブチルジメチルシリル、フェニルジメチルシリル)が挙げられる。
これらの基は、さらに置換可能な基である場合、さらに置換基を有してもよい。さらなる置換基としては、上述した置換基T群で説明した基が挙げられる。
本発明の着色組成物は、上述した化合物(1)~(4)以外の着色剤(他の着色剤)をさらに用いることができる。本発明の着色組成物は、他の着色剤を含んでいる方が好ましい。他の着色剤は、染料および顔料のいずれでもよく、両者を併用してもよい。顔料が好ましい。顔料としては、従来公知の種々の無機顔料又は有機顔料を挙げることができる。また、無機顔料であれ有機顔料であれ、高透過率であることが好ましいことを考慮すると、平均粒子径がなるべく小さい顔料の使用が好ましく、ハンドリング性をも考慮すると、上記顔料の平均粒子径は、0.01~0.1μmが好ましく、0.01~0.05μmがより好ましい。
カラーインデックス(C.I.)ピグメントイエロー1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214等、
C.I.ピグメントオレンジ 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等、
C.I.ピグメントレッド 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279
C.I.ピグメントグリーン 7,10,36,37,58,59
C.I.ピグメントバイオレット 1,19,23,27,32,37,42
C.I.ピグメントブルー 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80
<1> フタロシアニン1分子中のハロゲン原子の平均個数が8~12個であるハロゲン化亜鉛フタロシアニン顔料。この態様において、X1~X16は、塩素原子、臭素原子、水素原子を1個以上含むことが好ましい。また、X1~X16は、塩素原子が0~4個、臭素原子が8~12個、水素原子が0~4個であることが好ましい。具体例としては、特開2007-284592号公報の段落番号0013~0039、0084~0085の記載を参酌することができ、これらの内容は本明細書に組み込まれる。
<2> フタロシアニン1分子中のハロゲン原子の平均個数が14~16個であるハロゲン化亜鉛フタロシアニン顔料。この態様において、フタロシアニン1分子中のハロゲン原子の平均個数は、15~16個がより好ましい。また、フタロシアニン1分子中の臭素原子の平均個数が0~12個であることが好ましく、1~8個がより好ましく、1~7個がさらに好ましく、2~7個が一層好ましい。
<3> フタロシアニン1分子中のハロゲン原子の平均個数が10~14個であり、臭素原子の平均個数が8~12個であり、塩素原子の平均個数が2~5個であるハロゲン化亜鉛フタロシアニン顔料。具体例としては、WO2015/118720公報に記載の化合物が挙げられる。
本発明の着色組成物は、フタルイミド化合物を含有する。
フタルイミド化合物は、上記化合物(1)~(4)と相互作用を生じて、着色組成物を温度変動のある環境下で長期間保管した場合であっても、欠陥の発生が抑制された膜などを製造できる。本発明で用いるフタルイミド化合物は、下記一般式(PI)で表される化合物であることが好ましい。
特に式(1)で表される化合物と、フタルイミド化合物とを併用することで、塗布膜を作製した後に、塗布膜の状態で保管(引き置き)しても、異物の発生を抑制できる。
ハロゲン原子としては、塩素原子、臭素原子、フッ素原子が挙げられ、塩素原子またはフッ素原子が好ましい。
アルキル基の炭素数は、1~10が好ましく、1~5がより好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましく、直鎖がより好ましい。
A1~A4の少なくとも一つは、塩素原子、および、臭素原子から選ばれることが好ましく、臭素原子であることがより好ましい。また、A1~A4の全てが、塩素原子、および、臭素原子から選ばれることがより好ましく、A1~A4の全てが、臭素原子であることがより好ましい。
また、本発明の着色組成物において、フタルイミド化合物の含有量は、着色組成物中の全固形分に対して、0.001~5質量%が好ましい。下限は0.01質量%以上が好ましく、0.1質量%以上がより好ましく、0.15質量%以上がさらに好ましい。上限は、3質量%以下が好ましく、1質量%以下がより好ましく、0.9質量%以下がさらに好ましく、0.8質量%以下が特に好ましい。
フタルイミド化合物の含有量が上記範囲であれば、本発明の効果がより顕著に得られやすい。
フタルイミド化合物は、1種であってもよく、2種以上であってもよい。2種以上含む場合は、合計が上記範囲となることが好ましい。
本発明の着色組成物は、樹脂を含む。樹脂は、例えば、着色剤を組成物中で分散させる用途、バインダーの用途で配合される。なお、主に顔料などの着色剤を分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で使用することもできる。
本発明の着色組成物は、樹脂として分散剤を含むことが好ましい。特に、着色剤として顔料を用いた場合、分散剤を含むことが好ましい。分散剤は、酸性分散剤(酸性樹脂)、塩基性分散剤(塩基性樹脂)が挙げられる。
分散剤は、酸性分散剤を少なくとも含むことが好ましく、酸性分散剤のみであることがより好ましい。分散剤が、酸性分散剤を少なくとも含むことにより、着色剤の分散性が向上し、輝度ムラが生じにくくなる。更には、優れた現像性が得られるので、フォトリソグラフィにて、好適にパターン形成を行うことができる。なお、分散剤が酸性分散剤のみであるとは、例えば、分散剤の全質量中における、酸性分散剤の含有量が99質量%以上であることが好ましく、99.9質量%以上とすることもできる。
また、塩基性分散剤(塩基性樹脂)とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤(塩基性樹脂)は、酸基の量と塩基性基の量の合計量を100モル%としたときに、塩基性基の量が50モル%以上を占める樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミンが好ましい。
酸性分散剤(酸性樹脂)の酸価は、40~105mgKOH/gが好ましく、50~105mgKOH/gがより好ましく、60~105mgKOH/gがさらに好ましい。
なお、上記分散剤として説明した樹脂は、分散剤以外の用途で使用することもできる。例えば、バインダーとして用いることもできる。
本発明の着色組成物は、樹脂としてアルカリ可溶性樹脂を含有することができる。アルカリ可溶性樹脂を含有することにより、現像性・パターン形成性が向上する。なお、アルカリ可溶性樹脂は、分散剤やバインダーとして用いることもできる。
アルカリ可溶性樹脂としては、線状有機高分子重合体であってもよく、分子(好ましくは、アクリル系共重合体、スチレン系共重合体を主鎖とする分子)中に少なくとも1つのアルカリ可溶性を促進する基を有するアルカリ可溶性樹脂の中から適宜選択することができる。
アルカリ可溶性を促進する基(以下、酸基ともいう)としては、例えば、カルボキシル基、リン酸基、スルホン酸基、フェノール性ヒドロキシル基などが挙げられるが、有機溶剤に可溶で弱アルカリ水溶液により現像可能なものが好ましく、(メタ)アクリル酸が特に好ましいものとして挙げられる。これら酸基は、1種のみであってもよいし、2種以上であってもよい。
本発明の着色組成物は、溶剤を含有することが好ましい。溶剤は有機溶剤が好ましい。溶剤は、各成分の溶解性や着色組成物の塗布性を満足すれば特に制限はない。
また、2-メトキシ-1-プロピルアセテートの含有量は、溶剤の質量に対して、0.01~0.5質量%が好ましい。下限は、0.05質量%以上が好ましく、0.1質量%以上がより好ましい。上限は、0.4質量%以下が好ましく、0.2質量%以下がより好ましい。
本発明の着色組成物は、硬化性化合物を含有することが好ましい。硬化性化合物としては、ラジカル、酸、熱により架橋可能な公知の化合物を用いることができる。例えば、エチレン性不飽和結合を有する基、環状エーテル(エポキシ、オキセタン)基、メチロール基等を有する化合物が挙げられる。エチレン性不飽和結合を有する基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基などが挙げられる。
本発明において、硬化性化合物は、重合性化合物が好ましく、ラジカル重合性化合物がより好ましい。
本発明において、重合性化合物は、例えば、モノマー、プレポリマー、すなわち2量体、3量体及びオリゴマー、又はそれらの混合物並びにそれらの多量体などの化学的形態のいずれであってもよい。重合性化合物が光ラジカル重合性化合物の場合は、モノマーが好ましい。
重合性化合物の分子量は、100~3000が好ましい。上限は、2000以下が好ましく、1500以下が更に好ましい。下限は、150以上が好ましく、250以上が更に好ましい。
重合性化合物は、3~15官能の(メタ)アクリレート化合物であることが好ましく、3~6官能の(メタ)アクリレート化合物であることがより好ましい。これらの具体的な化合物としては、特開2009-288705号公報の段落番号0095~0108、特開2013-29760号公報の段落番号0227、特開2008-292970号公報の段落番号0254~0257に記載の化合物を参酌でき、これらの内容は本明細書に組み込まれる。
カプロラクトン構造を有する重合性化合物は、例えば、日本化薬(株)からKAYARAD DPCAシリーズとして市販されており、DPCA-20、DPCA-30、DPCA-60、DPCA-120等が挙げられる。
市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ社製)、UA-7200(新中村化学工業社製)、DPHA-40H(日本化薬社製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共栄社化学(株)製)などが挙げられる。
また、重合性化合物の含有量は、硬化性化合物の全質量に対して、10~100質量%が好ましく、30~100質量%がより好ましい。
本発明では、硬化性化合物として、エポキシ基を有する化合物を用いることもできる。エポキシ基を有する化合物としては、1分子内にエポキシ基を2つ以上有する化合物が好ましい。エポキシ基は、1分子内に2~100個有することが好ましい。上限は、例えば、10個以下とすることもでき、5個以下とすることもできる。
脂肪族環を有する化合物の場合、エポキシ基は、脂肪族環に直接結合(単結合)してなる化合物が好ましい。芳香族環を有する化合物の場合、エポキシ基は、芳香族環に、連結基を介して結合してなる化合物が好ましい。連結基は、アルキレン基、または、アルキレン基と-O-との組み合わせからなる基が好ましい。
また、エポキシ基を有する化合物は、2以上の芳香族環が炭化水素基で連結した構造を有する化合物を用いることもできる。炭化水素基は、炭素数1~6のアルキレン基が好ましい。エポキシ基は、上記連結基を介して連結していることが好ましい。
また、エポキシ基を有する化合物の含有量は、硬化性化合物の全質量に対して、1~80質量%が好ましく、1~50質量%がより好ましい。
また、重合性化合物と、エポキシ基を有する化合物とを併用する場合、重合性化合物と、エポキシ基を有する化合物との質量比は、重合性化合物:エポキシ基を有する化合物=100:1~100:400が好ましく、100:1~100:100がより好ましい。
本発明の着色組成物は、重合性化合物の反応を促進させたり、硬化温度を下げる目的で、硬化促進剤を添加してもよい。硬化促進剤としては、分子内に2個以上のメルカプト基を有する多官能チオール化合物などが挙げられる。多官能チオール化合物は安定性、臭気、解像性、現像性、密着性等の改良を目的として添加してもよい。多官能チオール化合物は、2級のアルカンチオール類であることが好ましく、特に下記一般式(T1)で表される構造を有する化合物であることが好ましい。
一般式(T1)
本発明の着色組成物は、さらに光重合開始剤を含有することが好ましい。光重合開始剤としては、重合性化合物の重合を開始する能力を有するものである限り、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有するものが好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよく、モノマーの種類に応じてカチオン重合を開始させるような開始剤であってもよい。また、光重合開始剤は、約300nm~800nm(330nm~500nmがより好ましい。)の範囲内に少なくとも約50の分子吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。
ヒドロキシアセトフェノン系開始剤としては、IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959,IRGACURE-127(商品名:いずれもBASF社製)を用いることができる。アミノアセトフェノン系開始剤としては、市販品であるIRGACURE-907、IRGACURE-369、及び、IRGACURE-379(商品名:いずれもBASF社製)を用いることができる。アミノアセトフェノン系開始剤として、365nm又は405nm等の光源に吸収波長がマッチングされた特開2009-191179号公報に記載の化合物も用いることができる。また、アシルホスフィン系開始剤としては市販品であるIRGACURE-819やDAROCUR-TPO(商品名:いずれもBASF社製)を用いることができる。
光重合開始剤の具体例としては、例えば、特開2013-29760号公報の段落0265~0268を参酌することができ、この内容は本明細書に組み込まれる。
市販品ではIRGACURE-OXE01(BASF社製)、IRGACURE-OXE02(BASF社製)も好適に用いられる。また、TRONLY TR-PBG-304、TRONLY TR-PBG-309、TRONLY TR-PBG-305(常州強力電子新材料有限公司(CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO.,LTD)製)、アデカアークルズNCI-930(ADEKA社製)も用いることができる。
一般式(OX-1)中、Rで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
一価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基等が挙げられる。また、これらの基は、1以上の置換基を有していてもよい。また、前述した置換基は、さらに他の置換基で置換されていてもよい。
置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基またはアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、アリール基等が挙げられる。
一般式(OX-1)中、Bで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
一般式(OX-1)中、Aで表される二価の有機基としては、炭素数1~12のアルキレン基、アルキニレン基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
光重合開始剤は、必要に応じて2種以上を組み合わせて使用しても良い。
本発明の着色組成物は、顔料誘導体を含有することが好ましい。顔料誘導体としては、有機顔料の一部分を、酸性基、塩基性基又はフタルイミドメチル基で置換した構造を有する化合物が挙げられる。顔料誘導体は、分散性及び分散安定性の観点から、酸性基又は塩基性基を有する顔料誘導体が好ましい。特に好ましくは、塩基性基を有する顔料誘導体である。また、上述した樹脂(分散剤)と、顔料誘導体の組み合わせとしては、樹脂が酸基を有する酸性型の樹脂で、顔料誘導体が塩基性基を有する組み合わせが好ましい。
本発明の着色組成物は、塗布性をより向上させる観点から、各種の界面活性剤を含有させてもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。
フッ素系界面活性剤は、フッ素原子を有する(メタ)アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基(好ましくはエチレンオキシ基、プロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができ、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開2010-164965号公報0050~0090段落および0289~0295段落に記載された化合物、例えばDIC社製のメガファックRS-101、RS-102、RS-718K等が挙げられる。
界面活性剤の含有量は、着色組成物の全固形分に対して、0.001~2.0質量%が好ましく、0.005~1.0質量%がより好ましい。
本発明の着色組成物は、シランカップリング剤を含有することができる。シランカップリング剤としては、一分子中に少なくとも2種の反応性の異なる官能基を有するシラン化合物も好ましく、特に、官能基としてアミノ基とアルコキシ基とを有するものが好ましい。このようなシランカップリング剤としては、例えば、N-β-アミノエチル-γ-アミノプロピル-メチルジメトキシシラン(信越化学工業社製商品名 KBM-602)、N-β-アミノエチル-γ-アミノプロピル-トリメトキシシラン(信越化学工業社製商品名 KBM-603)、N-β-アミノエチル-γ-アミノプロピル-トリエトキシシラン(信越化学工業社製商品名 KBE-602)、γ-アミノプロピル-トリメトキシシラン(信越化学工業社製商品名 KBM-903)、γ-アミノプロピル-トリエトキシシラン(信越化学工業社製商品名 KBE-903)、3-メタクリロキシプロピルトリメトキシシラン(信越化学工業社製商品名 KBM-503)等がある。シランカップリング剤の詳細については、特開2013-254047号公報の段落番号0155~0158の記載を参酌でき、この内容は本明細書に組み込まれる。
本発明の着色組成物は、重合禁止剤を含有することも好ましい。重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4'-チオビス(3-メチル-6-t-ブチルフェノール)、2,2'-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン塩(アンモニウム塩、第一セリウム塩等)等が挙げられる。
本発明の着色組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、着色組成物の全固形分に対して、0.01~5質量%が好ましい。本発明の着色組成物は、重合禁止剤を、1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の着色組成物には、必要に応じて、各種添加物、例えば、充填剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加物としては、特開2004-295116号公報の段落0155~0156に記載のものを挙げることができ、これらの内容は本明細書に組み込まれる。酸化防止剤としては、例えばフェノール化合物、リン系化合物(例えば特開2011-90147号公報の段落番号0042に記載の化合物)、チオエーテル化合物などを用いることができる。市販品としては、例えば(株)ADEKA製のアデカスタブシリーズ(AO-20、AO-30、AO-40、AO-50、AO-50F、AO-60、AO-60G、AO-80、AO-330など)が挙げられる。酸化防止剤は2種以上を混合して使用してもよい。本発明の着色組成物においては、特開2004-295116号公報の段落0078に記載の増感剤や光安定剤、同公報の段落0081に記載の熱重合防止剤を含有することができる。
本発明の着色組成物は、前述の成分を混合して調製できる。配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解・分散して組成物を調製してもよいし、必要に応じては、各成分を適宜2つ以上の溶液・分散液としておいて、使用時(塗布時)にこれらを混合して調製してもよい。
フィルタの孔径は、0.01~7.0μm程度が適しており、好ましくは0.01~3.0μm程度、さらに好ましくは0.05~0.5μm程度である。この範囲とすることにより、後工程において均一及び平滑な組成物の調製を阻害する、微細な異物を確実に除去することが可能となる。また、ファイバ状のろ材を用いることも好ましく、ろ材としては例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられ、具体的にはロキテクノ社製のSBPタイプシリーズ(SBP008など)、TPRタイプシリーズ(TPR002、TPR005など)、SHPXタイプシリーズ(SHPX003など)のフィルタカートリッジを用いることができる。
また、上述した範囲内で異なる孔径の第1のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社(DFA4201NXEYなど)、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
第2のフィルタは、上述した第1のフィルタと同様の材料等で形成されたものを使用することができる。
例えば、第1のフィルタでのフィルタリングは、分散液のみで行い、他の成分を混合した後で、第2のフィルタリングを行ってもよい。
次に、本発明のカラーフィルタについて説明する。
本発明のカラーフィルタは、上述した本発明の着色組成物を用いてなるものである。本発明のカラーフィルタの膜厚は、目的に応じて適宜調整できる。膜厚は、20μm以下が好ましく、10μm以下がより好ましく、5μm以下がさらに好ましい。膜厚の下限は、0.1μm以上が好ましく、0.2μm以上がより好ましく、0.3μm以上が更に好ましい。本発明のカラーフィルタは、CCD(電荷結合素子)やCMOS(相補型金属酸化膜半導体)などの固体撮像素子や、画像表示装置などに用いることができる。
本発明のパターン形成方法は、本発明の着色組成物を用いて支持体上に着色組成物層を形成する工程と、フォトリソグラフィ法またはドライエッチング法により、着色組成物層に対してパターンを形成する工程と、を含む。
また、ドライエッチング法によるパターン形成は、着色組成物を用いて支持体上に着色組成物層を形成し、硬化して硬化物層を形成する工程と、硬化物層上にフォトレジスト層を形成する工程と、露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程と、レジストパターンをエッチングマスクとして硬化物層をドライエッチングしてパターンを形成する工程とを含むことが好ましい。以下、各工程について説明する。
硬化性組成物層を形成する工程では、着色組成物を用いて、支持体上に着色組成物層を形成する。
本発明におけるパターンは、固体撮像素子用基板の固体撮像素子形成面側(おもて面)に形成してもよいし、固体撮像素子非形成面側(裏面)に形成してもよい。
支持体上には、必要により、上部の層との密着性の改良、物質の拡散防止或いは基板表面の平坦化のために下塗り層を設けてもよい。
プリベークを行う場合、プリベーク温度は、150℃以下が好ましく、120℃以下がより好ましく、110℃以下が更に好ましい。下限は、例えば、50℃以上とすることができ、80℃以上とすることもできる。プリベーク温度を150℃以下で行うことにより、例えば、イメージセンサの光電変換膜を有機素材で構成した場合において、これらの特性をより効果的に維持することができる。
プリベーク時間は、10秒~300秒が好ましく、40~250秒がより好ましく、80~220秒がさらに好ましい。乾燥は、ホットプレート、オーブン等で行うことができる。
<<露光工程>>
次に、着色組成物層を、パターン状に露光する(露光工程)。例えば、着色組成物層に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部分を硬化することができる。
露光に際して用いることができる放射線(光)としては、g線、i線等の紫外線が好ましく(特に好ましくはi線)用いられる。照射量(露光量)は、例えば、0.03~2.5J/cm2が好ましく、0.05~1.0J/cm2がより好ましい。
露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が19体積%以下の低酸素雰囲気下(例えば、15体積%、5体積%、実質的に無酸素)で露光してもよく、酸素濃度が21体積%を超える高酸素雰囲気下(例えば、22体積%、30体積%、50体積%)で露光してもよい。また、露光照度は適宜設定することが可能であり、通常1000W/m2~100000W/m2(例えば、5000W/m2、15000W/m2、35000W/m2)の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度10体積%で照度10000W/m2、酸素濃度35体積%で照度20000W/m2などとすることができる。
次に、未露光部を現像除去してパターンを形成する。未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の着色組成物層が現像液に溶出し、光硬化した部分だけが残る。
現像液としては、下地の固体撮像素子や回路などにダメージを起さない、有機アルカリ現像液が望ましい。
現像液の温度は、例えば、20~30℃が好ましい。現像時間は、20~180秒が好ましい。また、残渣除去性を向上するため、現像液を60秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。
また、現像液には無機アルカリを用いてもよい。無機アルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどが好ましい。
また、現像液には、界面活性剤を用いてもよい。界面活性剤の例としては、上述した硬化性組成物で説明した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。
なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に現像後純水で洗浄(リンス)することが好ましい。
ポストベークは、現像後の膜を、上記条件になるようにホットプレートやコンベクションオーブン(熱風循環式乾燥機)、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。また、低温プロセスによりパターンを形成する場合は、ポストベークは行わなくてもよい。
ドライエッチング法でのパターン形成は、支持体上に形成した組成物層を硬化して硬化物層を形成し、次いで、得られた硬化物層を、パターニングされたフォトレジスト層をマスクとしてエッチングガスを用いて行うことができる。
具体的には、硬化物層上にポジ型またはネガ型の感放射線性組成物を塗布し、これを乾燥させることによりフォトレジスト層を形成することが好ましい。フォトレジスト層の形成においては、さらにプリベーク処理を施すことが好ましい。特に、フォトレジストの形成プロセスとしては、露光後の加熱処理、現像後の加熱処理(ポストベーク処理)を実施する形態が望ましい。ドライエッチング法でのパターン形成については、特開2013-064993号公報の段落0010~0067の記載を参酌でき、この内容は本明細書に組み込まれる。
本発明の固体撮像素子は、上述した本発明のカラーフィルタを有する。本発明の固体撮像素子の構成としては、本発明のカラーフィルタを備え、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。
本発明のカラーフィルタは、液晶表示装置や有機エレクトロルミネッセンス表示装置などの、画像表示装置に用いることができる。表示装置の定義や各表示装置の詳細については、例えば「電子ディスプレイデバイス(佐々木 昭夫著、(株)工業調査会 1990年発行)」、「ディスプレイデバイス(伊吹 順章著、産業図書(株)平成元年発行)」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術(内田 龍男編集、(株)工業調査会 1994年発行)」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。
重量平均分子量は、以下の方法で測定した。
カラムの種類:TOSOH TSKgel Super HZM-Hと、TOSOH TSKgel Super HZ4000と、TOSOH TSKgel Super HZ2000とを連結したカラム
展開溶媒:テトラヒドロフラン
カラム温度:40℃
流量(サンプル注入量):1.0μL(サンプル濃度:0.1質量%)
装置名:東ソー製 HLC-8220GPC
検出器:RI(屈折率)検出器
検量線ベース樹脂:ポリスチレン
(実施例101)
化合物a11を30.72部、樹脂Aを10.8部、プロピレングリコールメチルエーテルアセテート(PGMEA)120部からなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)により3時間混合・分散して、顔料分散液を調製した。得られた顔料分散液に、フタルイミド化合物(FE-1)を0.60部添加して、実施例101の着色組成物を製造した。
実施例101において、化合物a11の代わりに、それぞれ化合物a12~14を用いた以外は、実施例101と同様の方法で、実施例102~104の着色組成物を製造した。
化合物a21を30.72部、樹脂Aを10.8部、PGMEAを120部からなる混合液に、フタルイミド化合物(FE-1)を0.60部添加して、実施例105の着色組成物を製造した。
実施例105において、化合物a21の代わりに、それぞれ化合物a31、a41、a51を用いた以外は、実施例105と同様の方法で、実施例106~108の着色組成物を製造した。
・分散液Y1の製造
化合物a11を30.72部、樹脂Aを10.8部、PGMEA120部からなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)により3時間混合・分散して、分散液Y1を製造した。
・分散液G1の製造
緑色顔料G1を30.72部、樹脂Aを10.8部、PGMEA120部からなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)により3時間混合・分散して、分散液G1を製造した。
・着色組成物の製造
下記の成分を混合して、実施例201の着色組成物を製造した。
分散液Y1: 51部
分散液G1: 110部
樹脂B: 36部
硬化性化合物(M-1): 33部
光重合開始剤(I-1): 9.92部
p-メトキシフェノール: 0.04部
PGMEA: 160部
フタルイミド化合物(FE-1): 0.2部
実施例201において、化合物a11のかわりに、化合物a12~a14を用いた以外は、分散液Y1と同様にして分散液Y2~4を製造した。
実施例201において、分散液Y1のかわりに、分散液Y2~4を用いた以外は、実施例201と同様にして、実施例202~204の着色組成物を製造した。
・混合液1の製造
化合物a21を30.72部、樹脂Aを10.8部、PGMEA120部を混合して、混合液1を製造した。
・着色組成物の製造
下記の成分を混合して、実施例205の着色組成物を製造した。
混合液1: 51部
分散液G1: 110部
樹脂B: 36部
硬化性化合物(M-1): 33部
光重合開始剤(I-1): 9.92部
p-メトキシフェノール: 0.04部
PGMEA: 160部
フタルイミド化合物(FE-1): 0.2部
実施例205において、化合物a21のかわりに、化合物a31、a41またはa51を用いた以外は、混合液1と同様にして混合液2~4を製造した。
実施例205において、混合液1のかわりに、混合液2~4を用いた以外は、実施例205と同様にして、実施例206~208の着色組成物を製造した。
実施例201~208において、2-メトキシ-1-プロピルアセテートを、着色組成物の質量に対して0.1質量%含有させた以外は、実施例201~208と同様にして、実施例301~308の着色組成物を製造した。
実施例301において、光重合開始剤(I-1)を、同質量の光重合開始剤(I-2)に変更した以外は、実施例301と同様にして、実施例309の着色組成物を製造した。
緑色顔料G2を30.72部、樹脂Aを10.8部、PGMEA120部からなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)により3時間混合・分散して、分散液G2を製造した。
実施例201~204において、分散液G1の代わりに、分散液G2を用いた以外は、実施例201~204と同様にして、実施例401~404の着色組成物を製造した。
実施例401において、光重合開始剤(I-1)を、同質量の光重合開始剤(I-2)に変更した以外は、実施例401と同様にして、実施例405の着色組成物を製造した。
実施例201において、フタルイミド化合物(FE-1)の代わりに、フタルイミド化合物(FE-2)~(FE-8)を用いた以外は、実施例201と同様にして、実施例502~508の着色組成物を製造した。
実施例201において、フタルイミド化合物(FE-1)の配合量を、それぞれ下記表に示す配合量に変更した以外は、実施例201と同様にして、実施例602~608の着色組成物を製造した。
実施例301において、2-メトキシ-1-プロピルアセテートの含有量を、それぞれ下記表に示す割合に変更した以外は、実施例301と同様にして、実施例702~707の着色組成物を製造した。
実施例101~108において、フタルイミド化合物を使用しなかった以外は、実施例101~108と同様の方法で、比較例1、9~15の着色組成物を製造した。
実施例101において、化合物a11の代わりに、それぞれ化合物b11~b14を用いた以外は、実施例101と同様の方法で、比較例2~5の着色組成物を製造した。
実施例105~107において、化合物a21、a31、a41の代わりに、それぞれ化合物b21、b31、b41を用いた以外は、実施例105~107と同様の方法で、比較例6~8の着色組成物を製造した。
各着色組成物を、密閉容器に入れ、5℃で4時間、25℃で2時間の温度サイクル試験を150日行なった後、密閉容器から着色組成物を取り出して、着色組成物を、ガラスウエハ上に乾燥後の膜厚が0.5μmになるようにスピンコーターを用いて塗布し、100℃のホットプレートを用いて180秒間加熱処理(プリベーク)を行ない、評価用の塗布膜を製造した。
ガラスウエハ上の塗布膜を光学顕微鏡にて、0.5mm四方の領域を100倍に拡大して目視観察し、膜表面上の欠陥数をカウントし、以下の基準で欠陥を評価した。
これに対し、比較例の着色組成物を用いた膜は、欠陥が多かった。
また、実施例101、201、301、401、および比較例1の塗布膜を、25℃の環境で、3日間保管したのち、光学顕微鏡にて、0.5mm四方の領域を100倍に拡大して目視観察し、膜表面上の欠陥数をカウントし、引き置き後の欠陥の評価を行ったところ、比較例1のサンプルは、引き置きしなかった場合に比べて欠陥がさらに増加していた。これに対し、実施例101、201、301、401のサンプルは引き置き後も欠陥の増加は見られず、いわいる「引き置き」の性能も良化していることがわかった。
G1:式A1のX1~X16のうち、臭素原子の平均個数が12個で、塩素原子の平均個数が4個である化合物。
G2:式A1のX1~X16のうち、臭素原子の平均個数が9個で、塩素原子の平均個数が3個で、水素原子の平均個数が4個である化合物。
FE-1:式PIのA1~A4がすべて臭素原子である化合物
FE-2:式PIのA1~A4がすべて塩素原子である化合物
FE-3:式PIのA1~A4のうち2つが臭素原子で、2つが塩素原子である化合物
FE-4:式PIのA1~A4のうち2つが臭素原子で、2つが水素原子である化合物
FE-5:式PIのA1~A4のうち2つが臭素原子で、1つが塩素原子で、1つが水素原子である化合物
FE-6:式PIのA1~A4がすべて水素原子である化合物
FE-7:式PIのA1~A4がすべてメチル基である化合物
FE-8:式PIのA1~A4がすべてn-ブチル基である化合物
樹脂A:下記構造(各繰り返し単位に併記される数値(主鎖繰り返し単位に併記される数値)は、各繰り返し単位の含有量〔質量%〕を表す。側鎖の繰り返し部位に併記される数値は、繰り返し部位の繰り返し数を示す。)酸価=50mgKOH/g、Mw=24000
Claims (10)
- 窒素原子を含む複素環含有着色剤と、フタルイミド化合物と、溶剤と、樹脂とを含み、前記複素環含有着色剤が下記式(1)~(4)から選ばれる少なくとも1種である、着色組成物;
式(2)において、R205およびR208は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、R201~R204、R206およびR207は、それぞれ独立に、水素原子または置換基を表し、Y1は、窒素原子または-CRY1-を表し、Y2は、硫黄原子または-NRY2-を表し、RY1およびRY2は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、Xは、ビス(スルホニル)イミドアニオン、トリス(スルホニル)メチドアニオンまたはホウ素原子を有するアニオンを表す;
式(3)において、R301、R311およびR310は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、R302~R305、R306~R309は、それぞれ独立に、水素原子または置換基を表し、Xは、ビス(スルホニル)イミドアニオン、トリス(スルホニル)メチドアニオンまたはホウ素原子を有するアニオンを表す;
式(4)において、R401およびR402は、それぞれ独立に、SO2R403またはCOR403を表す;R403は、アルキル基、アリール基またはヘテロアリール基を表す。 - フタルイミド化合物は、前記式(PI)のA1~A4の少なくとも一つが、臭素原子である、請求項2に記載の着色組成物。
- 前記式(1)~(4)で表される化合物の合計100質量部に対し、前記フタルイミド化合物を0.001~6.0質量部含有する、請求項1~3のいずれか1項に記載の着色組成物。
- さらに、硬化性化合物を含有する、請求項1~4のいずれか1項に記載の着色組成物。
- 前記硬化性化合物が、ラジカル重合性化合物を含み、
さらに、光重合開始剤を含有する、請求項5に記載の着色組成物。 - 請求項1~6のいずれか1項に記載の着色組成物を用いたカラーフィルタ。
- 請求項1~6のいずれか1項に記載の着色組成物を用いて支持体上に着色組成物層を形成する工程と、フォトリソグラフィ法またはドライエッチング法により、着色組成物層に対してパターンを形成する工程と、を有するパターン形成方法。
- 請求項7に記載のカラーフィルタを有する固体撮像素子。
- 請求項7に記載のカラーフィルタを有する画像表示装置。
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KR20180063193A (ko) | 2018-06-11 |
JP6574849B2 (ja) | 2019-09-11 |
US10641935B2 (en) | 2020-05-05 |
US20180252852A1 (en) | 2018-09-06 |
TW201734633A (zh) | 2017-10-01 |
TWI699617B (zh) | 2020-07-21 |
JPWO2017082226A1 (ja) | 2018-08-16 |
KR102032139B1 (ko) | 2019-10-15 |
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