WO2020171139A1 - 着色樹脂組成物、カラーフィルタ、及び画像表示装置 - Google Patents

着色樹脂組成物、カラーフィルタ、及び画像表示装置 Download PDF

Info

Publication number
WO2020171139A1
WO2020171139A1 PCT/JP2020/006617 JP2020006617W WO2020171139A1 WO 2020171139 A1 WO2020171139 A1 WO 2020171139A1 JP 2020006617 W JP2020006617 W JP 2020006617W WO 2020171139 A1 WO2020171139 A1 WO 2020171139A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
mass
preferable
less
solvent
Prior art date
Application number
PCT/JP2020/006617
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
大村　直也
Original Assignee
三菱ケミカル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to KR1020217016965A priority Critical patent/KR20210131990A/ko
Priority to CN202080008039.1A priority patent/CN113272388A/zh
Priority to JP2021502107A priority patent/JPWO2020171139A1/ja
Publication of WO2020171139A1 publication Critical patent/WO2020171139A1/ja

Links

Images

Classifications

    • 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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/18—Obtaining compounds having oxygen atoms directly bound to the phthalocyanine skeleton
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • 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

Definitions

  • the present invention relates to a colored resin composition, a color filter, and an image display device.
  • a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known as methods for manufacturing a color filter used in a liquid crystal display device or the like.
  • the pigment dispersion method which has excellent properties on average, is most widely adopted from the viewpoints of spectral characteristics, durability, pattern shape, accuracy, and the like.
  • color filters are required to have higher brightness, higher contrast, and higher color gamut.
  • a pigment is generally used from the viewpoint of heat resistance, light resistance, etc., but with the pigment, it has become impossible to satisfy the market demand for high brightness.
  • the use of dyes instead of pigments as agents is being actively studied. For green pixels, studies are being conducted using specific phthalocyanine compounds as dyes (see, for example, Patent Documents 1 to 3).
  • an object of the present invention is to provide a colored resin composition having high brightness and suppressing generation of residues.
  • the present invention has the following configurations.
  • a colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator,
  • the (A) colorant contains a phthalocyanine compound having a chemical structure represented by the following general formula (1)
  • the (B) solvent contains a high boiling point solvent having a boiling point of 160° C. or higher at 1013.25 hPa, which is a colored resin composition.
  • a 1 to A 16 each independently represent a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2), provided that at least one of A 1 to A 16 is represented. Represents a fluorine atom, and at least one of A 1 to A 16 represents a group represented by the following general formula (2).
  • X represents a divalent linking group.
  • the benzene ring in the formula (2) may have any substituent. * represents a bond.
  • FIG. 1 is a schematic sectional view showing an example of an organic EL display device having a color filter of the present invention.
  • the “weight average molecular weight” means a polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
  • the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the amount of base and equivalent weight of KOH per 1 g of solid content of the dispersant. is there.
  • C.I.” means a color index.
  • “(meth)acrylic”, “(meth)acrylate” and the like mean “acrylic and/or methacrylic”, “acrylate and/or methacrylate” and the like, for example, “(meth)acrylic acid” It means “acrylic acid and/or methacrylic acid”.
  • the “total solid content” means all components other than the solvent component contained in the pigment dispersion liquid or the colored resin composition.
  • the numerical range represented by “to” means the range including the numerical values before and after “to”.
  • the colored resin composition according to the present invention contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator as essential components, and if necessary, components other than the above components. Other additives and the like may be blended.
  • A a colorant
  • B a solvent
  • C an alkali-soluble resin
  • D a photopolymerization initiator
  • colorant (A) contained in the colored resin composition of the present invention is a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter, referred to as “phthalocyanine compound ( 1)” may be referred to)).
  • a 1 to A 16 each independently represent a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2). However, at least one of A 1 to A 16 represents a fluorine atom, and at least one of A 1 to A 16 represents a group represented by the following general formula (2).
  • X represents a divalent linking group.
  • the benzene ring in formula (2) may have an arbitrary substituent. * Represents a bond.
  • the (A) colorant contained in the colored resin composition of the present invention contains the phthalocyanine compound (1). Since the phthalocyanine compound (1) has a group represented by the general formula (2), it has high solubility in a solvent and does not require a dispersion treatment step, or the amount of a dispersant or the like required in the dispersion treatment step is reduced. Can be very small. Therefore, in the colored resin composition, around the phthalocyanine compound (1), there is no dispersant or an alkali-soluble resin, or only a very small amount thereof is present, and the phthalocyanine compound ( It is considered that the affinity between 1) and the alkali-soluble resin is weakened.
  • the molecules are likely to associate with each other by the ⁇ - ⁇ interaction between the phthalocyanine rings and the ⁇ - ⁇ interaction between the groups represented by the general formula (2), and further, the atomic radius is It is considered that the presence of small fluorine atoms makes the packing of molecules more dense, increases the brightness, and weakens the affinity with the alkali-soluble resin.
  • the high solubility in a solvent results in high brightness, but the interaction between the alkali developing solution and the phthalocyanine compound (1) is small during the alkali developing process, and the phthalocyanine compound (1) is sufficiently dissolved in the alkali developing solution. However, it is considered that the glass tends to remain on the glass substrate.
  • the coating film is prevented from being dried during the alkali developing step, and becomes sufficiently wet. It is considered that the liquid sufficiently penetrates into the coating film to promote the neutralization reaction, and the residue derived from the colored resin composition is less likely to be generated on the glass substrate.
  • a 1 to A 16 each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, at least one of A 1 to A 16 represents a fluorine atom, and at least one of A 1 to A 16 represents a group represented by the following general formula (2).
  • X represents a divalent linking group.
  • the benzene ring in formula (2) may have an arbitrary substituent. * Represents a bond.
  • X in the general formula (2) represents a divalent linking group.
  • the divalent linking group is not particularly limited, but is an oxygen atom, a sulfur atom, or a —N(R a1 )— group (R a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms). Is mentioned. Among these, an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable, from the viewpoint of stability of the phthalocyanine compound (1) during baking.
  • the benzene ring in formula (2) may have an arbitrary substituent.
  • the substituent is not particularly limited, but is a halogen atom, an alkyl group (—R A group (where R A represents an alkyl group)), an alkoxy group (—OR A group (where R A represents an alkyl group). )), an alkoxycarbonyl group (—COOR A group (where R A represents an alkyl group)), an aryl group (—R B group (where R B represents an aryl group)), an aryloxy group.
  • alkyl group (—R A group) or aryl group (—R B group) to be substituted may be further substituted with these substituents.
  • an alkoxycarbonyl group is preferable from the viewpoint of solubility in a solvent and brightness.
  • the alkyl group contained in these groups may be linear, branched or cyclic, but is preferably linear from the viewpoint of solubility in a solvent.
  • the carbon number of the alkyl group is not particularly limited, it is usually preferably 1 or more and 2 or more, more preferably 6 or less, more preferably 5 or less, and further preferably 4 or less.
  • the content is at least the lower limit, lipophilicity is improved, and the solubility of the phthalocyanine compound (1) in the solvent tends to be improved.
  • it is at most the upper limit hydrophilicity is improved, The solubility of the colored resin composition containing the phthalocyanine compound (1) in an alkaline developer tends to be improved.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Both lipophilicity and hydrophilicity are compatible, that is, the phthalocyanine compound (1) is dissolved in a solvent. From the viewpoint of achieving both compatibility and the solubility of the colored resin composition containing the phthalocyanine compound (1) in an alkaline developer, a methyl group or an ethyl group is preferable, and an ethyl group is more preferable.
  • the aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • the carbon number of the aryl group is not particularly limited, but is usually preferably 4 or more and 6 or more, more preferably 12 or less, more preferably 10 or less, and further preferably 8 or less.
  • the solubility of the phthalocyanine compound (1) in the solvent tends to be improved, and when it is at most the upper limit, the hue change due to the aryl group tends to be suppressed.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the aromatic hydrocarbon ring group include groups having one free valence such as a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring.
  • the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • aromatic heterocyclic group examples include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, and isoxazole each having one free valence.
  • the number of substitutions is not particularly limited, but it affects the polarity of the phthalocyanine compound (1), that is, the solubility of the phthalocyanine compound (1) in a solvent. From the viewpoint of achieving both lipophilicity and hydrophilicity that affects the solubility of the colored resin composition containing the phthalocyanine compound (1) in an alkaline developer, it is preferable that the number of substitutions be 1 for each benzene ring. ..
  • the substitution position may be the o-position, the m-position or the p-position, but the polarity of the phthalocyanine compound (1), that is, From the viewpoint of achieving both lipophilicity that affects the solubility of the phthalocyanine compound (1) in a solvent and hydrophilicity that affects the solubility of the colored resin composition containing the phthalocyanine compound (1) in an alkaline developer, p The-position is preferred.
  • At least one of A 1 to A 16 represents a fluorine atom, but the lipophilicity that affects the brightness and the solubility of the phthalocyanine compound (1) in a solvent and the alkali of the colored resin composition containing the phthalocyanine compound (1)
  • two or more are preferably fluorine atoms, more preferably four or more, further preferably six or more, and preferably 14 or less, 12 or less. More preferably, it is even more preferably 10 or less.
  • the fluorine atom is preferably 1 to 14, more preferably 2 to 14, still more preferably 4 to 12, and particularly preferably 6 to 10.
  • At least one of A 1 to A 16 represents a fluorine atom, and the lipophilicity which affects the brightness and the polarity of the phthalocyanine compound (1), that is, the solubility of the phthalocyanine compound (1) in a solvent, and the phthalocyanine compound.
  • At least one of A 1 to A 4 is a fluorine atom and one of A 5 to A 8 is above is a fluorine atom, one or more of the a 9 ⁇ a 12 is a fluorine atom, and is preferably one or more of the a 13 ⁇ a 16 is a fluorine atom, the a 1 ⁇ a 4 2 or more of them are fluorine atoms, 2 or more of A 5 to A 8 are fluorine atoms, 2 or more of A 9 to A 12 are fluorine atoms, and A 13 to A 16 More preferably, two or more of them are fluorine atoms.
  • At least one of A 1 to A 16 represents a group represented by the general formula (2), but from the viewpoint of solubility in a solvent, 2 or more are preferable, 4 or more are more preferable, and 6 are The above is more preferable, 14 or less is preferable, 12 or less is more preferable, and 10 or less is further preferable.
  • the group represented by the general formula (2) is preferably 1 to 14, more preferably 2 to 14, still more preferably 4 to 12, and particularly preferably 6 to 10.
  • At least one of A 1 to A 16 represents a group represented by the general formula (2), but from the viewpoint of solubility in a solvent, at least one of A 1 to A 4 is the above general formula.
  • a 13 to A 16 is a group represented by the general formula (2), and 2 of A 1 to A 4
  • One or more is a group represented by the general formula (2), two or more of A 5 to A 8 are a group represented by the general formula (2), and two of A 9 to A 12 are It is more preferable that at least one is a group represented by the general formula (2), and at least two of A 13 to A 16 are groups represented by the general formula (2).
  • a 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 are represented by the general formula (2). It is particularly preferable that it is a group represented by the formula ( 1 ), and A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 and A 16 are fluorine atoms.
  • phthalocyanine compound (1) examples include the followings.
  • Et in the formula represents ethyl.
  • a known method can be adopted, for example, the method described in Japanese Patent Laid-Open No. 5-345861 can be adopted.
  • the (A) colorant may contain other colorants in addition to the phthalocyanine compound (1).
  • Other colorants include pigments and dyes.
  • green pigments include C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like, and C.I. I. Pigment Green 58 is preferable.
  • the green dyes which are classified as dyes by the color index, C.I. I. C. as a solvent dye.
  • I. Solvent Green 1 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, and C.I. I. C.
  • C.I. I. Pigment Yellow 1 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127:1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180
  • C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and the nickel azo complex represented by the formula (i) are preferable, and C.I. I. Pigment Yellow 83, 138, 139, 180, 185 and the nickel azo complex represented by the formula (i) are more preferable.
  • yellow dyes examples include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples thereof include specific compounds described in Japanese Patent Laid-Open No. 2010-168531.
  • C.I. I. As a solvent dye, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 and the like.
  • C.I. I. C. as an acid dye.
  • C.I. I. C. as a direct dye.
  • I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 Dyes such as 136, 138 and 141.
  • C.I. I. C. as a modant dye.
  • Examples include dyes such as Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, and preferably C.I. I.
  • Solvent Yellow 4 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184.
  • C.I. I It is preferably at least one selected from the group consisting of Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162 and 163.
  • the average primary particle diameter of the pigment is usually 0.2 ⁇ m or less, preferably 0.1 ⁇ m or less, more preferably 0.04 ⁇ m or less.
  • a method such as solvent salt milling is preferably used.
  • the content of the (A) colorant in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass in the total solid content of the colored resin composition.
  • the above is more preferable, 30% by mass or more is further preferable, 35% by mass or more is particularly preferable, 70% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, 45% by mass
  • the content ratio of the (A) colorant is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, further preferably 20 to 50% by mass, further preferably 30 to 45% by mass, and 35 to 45% by weight is particularly preferred.
  • the content ratio of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass in the total solid content of the colored resin composition.
  • the above is more preferable, 30% by mass or more is still more preferable, 35% by mass or more is particularly preferable, 70% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, and 45% by mass or less is Particularly preferred.
  • color characteristics such as brightness and color gamut tend to be improved, and when it is at most the upper limit, pattern formability tends to be good.
  • the content ratio is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more based on the total solid content of the colored resin composition. 5 mass% or more is more preferable, 10 mass% or more is particularly preferable, 60 mass% or less is preferable, 50 mass% or less is more preferable, 40 mass% or less is further preferable, and 30 mass% or less is particularly preferable. When it is at least the lower limit, color characteristics such as brightness and color gamut tend to be improved, and when it is at most the upper limit, pattern formability tends to be good.
  • the solvent (B) has a function of dissolving or dispersing a colorant, an alkali-soluble resin, a photopolymerization initiator, and other components in the colored resin composition of the present invention to adjust the viscosity.
  • the (B) solvent may be any solvent that can dissolve or disperse each component.
  • the solvent (B) contains a high boiling point solvent having a boiling point of 160° C. or higher at 1013.25 hPa (hereinafter sometimes referred to as “high boiling point solvent”).
  • high boiling point solvent a high boiling point solvent having a boiling point of 160° C. or higher at 1013.25 hPa
  • the high boiling point solvent By including the high boiling point solvent in this way, the drying of the coating film during the alkali development step is suppressed, and it becomes a sufficiently wet state, and the alkali developer sufficiently penetrates into the coating film to promote the neutralization reaction. Therefore, it is considered that even with a coating film containing the phthalocyanine compound (1), the residue is less likely to be generated on the glass substrate.
  • the boiling point of the high-boiling solvent at 1013.25 hPa (hereinafter, simply referred to as "boiling point" unless otherwise specified) is usually 160°C or higher, preferably 165°C or higher, more preferably 170°C or higher, and further preferably. Is 180° C. or higher, more preferably 190° C. or higher, particularly preferably 200° C. or higher, most preferably 220° C. or higher, preferably 340° C. or lower, more preferably 300° C. or lower, further preferably 280° C. or lower. Is.
  • the boiling point of the high boiling point solvent is preferably 160 to 340° C., more preferably 165 to 340° C., further preferably 170 to 300° C., further preferably 180 to 300° C., and further preferably 190 to 300° C. 200 to 280° C. is particularly preferable, and 220 to 280° C. is most preferable.
  • the high boiling point solvent may be used alone or in combination of two or more.
  • the vapor pressure of the high-boiling solvent at 20° C. is not particularly limited, but is preferably 1 Pa or higher, more preferably 5 Pa or higher, still more preferably 10 Pa or higher, and preferably 2000 Pa or lower, more preferably 1500 Pa or lower, further preferably Is 1000 Pa or less, particularly preferably 500 Pa or less.
  • the efficiency of VCD (vacuum drying) in the color filter manufacturing process tends to be improved, and when it is at most the upper limit value, the alkali solubility is improved and the color filter manufacturing process is performed.
  • the occurrence of bumping during VCD (drying under reduced pressure) tends to be suppressed.
  • the vapor pressure of the high boiling point solvent at 20° C. is preferably 1 to 2000 Pa, more preferably 1 to 1500 Pa, further preferably 5 to 1000 Pa, particularly preferably 10 to 500 Pa.
  • the high boiling point solvent examples include ethylene glycol mono-n-butyl ether (boiling point: 171° C.), propylene glycol mono-n-butyl ether (boiling point: 170° C.), diethylene glycol diethyl ether (boiling point: 188° C.), diethylene glycol mono Ethyl ether (boiling point: 202°C), ethyl 3-ethoxypropionate (boiling point: 170°C), 3-methoxybutyl acetate (boiling point: 171°C), 3-methoxy-3-methylbutyl acetate (boiling point: 187°C), etc.
  • a high boiling point solvent having a boiling point of 160° C. or higher and lower than 200° C. (hereinafter, referred to as “high boiling point solvent”).
  • high boiling point solvent a high boiling point solvent having a boiling point of 160° C. or higher and lower than 200° C.
  • the boiling point of the high boiling point solvent A is not particularly limited as long as it is 160°C or higher and lower than 200°C, but is preferably 165°C or higher, more preferably 170°C or higher, further preferably 175°C or higher, and preferably 195°C or lower, 190 C. or lower is more preferable, and 185.degree. C. or lower is further preferable.
  • the boiling point of the high-boiling solvent A is preferably 165°C to 195°C, more preferably 170°C to 190°C, still more preferably 175°C to 185°C.
  • the high boiling point solvent A may be used alone or in combination of two or more.
  • the high boiling point solvent A examples include ethylene glycol mono-n-butyl ether (boiling point: 171° C.), propylene glycol mono-n-butyl ether (boiling point: 170° C.), diethylene glycol diethyl ether (boiling point: 188° C.), 3- Glycol ethers such as ethyl ethoxypropionate (boiling point: 170° C.), 3-methoxybutyl acetate (boiling point: 171° C.), 3-methoxy-3-methylbutyl acetate (boiling point: 187° C.); Glycol ether acetates such as ethylene glycol mono-n-butyl ether acetate (boiling point: 192°C); Glycol diacetates such as ethylene glycol diacetate (boiling point: 191° C.); and glycol ethers and glycol ether acetates are preferable
  • high-boiling solvents having a boiling point of 200° C. or higher and 340° C. or lower (hereinafter referred to as “from the viewpoint of efficient residue suppression and occurrence of bumping during VCD (vacuum drying) during the color filter manufacturing process)” It may be referred to as “high boiling point solvent B”).
  • the boiling point of the high boiling point solvent B is not particularly limited as long as it is 200° C. or higher and 340° C. or lower, but 210° C. or higher is preferable, 220° C. or higher is more preferable, 230° C. or higher is further preferable, and 320° C. or lower is preferable, 300 C. or lower is more preferable, and 280.degree.
  • the boiling point of the high boiling point solvent B is preferably 210° C. to 320° C., more preferably 220° C. to 300° C., further preferably 230° C. to 280° C.
  • the high boiling point solvent B may be used alone or in combination of two or more.
  • the high boiling point solvent B examples include glycol ethers such as diethylene glycol monoethyl ether (boiling point: 202° C.); Glycol ether acetates such as diethylene glycol monoethyl ether acetate (boiling point: 217° C.), diethylene glycol monomonobutyl ether acetate (boiling point: 245° C.); Glycol diacetates such as 1,3-butylene glycol diacetate (boiling point: 232°C); Amides such as N-methylpyrrolidone (boiling point: 202° C.); and glycol ethers and glycol ether acetates are preferable from the viewpoint of solubility of the phthalocyanine compound (1) in the colored resin composition, and glycols are preferable. Ether acetates are more preferred.
  • the high-boiling solvents it is preferable to use the high-boiling solvent A alone from the viewpoint of moderate residue suppression and improvement of VCD (vacuum drying) efficiency during the color filter manufacturing process. Further, it is preferable to use the high-boiling point solvent B alone from the viewpoints of efficiently suppressing residues and suppressing occurrence of bumping during VCD (drying under reduced pressure) during the color filter manufacturing process.
  • the high boiling solvent A and the high boiling solvent B Is preferably used in combination.
  • the solvent (B) preferably contains a low boiling point solvent having a boiling point of less than 160° C. (hereinafter sometimes referred to as “low boiling point solvent”).
  • a low boiling point solvent By including a low boiling point solvent, the efficiency of VCD (vacuum drying) in the color filter manufacturing process is improved, and the coating film becomes thin easily after being dried by VCD or heat drying. Occasionally, the ultraviolet light reaches the inside of the coating film to increase the curability of the coating film, which tends to make pattern formation advantageous.
  • the boiling point of the low boiling point solvent is not particularly limited as long as it is lower than 160°C, but is preferably 150°C or lower, more preferably 140°C or lower, further preferably 130°C or lower, particularly preferably 120°C or lower, and 80°C or higher. Is preferable, 90° C. or higher is more preferable, and 100° C. or higher is further preferable. When it is at most the upper limit, the efficiency of VCD (vacuum drying) in the color filter manufacturing process tends to be improved, and when it is at least the lower limit, alkali solubility tends to be improved.
  • the low boiling point solvent examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 2-peptanone, n-butyl acetate, i-butyl acetate, i-pentyl acetate, ethyl butyrate and n-butyrate.
  • propylene glycol monomethyl ether propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate is preferable, propylene glycol monomethyl ether acetate. Is more preferable.
  • the content ratio of the (B) solvent in the colored resin composition of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass. It is at least 95% by mass, preferably 90% by mass or less, more preferably 88% by mass or less. When it is at least the above lower limit, the storage stability and coatability of the colored resin composition tend to be improved, and when it is at most the above upper limit, the film thickness during coating tends to be below a certain level.
  • the content ratio of the solvent is preferably 50 to 95% by mass, more preferably 60 to 95% by mass, further preferably 70 to 90% by mass, and particularly preferably 80 to 88% by mass.
  • the content of the high boiling point solvent in the solvent (B) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, most preferably 20% by mass or more, and preferably 80% by mass or less, It is preferably 60% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.
  • the content ratio of the high boiling point solvent in the solvent (B) is preferably 0.5 to 80% by mass, more preferably 1 to 80% by mass, further preferably 2 to 60% by mass. Is more preferable, 10 to 40 mass% is even more preferable, 15 to 40 mass% is particularly preferable, and 20 to 30 mass% is the most preferable.
  • the content ratio of the low boiling point solvent in the solvent (B) is not particularly limited, but preferably 20% by mass or more, more preferably 40% by mass.
  • the above is more preferably 60% by mass or more, particularly preferably 70% by mass or more, preferably 99% by mass or less, more preferably 98% by mass or less, and further preferably 95% by mass or less.
  • the efficiency of VCD (vacuum drying) in the color filter manufacturing process tends to be improved, and when it is at most the upper limit value, the alkali solubility is improved and the color filter manufacturing process is performed.
  • the occurrence of bumping during VCD tends to be suppressed.
  • the content ratio of the low boiling point solvent in the solvent (B) is preferably 20 to 99% by mass, more preferably 40 to 98% by mass, further preferably 60 to 95% by mass, and particularly preferably 70 to 95% by mass. preferable.
  • the content ratio of the high boiling point solvent A in the (B) solvent is not particularly limited, but is 1 mass. % Or more is preferable, 5% by mass or more is more preferable, 10% by mass or more is further preferable, 15% by mass or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less Is more preferable and 20% by mass or less is particularly preferable.
  • the content ratio of the high boiling point solvent A in the solvent (B) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, further preferably 10 to 30% by mass, and 15 to 20% by mass. Particularly preferred.
  • the content of the low-boiling solvent in the (B) solvent is not particularly limited, but 50% by mass or more. Is preferred, 60% by mass or more is more preferred, 70% by mass or more is more preferred, 80% by mass or more is particularly preferred, 99% by mass or less is preferred, 95% by mass or less is more preferred, and 90% by mass or less is further preferred. It is preferably 85% by mass or less, and particularly preferably 85% by mass or less.
  • the efficiency of VCD (vacuum drying) in the color filter manufacturing process tends to be improved, and when it is at most the upper limit value, the alkali solubility is improved and the color filter manufacturing process is performed.
  • the occurrence of bumping during VCD (drying under reduced pressure) tends to be suppressed.
  • the content ratio of the low boiling point solvent in the solvent (B) is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, further preferably 70 to 90% by mass, and particularly preferably 80 to 85% by mass. preferable.
  • the content ratio of the high boiling point solvent B in the (B) solvent is not particularly limited. 1 mass% or more is preferable, 0.5 mass% or more is more preferable, 1 mass% or more is further preferable, 2 mass% or more is particularly preferable, 20 mass% or less is preferable, and 15 mass% or less is more preferable. It is more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
  • the content ratio of the high boiling point solvent B in the solvent (B) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, further preferably 1 to 10% by mass, and 2 to 5% by mass is particularly preferred.
  • the content ratio of the low-boiling solvent in the (B) solvent is not particularly limited, but is 80% by mass or more. Is preferable, 85% by mass or more is more preferable, 90% by mass or more is further preferable, 95% by mass or more is particularly preferable, 99.9% by mass or less is preferable, 99.5% by mass or less is more preferable, and 99% by mass is preferable. % Or less is more preferable, and 98% by mass or less is particularly preferable.
  • the efficiency of VCD (vacuum drying) in the color filter manufacturing process tends to be improved, and when it is at most the upper limit value, the alkali solubility is improved and the color filter manufacturing process is performed.
  • the occurrence of bumping during VCD (drying under reduced pressure) tends to be suppressed.
  • the content ratio of the low boiling point solvent in the solvent (B) is preferably 80 to 99.9% by mass, more preferably 85 to 99.5% by mass, further preferably 90 to 99% by mass, and 95 to 98% by mass. Mass% is particularly preferred.
  • the content ratio of the high boiling point solvent A in the (B) solvent is particularly Although not limited, 1% by mass or more is preferable, 5% by mass or more is more preferable, 10% by mass or more is further preferable, 15% by mass or more is particularly preferable, 50% by mass or less is preferable, and 40% by mass or less is more preferable.
  • the content is preferably 30% by mass or less, more preferably 20% by mass or less.
  • the content ratio of the high boiling point solvent A in the solvent (B) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, further preferably 10 to 30% by mass, and 15 to 20% by mass. Particularly preferred.
  • the content ratio of the high-boiling solvent B in the (B) solvent is particularly Although not limited, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, particularly preferably 2% by mass or more, and preferably 20% by mass or less, 15% by mass. % Or less is more preferable, 10% by mass or less is further preferable, and 5% by mass or less is particularly preferable.
  • the content ratio of the high boiling point solvent B in the solvent (B) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, further preferably 1 to 10% by mass, and 2 to 5% by weight is particularly preferred.
  • the content ratio of the low boiling solvent in the (B) solvent is not particularly limited. Is preferably 30% by mass or more, more preferably 45% by mass or more, further preferably 60% by mass or more, particularly preferably 75% by mass or more, and preferably 98.9% by mass or less and 94.5% by mass or less. Is more preferable, 89 mass% or less is further preferable, and 83 mass% or less is particularly preferable.
  • the efficiency of VCD (vacuum drying) in the color filter manufacturing process tends to be improved, and when it is at most the upper limit value, the alkali solubility is improved and the color filter manufacturing process is performed.
  • the occurrence of bumping during VCD (drying under reduced pressure) tends to be suppressed.
  • the content ratio of the low boiling point solvent in the solvent (B) is preferably 30 to 98.9% by mass, more preferably 45 to 94.5% by mass, further preferably 60 to 89% by mass, and 75 to 83% by mass. Mass% is particularly preferred.
  • the colored resin composition of the present invention contains (C) an alkali-soluble resin.
  • an alkali-soluble resin By containing (C) an alkali-soluble resin, both film curability by photopolymerization and solubility by a developer can be achieved.
  • the alkali-soluble resin (C) include, for example, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-140144, Known polymer compounds described in JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, etc. can be used.
  • (C-1) An unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer with respect to the copolymer of the epoxy group-containing (meth)acrylate and another radically polymerizable monomer.
  • the resulting resin, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction hereinafter sometimes referred to as "resin (C-1)".
  • (C-2) A straight-chain alkali-soluble resin having a carboxyl group in its main chain (hereinafter sometimes referred to as "resin (C-2)").
  • (C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter, also referred to as “resin (C-3)”).
  • (C-4) (meth)acrylic resin (hereinafter sometimes referred to as “resin (C-4)")
  • Epoxy (meth)acrylate resin having (C-5) carboxyl group hereinafter, may be referred to as "resin (C-5)”.
  • the resin (C-1) is particularly preferable and will be described in detail below.
  • the resins (C-2) to (C-5) are not limited as long as they are dissolved by an alkaline developer and have such a solubility that the intended developing treatment is carried out. What is described as the same item in Japanese Patent Laid-Open No. 2009-025813 can be preferably adopted.
  • An unsaturated monobasic acid is added to at least a part of the epoxy groups of the copolymer with respect to the copolymer of the epoxy group-containing (meth)acrylate and other radically polymerizable monomer.
  • an alkali-soluble resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction of the resin Based on the copolymer of 5 to 90 mol% of meth)acrylate and 10 to 95 mol% of other radically polymerizable monomer, unsaturated monobasic acid is contained in 10 to 100 mol% of the epoxy groups of the copolymer.
  • an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of hydroxyl groups generated by the addition reaction is contained in 10 to 100 mol% of the epoxy groups of the copolymer.
  • epoxy group-containing (meth)acrylate examples include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • An acrylate glycidyl ether etc. are mentioned. Of these, glycidyl (meth)acrylate is preferable.
  • These epoxy group-containing (meth)acrylates may be used alone or in combination of two or more.
  • R 91 to R 98 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 96 and R 98 , or R 95 and R 97 may be linked to each other to form a ring.
  • the ring formed by linking R 96 and R 98 or R 95 and R 97 is preferably an aliphatic ring and may be saturated or unsaturated.
  • the ring formed by connecting R 95 and R 97 preferably has 5 to 6 carbon atoms.
  • the structure represented by the general formula (V) is preferably a structure represented by the following formula (Va), (Vb) or (Vc).
  • the mono(meth)acrylate having the structure represented by the general formula (V) may be used alone or in combination of two or more.
  • the mono(meth)acrylate having the structure represented by the general formula (V) various known ones can be used as long as they have the structure, but in particular, the mono(meth)acrylate represented by the following general formula (VI) is used. ) Acrylate is preferred.
  • R 89 represents a hydrogen atom or a methyl group
  • R 90 represents a structure represented by the general formula (V).
  • the content ratio of the repeating unit derived from the mono(meth)acrylate represented by the general formula (VI) is as described above.
  • the repeating unit derived from another radically polymerizable monomer 5 to 90 mol% is preferable, 10 to 70 mol% is more preferable, and 15 to 50 mol% is further preferable.
  • the radical-polymerizable monomer other than the mono(meth)acrylate represented by the general formula (VI) is not particularly limited, but specific examples thereof include styrene and styrene.
  • Vinyl aromatics such as ⁇ -, o-, m-, p-alkyl, nitro, cyano, amide and ester derivatives; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene;
  • radically polymerizable monomers from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition, it is selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimide. It is preferable to contain one or more species.
  • the content of the repeating unit derived from at least one selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimide in the repeating units derived from other radically polymerizable monomers is 1 to 70 mol% is preferable, and 3 to 50 mol% is more preferable.
  • a known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth)acrylate and the other radically polymerizable monomer.
  • the solvent used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
  • the solvent include ethylene glycol monoalkyl ether acetates such as cellosolve acetate and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate; propylene glycol monoalkyl ether acetate.
  • Acetates such as ethyl acetate, isopropyl acetate, dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; benzene, toluene, xylene, octane, Hydrocarbons such as decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; lactic acid esters
  • the amount of these solvents used is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, based on 100 parts by mass of the obtained copolymer. When the amount of the solvent used is within the above range, it tends to be easy to control the molecular weight of the copolymer.
  • the radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and an organic peroxide catalyst or an azo compound catalyst which is usually used should be used. You can Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters and peroxydicarbonates.
  • azo compound catalyst examples include azobisisobutyronitrile and azobiscarbonamide. Of these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature.
  • the amount of the radical polymerization initiator used is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the monomers used in the copolymerization reaction.
  • the copolymerization reaction may be carried out by dissolving the monomer used in the copolymerization reaction and the radical polymerization initiator in a solvent and heating the mixture while stirring, or by adding the monomer to which the radical polymerization initiator is added. Alternatively, the temperature may be elevated and the mixture may be added dropwise to a stirred solvent. Further, the monomer may be added dropwise while the radical polymerization initiator is added to the solvent and the temperature is raised.
  • the reaction conditions can be freely changed according to the target molecular weight.
  • a repeating unit of 5 to 90 mol% derived from the epoxy group-containing (meth)acrylate and other It is preferably composed of 10 to 95 mol% of the repeating unit derived from a radically polymerizable monomer, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and 30 to 70 mol% of the former. And the latter 70 to 30 mol% are particularly preferable.
  • unsaturated monobasic acid added to the epoxy group known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond. Specific examples include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, ⁇ -position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or the like. Examples thereof include monocarboxylic acids such as (meth)acrylic acid. Of these, (meth)acrylic acid is preferable. These 1 type may be used individually and may use 2 or more types together.
  • Polymerization can be imparted to the resin (C-1) by adding such components.
  • These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy groups contained in the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. When it is at least the lower limit value, the temporal stability of the colored resin composition tends to be good.
  • a known method can be adopted as a method of adding an unsaturated monobasic acid to the epoxy group of the copolymer.
  • polybasic acid anhydride to be added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer known compounds can be used.
  • dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone
  • An anhydride of an acid having three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride can be used. Among them, tetrahydrophthalic anhydride and/or succinic anhydride are preferable.
  • These polybasic acid anhydrides may be used alone or in combination of two or more.
  • polybasic acid anhydrides are usually added to the epoxy group of the above copolymer in an amount of 10 to 100 mol% of hydroxyl groups generated by adding an unsaturated monobasic acid, and preferably 20 to 90 mol. %, more preferably 30 to 80 mol %. When it is at most the upper limit, the residual film rate during development tends to be good, and when it is at least the lower limit, the solubility tends to be sufficient.
  • a method for adding a polybasic acid anhydride to a hydroxyl group a known method can be adopted.
  • a glycidyl ether compound having a glycidyl (meth)acrylate or a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Further, in order to improve the developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl group.
  • glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group.
  • examples of commercially available products include "Denacol EX-111", “Denacor EX-121", “Denacor EX-141”, “Denacor EX-145”, “Denacol EX-146", and “Denacor EX-146" manufactured by Nagase Chemtex Corporation. Examples include Denacol EX-171" and "Denacor EX-192".
  • the structure of such a resin is described in, for example, Japanese Unexamined Patent Publication No. 8-297366 and Japanese Unexamined Patent Publication No. 2001-89533 and is already known.
  • the polystyrene-equivalent weight average molecular weight (Mw) of the resin (C-1) measured by GPC is not particularly limited, but is preferably 3,000 to 100,000, particularly preferably 5,000 to 50,000. When it is at least the above lower limit, heat resistance and film strength will tend to be good, and when it is at most the above upper limit, solubility in a developer will tend to be good.
  • the weight average molecular weight (Mw)/number average molecular weight (Mn) ratio is preferably 2.0 to 5.0.
  • (c1) acrylic copolymer resins having an ethylenically unsaturated group in the side chain (hereinafter referred to as “(c1) acrylic copolymer”).
  • (c1) acrylic copolymer) is preferred.
  • the partial structure containing a side chain having an ethylenically unsaturated group, which the (c1) acrylic copolymer resin has, is not particularly limited, but from the viewpoint of compatibility of the coating film curability upon exposure to ultraviolet light and the alkali solubility during alkali development.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group. * Represents a bond.
  • the partial structure represented by the above formula (I) is preferable from the viewpoint of sensitivity and alkali developability.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • R X represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid.
  • examples thereof include one or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable from the viewpoint of patterning characteristics, and more preferable.
  • tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferable from the viewpoint of patterning characteristics, and more preferable.
  • the content ratio of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is not particularly limited, but is preferably 10 mol% or more, and 20 mol % Or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, particularly preferably 50 mol% or more, and preferably 95 mol% or less, more preferably 90 mol% or less, 85 mol% % Or less is more preferable, 80 mol% or less is still more preferable, 75 mol% or less is particularly preferable, and 70 mol% or less is most preferable.
  • the coating film curability upon exposure to ultraviolet light will tend to be improved, and when it is at most the above upper limit, the alkali solubility during alkali development will tend to be improved.
  • the content ratio of the partial structure represented by the general formula (I) is preferably 10 to 95 mol %, more preferably 20 to 90 mol %, further preferably 30 to 85 mol %, and 40 to 80 mol %. Is more preferable, 50 to 75 mol% is particularly preferable, and 50 to 70 mol% is the most preferable.
  • the content ratio of the partial structure represented by the general formula (I′) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is not particularly limited, but is preferably 10 mol% or more, 20 mol% or more is more preferable, 30 mol% or more is further preferable, 40 mol% or more is still more preferable, 50 mol% or more is particularly preferable, 95 mol% or less is preferable, 90 mol% or less is more preferable, It is more preferably 85 mol% or less, still more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less.
  • the coating film curability upon exposure to ultraviolet light will tend to be improved, and when it is at most the above upper limit, the alkali solubility during alkali development will tend to be improved.
  • the content ratio of the partial structure represented by the general formula (I′) is preferably 10 to 95 mol %, more preferably 20 to 90 mol %, further preferably 30 to 85 mol %, and 40 to 80 mol %. % Is even more preferable, 50 to 75 mol% is particularly preferable, and 50 to 70 mol% is the most preferable.
  • the acrylic copolymer resin having an ethylenically unsaturated group in the side chain includes the partial structure represented by the general formula (I), the other partial structure is not particularly limited, From the viewpoint of alkali solubility, for example, it is also preferable to have a partial structure represented by the following general formula (II).
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent.
  • R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. ..
  • alkyl group for R 4 include linear, branched or cyclic alkyl groups.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and 14 or less. It is even more preferable, and 12 or less is particularly preferable. Lipophilicity is improved by setting the above lower limit or more, solubility in a solvent tends to be improved, and hydrophilicity is improved by setting the above upper limit or less, and alkali solubility tends to be improved. is there.
  • the alkyl group examples include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group and a dodecanyl group.
  • a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable, from the viewpoint of developability.
  • the substituent that the alkyl group may have is a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group.
  • An acryloyl group, a methacryloyl group, and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.
  • Examples of the aromatic ring group for R 4 include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the carbon number is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, further preferably 20 or less, particularly preferably 18 or less. Lipophilicity is improved by setting the above lower limit or more, solubility in a solvent tends to be improved, and hydrophilicity is improved by setting the above upper limit or less, and alkali solubility tends to be improved. is there.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene. Examples thereof include ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring and fluorene ring.
  • the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring and a pyrazole ring.
  • a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable.
  • the substituent which the aromatic ring group may have, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group , An oligoethylene glycol group, a phenyl group, a carboxyl group, and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.
  • the alkenyl group for R 4 includes a linear, branched or cyclic alkenyl group.
  • the carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. Lipophilicity is improved by setting the above lower limit or more, solubility in a solvent tends to be improved, and hydrophilicity is improved by setting the above upper limit or less, and alkali solubility tends to be improved. is there.
  • alkenyl group examples include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 2-penten-1-yl group, Examples thereof include a 3-penten-2-yl group, a hexenyl group, a cyclobutenyl group, a cyclopentenyl group, and cyclohexenyl.
  • a vinyl group or an allyl group is preferable, and a vinyl group is more preferable, from the viewpoint of developability.
  • the substituent which the alkenyl group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group And the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.
  • an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoints of developability and film strength.
  • the content ratio of the partial structure represented by the general formula (II) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is not particularly limited, but is preferably 1 mol% or more, and 5 mol% or more Is more preferable, 10 mol% or more is further preferable, 20 mol% or more is particularly preferable, 70 mol% or less is preferable, 60 mol% or less is more preferable, 50 mol% or less is further preferable, and 40 mol% or less is Particularly preferred.
  • the content ratio of the partial structure represented by the general formula (II) is preferably 1 to 70 mol %, more preferably 5 to 60 mol %, further preferably 10 to 50 mol %, particularly 20 to 40 mol %. preferable.
  • the acrylic copolymer resin contains a partial structure represented by the general formula (I)
  • the affinity between the phthalocyanine compound (1) and the (c1) acrylic copolymer resin is improved as the other partial structure.
  • the partial structure represented by the following general formula (III) is preferably contained.
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent.
  • Optionally represents an alkynyl group, a hydroxy group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group.
  • t represents an integer of 0 to 5.
  • R 6 is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxy group, a carboxyl group. Represents a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent.
  • alkyl group for R 6 include linear, branched or cyclic alkyl groups.
  • the carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less, and 12 or less. Is particularly preferable. Lipophilicity is improved by setting the above lower limit or more, solubility in a solvent tends to be improved, and hydrophilicity is improved by setting the above upper limit or less, and alkali solubility tends to be improved. is there.
  • the alkyl group examples include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group and a dodecanyl group. Of these, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable, from the viewpoint of heat resistance.
  • the substituent that the alkyl group may have is a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group.
  • An acryloyl group, a methacryloyl group, and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.
  • the alkenyl group for R 6 includes a linear, branched or cyclic alkenyl group.
  • the carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. Lipophilicity is improved by setting the above lower limit or more, solubility in a solvent tends to be improved, and hydrophilicity is improved by setting the above upper limit or less, and alkali solubility tends to be improved. is there.
  • alkenyl group examples include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 2-penten-1-yl group, Examples thereof include a 3-penten-2-yl group, a hexenyl group, a cyclobutenyl group, a cyclopentenyl group, and cyclohexenyl.
  • a vinyl group or an allyl group is preferable, and a vinyl group is more preferable, from the viewpoint of exposure sensitivity during ultraviolet exposure.
  • the substituent which the alkenyl group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group And the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • alkynyl group for R 6 examples include a linear, branched or cyclic alkynyl group.
  • the carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. Lipophilicity is improved by setting the above lower limit or more, solubility in a solvent tends to be improved, and hydrophilicity is improved by setting the above upper limit or less, and alkali solubility tends to be improved. is there.
  • alkynyl group examples include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group, 1, 4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyne-6-yl group and the like can be mentioned.
  • the substituent which the alkynyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group. And the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • halogen atom in R 6 examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom is preferable from the viewpoint of the storage stability of the (c1) acrylic copolymer resin.
  • alkoxy group for R 6 examples include linear, branched or cyclic alkoxy groups.
  • the carbon number is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, particularly preferably 12 or less. Lipophilicity is improved by setting the above lower limit or more, solubility in a solvent tends to be improved, and hydrophilicity is improved by setting the above upper limit or less, and alkali solubility tends to be improved. is there.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and an isobutoxy group.
  • the substituent which the alkoxy group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group , An acryloyl group, a methacryloyl group, and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.
  • alkyl sulfide group for R 6 examples include linear, branched or cyclic alkyl sulfide groups.
  • the carbon number is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, particularly preferably 12 or less. Lipophilicity is improved by setting the above lower limit or more, solubility in a solvent tends to be improved, and hydrophilicity is improved by setting the above upper limit or less, and alkali solubility tends to be improved. is there.
  • alkyl sulfide group examples include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group and a butyl sulfide group.
  • a methyl sulfide group or an ethyl sulfide group is preferable from the viewpoint of developability.
  • the substituent which the alkyl group in the alkyl sulfide group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl Group, a carboxyl group, an acryloyl group, a methacryloyl group, and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.
  • R 6 is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxy group, a carboxyl group, a halogen group.
  • An atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an alkylsulfide group which may have a substituent is represented, and among these, from the viewpoint of developability, a hydroxy group or a carboxyl group is preferable, and a carboxyl group is more preferable. preferable.
  • t represents an integer of 0 to 5, but it is preferable that t is 0 from the viewpoint of ease of production.
  • the content ratio of the partial structure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is not particularly limited, but is preferably 1 mol% or more, and 2 mol% or more Is more preferable, 5 mol% or more is further preferable, 8 mol% or more is particularly preferable, 50 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is further preferable, and 20 mol% or less is Particularly preferred.
  • the content is at least the lower limit, the affinity between the phthalocyanine compound (1) and the (c1) acrylic copolymer resin is improved, and the alkali solubility is likely to be improved.
  • the content ratio of the structure increases, and the alkali solubility tends to improve.
  • the content ratio of the partial structure represented by the general formula (III) is preferably 1 to 50 mol %, more preferably 2 to 40 mol %, further preferably 5 to 30 mol %, and 8 to 20 mol %. Is particularly preferable.
  • R 7 represents a hydrogen atom or a methyl group.
  • the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) has a partial structure represented by the general formula (IV)
  • its content is not particularly limited, but is preferably 5 mol% or more, 10 mol% or more is more preferable, 20 mol% or more is further preferable, 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60% mol or less is further preferable.
  • the amount is not less than the lower limit, the alkali solubility tends to be improved, and when the amount is not more than the upper limit, the storage stability of the colored resin composition tends to be improved.
  • the partial structure represented by the general formula (IV) is included, the content ratio is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and further preferably 20 to 60 mol%.
  • the acid value of the (C) alkali-soluble resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 40 mgKOH/g or more, even more preferably 50 mgKOH/g or more, 60 mgKOH/g or more is particularly preferable, 300 mgKOH/g or less is preferable, 250 mgKOH/g or less is more preferable, 200 mgKOH/g or less is further preferable, and 150 mgKOH/g or less is even more preferable.
  • the amount is not less than the lower limit, the alkali solubility tends to be improved, and when the amount is not more than the upper limit, the storage stability of the colored resin composition tends to be improved.
  • the acid value of the (C) alkali-soluble resin is preferably 10 to 300 mgKOH/g, more preferably 30 to 300 mgKOH/g, further preferably 40 to 250 mgKOH/g, further preferably 50 to 200 mgKOH/g, 60 Especially preferred is ⁇ 150 mg KOH/g.
  • the weight average molecular weight (Mw) of the (C) alkali-soluble resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, still more preferably 6000 or more, still more preferably 7,000 or more, particularly preferably It is 8,000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the (C) alkali-soluble resin is preferably from 1,000 to 30,000, more preferably from 2,000 to 30,000, even more preferably from 4,000 to 20,000, even more preferably from 6,000 to 20,000, particularly preferably from 7,000 to 15,000. It is preferably 8,000 to 10,000 and most preferably.
  • the content ratio of the (C) alkali-soluble resin in the colored resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably in the total solid content of the colored resin composition. 10 mass% or more, more preferably 20 mass% or more, even more preferably 25 mass% or more, particularly preferably 30 mass% or more, and usually 80 mass% or less, preferably 60 mass% or less, more preferably It is 50 mass% or less, and more preferably 40 mass% or less. When it is at least the above lower limit, a strong film is obtained, and the adhesion to the substrate tends to be excellent.
  • the content ratio of the (C) alkali-soluble resin is preferably 1 to 80% by mass, more preferably 5 to 80% by mass, further preferably 10 to 60% by mass, still more preferably 20 to 60% by mass, and 25 It is particularly preferably from 50 to 50% by mass, most preferably from 30 to 40% by mass.
  • the colored resin composition of the present invention contains (D) a photopolymerization initiator.
  • a photopolymerization initiator By containing (D) a photopolymerization initiator, film curability by photopolymerization can be obtained.
  • the photopolymerization initiator (D) can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye added as necessary.
  • the photopolymerization initiation system is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.
  • photopolymerization initiator examples include metallocene compounds containing a titanocene compound described in JP-A-59-152396 and JP-A-61-151197, and JP-A-10-39503. Described hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-aryl- ⁇ -amino acids such as N-phenylglycine, N-aryl- ⁇ -amino acid salts, N-aryl- ⁇ -amino acid esters, etc. Radical activators, ⁇ -aminoalkylphenone-based compounds, oxime ester-based initiators described in Japanese Patent Laid-Open No. 2000-80068 and the like can be mentioned.
  • photopolymerization initiator that can be used in the present invention are listed below.
  • Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, ⁇ -hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p -Isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 1,1,1 -Acetophenone derivatives such as trichloromethyl-(p-butylphenyl)ketone; Thioxanthone derivatives such as thioxanthone, 2-ethy
  • Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; Phenazine derivatives such as 9,10-dimethylbenzphenazine; Anthrone derivatives such as benzanthrone; Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl, dicyclopentadi Enyl-Ti-bis-2,3,5,6-tetrafluorophenyl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl, dicyclopentadienyl-Ti-2
  • an oxime ester-based compound (oxime ester-based photopolymerization initiator) is preferable from the viewpoint of sensitivity and surface properties.
  • Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, and therefore has a high sensitivity even in a small amount and is stable against thermal reaction. Therefore, a small amount of highly sensitive colored resin composition can be designed.
  • an oxime ester compound having a carbazole ring which may have a substituent is preferable from the viewpoint of the light absorption property for the i-line (365 nm) of the exposure light source.
  • Examples of the oxime ester compound include compounds represented by the following general formula (I-1).
  • R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
  • R 21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
  • R 22a represents an alkanoyl group which may have a substituent or an aryloyl group which may have a substituent.
  • the number of carbon atoms of the alkyl group in R 21a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably from the viewpoint of solubility in a solvent and sensitivity to exposure. It is 10 or less, more preferably 5 or less.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a cyclopentylethyl group.
  • the substituent which the alkyl group may have is an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl. Group or N-acetyl-N-acetoxyamino group, and the like, and is preferably unsubstituted from the viewpoint of ease of synthesis.
  • Examples of the aromatic ring group for R 21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored resin composition. From the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, further preferably 12 or less, particularly preferably 8 or less.
  • aromatic ring group examples include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, a fluorenyl group and the like.
  • a phenyl group, a naphthyl group or a fluorenyl group is preferable, and a phenyl group. More preferred are groups or fluorenyl groups.
  • substituent which the aromatic ring group may have, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a carboxy group, a halogen atom, an amino group , An amide group, an alkyl group, and the like.
  • a hydroxyl group and a carboxy group are preferable, and a carboxy group is more preferable.
  • substituent in the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group, a halogen atom and a nitro group.
  • R 21a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group. ..
  • R 21b is an arbitrary substituent containing an aromatic ring or a heteroaromatic ring, but from the viewpoint of solubility in a solvent and sensitivity to exposure, it may have a carbazolyl group or a substituent.
  • Preferred examples thereof include a thioxanthonyl group which may be present, a diphenyl sulfide group which may have a substituent, a fluorenyl group which may have a substituent, and a group in which these groups and a carbonyl group are linked.
  • a carbazolyl group which may have a substituent or a carbazolyl group which may have a substituent and a carbonyl group are linked from the viewpoint of light absorptivity to the i-line (365 nm) of the exposure light source. Groups are preferred.
  • the carbon number of the alkanoyl group in R 22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less from the viewpoint of solubility in a solvent and sensitivity. , And more preferably 5 or less.
  • Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, a butanoyl group and the like.
  • Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group and an amide group, and from the viewpoint of ease of synthesis, it is unsubstituted. Is preferred.
  • the carbon number of the aryloyl group in R 22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less from the viewpoint of solubility in a solvent and sensitivity.
  • Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
  • Examples of the substituent that the aryloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group, and from the viewpoint of ease of synthesis, it is preferably unsubstituted. ..
  • R 21a and R 22a have the same meaning as in the general formula (I-1).
  • R 23a represents an alkyl group which may have a substituent.
  • R 24a represents an alkyl group which may have a substituent, an aryloyl group which may have a substituent, a heteroaryloyl group which may have a substituent, or a nitro group.
  • the benzene ring constituting the carbazole ring may be further condensed with an aromatic ring to form a polycyclic aromatic ring.
  • the carbon number of the alkyl group in R 23a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent. It is preferably 5 or less.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group and the like.
  • Examples of the substituent that the alkyl group may have include a carboxy group, a hydroxy group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, it is unsubstituted. Is preferred.
  • R 23a is more preferably an ethyl group from the viewpoint of solubility in a solvent and easiness of synthesis.
  • the number of carbon atoms of the alkyl group in R 24a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent. It is preferably 5 or less.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group and the like.
  • the carbon number of the aryloyl group in R 24a is not particularly limited, but is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility in a solvent. It is preferably 10 or less, more preferably 9 or less.
  • Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
  • aryloyl group may have examples of the substituent that the aryloyl group may have include a carboxy group, a hydroxy group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group and the like, and from the viewpoint of ease of synthesis, an ethyl group. Is preferred.
  • the number of carbon atoms of the heteroaryloyl group in R 24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. , More preferably 10 or less, still more preferably 9 or less.
  • Specific examples of the heteroaryloyl group include a furancarbonyl group, a thiophenecarbonyl group, a pyrrolylcarbonyl group and a pyridinecarbonyl group.
  • R 24a is preferably an aryloyl group which may have a substituent, and more preferably a benzoyl group, from the viewpoint of sensitivity.
  • the benzene ring constituting the carbazole ring may be further condensed with an aromatic ring to form a polycyclic aromatic ring.
  • oxime ester compounds include OXE-02, OXE-03 manufactured by BASF, TR-PBG-304, TR-PBG-314 manufactured by Changzhou Power Electronics Co., Ltd., or N- manufactured by ADEKA. 1919, NCI-930, NCI-831 and the like.
  • oxime ester compound examples include the following compounds, but the compounds are not limited to these compounds.
  • Each of these photopolymerization initiators may be used alone or in combination of two or more.
  • a chain transfer agent may be used in addition to the photopolymerization initiator (D).
  • the chain transfer agent is a compound having a function of receiving a generated radical and transferring the received radical to another compound.
  • various compounds can be used as long as they have the above-mentioned functions, but examples thereof include a mercapto group-containing compound and carbon tetrachloride, which tend to have a high chain transfer effect. It is more preferable to use a compound having a mercapto group. It is considered that this is because bond cleavage is likely to occur due to the small SH bond energy, and hydrogen abstraction reaction and chain transfer reaction are likely to occur. It is effective in improving sensitivity and surface curability.
  • Examples of the mercapto group-containing compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, ⁇ - Mercapto group-containing compounds having an aromatic ring such as mercaptonaphthalene and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol Bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyltristhiopropionate, pentaerythritol tetrakis (3-
  • 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable among the mercapto group-containing compounds having an aromatic ring, and among the aliphatic mercapto group-containing compounds, trimethylolpropane tris(3- Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) Rate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H) -Trione is preferred.
  • an aliphatic mercapto group-containing compound is preferable, and specifically, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol.
  • the content of the (D) photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total solid content of the colored resin composition. 3 mass% or more is more preferable, 4 mass% or more is still more preferable, 5 mass% or more is particularly preferable, 15 mass% or less is preferable, 10 mass% or less is more preferable, 8 mass% or less is further preferable, It is particularly preferably 6% by mass or less.
  • the content ratio of the (D) photopolymerization initiator is preferably 1 to 15% by mass, more preferably 2 to 15% by mass, further preferably 3 to 10% by mass, further preferably 4 to 8% by mass, 5 to 6 mass% is particularly preferable.
  • the colored resin composition of the present invention contains a chain transfer agent
  • its content is not particularly limited, but preferably 0.01% by mass or more, and 0.1% by mass or more in the total solid content of the colored resin composition. More preferably, it is more preferably 0.2 mass% or more, still more preferably 0.5 mass% or more, still more preferably 1 mass% or more, particularly preferably 1.5 mass% or more, and preferably 5 mass% or less. 3 mass% or less is more preferable, and 2 mass% or less is further preferable. Within the above range, storage stability and patterning ability during alkali development tend to be secured.
  • the content ratio thereof is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, further preferably 0.2 to 3% by mass, and 0.5 to 3% by mass. Mass% is more preferable, 1 to 2 mass% is still more preferable, and 1.5 to 2 mass% is particularly preferable.
  • the colored resin composition of the present invention may further contain a solid content other than the above components, if necessary.
  • a solid content other than the above components, if necessary.
  • examples of such components include photopolymerizable monomers, dispersants, dispersion aids, and surfactants.
  • the photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular weight compound, but it is an addition polymerizable compound having at least one ethylenic double bond (hereinafter, (Referred to as "ethylenic compound”) is preferred.
  • the ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization by the action of a photopolymerization initiator and is cured when the colored resin composition of the present invention is irradiated with an actinic ray.
  • the monomer in the present invention means a concept facing a so-called polymer substance, and means a concept including a dimer, a trimer, and an oligomer in addition to the narrowly defined monomer.
  • a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule.
  • the number of ethylenic double bonds contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably It is 8 or less, and more preferably 7 or less. When it is at least the lower limit, the sensitivity tends to be high, and when it is at most the upper limit, the solubility in a solvent tends to be improved.
  • Examples of the ethylenic compound include unsaturated carboxylic acids, esters of unsaturated carboxylic acids with monohydroxy compounds, esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids, aromatic polyhydroxy compounds with unsaturated carboxylic acids.
  • An ester obtained by an esterification reaction of an unsaturated carboxylic acid with a polycarboxylic acid and a polyhydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound, a polyisocyanate compound and a (meth)acryloyl-containing hydroxy
  • Examples thereof include ethylenic compounds having a urethane skeleton reacted with a compound.
  • ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate.
  • acrylic acid esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate.
  • acrylic acid moiety of these acrylates examples include esters.
  • ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid examples include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
  • the ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single substance, but may be a mixture.
  • condensates of acrylic acid, phthalic acid and ethylene glycol condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol.
  • a condensate of glycerin and the like condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol.
  • a condensate of glycerin and the like condensates of acrylic acid, phthalic acid and ethylene glycol
  • condensates of acrylic acid, maleic acid and diethylene glycol condensates of methacrylic acid, terephthalic acid and pentaerythrito
  • Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate, isophorone diisocyanate and the like.
  • Alicyclic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, 3- Examples thereof include a reaction product with a (meth)acryloyl group-containing hydroxy compound such as hydroxy(1,1,1-trimethacryloyloxymethyl)propane.
  • the ethylenic compound used in the present invention for example, acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinylphthalate are also useful.
  • the ethylenic compound may be a monomer having an acid value.
  • the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group.
  • a polyfunctional monomer contained therein is preferable, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol.
  • the acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g.
  • the acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g.
  • a more preferable polyfunctional monomer having an acid group is mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate, which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture.
  • Other polyfunctional monomers of this polyfunctional monomer can also be used in combination. Further, those described in paragraphs [0056] and [0057] of Japanese Patent Laid-Open No. 2013-140346 can also be used.
  • the polymerizable monomer described in Japanese Patent Laid-Open No. 2013-195971 from the viewpoint of improving the chemical resistance of the pixel and the linearity of the edge of the pixel. From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the development time, it is preferable to use the polymerizable monomer described in JP-A-2013-195974.
  • the content ratio of the photopolymerizable monomer is not particularly limited, but is usually 0% by mass or more, preferably 5% by mass in the total solid content of the colored resin composition. % Or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass. It is preferably 40% by mass or less, more preferably 30% by mass or less. When it is at least the above lower limit, the curability of the coating film tends to be high, and when it is at most the above upper limit, the decrease in alkali developability tends to be suppressed.
  • the content ratio of the photopolymerizable monomer is preferably 0 to 70% by mass, more preferably 5 to 60% by mass, and 10 to 50% by mass. More preferably, 15 to 40 mass% is particularly preferable, and 20 to 30 mass% is most preferable.
  • Dispersant and Dispersion Aid When the colored resin composition of the present invention contains a pigment as the (A) colorant, it is preferable to include a dispersant for the purpose of stably dispersing the pigment.
  • a dispersant for the purpose of stably dispersing the pigment.
  • the dispersants it is preferable to use a polymer dispersant because the dispersion stability over time is excellent.
  • the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters.
  • a system dispersant can be mentioned.
  • dispersants include EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), and SOLSPERSE (registered trademark, Lubri). Zol Co., KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), and those described in JP-A-2013-119568.
  • a block copolymer having a functional group containing a nitrogen atom is preferable, and an acrylic block copolymer is more preferable.
  • the block copolymer having a functional group containing a nitrogen atom includes an A block having a quaternary ammonium salt group and/or an amino group in a side chain and a B block having no quaternary ammonium salt group and/or an amino group. It is preferable that the AB block copolymer and/or the BAB block copolymer are
  • Examples of the functional group containing a nitrogen atom include a primary to tertiary amino group and a quaternary ammonium base. From the viewpoint of dispersibility and storage stability, it is preferable to have a primary to tertiary amino group. It is more preferable to have a group.
  • the structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but from the viewpoint of dispersibility and storage stability, a repeating unit represented by the following general formula (1) is preferable. ..
  • R 1 and R 2 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. And R 1 and R 2 may be bonded to each other to form a cyclic structure.
  • R 3 is a hydrogen atom or a methyl group.
  • X is a divalent linking group.
  • the number of carbon atoms of the alkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 1 or more, and is preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. preferable.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group.
  • a group, a pentyl group, or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Further, it may be linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the carbon number of the aryl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 6 or more, and 16 or less is preferable, 12 or less is more preferable, and 8 or less is more preferable. ..
  • Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group, and the like. Among these, a phenyl group, a methylphenyl group, an ethylphenyl group. , Dimethylphenyl group, or diethylphenyl group is preferable, and phenyl group, methylphenyl group, or ethylphenyl group is more preferable.
  • the number of carbon atoms of the aralkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 7 or more, 16 or less is preferable, 12 or less is more preferable, and 9 or less is further. preferable.
  • Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group, and the like.
  • a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.
  • R 1 and R 2 are each independently an alkyl group which may have a substituent, and a methyl group or an ethyl group is preferable. More preferable.
  • Examples of the substituent which the alkyl group, aralkyl group or aryl group in the above formula (1) may have include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like, and from the viewpoint of easiness of synthesis, Substitution is preferred.
  • the cyclic structure formed by combining R 1 and R 2 with each other includes, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. Is mentioned.
  • the nitrogen-containing heterocycle preferably has no aromaticity, and is more preferably a saturated ring. Specific examples include the following (IV).
  • the divalent linking group X is, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 13 — group, or a —COO—R 14 — group.
  • the content ratio of the repeating unit represented by the formula (1) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more.
  • 15 mol% or more is more preferable, 20% or more is particularly preferable, 25 mol% or more is the most preferable, 90 mol% or less is preferable, 70 mol% or less is more preferable, and 50 mol% or less is further preferable.
  • 40 mol% or less is particularly preferable.
  • the content ratio of the repeating unit represented by the formula (1) in all repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, and further preferably 10 to 70 mol%. % Is more preferred, 15-70 mol% is even more preferred, 20-50% is particularly preferred, and 25-40 mol% is most preferred.
  • the block copolymer preferably has a repeating unit represented by the following formula (2) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability.
  • R 10 is an ethylene group or a propylene group
  • R 11 is an alkyl group which may have a substituent
  • R 12 is a hydrogen atom or a methyl group.
  • n is an integer of 1 to 20.
  • the number of carbon atoms of the alkyl group which may have a substituent in R 11 of the above formula (2) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, and 6 or less. Is more preferable, and 4 or less is further preferable.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group.
  • a group, a pentyl group, or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Further, it may be linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group. Examples of the substituent that may have include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like, and it is preferably unsubstituted from the viewpoint of ease of synthesis.
  • n in the above formula (2) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, from the viewpoint of compatibility and dispersibility with a binder component such as a solvent.
  • the content ratio of the repeating unit represented by the formula (2) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 4 mol% or more. It is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. Within the above range, compatibility with a binder component such as a solvent and dispersion stability tend to be compatible.
  • the content ratio of the repeating unit represented by the formula (2) in all repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and further preferably 4 to 10 mol%. % Is more preferable.
  • the block copolymer preferably has a repeating unit represented by the following formula (3) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability.
  • R 8 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
  • R 9 is a hydrogen atom or a methyl group.
  • the number of carbon atoms of the alkyl group which may have a substituent in R 8 of the above formula (3) is not particularly limited, but is usually 1 or more, preferably 1 or more, and preferably 10 or less, and 6 or less. Is more preferable.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group.
  • a group, a pentyl group, or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable. Further, it may be linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the number of carbon atoms of the aryl group which may have a substituent in R 8 of the above formula (3) is not particularly limited, but is usually 6 or more, and is preferably 16 or less, more preferably 12 or less.
  • Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group, and the like.
  • a phenyl group, a methylphenyl group, an ethylphenyl group , Dimethylphenyl group, or diethylphenyl group is preferable, and phenyl group, methylphenyl group, or ethylphenyl group is more preferable.
  • the number of carbon atoms of the aralkyl group which may have a substituent in R 8 of the above formula (3) is not particularly limited, but is usually 7 or more, and is preferably 16 or less, more preferably 12 or less.
  • Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group and the like.
  • a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.
  • R 8 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethylene group.
  • substituent which the alkyl group may have in R 8 include a halogen atom and an alkoxy group.
  • the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom and an alkoxy group.
  • the chain alkyl group represented by R 8 includes both straight chain and branched chain groups.
  • the content ratio of the repeating unit represented by the formula (3) in all the repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more. It is preferably 80 mol% or less, more preferably 70 mol% or less. Within the above range, dispersion stability and high brightness tend to be compatible.
  • the content ratio of the repeating unit represented by the formula (3) in all the repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and 50 to 70 mol%. % Is more preferable.
  • the block copolymer has a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (2), and a repeating unit other than the repeating unit represented by the general formula (3).
  • repeating units include styrene-based monomers such as styrene and ⁇ -methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- (Meth)acrylamide-based monomers such as methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine.
  • the block having a repeating unit represented by the general formula (1) and a B block having no repeating unit represented by the general formula (1) It is preferably a block copolymer.
  • the block copolymer is preferably an AB block copolymer or a BAB block copolymer.
  • the B block has a repeating unit represented by the general formula (2) and a repeating unit represented by the general formula (3).
  • a repeating unit other than the repeating unit represented by the general formula (1) may be contained in the A block, and examples of such a repeating unit include the above-mentioned (meth)acrylic acid ester series. Examples include repeating units derived from monomers.
  • the content of the repeating unit other than the repeating unit represented by the general formula (1) in the A block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %. Most preferably, it is not contained in the A block.
  • a repeating unit other than the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) may be contained in the B block, and examples of such a repeating unit include Styrene-based monomers such as styrene, styrene and ⁇ -methylstyrene; (meth)acrylic acid salt-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide-based compounds such as (meth)acrylamide and N-methylolacrylamide Monomers; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; repeating units derived from monomers such as N-methacryloylmorpholine.
  • the content of the repeating unit represented by the general formula (2) and the repeating unit other than the repeating unit represented by the general formula (3) in the B block is preferably 0 to 50 mol %, and more preferably It is 0 to 20 mol %, but it is most preferable that such a repeating unit is not contained in the B block.
  • the acid value of the block copolymer is preferably low from the viewpoint of dispersibility, and particularly preferably 0 mgKOH/g.
  • the acid value represents the number of mg of KOH necessary to neutralize 1 g of the dispersant solid content.
  • the amine value of the block copolymer is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, further preferably 70 mgKOH/g or more, and more preferably 90 mgKOH/g or more from the viewpoint of dispersibility and developability. More preferably, 100 mgKOH/g or more is particularly preferable, 110 mgKOH/g or more is most preferable, 150 mgKOH/g or less is preferable, and 130 mgKOH/g or less is more preferable.
  • the amine value represents an amine value in terms of effective solid content, and is a value represented by the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant.
  • the amine value of the block copolymer is preferably 30 to 150 mgKOH/g, more preferably 50 to 150 mgKOH/g, further preferably 70 to 150 mgKOH/g, further preferably 90 to 130 mgKOH/g, and 100 to 130 mg KOH/g is particularly preferable, and 110 to 130 mg KOH/g is most preferable.
  • the molecular weight of the block copolymer is preferably in the range of 1,000 to 30,000 in terms of polystyrene-reduced weight average molecular weight (hereinafter sometimes referred to as “Mw”). Within the above range, the dispersion stability tends to be good, and dry foreign matter tends to be less likely to occur during coating by the slit nozzle method.
  • the block copolymer can be produced by a known method.
  • the block copolymer can be produced by living polymerization of the monomer into which each of the repeating units is introduced.
  • Examples of the living polymerization method include JP-A-9-62002, JP-A-2002-31713, and P.I. Lutz, P.; Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrews et al., Macromolecules, 14, 1601 (1981), K.S. Hatada, K.; Ute, et al, Polym. J.
  • the content ratio of the dispersant is not particularly limited, but is preferably 0.001 mass% or more, and 0.01 mass% in the total solid content of the colored resin composition.
  • the above is more preferable, 0.1% by mass or more is more preferable, 1% by mass or more is particularly preferable, 25% by mass or less is preferable, 20% by mass or less is more preferable, 15% by mass or less is further preferable, 10% by mass % Or less is particularly preferable.
  • dispersibility and storage stability tend to be improved, and when it is at most the above upper limit, electrical reliability and developability tend to be improved.
  • the content ratio of the dispersant is preferably 0.001 to 25% by mass, more preferably 0.01 to 20% by mass, and further preferably 0.1 to 15% by mass based on the total solid content of the colored resin composition. It is preferably from 1 to 10% by mass, and particularly preferably.
  • the content ratio of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, and more preferably 100 parts by mass of the pigment. Is 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass or less, It is more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. Within the above range, a coloring resin composition having excellent dispersion stability and high brightness tends to be obtained.
  • the content ratio of the dispersant is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, and further preferably 10 to 50 parts by mass with respect to 100 parts by mass of the pigment. More preferably, 15 to 40 parts by mass is even more preferable, and 20 to 30 parts by mass is particularly preferable.
  • a pigment derivative or the like may be contained as a dispersion aid in order to improve the dispersibility of the pigment and the dispersion stability.
  • pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolone.
  • examples include derivatives such as pyrrole pigments and dioxazine pigments.
  • a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amide group or the like may be directly attached to the pigment skeleton or may be an alkyl group, an aryl group, a hetero group. Examples thereof include those bonded via a ring group or the like, preferably a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group.
  • pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, isoindoline pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, and quinacridone pigment sulfonic acid derivatives.
  • examples thereof include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.
  • surfactant Various types of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but they may adversely affect various properties. It is preferable to use a nonionic surfactant because of its low value.
  • the content ratio of the surfactant is not particularly limited, but is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total solid content of the colored resin composition. It is preferably used in an amount of 0.1% by mass or more, usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.
  • the content ratio of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass based on the total solid content of the colored resin composition.
  • 0.05 to 0.5 mass% is more preferable, and 0.1 to 0.3 mass% is even more preferable.
  • a colorant-containing pigment When preparing a colorant-containing pigment, first weigh each predetermined amount of pigment, solvent, and dispersant, and disperse the pigment in the dispersion treatment step to prepare a pigment dispersion liquid.
  • a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like can be used.
  • the pigment is made into fine particles, so that the coating characteristics of the colored resin composition are improved and the transmittance of the pixels on the color filter substrate of the product is improved.
  • the pigment is dispersed, as described above, it is preferable to appropriately use a dispersion aid, a dispersion resin, or the like.
  • a dispersion aid When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several mm or zirconia beads.
  • the temperature for the dispersion treatment is usually set to 0° C. or higher, preferably room temperature or higher, and usually 100° C. or lower, preferably 80° C. or lower.
  • the dispersion time varies depending on the composition of the pigment dispersion liquid, the size of the sand grinder device, and the like, and therefore may be appropriately adjusted.
  • a solvent, an alkali-soluble resin, a photopolymerization initiator and, in some cases, components other than the above may be mixed with the pigment dispersion obtained by the above dispersion treatment to form a uniform dispersion solution.
  • fine dust since fine dust may be mixed in each of the dispersion treatment step and the mixing step, it is preferable to filter the obtained pigment dispersion liquid with a filter or the like.
  • a pigment When a pigment is not contained as a colorant, a colorant, a solvent, an alkali-soluble resin, a photopolymerization initiator and, in some cases, components other than the above may be mixed to obtain a uniform solution.
  • the obtained solution is preferably filtered by a filter or the like.
  • the color filter according to the present invention has pixels formed using the colored resin composition of the present invention.
  • the colored resin composition of the present invention is preferably a colored resin composition for forming pixels of a color filter.
  • the transparent substrate of the color filter is not particularly limited in material as long as it is transparent and has appropriate strength.
  • the material include polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, thermoplastic resin sheet of polycarbonate, polymethylmethacrylate, polysulfone, epoxy resin, unsaturated polyester resin, poly(meth)acrylic.
  • thermosetting resin sheets such as resin and various glasses. Among these, glass or heat resistant resin is preferable from the viewpoint of heat resistance.
  • Corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc. for improvement of surface properties such as adhesiveness on transparent substrate and black matrix forming substrate May be performed.
  • the thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less.
  • the film thickness is usually in the range of 0.01 ⁇ m or more, preferably 0.05 ⁇ m or more, and usually 10 ⁇ m or less, preferably 5 ⁇ m or less.
  • the color filter according to the present invention can be manufactured by providing a black matrix on the transparent substrate and forming red, green, and blue pixel images. It is preferable to use the colored resin composition as a coating liquid for forming a green pixel (resist pattern) among red, green, and blue pixels (hereinafter, may be abbreviated as “green resist”). Coating, heat drying, image exposure, and development on a resin black matrix forming surface formed on a transparent substrate using a green resist or on a metal black matrix forming surface formed using a chrome compound or other light shielding metal material. And each process of heat curing are performed to form a pixel image.
  • the black matrix is formed on the transparent substrate by using the light-shielding metal thin film or the colored resin composition for black matrix.
  • the light-shielding metal material chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloys, and the like are used, and these may be laminated in a plurality of layers.
  • These metal light-shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, cerium ammonium nitrate and perchloric acid and/or nitric acid are added to chromium. Etching solution mixed with the above is used, and other materials are etched by using an etching solution suitable for the material. Finally, the positive photoresist is removed with a dedicated release agent to form a black matrix. be able to.
  • a thin film of these metals or metal/metal oxides is formed on the transparent substrate by vapor deposition or sputtering. Then, after forming a coating film of the colored resin composition on this thin film, the coating film is exposed and developed using a photomask having a repeating pattern of stripes, mosaics, triangles, etc. to form a resist image. Then, the coating film can be subjected to etching treatment to form a black matrix.
  • the colored resin composition containing a black colorant is used to form the black matrix.
  • a black colorant such as carbon black, graphite, iron black, aniline black, cyanine black, and titanium black, or a plurality of black colorants, or a red, green, blue, or the like appropriately selected from inorganic or organic pigments and dyes.
  • a black matrix can be formed by using a colored resin composition containing a black colorant obtained by mixing in the same manner as in the method of forming a red, green and blue pixel image described below.
  • a colored resin composition of one of red, green, and blue is applied on a transparent substrate provided with a black matrix, dried, and a photomask is overlaid on the applied film.
  • a pixel image is formed through image exposure through a photomask, development, and if necessary, thermosetting or photocuring. By performing this operation for each of the three colored resin compositions of red, green and blue, a color filter image can be formed.
  • the application of the colored resin composition for the color filter can be performed by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like.
  • a spinner method a wire bar method
  • a flow coating method a die coating method
  • a roll coating method a spray coating method
  • the amount of the coating liquid used is significantly reduced, and there is no influence of mist or the like adhered when the spin coating method is used, and further, the generation of foreign matter is suppressed. From the viewpoint, it is preferable.
  • the thickness of the coating film after drying is usually 0.2 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, and usually 20 ⁇ m or less, preferably 10 ⁇ m or less, more preferably 5 ⁇ m.
  • the range is as follows.
  • Drying of Coating Film Drying of the coating film after coating the substrate with the colored resin composition is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, heating is performed again to dry. Preliminary drying conditions can be appropriately selected depending on the type of the solvent component, the performance of the dryer used, and the like.
  • the drying temperature and the drying time are selected according to the type of solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40°C or higher, preferably 50°C or higher, and usually 80°C.
  • the temperature is in the range of not higher than 70°C, preferably not higher than 70°C, and the drying time is usually not shorter than 15 seconds, preferably not shorter than 30 seconds, and usually not longer than 5 minutes, preferably not longer than 3 minutes.
  • the temperature condition for the reheating drying is preferably higher than the predrying temperature, specifically, usually 50°C or higher, preferably 70°C or higher, and usually 200°C or lower, preferably 160°C or lower, particularly preferably 130°C. It is in the range of °C or less.
  • the drying time which depends on the heating temperature, is usually 10 seconds or longer, preferably 15 seconds or longer, and usually 10 minutes or shorter, preferably 5 minutes. The higher the drying temperature is, the higher the adhesion to the transparent substrate is. However, if the drying temperature is too high, the alkali-soluble resin may be decomposed and thermal polymerization may be induced to cause poor development.
  • a reduced pressure drying method in which the temperature is not raised and drying is performed in a reduced pressure chamber may be used.
  • Exposure Step Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating a light source of ultraviolet rays or visible light through the mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer.
  • the light source used for the above image exposure is not particularly limited.
  • a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, an argon ion laser, a YAG laser
  • laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser.
  • An optical filter can also be used when irradiating and using the light of a specific wavelength.
  • the coating film using the colored resin composition according to the present invention is subjected to image exposure with the above-mentioned light source, and then an organic solvent or a surfactant.
  • an organic solvent or a surfactant By developing using an aqueous solution containing an alkali compound and an image, an image can be formed on the substrate to be manufactured.
  • the aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.
  • Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide, and mono-, di- or triethanolamine, mono-, di- or trimethylamine
  • TMAH tetramethylammonium hydroxide
  • TMAH tetramethylammonium hydroxide
  • the surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acid.
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acid.
  • anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts
  • amphoteric surfactants such as alkyl betaines and amino acids.
  • the organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like.
  • the organic solvent can be used in combination with the aqueous solution.
  • the conditions of the development treatment are not particularly limited, but the development temperature is usually 10° C. or higher, particularly 15° C. or higher, further 20° C. or higher, and usually 50° C. or lower, particularly 45° C. or lower, further 40° C. or lower. Is preferred.
  • the developing method can be any method such as an immersion developing method, a spray developing method, a brush developing method, and an ultrasonic developing method.
  • the color filter after development is subjected to heat curing treatment.
  • the heat curing treatment conditions at this time are selected such that the temperature is usually 100° C. or higher, preferably 150° C. or higher, and usually 280° C. or lower, preferably 250° C. or lower, and the time is 5 minutes or longer and 60 minutes or shorter. Selected in a range.
  • the patterning image formation for one color is completed through these series of steps. This process is sequentially repeated to pattern black, red, green and blue to form a color filter.
  • the order of patterning the four colors is not limited to the order described above.
  • the color filter according to the present invention is used as a part of parts such as a color display and a liquid crystal display device by forming a transparent electrode such as ITO on an image in this state.
  • a transparent electrode such as ITO
  • a top coat layer of polyamide, polyimide or the like can be provided on the image, if necessary.
  • the transparent electrode may not be formed in some applications such as a plane alignment driving method (IPS mode).
  • image display device panel
  • image display device of the present invention has the color filter described above.
  • a liquid crystal display device and an organic EL display device will be described in detail as image display devices.
  • [4-1] Liquid Crystal Display Device A method for manufacturing the liquid crystal display device according to the present invention will be described.
  • an alignment film is usually formed on the color filter according to the present invention, spacers are scattered on the alignment film, and then a liquid crystal cell is formed by bonding with a counter substrate to form a liquid crystal cell.
  • the liquid crystal is injected into the liquid crystal cell, and connected to the counter electrode to complete the process.
  • the orientation film is preferably a resin film such as polyimide.
  • a gravure printing method and/or a flexographic printing method is usually adopted, and the thickness of the alignment film is set to several tens nm. After the alignment film is cured by thermal baking, it is subjected to surface treatment by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface state in which the tilt of the liquid crystal can be adjusted.
  • the spacer a size corresponding to the gap with the counter substrate is used, and usually a size of 2 to 8 ⁇ m is suitable. It is also possible to form a photo spacer (PS) of a transparent resin film on the color filter substrate by a photolithography method and use this as a spacer.
  • An array substrate is usually used as the counter substrate, and a TFT (thin film transistor) substrate is particularly suitable.
  • the bonding gap with the counter substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 ⁇ m or more and 8 ⁇ m or less.
  • a sealing material such as epoxy resin.
  • the sealing material is cured by UV irradiation and/or heating, and the periphery of the liquid crystal cell is sealed.
  • the liquid crystal cell whose periphery is sealed is cut into panel units, the pressure is reduced in a vacuum chamber, the liquid crystal inlet is immersed in the liquid crystal, and then the chamber is leaked to inject the liquid crystal into the liquid crystal cell. ..
  • the degree of pressure reduction in the liquid crystal cell is usually in the range of 1 ⁇ 10 ⁇ 2 Pa or higher, preferably 1 ⁇ 10 ⁇ 3 or higher, and usually 1 ⁇ 10 ⁇ 7 Pa or lower, preferably 1 ⁇ 10 ⁇ 6 Pa or lower. .. Further, it is preferable to heat the liquid crystal cell during depressurization, and the heating temperature is usually 30° C. or higher, preferably 50° C. or higher, and usually 100° C. or lower, preferably 90° C. or lower.
  • liquid crystal display device panel
  • the type of liquid crystal is not particularly limited, and conventionally known liquid crystals such as aromatic compounds, aliphatic compounds, and polycyclic compounds, and may be any of lyotropic liquid crystals and thermotropic liquid crystals.
  • thermotropic liquid crystals are nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals and the like, but any of them may be used.
  • FIG. 1 An organic EL display device having a color filter of the present invention is produced, for example, as shown in FIG. 1, a pixel 20 is formed on a transparent support substrate 10 by the colored resin composition of the present invention.
  • a multicolor organic EL element is manufactured by stacking the organic light-emitting body 500 on the blue color filter formed with the organic protective layer 30 and the inorganic oxide film 40.
  • the organic light emitting device 500 As a method of stacking the organic light emitting device 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, Another method is to bond the organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40.
  • the organic EL element 100 thus manufactured is applicable to both a passive drive type organic EL display device and an active drive type organic EL display device.
  • ⁇ Phthalocyanine compound A> A phthalocyanine compound A having the following chemical structure, which was synthesized based on Example 30 of JP-A 05-345861, was used.
  • Et in the formula represents ethyl.
  • ⁇ Phthalocyanine compound B> Tetrachlorophthalonitrile (5.00 g, 18.8 mmol), 2-cyclohexyl-5-methylphenol (3.32 g, 18.8 mmol), potassium carbonate (3.89 g, 28.2 mmol) and acetonitrile (50 mL) were mixed and heated to 70°C. Heat and stir for 4 hours. After the reaction was completed, it was cooled to room temperature, and the reaction solution was filtered and concentrated. The resulting residue was recrystallized from acetonitrile to give 4.70 g of a mixture of intermediate A and intermediate B (yield 59%, purity 77.9%, intermediate A/intermediate B 73/23). Obtained. The purity is a value of area% calculated from the result of high performance liquid chromatography analysis.
  • Et in the formula represents ethyl.
  • Et in the formula represents ethyl.
  • phthalocyanine compound C When 1 mg of phthalocyanine compound C was dissolved in 100 mL of THF (tetrahydrofuran) and the visible absorption spectrum was measured with an ultraviolet-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) using a 1 cm square quartz cell, the maximum The absorption wavelength was 695.0 nm, and the molar absorption coefficient ( ⁇ ) was 1.11 ⁇ 10 5 .
  • Me in the formula represents methyl.
  • Me in the formula represents methyl.
  • ⁇ Phthalocyanine compound F Tetrafluorophthalonitrile (3.02 g, 15.0 mmol), potassium carbonate (4.14 g, 30.0 mmol) and acetone (50 mL) were mixed and ice-cooled. A solution of 5.40 g (30.0 mmol) of n-propyl p-hydroxybenzoate in acetone (30 mL) was added at 2 to 4° C., and the mixture was stirred for 5 hours as it was. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and ethanol was added for recrystallization. The obtained solid was filtered and vacuum dried to obtain 4.0 g (yield 51%, purity 95.9%) of intermediate F. The purity is a value of area% calculated from the result of high performance liquid chromatography analysis.
  • N-Pr in the formula represents n-propyl.
  • N-Pr in the formula represents n-propyl.
  • ⁇ Phthalocyanine compound G Tetrafluorophthalonitrile (2.00 g, 10 mmol), potassium fluoride (1.45 g, 2.5 mmol) and acetone (5 mL) were mixed and ice-cooled, and then methyl 3-(4-hydroxyphenyl)propanoate (3.78 g, 21 mmol). ) In acetone (5 mL) was added, and the mixture was stirred as it was for 5 hours.
  • reaction solution was extracted with chloroform-water, the organic layer was extracted with saturated saline, and the concentrated product was subjected to medium pressure preparative liquid chromatography (developing solvent was a mixed solvent of hexane and ethyl acetate, 94:6 ⁇ ). Purification with a gradient of 73:27 (volume ratio) gave 3.00 g (yield 58%, purity 97.8%) of intermediate G. The purity is a value of area% calculated from the result of high performance liquid chromatography analysis.
  • phthalocyanine compound G When 1 mg of phthalocyanine compound G was dissolved in 100 mL of DMSO and the visible absorption spectrum was measured with a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) using a 1 cm square quartz cell, the maximum absorption wavelength was 700. 0.0 nm, molar extinction coefficient ( ⁇ ) was 2.278 ⁇ 10 5 .
  • Dispersant A Dispersant “BYK-LPN6919” manufactured by Big Chemie> A methacrylic acid type AB block copolymer comprising an A block having a nitrogen atom-containing functional group and a B block having a solvophilic group. It has the repeating units of the following formulas (2a) and (3a) and does not have the repeating unit of the following formula (1a).
  • the amine value is 120 mgKOH/g and the acid value is 1 mgKOH/g or less.
  • the content ratios of the following formulas (2a) and (3a) in all the repeating units are 33.3 mol% and 6.7 mol%, respectively.
  • Pigment Green 58 is 11.0 parts by mass
  • Dispersant A is 1.6 parts by mass in terms of solid content
  • Alkali-soluble resin A described later is 3.3 parts by mass in terms of solid content
  • propylene glycol monomethyl ether acetate is 84 as a solvent.
  • 1 part by mass (including the solvent derived from the dispersant A and the solvent derived from the alkali-soluble resin A) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container and dispersed for 6 hours with a paint shaker. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare a green pigment dispersion liquid 1.
  • Pigment Green 59 is 11.0 parts by mass
  • Dispersant A is 1.6 parts by mass in terms of solid content
  • alkali-soluble resin A described later is 3.3 parts by mass in terms of solid content
  • propylene glycol monomethyl ether acetate is 84 as a solvent.
  • 1 part by mass (including the solvent derived from the dispersant A and the solvent derived from the alkali-soluble resin A) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container and dispersed for 6 hours with a paint shaker. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare a green pigment dispersion liquid 2.
  • the inside of the reaction vessel was changed to air displacement, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 27 parts by mass of acrylic acid, and the reaction was continued at 120° C. for 6 hours. Then, 52 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 120° C. for 3.5 hours. After cooling to room temperature, an alkali-soluble resin A having a polystyrene-equivalent weight average molecular weight Mw of 8,000 and an acid value of 80 mgKOH/g measured by GPC was obtained.
  • THPA tetrahydrophthalic anhydride
  • Me in the formula represents methyl.
  • ⁇ Preparation of colored resin composition The respective components were mixed at the solid content ratio and the solvent content ratio shown in Tables 1 and 2 to prepare respective colored resin compositions having a total solid content of 15% by mass.
  • the “ratio in solid content” means the ratio (mass %) of the solid content of various components in the total solid content.
  • the “ratio in solvent” means the ratio (mass %) of various solvents in all the solvents, and the amount of each solvent includes an alkali-soluble resin and a solvent derived from a pigment dispersion liquid.
  • C. in Comparative Examples 7 and 8 I. Pigment Green 58 and C.I. I.
  • the content ratio of Pigment Green 59 was set to 40.0 mass% in the total solid content.
  • the evaluation substrate obtained by the same procedure was subjected to development treatment using a 0.4% by mass potassium hydroxide aqueous solution at 23° C. for a time twice as long as the dissolution time, and a water pressure of 1 kg/cm 2 .
  • the residue evaluation substrate 2 was produced in the same procedure except that the development processing time was changed to 60 seconds.
  • the residue evaluation substrate 1 was visually observed, and the area (A) of the portion where no residue was found and the area (B) of the portion where residue was found were measured on the 50 mm square glass substrate, and the residue generation area was measured.
  • the ratio (%) (B)/ ⁇ (A)+(B) ⁇ 100 was evaluated. The results are shown in Table 4.
  • Example 1 was 1% and Example 2 was 0%, Example 3 is 1%, Example 4 is 0%, Example 5 is 0%, Example 6 is 0%, Example 7 is 0%, Example 8 is 0%, and Example 9 is 0%.
  • Example 10 is 0%, Example 11 is 1%, Example 12 is 0%, Example 13 is 0%, Example 14 is 0%, Example 15 is 1%, and Example 16 is 1%. Met.
  • Example 1 ⁇ Evaluation of color characteristics> Example 1, Example 4, Example 8, Example 13, Example 14, Example 15, Example 16, on a glass substrate (AN100 manufactured by AGC Co., Ltd.) having a size of 50 mm square and a thickness of 0.7 mm, a comparison.
  • the colored resin compositions of Example 5, Comparative Example 6, Comparative Example 7, and Comparative Example 8 were applied with a spin coater and then dried at 80° C. for 3 minutes. Next, the entire surface was exposed with a 2 kW high pressure mercury lamp at an exposure dose of 40 mJ/cm 2 . Then, development processing was performed using a 0.4 mass% potassium hydroxide aqueous solution at 23°C.
  • a transmission spectrum was measured with a C light source using a spectrophotometer U-3310 manufactured by Hitachi Ltd., and chromaticity (sx, sy) and luminance were calculated.
  • the phthalocyanine compound (1) is a fluorine-containing compound having a small atomic radius, because the molecules are likely to associate with each other by the ⁇ - ⁇ interaction between the phthalocyanine rings and the ⁇ - ⁇ interaction between the groups represented by the formula (2).
  • the packing of molecules becomes denser, the affinity with the alkali-soluble resin is weak, and it becomes difficult for the alkali developer to permeate the phthalocyanine compound (1) at the time of alkali development, resulting in a decrease in alkali solubility. It is considered that the residue is likely to remain on the glass substrate.
  • the phthalocyanine compounds B and C not satisfying the formula (1) have a larger residual area than the phthalocyanine compound (1). It is considered that the phthalocyanine compound B has a chlorine atom instead of a fluorine atom, and the polarity of the phthalocyanine compound is thereby lowered, so that the solubility in a highly polar developing solution (alkali aqueous solution) is lowered. Further, it is considered that the central metal of the phthalocyanine compound C is copper, which reduces the ionization tendency of the phthalocyanine compound and reduces the solubility in the developing solution (alkali aqueous solution).
  • Example 1 the luminance is higher in Example 1 than in Comparative Examples 5 and 6.
  • the phthalocyanine compound (1) contained in Example 1 has a fluorine atom and thus the polarity of the phthalocyanine compound is high, so that the solubility in the solvent in the colored resin composition is high and the phthalocyanine compound is This is considered to be because the aggregation and the like of the two were suppressed, and the crystal form was optimized by the central metal being zinc.
  • Transparent Support Substrate 20 Pixel 30 Organic Protective Layer 40 Inorganic Oxide Film 50 Transparent Anode 51 Hole Injection Layer 52 Hole Transport Layer 53 Light Emitting Layer 54 Electron Injection Layer 55 Cathode 100 Organic EL Element 500 Organic Light Emitting Element

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
PCT/JP2020/006617 2019-02-22 2020-02-19 着色樹脂組成物、カラーフィルタ、及び画像表示装置 WO2020171139A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020217016965A KR20210131990A (ko) 2019-02-22 2020-02-19 착색 수지 조성물, 컬러 필터, 및 화상 표시 장치
CN202080008039.1A CN113272388A (zh) 2019-02-22 2020-02-19 着色树脂组合物、滤色片、以及图像显示装置
JP2021502107A JPWO2020171139A1 (ja) 2019-02-22 2020-02-19 着色樹脂組成物、カラーフィルタ、及び画像表示装置

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2019-030548 2019-02-22
JP2019030548 2019-02-22
JP2019119240 2019-06-27
JP2019-119240 2019-06-27

Publications (1)

Publication Number Publication Date
WO2020171139A1 true WO2020171139A1 (ja) 2020-08-27

Family

ID=72144977

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/006617 WO2020171139A1 (ja) 2019-02-22 2020-02-19 着色樹脂組成物、カラーフィルタ、及び画像表示装置

Country Status (5)

Country Link
JP (1) JPWO2020171139A1 (ko)
KR (1) KR20210131990A (ko)
CN (1) CN113272388A (ko)
TW (1) TWI812845B (ko)
WO (1) WO2020171139A1 (ko)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023063336A1 (ja) * 2021-10-12 2023-04-20 三菱ケミカル株式会社 着色樹脂組成物、カラーフィルタ及び画像表示装置
WO2023090221A1 (ja) * 2021-11-19 2023-05-25 富士フイルム株式会社 フッ化フタロシアニン化合物、着色組成物、及びインクジェット用インク

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113272346A (zh) * 2019-02-21 2021-08-17 三菱化学株式会社 着色树脂组合物、滤色片、以及图像显示装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09171108A (ja) * 1995-10-16 1997-06-30 Nippon Shokubai Co Ltd フタロシアニン化合物を含んでなるカラーフィルター
JP2000281927A (ja) * 1999-03-31 2000-10-10 Nippon Shokubai Co Ltd 顔料分散剤およびその用途
JP2014028950A (ja) * 2012-07-04 2014-02-13 Nippon Shokubai Co Ltd 組成物およびカラーフィルタ
JP2014043555A (ja) * 2012-07-30 2014-03-13 Fujifilm Corp 着色硬化性組成物およびカラーフィルタ
JP2020046655A (ja) * 2018-09-14 2020-03-26 Jsr株式会社 感光性着色組成物、カラーフィルタ及び表示素子

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5581566B2 (ja) 2007-08-24 2014-09-03 住友化学株式会社 着色硬化性組成物
JP6205193B2 (ja) 2012-07-30 2017-09-27 富士フイルム株式会社 着色硬化性組成物、これを用いたカラーフィルタ
JP6005258B2 (ja) 2013-03-27 2016-10-12 富士フイルム株式会社 着色組成物、感光性着色組成物、カラーフィルタ及びその製造方法、固体撮像素子、並びに画像表示装置
CN110908241A (zh) * 2018-09-14 2020-03-24 Jsr株式会社 感光性着色组合物、彩色滤光片及显示元件

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09171108A (ja) * 1995-10-16 1997-06-30 Nippon Shokubai Co Ltd フタロシアニン化合物を含んでなるカラーフィルター
JP2000281927A (ja) * 1999-03-31 2000-10-10 Nippon Shokubai Co Ltd 顔料分散剤およびその用途
JP2014028950A (ja) * 2012-07-04 2014-02-13 Nippon Shokubai Co Ltd 組成物およびカラーフィルタ
JP2014043555A (ja) * 2012-07-30 2014-03-13 Fujifilm Corp 着色硬化性組成物およびカラーフィルタ
JP2020046655A (ja) * 2018-09-14 2020-03-26 Jsr株式会社 感光性着色組成物、カラーフィルタ及び表示素子

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023063336A1 (ja) * 2021-10-12 2023-04-20 三菱ケミカル株式会社 着色樹脂組成物、カラーフィルタ及び画像表示装置
WO2023090221A1 (ja) * 2021-11-19 2023-05-25 富士フイルム株式会社 フッ化フタロシアニン化合物、着色組成物、及びインクジェット用インク

Also Published As

Publication number Publication date
TWI812845B (zh) 2023-08-21
KR20210131990A (ko) 2021-11-03
TW202045627A (zh) 2020-12-16
CN113272388A (zh) 2021-08-17
JPWO2020171139A1 (ja) 2021-12-16

Similar Documents

Publication Publication Date Title
JP7451906B2 (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
JP7003637B2 (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
WO2020171139A1 (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
JP5316034B2 (ja) カラーフィルタ用着色組成物、カラーフィルタ、及び液晶表示装置
JP2019144543A (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
WO2022038948A1 (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
JP7207173B2 (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
JP6885075B2 (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
JP7180545B2 (ja) カラーフィルタ用着色組成物、及び感光性着色樹脂組成物
WO2020171060A1 (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
WO2022039224A1 (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
JP5919689B2 (ja) 顔料分散液、着色樹脂組成物、カラーフィルタ、液晶表示装置及び有機ｅｌ表示装置
WO2023176888A1 (ja) カラーフィルタの製造方法、及び画像表示装置の製造方法
WO2023176882A1 (ja) 着色樹脂組成物、硬化物、カラーフィルタ及び画像表示装置
JP7447397B2 (ja) 感光性着色樹脂組成物、カラーフィルタ、及び画像表示装置
WO2023063336A1 (ja) 着色樹脂組成物、カラーフィルタ及び画像表示装置
JP7159948B2 (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
WO2024075837A1 (ja) 着色剤含有液、着色樹脂組成物、カラーフィルタ、画像表示装置、及び着色樹脂組成物の製造方法
WO2022024876A1 (ja) 着色樹脂組成物、カラーフィルタ、画像表示装置、及び着色剤分散液
WO2023095828A1 (ja) 着色樹脂組成物、着色樹脂組成物セット、及びカラーフィルタ
JP2021056382A (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
JP2024040909A (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
CN118843811A (zh) 滤色器的制造方法和图像显示装置的制造方法
JP2021067706A (ja) 顔料分散液及び着色樹脂組成物
CN118843831A (zh) 着色树脂组合物、固化物、滤色器和图像显示装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20759028

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021502107

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20759028

Country of ref document: EP

Kind code of ref document: A1