WO2020031633A1 - 分散剤組成物、着色組成物、および、カラーフィルタ - Google Patents
分散剤組成物、着色組成物、および、カラーフィルタ Download PDFInfo
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- WO2020031633A1 WO2020031633A1 PCT/JP2019/028051 JP2019028051W WO2020031633A1 WO 2020031633 A1 WO2020031633 A1 WO 2020031633A1 JP 2019028051 W JP2019028051 W JP 2019028051W WO 2020031633 A1 WO2020031633 A1 WO 2020031633A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
Definitions
- the present invention relates to a dispersant composition containing a polymer.
- a dyeing method for a liquid crystal display or the like
- a printing method for a coloring material to a substrate
- an ink jet method for a coloring material to a substrate
- an electrodeposition method for a pigment dispersion method
- the pigment dispersion method is mainly used from the viewpoints of spectral characteristics, durability, pattern shape and accuracy.
- a coating film made of a coloring composition in which a pigment, a dispersant, a dispersion medium (solvent), a binder resin, and the like are mixed is formed on a substrate, and radiation is applied through a photomask having a desired pattern shape. Irradiation cures and alkali development is performed.
- Patent Document 2 discloses, as a pigment dispersion, an AB block copolymer comprising an A block having a polylactone chain in a side chain and a B block having a tertiary amino group in a side chain. It is described to be used (see Patent Document 2 (paragraphs 0023 to 0045)).
- the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a dispersant composition that generates a small amount of formaldehyde over time.
- the dispersant composition of the present invention that has solved the above-mentioned problems is characterized by containing a polymer having a structure represented by the general formula (5) in a side chain.
- * -Y 1 -NR 11 R 12 (5) [In the general formula (5), R 11 represents a hydrogen atom, an optionally substituted linear or cyclic hydrocarbon group having 2 or more carbon atoms. R 12 represents a linear or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R 11 and R 12 may combine with each other to form a cyclic structure. Y 1 represents a divalent hydrocarbon group. * Represents a bond. ]
- the present invention also includes a coloring composition comprising the dispersant composition, a coloring material, a binder resin and a dispersion medium.
- the present invention also includes a color filter comprising a coloring layer formed using the coloring composition.
- a dispersant composition having a small amount of formaldehyde generated over time can be obtained.
- (meth) acryl means “at least one of acryl and methacryl”.
- (Meth) acrylic monomer refers to a monomer having a “(meth) acryloyl group” in the molecule.
- (Meth) acryloyl refers to “at least one of acryloyl and methacryloyl”.
- “Vinyl monomer” refers to a monomer having a radically polymerizable carbon-carbon double bond in the molecule.
- “Structural unit derived from (meth) acrylic monomer” refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a (meth) acrylic monomer is polymerized into a carbon-carbon single bond.
- the “structural unit derived from a vinyl monomer” refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized into a carbon-carbon single bond.
- the dispersant composition of the present invention is characterized in that the side chain contains a polymer having a structure represented by the general formula (5). * -Y 1 -NR 11 R 12 (5)
- R 11 represents a hydrogen atom, an optionally substituted linear or cyclic hydrocarbon group having 2 or more carbon atoms.
- R 12 represents a linear or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent.
- R 11 and R 12 may combine with each other to form a cyclic structure.
- Y 1 represents a divalent hydrocarbon group. * Represents a bond. ]
- Examples of the chain hydrocarbon group represented by R 11 and R 12 include a linear alkyl group and a branched chain alkyl group.
- the linear alkyl group preferably has 2 to 20 carbon atoms, more preferably has 2 to 10 carbon atoms, and still more preferably has 2 to 5 carbon atoms.
- Examples of the linear alkyl group include an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group and an n-lauryl group. .
- the branched chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 3 to 5 carbon atoms.
- Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a neopentyl group, and an isooctyl group.
- Examples of the substituent of the chain hydrocarbon group represented by R 11 and R 12 include a halogen group, an alkoxy group, a benzoyl group (—COC 6 H 5 ), and a hydroxy group.
- Examples of the cyclic hydrocarbon group represented by R 11 and R 12 include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain portion.
- the cyclic alkyl group preferably has 4 to 18 carbon atoms, more preferably has 6 to 12 carbon atoms, and still more preferably has 6 to 10 carbon atoms.
- Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
- the aromatic group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms.
- the aromatic group include a phenyl group, a tolyl group, a xylyl group, and a mesityl group.
- the cyclic alkyl group having a chain portion and the chain portion of the aromatic group having a chain portion include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably Examples include alkylene groups of formulas 1 to 3.
- Examples of the substituent of the cyclic hydrocarbon group represented by R 11 and R 12 include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxy group.
- Examples of the cyclic structure formed by combining R 11 and R 12 with each other include a 5- to 7-membered nitrogen-containing heterocycle or a condensed ring formed by condensing two of them.
- the nitrogen-containing hetero ring preferably has no aromaticity, and is more preferably a saturated ring.
- Examples of the divalent hydrocarbon group represented by Y 1 include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, and an arenediyl group having 6 to 10 carbon atoms. Among these, an alkylene group having 1 to 10 carbon atoms is preferable.
- the alkylene group may be linear or branched, but is preferably linear.
- Y 1 is preferably an alkylene group having 1 to 5 carbon atoms.
- the —NR 11 R 12 moiety of the structure represented by the general formula (5) includes a monoalkylamino group such as an ethylamino group, a propylamino group, and a tert-butylamino group; a diethylamino group, a dipropylamino group And a dialkylamino group such as a bis (2-hydroxyethyl) amino group.
- Examples of the polymer having a structure represented by the general formula (5) in the side chain include a (meth) acrylic polymer, a polyurethane polymer, a polyester polymer, a polyallylamine polymer, and a carbodiimide polymer. Can be mentioned.
- the amine value of the polymer having a structure represented by the general formula (5) in the side chain is preferably 10 mgKOH / g or more, more preferably 50 mgKOH / g, from the viewpoints of adsorbability to the colorant and dispersibility of the colorant. g or more, more preferably 80 mgKOH / g or more, preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, even more preferably 120 mgKOH / g or less.
- the molecular weight of the polymer having a structure represented by the general formula (5) in the side chain is measured by gel permeation chromatography.
- the weight average molecular weight (Mw) of the polymer is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, particularly preferably 6,000 or more, and 40,000 or less. Is more preferably 30,000 or less, further preferably 25,000 or less, and particularly preferably 20,000 or less. When the weight average molecular weight is within the above range, the dispersing performance when used as a dispersant becomes better.
- the polymer preferably has a block copolymer having an A block having a structural unit derived from a (meth) acrylic monomer and a B block having a structural unit represented by the general formula (1). Coalescence is preferred.
- R 11 represents a hydrogen atom, a linear or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent.
- R 12 represents a linear or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent.
- R 11 and R 12 may combine with each other to form a cyclic structure.
- R 13 represents a hydrogen atom or a methyl group.
- X 1 represents an amide group, an ester group, or a single bond.
- Y 1 represents a divalent hydrocarbon group.
- the A block is a polymer block containing a structural unit derived from a (meth) acrylic monomer.
- the structural unit derived from the (meth) acrylic monomer in the A block may be only one type, or may have two or more types.
- the content of the structural unit derived from the (meth) acrylic monomer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably 100% by mass of the A block. Is 100% by mass.
- the (meth) acrylic monomer includes a (meth) acrylate having a chain alkyl group (a linear alkyl group or a branched chain alkyl group), a (meth) acrylate having a cyclic alkyl group, and a (meth) acrylate having a polycyclic structure.
- (Meth) acrylate having an aromatic group (meth) acrylate having a polyalkylene glycol structural unit, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone-modified hydroxy group, and (meth) having an alkoxy group
- Acrylates (meth) acrylates having an oxygen-containing heterocyclic group, (meth) acrylates having an acidic group, (meth) acrylic acid, and the like can be used, and one or more of these can be used in combination. Can be.
- the (meth) acrylate having a straight-chain alkyl group is preferably a (meth) acrylate having a straight-chain alkyl group having 1 to 20 carbon atoms, and a straight-chain alkyl group having 1 to 20 carbon atoms.
- a (meth) acrylate having a linear alkyl group of 10 is more preferred.
- Examples of the (meth) acrylate having a linear alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, Examples include n-octyl (meth) acrylate, n-nonyl (meth) acrylate, decyl (meth) acrylate, n-lauryl (meth) acrylate, and n-stearyl (meth) acrylate.
- the (meth) acrylate having a branched alkyl group is preferably a (meth) acrylate having a branched alkyl group having 3 to 20 carbon atoms, and a branched alkyl group having 3 to 20 carbon atoms.
- a (meth) acrylate having a branched alkyl group of 10 is preferred.
- Examples of the (meth) acrylate having a branched alkyl group include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, 2- Examples include ethylhexyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth) acrylate.
- the (meth) acrylate having a cyclic alkyl group is preferably a (meth) acrylate having a cyclic alkyl group having 6 to 12 carbon atoms.
- the cyclic alkyl group include a cyclic alkyl group having a single ring structure (for example, a cycloalkyl group).
- Specific examples of (meth) acrylates having a monocyclic cyclic alkyl group include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate.
- the (meth) acrylate having a polycyclic structure is preferably a (meth) acrylate having a polycyclic structure having 6 to 12 carbon atoms.
- the polycyclic structure include a cyclic alkyl group having a bridged ring structure (for example, an adamantyl group, a norbornyl group, and an isobornyl group).
- Specific examples of the (meth) acrylate having a polycyclic structure include isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and 2-methyl-2-adamantyl. (Meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and the like.
- the (meth) acrylate having an aromatic group is preferably a (meth) acrylate having an aromatic group having 6 to 12 carbon atoms.
- the aromatic group include an aryl group and the like, and may have a chain portion such as an alkylaryl group, an aralkyl group, and an aryloxyalkyl group.
- Specific examples of the (meth) acrylate having an aromatic group include benzyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
- Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6- Examples include hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate.
- a (meth) acrylate having a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable.
- Examples of the (meth) acrylate having a lactone-modified hydroxy group include those obtained by adding a lactone to the (meth) acrylate having a hydroxy group, and those obtained by adding caprolactone are preferable.
- the added amount of caprolactone is preferably 1 mol to 10 mol, more preferably 1 mol to 5 mol.
- Examples of the (meth) acrylate having a lactone-modified hydroxy group include 2-hydroxyethyl (meth) acrylate adduct of 1 mol of caprolactone, 2-hydroxyethyl (meth) acrylate adduct of 2 mol of caprolactone, and 2-hydroxyethyl (meth) acrylate Are preferably 3 mol adduct of caprolactone, 4 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, 5 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, and 10 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate. .
- Examples of the (meth) acrylate having an alkoxy group include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.
- a (meth) acrylate having an oxygen-containing heterocyclic group a (meth) acrylate having a 4- to 6-membered oxygen-containing heterocyclic group is preferable.
- Specific examples of the (meth) acrylate having an oxygen-containing heterocyclic group include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, and (2- Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropaneformal (meth) acrylate, 2-[(2-tetrahydropyranyl) oxy] ethyl (meth) acrylate, 1,3-dioxane- (meth) acrylate and the like.
- Examples of the acidic group include a carboxy group (—COOH), a sulfonic acid group (—SO 3 H), a phosphoric acid group (—OPO 3 H 2 ), a phosphonic acid group (—PO 3 H 2 ), and a phosphinic acid group (— PO 2 H 2 ).
- Examples of the (meth) acrylate having an acidic group include (meth) acrylate having a carboxy group, (meth) acrylate having a phosphoric acid group, and (meth) acrylate having a sulfonic acid group.
- Examples of the (meth) acrylate having a carboxy group include carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, Examples include monomers obtained by reacting a (meth) acrylate having a hydroxy group such as (meth) acryloyloxyethyl phthalate with an acid anhydride such as maleic anhydride, succinic anhydride, or phthalic anhydride.
- Examples of the (meth) acrylate having a sulfonic acid group include ethyl sulfonic acid (meth) acrylate.
- Examples of the (meth) acrylate having a phosphate group include 2- (phosphonooxy) ethyl (meth) acrylate.
- the A block may have a structural unit other than the structural unit derived from the (meth) acrylic monomer.
- Other structural units that can be included in the A block are not particularly limited as long as they are formed of a vinyl monomer that can be copolymerized with both a (meth) acrylic monomer and a vinyl monomer that forms a B block described below.
- Vinyl monomers capable of forming other structural units of the A block may be used alone or in combination of two or more.
- Examples of the ⁇ -olefin include 1-hexene, 1-octene, 1-decene and the like.
- Examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene, and the like.
- Examples of the vinyl monomer containing a hetero ring include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine, N-phenylmaleimide, and N-benzyl Maleimide, N-cyclohexylmaleimide and the like.
- Examples of vinylamide include N-vinylformamide, N-vinylacetamide, N-vinyl- ⁇ -caprolactam, and the like.
- Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate and the like.
- Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like.
- the A block preferably contains a structural unit represented by the general formula (10), that is, a structural unit derived from the (meth) acrylate having a lactone-modified hydroxy group. Since the structural unit represented by the general formula (10) has an ester bond portion and a terminal hydroxy group in a side chain, it has high affinity for a dispersion medium and a binder resin, and has an alkali developability of a block copolymer. Enhance.
- n1 represents an integer of 1 to 10.
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents an alkylene group having 1 to 10 carbon atoms.
- R 3 represents an alkylene group having 1 to 10 carbon atoms.
- Nn1 in the above formula (10) is preferably an integer of 1 to 7, more preferably an integer of 1 to 5.
- the alkylene group having 1 to 10 carbon atoms represented by R 2 may be linear or branched, but is preferably linear. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R 2 include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, Examples include a nonamethylene group, a decamethylene group, and a 1-methylethylene group. R 2 is preferably an alkylene group having 1 to 5 carbon atoms.
- the alkylene group having 1 to 10 carbon atoms represented by R 3 may be linear or branched, but is preferably linear. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R 3 include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, Examples include a nonamethylene group and a decamethylene group. R 3 is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 3 to 8 carbon atoms.
- the content is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 100% by mass of the A block. Is 30% by mass or more, particularly preferably 60% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
- the A block preferably has a structural unit derived from a vinyl monomer having an acidic group (preferably, (meth) acrylate or (meth) acrylic acid having an acidic group).
- a vinyl monomer having an acidic group preferably, (meth) acrylate or (meth) acrylic acid having an acidic group.
- the content is preferably 2% by mass or more and 100% by mass or less in 100% by mass of the A block.
- the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate upon neutralization with an alkali increases in alkali development, and when the content is 20% by mass or less, the hydrophilicity is high. This makes it possible to prevent the formed pixels from being cluttered.
- the content of the structural unit represented by the general formula (1) described below is less than 10% by mass, preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass or less. Most preferably, it does not contain the structural unit represented by the general formula (1) by mass% or less. As the content of the structural unit represented by the general formula (1) in the A block is lower, the dispersibility of the coloring material is improved.
- the ⁇ ⁇ ⁇ ⁇ A block preferably has no amino group. That is, it is preferable that the vinyl monomer constituting the A block does not contain a vinyl monomer having an amino group.
- the coloring material when used as a dispersant, the coloring material is adsorbed on both the A block and the B block, and the dispersing performance of the coloring material is reduced.
- the content of the structural unit derived from the vinyl monomer having an amino group in the A block is preferably 3% by mass or less, more preferably 1% by mass or less, The content is more preferably 0.1% by mass or less, and most preferably 0% by mass.
- the various structural units contained in the A block may be contained in the A block in any mode such as random copolymerization and block copolymerization. From the viewpoint of uniformity, it is preferable that the compound is contained in a mode of random copolymerization.
- the A block may be formed of a copolymer of a structural unit composed of an a1 block and a structural unit composed of an a2 block.
- the B block is a polymer block containing a structural unit represented by the following general formula (1).
- the structural unit represented by the general formula (1) may be only one type, or may have two or more types. By having the structural unit represented by the general formula (1), the adsorptivity to a coloring material is high, and generation of formaldehyde over time can be suppressed.
- -Y 1 -NR 11 R 12 bonded to X 1 is a structure represented by the general formula (5).
- R 11 represents a hydrogen atom, a linear or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent.
- R 12 represents a linear or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent.
- R 11 and R 12 may combine with each other to form a cyclic structure.
- R 13 represents a hydrogen atom or a methyl group.
- X 1 represents an amide group, an ester group, or a single bond.
- Y 1 represents a divalent hydrocarbon group.
- R 11 and R 12 in the general formula (1) has the same meaning as R 11 and R 12 in the general formula (5).
- Examples of the chain hydrocarbon group and the cyclic hydrocarbon group represented by R 11 and R 12 in the general formula (1) include those exemplified as R 11 and R 12 in the general formula (5).
- the carbon number of the linear alkyl group represented by R 11 and R 12 in the general formula (1) is preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 2 to 5 carbon atoms.
- the number of carbon atoms in the branched alkyl group is preferably from 3 to 20, more preferably from 3 to 10, and even more preferably from 3 to 5.
- Examples of the cyclic structure formed by combining R 11 and R 12 with each other include a 5- to 7-membered nitrogen-containing heterocycle or a condensed ring formed by condensing two of them.
- the nitrogen-containing hetero ring preferably has no aromaticity, and is more preferably a saturated ring.
- Specific examples include structures represented by the following formulas (1-1), (1-2), and (1-3).
- R 14 represents an alkyl group having 1 to 6 carbon atoms.
- l represents an integer of 0 to 5.
- m represents an integer of 0 to 4.
- n represents an integer of 0 to 4. * Represents a bond. When 1 is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R 14 may be the same or different.
- X 1 represents an amide group (—CO—NH—), an ester group (—CO—O—), or a single bond.
- the bonding direction of the amide group and the ester group is not particularly limited.
- Examples of the bonding mode of the amide group include C-CO-NH-Y 1 and C-NH-CO-Y 1 , and C-CO-NH-Y 1 is preferable.
- Examples of the bonding mode of the ester group include C—CO—O—Y 1 and C—O—CO—Y 1 , with C—CO—O—Y 1 being preferred.
- Y 1 in the general formula (1) has the same meaning as Y 1 in the general formula (5).
- Y 1 is preferably an alkylene group having 1 to 10 carbon atoms.
- the alkylene group may be linear or branched, but is preferably linear.
- Y 1 is preferably an alkylene group having 1 to 5 carbon atoms.
- vinyl monomer forming the structural unit represented by the general formula (1) examples include ethylaminoethyl (meth) acrylate, ethylaminopropyl (meth) acrylate, ethylaminobutyl (meth) acrylate, and diethylaminoethyl (meth).
- the content of the structural unit represented by the general formula (1) is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more in 100% by mass of the B block, and 98% by mass. % Or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
- the B block may have a structural unit represented by the general formula (2).
- the structural unit represented by the general formula (2) in the B block may be only one type, or may have two or more types.
- strong adsorption to the colorant surface can be maintained for a long time, and storage stability is further improved.
- R 21 represents a hydrogen atom, a linear or cyclic hydrocarbon group which may have a substituent.
- R 22 and R 23 each independently represent a linear or cyclic hydrocarbon group which may have a substituent.
- R 22 and R 23 may combine with each other to form a cyclic structure.
- R 24 represents a hydrogen atom or a methyl group.
- X 2 represents an amide group, an ester group, or a single bond.
- Y 2 represents a divalent hydrocarbon group.
- Examples of the chain hydrocarbon group represented by R 21 to R 23 include a linear alkyl group and a branched alkyl group.
- the linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 2 to 20 carbon atoms, further preferably has 2 to 10 carbon atoms, and particularly preferably has 2 to 5 carbon atoms.
- Examples of the linear alkyl group include an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group and an n-lauryl group. .
- the branched chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 3 to 5 carbon atoms.
- Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a neopentyl group, and an isooctyl group.
- Examples of the substituent on the chain hydrocarbon group represented by R 21 to R 23 include a halogen group, an alkoxy group, a benzoyl group (—COC 6 H 5 ), and a hydroxy group.
- Examples of the cyclic hydrocarbon group represented by R 21 to R 23 include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain portion.
- the cyclic alkyl group preferably has 4 to 18 carbon atoms, more preferably has 6 to 12 carbon atoms, and still more preferably has 6 to 10 carbon atoms.
- Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
- the aromatic group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms.
- the aromatic group include a phenyl group, a tolyl group, a xylyl group, and a mesityl group.
- the cyclic alkyl group having a chain portion and the chain portion of the aromatic group having a chain portion include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably Examples include alkylene groups of formulas 1 to 3.
- Examples of the substituent on the cyclic hydrocarbon group represented by R 21 to R 23 include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxy group.
- Examples of the cyclic structure formed by combining R 22 and R 23 with each other include a 5- to 7-membered nitrogen-containing heterocycle or a condensed ring formed by condensing two of them.
- the nitrogen-containing hetero ring preferably has no aromaticity, and is more preferably a saturated ring.
- Specific examples include structures represented by the following formulas (2-1), (2-2), and (2-3).
- R 25 is R 21 .
- R 26 represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5. m represents an integer of 0 to 4. n represents an integer of 0 to 4. * Represents a bond. When 1 is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R 26 may be the same or different.
- X 2 represents an amide group (—CO—NH—), an ester group (—CO—O—), or a single bond.
- the bonding direction of the amide group and the ester group is not particularly limited.
- Examples of the bonding mode of the amide group include C-CO-NH-Y 2 and C-NH-CO-Y 2 , and C-CO-NH-Y 2 is preferable.
- Examples of the bonding mode of the ester group include C—CO—O—Y 2 and C—O—CO—Y 2 , with C—CO—O—Y 2 being preferred.
- Examples of the divalent hydrocarbon group represented by Y 2 include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, and an areendiyl group having 6 to 10 carbon atoms. Among these, an alkylene group having 1 to 10 carbon atoms is preferable.
- the alkylene group may be linear or branched, but is preferably linear.
- Y 2 is preferably an alkylene group having 1 to 5 carbon atoms.
- Z - examples include a halogen anion, a carboxylate anion, a sulfate anion, a sulfonate anion, a phosphate anion, and a nitroxide anion.
- the halogen anion include a fluoro anion, a chloro anion, a bromo anion and an iodo anion.
- the carboxylate anion include an alkyl carboxylate anion such as an acetate anion and a propionate anion; and an aromatic carboxylate anion such as a benzoate anion.
- the sulfate anion examples include an alkyl sulfate anion such as a methyl sulfate anion and an ethyl sulfate anion; and an aromatic sulfate anion such as a phenyl sulfate anion and a benzyl sulfate anion.
- the sulfonate anion examples include alkyl sulfonate anions such as methanesulfonic acid anion and ethanesulfonic acid anion; and aromatic sulfonate anions such as benzenesulfonic acid anion and toluenesulfonic acid anion.
- phosphate anion examples include alkyl phosphate anions such as methyl phosphonate anion and ethyl phosphonate anion; and aromatic phosphate anions such as phenyl phosphonate anion and benzyl phosphonate anion.
- vinyl monomer forming the structural unit represented by the formula (2) include (meth) acryloyloxyethylbenzyldiethylammonium chloride, (meth) acryloyloxypropylbenzyldiethylammonium chloride, and (meth) acryloyloxybutylbenzyl.
- Diethyl ammonium chloride (meth) acryloyloxyethylbenzyl diethylammonium bromide, (meth) acryloyloxypropylbenzyldiethylammonium bromide, (meth) acryloyloxybutylbenzyldiethylammonium bromide, (meth) acryloyloxyethylbenzyldiethylammonium iodide, (Meth) acryloyloxypropylbenzyldiethylammonium iodide, (meth) acryloyloxy Chill benzyl diethyl ammonium iodide, (meth) acryloyloxyethyl benzyl diethyl ammonium fluoride, (meth) acryloyloxy propyl benzyl diethyl ammonium fluoride, and (meth) acryloyloxy butyl benzyl
- the content is preferably 2% by mass or more, more preferably 20% by mass or more, and 90% by mass or less in 100% by mass of the B block. Preferably, it is 70% by mass or less.
- the B block may include only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may include another structural unit. From the viewpoint of maintaining the affinity with the coloring material, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the B block is 100 mass of the B block. %, Preferably at least 80% by mass, more preferably at least 90% by mass, even more preferably at least 95% by mass. Further, the B block preferably does not substantially contain a structural unit derived from a vinyl monomer having an acidic group. That is, the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 5% by mass or less, more preferably 2% by mass or less in 100% by mass of the B block.
- vinyl monomer capable of forming the other structural unit of the block B include the same as those exemplified as specific examples of the vinyl monomer capable of forming the other structural unit of the block A.
- the B block When two or more structural units are contained in the B block, various structural units contained in the B block may be contained in the B block in any mode such as random copolymerization and block copolymerization. From the viewpoint of uniformity, it is preferable that the compound is contained in a mode of random copolymerization.
- the B block may be formed of a copolymer of a structural unit composed of a b1 block and a structural unit composed of a b2 block.
- the structure of the block copolymer is preferably a linear block copolymer.
- the linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, A block is A and B block is B.
- the copolymer has at least one structure selected from the group consisting of: Among these, an AB type diblock copolymer is preferred from the viewpoint of handleability during processing and physical properties of the composition.
- the structural unit derived from the (meth) acrylic monomer in the A block and the structural unit represented by the general formula (1) in the B block are localized. It is considered that the colorant, the dispersing medium (solvent), and the binder resin (alkali-soluble resin) can efficiently act suitably.
- the block copolymer may have other blocks other than the A block and the B block.
- the content of the A block is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and preferably 85% by mass or less, based on 100% by mass of the entire block copolymer. It is more preferably at most 80% by mass, further preferably at most 75% by mass.
- the content of the B block is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and preferably 65% by mass or less, based on 100% by mass of the whole block copolymer.
- the content is more preferably 60% by mass or less, and further preferably 55% by mass or less.
- the mass ratio between the A block and the B block (A block / B block) in the block copolymer is preferably 50/50 or more, more preferably 55/45 or more, further more preferably 60/40 or more. / 5 or less, more preferably 90/10 or less, and even more preferably 80/20 or less.
- the mass ratio of the A block and the B block is within the above range, the dispersing performance when used as a dispersant is further improved.
- the content of the structural unit derived from a vinyl monomer having an acidic group in the block copolymer is preferably 1% by mass or more, and more preferably 10% by mass or less. Is preferred.
- the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the block copolymer is preferably 5% by mass or more, more preferably 10% by mass. As described above, the content is more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.
- the molecular weight of the block copolymer is measured by gel permeation chromatography (hereinafter referred to as “GPC”).
- the weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, and particularly preferably 6,000 or more. It is preferably at most 000, more preferably at most 30,000, further preferably at most 25,000, particularly preferably at most 20,000. When the weight average molecular weight is within the above range, the dispersing performance when used as a dispersant becomes better.
- the molecular weight distribution (PDI) of the block copolymer is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.6 or less.
- the molecular weight distribution (PDI) is determined by (weight average molecular weight of block copolymer (Mw)) / (number average molecular weight of block copolymer (Mn)).
- Mw weight average molecular weight of block copolymer
- Mn number average molecular weight of block copolymer
- the amine value of the block copolymer is preferably 10 mgKOH / g or more, more preferably 50 mgKOH / g or more, further more preferably 80 mgKOH / g or more, from the viewpoints of adsorbability to the colorant and dispersibility of the colorant. It is preferably at most 200 mgKOH / g, more preferably at most 150 mgKOH / g, even more preferably at most 120 mgKOH / g.
- the acid value of the block copolymer is preferably 5 mgKOH / g or more, and more preferably 50 mgKOH / g or less.
- the block copolymer can suitably act on the binder resin (alkali-soluble resin) without impairing the affinity for the colorant.
- Method for producing block copolymer As a method for producing the block copolymer, a method in which an A block is first produced by a polymerization reaction of a vinyl monomer, and a monomer of a B block is polymerized in an A block; A method of polymerizing the monomer of the block; a method of separately producing the A block and the B block, and then coupling the A block and the B block.
- the polymerization method is not particularly limited, but living radical polymerization is preferred. That is, the block copolymer is preferably a polymer obtained by living radical polymerization.
- the conventional radical polymerization method not only the initiation reaction and the growth reaction, but also the termination reaction and the chain transfer reaction cause the deactivation of the growth terminal, which tends to easily produce a mixture of polymers having various molecular weights and heterogeneous compositions.
- the living radical polymerization method while maintaining the simplicity and versatility of the conventional radical polymerization method, is unlikely to cause a termination reaction or chain transfer and grows without deactivating the growth terminal, so that the molecular weight distribution This is preferred because it is easy to produce a polymer having a precise composition and a uniform composition.
- a method using a transition metal catalyst ATRP method
- RAFT method a method using a sulfur-based reversible chain transfer agent
- TERP method a method used since the ATRP method uses an amine-based complex, it cannot be used without protecting the acidic group of the vinyl monomer having an acidic group.
- RAFT method when various types of monomers are used, a low molecular weight distribution is unlikely to occur, and there may be a problem such as a sulfur odor or coloring.
- the TERP method is a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent.
- a radical polymerizable compound vinyl monomer
- organic tellurium compound for example, WO2004 / 14848, WO2004 / 14962, WO No. 2004/072126 and WO 2004/096870.
- Specific polymerization methods of the TERP method include the following (a) to (d).
- a vinyl monomer is polymerized using an organic tellurium compound represented by the general formula (3).
- B A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (3) and an azo-based polymerization initiator.
- C A vinyl monomer is polymerized using a mixture of an organic telluride compound represented by the general formula (3) and an organic ditelluride compound represented by the general formula (4).
- D A vinyl monomer is polymerized using a mixture of an organic telluride compound represented by the general formula (3), an azo-based polymerization initiator, and an organic ditelluride compound represented by the general formula (4).
- R 31 represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group.
- R 32 and R 33 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- R 34 represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
- R 31 represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group.
- the group represented by R 31 is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group, and is specifically as follows.
- Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl.
- a straight-chain or branched-chain alkyl group such as an octyl group
- a cyclic alkyl group such as a cyclohexyl group.
- It is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
- the aryl group include a phenyl group and a naphthyl group.
- the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
- the groups represented by R 32 and R 33 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows.
- Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl.
- a straight-chain or branched-chain alkyl group such as an octyl group
- a cyclic alkyl group such as a cyclohexyl group. It is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
- the group represented by R 34 is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, It is a propargyl group, which is specifically as follows.
- Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl.
- a linear or branched alkyl group such as a octyl group, and a cyclic alkyl group such as a cyclohexyl group. It is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
- the aryl group include a phenyl group and a naphthyl group. Preferably it is a phenyl group.
- the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent.
- substituent of the aryl group having a substituent examples include a halogen atom, a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR 341 (where R 341 is carbon Examples thereof include an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group having 1 to 8 carbon atoms or an aryloxy group), a sulfonyl group, and a trifluoromethyl group. Further, these substituents are preferably substituted one or two times.
- Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
- the alkoxy group a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom is preferable.
- the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
- Examples of the amide group include —CONR 3421 R 3422 (R 3421 and R 3422 are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms).
- R 3421 and R 3422 are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms.
- a group represented by —COOR 3431 R 3431 is a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms
- examples thereof include a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group.
- oxycarbonyl groups include a methoxycarbonyl group and an ethoxycarbonyl group.
- propargyl group examples include —CR 3451 R 3452 —C ⁇ CR 3453 (R 3451 and R 3452 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R 3453 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. , An aryl group or a silyl group).
- organic tellurium compound represented by the general formula (3) examples include (methylteranylmethyl) benzene, (methylteranylmethyl) naphthalene, ethyl-2-methyl-2-methylteranyl-propionate, and ethyl-2-yl.
- Methyl-2-n-butylteranyl-propionate (2-trimethylsiloxyethyl) -2-methyl-2-methylterranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methylterranyl-propionate or (3-trimethylsilylpropargyl) ) -2-Methyl-2-methylterranyl-propionate and the like organic compounds described in WO 2004/14848, WO 2004/14962, WO 2004/072126, and WO 2004/096870. All of tellurium compounds It can be exemplified.
- organic ditelluride compound represented by the general formula (4) examples include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, -N-butyl ditelluride, di-s-butyl ditelluride, di-t-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis Examples include-(p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride, dipyridyl ditelluride, and the like.
- the azo polymerization initiator can be used without any particular limitation as long as it is an azo polymerization initiator used in ordinary radical polymerization.
- 2,2′-azobis isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) ) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid) ) (ACVA), 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutylamide), 2,2′-azobis (4-methoxy-2,4 -Dimethylvaleronitrile) (V-70), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azobis (2
- the vinyl monomer and the organic tellurium compound of the general formula (3) are further substituted with an inert gas for the purpose of accelerating the reaction and controlling the molecular weight and the molecular weight distribution according to the type of the vinyl monomer.
- an inert gas for the purpose of accelerating the reaction and controlling the molecular weight and the molecular weight distribution according to the type of the vinyl monomer.
- a system polymerization initiator and / or an organic ditelluride compound of the general formula (4) are mixed.
- the inert gas include nitrogen, argon, and helium.
- argon and nitrogen are good.
- the amount of the vinyl monomer used in (a), (b), (c) and (d) may be appropriately adjusted depending on the physical properties of the desired copolymer. It is preferable that the vinyl monomer is 5 mol to 10000 mol per 1 mol of the organic tellurium compound of the general formula (3).
- the azo-based polymerization initiator is used in an amount of 0.01 mol to 10 mol per 1 mol of the organic tellurium compound of the general formula (3). It is preferable that
- the organic telluride compound represented by the general formula (3) and the organic ditelluride compound represented by the general formula (4) are used in combination, 1 mol of the organic tellurium compound represented by the general formula (3) is added to the organic tellurium compound represented by the general formula (4). It is preferable that the ditelluride compound be 0.01 mol to 100 mol.
- the organic telluride compound of the general formula (3) In the case where the organic telluride compound of the general formula (3), the organic ditelluride compound of the general formula (4) and the azo-based polymerization initiator are used in combination with each other, 1 mol of the organic tellurium compound of the general formula (3) is generally used.
- the amount of the organic ditelluride compound of the formula (4) is preferably from 0.01 mol to 100 mol, and the amount of the azo-based polymerization initiator is preferably from 0.01 mol to 10 mol per 1 mol of the organic telluride compound of the general formula (3).
- the polymerization reaction can be carried out without a solvent, but may be carried out by using an aprotic solvent or a protic solvent generally used in radical polymerization and stirring the mixture.
- aprotic solvents include anisole, benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, and chloroform. , Carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate or trifluoromethylbenzene.
- protic solvent examples include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol and diacetone alcohol.
- the amount of the solvent to be used may be appropriately adjusted.
- the amount is preferably 0.01 ml or more, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, and 50 ml or less, per 1 g of the vinyl monomer. It is preferably 10 ml or less, more preferably 1 ml or less.
- the reaction temperature and the reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the obtained copolymer.
- the mixture is stirred at 0 ° C. to 150 ° C. for 1 minute to 100 hours.
- the TERP method can obtain a high yield and a precise molecular weight distribution even at a low polymerization temperature and a short polymerization time.
- the pressure is usually set at normal pressure, but may be increased or decreased.
- the target copolymer can be separated from the obtained reaction mixture by removing the solvent used, residual vinyl monomer, and the like by ordinary separation and purification means.
- the growth terminal of the copolymer obtained by the polymerization reaction is in the form of -TeR 31 derived from a tellurium compound (where R 31 is the same as above), and is deactivated by the operation in the air after the completion of the polymerization reaction.
- R 31 is the same as above
- tellurium atoms may remain. Since the copolymer having a tellurium atom at the terminal is colored or has poor thermal stability, it is preferable to remove the tellurium atom.
- a radical reduction method using tributylstannane or a thiol compound As a method for removing tellurium atoms, a radical reduction method using tributylstannane or a thiol compound; a method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieves, a polymer adsorbent, etc .; A method for adsorbing a metal: a peroxide such as hydrogen peroxide or benzoyl peroxide is added, or air or oxygen is blown into the system to oxidize and decompose the tellurium atom at the terminal of the copolymer, and to wash with water or an appropriate solution.
- a peroxide such as hydrogen peroxide or benzoyl peroxide is added, or air or oxygen is blown into the system to oxidize and decompose the tellurium atom at the terminal of the copolymer, and to wash with water
- a liquid-liquid extraction method or solid-liquid extraction method for removing residual tellurium compounds by combining solvents; a purification method in a solution state such as ultrafiltration for extracting and removing only those having a specific molecular weight or less can be used. Also, these methods can be used in combination.
- the other end of the copolymer obtained by the polymerization reaction (the end opposite to the growth end) is -CR 32 R 33 R 34 derived from the tellurium compound (where R 32 , R 33 and R 34 are represented by the formula: (The same as R 32 , R 33 and R 34 in (3).)
- quaternizing agents include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; benzyl chloride Aralkyl halides such as benzyl bromide and benzyl iodide; dimethyl sulfate; and dialkyl sulfates such as diethyl sulfate and di-n-propyl sulfate.
- aralkyl halides such as benzyl chloride, benzyl bromide and benzyl iodide are preferred, and benzyl chloride is more preferred.
- An alkyl group and an aralkyl group derived from a quaternizing agent are introduced into the quaternized structure. Therefore, by measuring the amount of the alkyl group and the aralkyl group introduced by the quaternization, the amount of the structural unit represented by the formula (2) can be estimated.
- a method of quaternizing a part of the tertiary amine structure of the structural unit represented by the formula (1) in the polymer a method of contacting the polymer with a quaternizing agent may be mentioned. Specifically, after polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (1), a quaternizing agent is added to the reaction solution, followed by stirring. .
- the temperature of the reaction solution to which the quaternizing agent is added is preferably 55 ° C. to 65 ° C., and the stirring time is preferably 5 hours to 20 hours.
- the solvent to be added for dilution include a solvent that can be used for a polymerization reaction, a protic solvent is preferable, and methanol is more preferable.
- the dispersant composition may use a polymerization product containing the block copolymer as a dispersant component.
- the polymerization product refers to a product obtained by performing a polymerization operation (a quaternization treatment as necessary) to obtain the block copolymer.
- the polymerization product contains a desired block copolymer and a polymer impurity by-produced when synthesizing the block copolymer.
- the polymer impurities are other polymers that are inevitably produced as by-products when synthesizing a desired block copolymer.
- a polymer impurity by-produced when synthesizing the AB diblock copolymer a random polymer having the same composition as the A block and a random polymer having the same composition as the B block can be given.
- the polymer impurity is a polymer by-produced when synthesizing a desired block copolymer, and does not include a polymer added separately.
- the content of the block copolymer in the polymerization product is preferably 50% by mass or more based on 100% by mass of the polymerization product.
- the content of the block copolymer in the polymerization product is 50% by mass or more, the dispersing performance is improved when the polymerization product is used as a dispersant.
- the dispersant composition may contain a dispersion medium.
- the dispersing medium can be appropriately selected and used as long as it disperses or dissolves the block copolymer, does not react with these components, and has an appropriate volatility.
- organic solvents can be used, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, methoxypropanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether ,
- the content of the dispersion medium in the dispersant composition is not particularly limited, and can be appropriately adjusted.
- the upper limit of the content of the dispersion medium in the dispersant composition is usually 99% by mass.
- the lower limit of the content of the dispersion medium in the dispersant composition is usually 10% by mass, and preferably 30% by mass, in consideration of a viscosity suitable for producing a coloring composition described later.
- the coloring composition of the present invention contains the dispersant composition, a coloring material, a binder resin and a dispersion medium.
- the type of the coloring material may be appropriately selected according to its use, and examples thereof include pigments and dyes. It is preferable that the coloring composition contains a pigment as a coloring material from the viewpoint of light resistance and heat resistance.
- the pigment may be either an organic pigment or an inorganic pigment, but an organic pigment containing an organic compound as a main component is particularly preferable. Examples of the pigment include pigments of each color such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a violet pigment.
- Pigment structures include azo pigments such as monoazo pigments, diazo pigments, and condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo And polycyclic pigments such as thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments.
- the pigment contained in the coloring composition may be only one type or a plurality of types.
- pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 166, 168, Red pigments such as 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264, 269; I.
- Pigment Yellow 1 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, Yellow pigments such as 150, 151, 154, 155, 166, 167, 168, 170, 180, 185, 188, 193, 194, 213;
- Orange pigments such as CI Pigment Orange 36, 38, 43;
- Blue pigments such as C.I. Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60; I.
- Pigment Red 264 C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 or the like is preferable.
- a black pigment can be used.
- the black pigment may be used alone, or the red pigment, the green pigment, the blue pigment, and the like may be mixed and used.
- the black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoint of light blocking ratio and image characteristics.
- the average particle size of the colorant may be appropriately selected according to the application, and is not particularly limited. It is preferable that the coloring composition contains a coloring material having an average particle diameter of 10 nm to 150 nm from the viewpoint of high transparency and high contrast.
- the coloring material may contain a pigment derivative as a dispersing aid.
- the dye derivative preferably contains an acidic dye derivative having an acidic group so as to be ionically bonded to and adsorbed to an amino group in the polymer contained in the dispersant composition. This dye derivative has an acidic functional group introduced into the dye skeleton.
- a skeleton that is the same or similar to the coloring material constituting the coloring composition, or a skeleton that is the same or similar to the compound that is a raw material of the pigment is preferable.
- the dye skeleton examples include an azo dye skeleton, a phthalocyanine dye skeleton, an anthraquinone dye skeleton, a triazine dye skeleton, an acridine dye skeleton, and a perylene dye skeleton.
- the acidic group introduced into the dye skeleton a carboxy group, a phosphoric acid group, and a sulfonic acid group are preferable.
- a sulfonic acid group is preferable on account of the synthesis and the strength of the acidity.
- the acidic group may be directly bonded to the dye skeleton, or may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, an ether, a sulfonamide, or a urethane bond.
- the amount of the dye derivative used is not particularly limited, but is preferably, for example, 4 to 17 parts by mass with respect to 100 parts by mass of the coloring material.
- the upper limit of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 70% by mass, and more preferably 60% by mass in the total solid content of the coloring composition. Is more preferable.
- the lower limit of the content of the coloring material in the coloring composition is usually 10% by mass, preferably 20% by mass, and more preferably 30% by mass in the total solid content of the coloring composition. preferable.
- the solid content is a component other than the dispersion medium described below.
- the content of the dispersant component (block copolymer and polymerization product) with respect to the coloring material in the coloring composition is preferably 5 parts by mass to 200 parts by mass, and more preferably 10 parts by mass to 100 parts by mass of the coloring material. It is preferably 100 parts by mass, more preferably 10 parts by mass to 80 parts by mass.
- the coloring composition contains a binder resin (however, a polymer having a structure represented by the general formula (5) in the side chain is excluded). Thereby, the alkali developability of the coloring composition and the binding property to the substrate can be improved.
- a binder resin is not particularly limited, but is preferably a resin having an acidic group such as a carboxy group and a phenolic hydroxy group.
- a random copolymer containing a structural unit derived from a carboxy group-containing vinyl monomer and a structural unit derived from (meth) acrylate is preferable.
- the carboxy group-containing vinyl monomer (meth) acrylic acid is preferable.
- the (meth) acrylate include methyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate.
- the total content of structural units derived from a carboxy group-containing vinyl monomer and structural units derived from (meth) acrylate is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more.
- the binder resin has a content of a structure derived from a carboxy group-containing vinyl monomer of preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and 90% by mass or less. And more preferably 70% by mass or less.
- a random copolymer of a carboxy group-containing vinyl monomer and (meth) acrylate is preferable.
- a copolymer include a random copolymer of (meth) acrylic acid and butyl (meth) acrylate, a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate, ) A random copolymer of acrylic acid, butyl (meth) acrylate, and benzyl (meth) acrylate.
- the binder resin is particularly preferably a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate.
- the content of (meth) acrylic acid is usually from 5% by mass to 90% by mass, and preferably from 10% by mass to 70% by mass of all monomer components. Is more preferable, and more preferably 20% by mass to 70% by mass.
- the binder resin may have a radically polymerizable carbon-carbon double bond in a side chain.
- a method of introducing a radically polymerizable carbon-carbon double bond into a side chain include, for example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p- A) a method of reacting a compound such as vinylbenzyl glycidyl ether with an acidic group of the binder resin.
- MMw of the binder resin is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, even more preferably from 5,000 to 20,000.
- Mw of the binder resin is 3,000 or more, the heat resistance and the film strength of the colored layer formed from the colored composition are improved, and when the Mw is 100,000 or less, the alkali developability of the coating film is improved. Is further improved.
- the acid value of the binder resin is preferably from 20 mgKOH / g to 170 mgKOH / g, more preferably from 50 mgKOH / g to 150 mgKOH / g, and still more preferably from 90 mgKOH / g to 150 mgKOH / g.
- the acid value of the binder resin is 20 mgKOH / g or more / g, the alkali developability of the colored composition as a colored layer is further improved, and when it is 170 mgKOH / g or less, the heat resistance becomes good.
- the binder resin contained in the coloring composition may be only one kind or plural kinds.
- the content of the binder resin is preferably 3 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass, and more preferably 20 parts by mass with respect to 100 parts by mass of the coloring material. More preferably, the amount is from 80 parts by mass to 80 parts by mass.
- the coloring composition may contain a crosslinking agent as necessary.
- a crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group.
- the crosslinking agent a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.
- the compound having two or more (meth) acryloyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, and caprolactone-modified polyfunctional ( (Meth) acrylate, polyfunctional (meth) acrylate modified with alkylene oxide, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having a hydroxy group with polyfunctional isocyanate, (meth) acrylate having a hydroxy group And a polyfunctional (meth) acrylate having a carboxy group obtained by reacting an acid anhydride with an acid anhydride.
- aliphatic polyhydroxy compound examples include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and trivalent or higher valent compounds such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Aliphatic polyhydroxy compounds.
- Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, glycerol di (meth) acrylate and the like can be mentioned.
- Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.
- the acid anhydride examples include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; pyromellitic anhydride, biphenyltetracarboxylic acid Tetrabasic dianhydrides such as acid dianhydride and benzophenonetetracarboxylic dianhydride are exemplified.
- dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride
- pyromellitic anhydride, biphenyltetracarboxylic acid Tetrabasic dianhydrides such as acid dianhydride and benzophenonetetracarboxylic dianhydride are exemplified.
- the content of the crosslinking agent is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, per 100 parts by mass of the coloring material. If the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the amount of the cross-linking agent is too large, the alkali developability of the coloring composition of the present invention is reduced, and background contamination on the unexposed portion of the substrate or the light-shielding layer, a film residue, and the like tend to be easily generated. .
- the coloring composition may contain a photopolymerization initiator as needed. Thereby, radiation sensitivity can be imparted to the coloring composition.
- the photopolymerization initiator is a compound that generates an active species capable of initiating polymerization of a crosslinking agent upon exposure to radiation such as visible light, ultraviolet light, far infrared light, electron beam, and X-ray.
- photopolymerization initiator examples include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, ⁇ -diketones Compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, aminoketone compounds and the like.
- the photopolymerization initiators can be used alone or in combination of two or more.
- the content of the photopolymerization initiator is preferably from 0.01 to 120 parts by mass, particularly preferably from 1 to 100 parts by mass, per 100 parts by mass of the crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, curing may be insufficient due to exposure, while if it is too large, the formed colored layer tends to easily fall off the substrate during development.
- the coloring composition contains a dispersion medium.
- the dispersing medium can be appropriately selected and used as long as it disperses or dissolves other components constituting the coloring composition, does not react with these components, and has an appropriate volatility.
- a conventionally known organic solvent can be used, and examples thereof include an organic solvent (dispersion medium) that can be used in the dispersant composition.
- the organic solvent is preferably a glycol alkyl ether acetate, a monohydric or polyhydric alcohol from the viewpoints of dispersibility of the pigment and the like, solubility of the dispersant, and applicability of the pigment dispersion composition.
- the solvent contained in the pigment dispersion composition may be only one type or a plurality of types.
- the boiling point of the dispersion medium (under a pressure of 1013.25 hPa; hereinafter, the same applies to all boiling points) is preferably 100 ° C. to 200 ° C.
- the above-mentioned dispersion media glycol alkyl ether acetates are preferable because they have a good balance of coatability, surface tension, and the like, and relatively high solubility of the components in the coloring composition. It is also preferable to use a dispersion medium having a boiling point of 150 ° C. or higher. By using a dispersion medium having a high boiling point, it is possible to suppress the mutual destruction of the coloring composition due to rapid drying of the coloring composition.
- the dispersion medium having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates.
- the content of the dispersion medium having a boiling point of 150 ° C. or higher is preferably 3 to 50% by mass based on 100% by mass of the entire dispersion medium.
- the content of the dispersion medium in the coloring composition is not particularly limited, and can be appropriately adjusted.
- the upper limit of the content of the dispersion medium in the coloring composition is usually 99% by mass.
- the lower limit of the content of the dispersion medium in the coloring composition is usually 70% by mass, and preferably 80% by mass, in consideration of the viscosity suitable for applying the coloring composition.
- the dispersion medium can be used as a solvent for dissolving and removing the precipitate formed from the coloring composition.
- the coloring composition may contain other compounding agents in addition to the compounding agents as long as the preferable physical properties of the present invention are not impaired.
- Other compounding agents include a sensitizing dye, a thermal polymerization inhibitor, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a plasticizer, an organic carboxylic acid compound, and an organic carboxylic acid. Acid anhydrides, pH adjusters, antioxidants, ultraviolet absorbers, light stabilizers, preservatives, fungicides, surfactants, anti-agglomeration agents, adhesion improvers, development improvers, storage stabilizers, etc. be able to.
- sensitizing dye examples include 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, and , 4-Diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- ( p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p -Diethylaminophenyl) benzothiazo 2- (p
- thermal polymerization inhibitor examples include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, ⁇ -naphthol and the like.
- nonionic surfactant examples include a fluorine-based surfactant, a silicone-based surfactant, and a polyoxyethylene-based surfactant.
- anionic surfactants include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate salts, higher alcohol sulfate salts, and aliphatic alcohols.
- the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.
- amphoteric surfactant include betaine-type compounds, imidazolium salts, imidazolines, and amino acids.
- Plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like.
- Examples of the organic carboxylic acid compound include a monocarboxylic acid, a carboxylic acid in which a carboxy group is directly bonded to a phenyl group, and a carboxylic acid in which a carboxy group is bonded to a phenyl group via a carbon bond.
- Organic carboxylic anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2- Examples include cyclohexene dicarboxylic acid, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride and the like.
- the coloring composition can be prepared by mixing a coloring material, a dispersant composition, a binder resin, a dispersion medium, and, if necessary, a crosslinking agent, a photopolymerization initiator, and other compounding agents.
- a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, and a kneader can be used. It is preferable that the coloring composition is filtered after mixing. Since the coloring composition has alkali developability, it can be suitably used for color filters.
- coloring material those which have been surface-treated with the dispersant composition of the present invention in advance can be used.
- Surface treatment methods include a dry method in which a dispersant is added and mixed while stirring a coloring material using a Henschel mixer, a ball mill, an atomizer colloid mill, and a Banbury mixer, and a wet method in which the solvent is removed after treatment in a solvent. Can be used.
- the color filter of the present invention includes a coloring layer formed using the coloring composition.
- thermoplastic resin sheets such as polyester resin, polyolefin resin, polycarbonate resin, and polymethyl methacrylate resin; thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, and poly (meth) acrylic resin; Having a color pixel that transmits light of three primary colors of red (R), green (G) and blue (B) on a transparent substrate, and preferably having a black matrix formed from the coloring composition. It is.
- a black colored composition is applied, and then prebaked to evaporate a solvent (dispersion medium) to form a coating film.
- the coating film is exposed through a photomask, and then developed using an alkaline developer (an aqueous solution containing an organic solvent or a surfactant and an alkaline compound) to dissolve and remove unexposed portions of the coating film. Then, a black pattern (black matrix) is formed. Thereafter, post-baking is performed as necessary, and the same operation is sequentially repeated for red (R), green (G), and blue (B), so that pixel arrays of three primary colors of red, green, and blue are arranged on the substrate. The obtained color filter is obtained.
- the order of forming pixels of each color is not limited to the above.
- an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, and a bar coating method can be used.
- a spin coating method or a slit die coating method it is preferable to employ a spin coating method or a slit die coating method.
- a transparent conductive film such as indium tin oxide (ITO)
- ITO indium tin oxide
- the color filter of the present invention has high dimensional accuracy and the like, and can be suitably used for a color liquid crystal display device, a color image pickup tube device, a color sensor, an organic EL display device, electronic paper, and the like.
- the coloring composition has a low viscosity and excellent dispersibility of a coloring material, it is suitable as a coloring column spacer to be supported on a thin film transistor (TFT) substrate and a color filter substrate which are positioned with a liquid crystal layer interposed therebetween.
- TFT thin film transistor
- a color filter substrate which are positioned with a liquid crystal layer interposed therebetween.
- TFT thin film transistor
- a composition having a high optical density (Optical @ Depth: OD) described in JP-A-2015-191234 can be mentioned.
- the present invention is not limited to the following embodiments at all, and can be implemented with appropriate changes within a scope that does not change the gist of the present invention.
- the polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI) and amine value of the block copolymer and the binder resin, the formaldehyde amount of the dispersant composition, and the dispersibility (viscosity and particle diameter) of the coloring composition was evaluated according to the following method.
- BMA butyl methacrylate
- PCL5 5-mol caprolactone adduct of 2-hydroxyethyl methacrylate (Placel (registered trademark) FM5, manufactured by Daicel Chemical Industries, Ltd.)
- DMAEMA dimethylaminoethyl methacrylate
- DEAEMA diethylaminoethyl methacrylate
- TBAEMA tert-butylaminoethyl methacrylate
- BTEE ethyl-2-methyl-2-n-butylteranyl-propionate
- DBDT dibutyl ditelluride
- AIBN 2,2′-azobis (iso Butyronitrile)
- PMA Propylene glycol monomethyl ether acetate
- the measurement conditions were a column temperature of 40 ° C., a sample concentration of 20 mg / mL, a sample injection amount of 10 ⁇ m, and a flow rate of 0.2 mL / min.
- a calibration curve (calibration curve) was prepared using polystyrene (molecular weight: 427,000, 190,000, 96,400, 37,400, 10,200, 2,630, 906) as a standard substance, and the weight average molecular weight ( Mw) and number average molecular weight (Mn).
- Mw weight average molecular weight
- Mn number average molecular weight
- the molecular weight distribution (PDI Mw / Mn) was calculated from the measured values.
- the amine value represents the mass of potassium hydroxide (KOH) equivalent to the basic component per 1 g of solid content.
- KOH potassium hydroxide
- the measurement sample was dissolved in tetrahydrofuran, and the obtained solution was subjected to neutralization titration with a 0.1 mol / L hydrochloric acid / 2-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation).
- the amine value (B) was calculated by the following equation using the inflection point of the titration pH curve as the end point of the titration.
- Particle size The particle size was measured at 25 ° C. using a concentrated particle size analyzer (trade name: FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.). The measurement was performed on the colored composition stored at 25 ° C. for 2 hours after the adjustment. The sample was diluted with propylene glycol monomethyl ether acetate (PGMEA) as needed.
- PGMEA propylene glycol monomethyl ether acetate
- a cartridge (Sep Pak (registered trademark) DNPH silica plus cartridge (product number: WAT037500, manufactured by Waters)) filled with 0.5 g of the dispersant composition and silica gel impregnated with DNPH (2,4-dinitrophenylhydrazine) was used. The mixture was injected and allowed to stand at room temperature for 2 hours. After washing with 4 mL of acetonitrile, the volume was increased to 5 mL.
- Block copolymer No. 1 Block copolymer No. 1
- PCL5 275.8 g
- BMA 45.3 g
- AIBN 1.64 g
- PMA 80.3 g
- BTEE 14. 99g
- DBDT DBDT
- Block copolymer Nos. 2, 3 Block copolymer No.
- Table 1 shows the used monomers, organic tellurium compounds, organic ditelluride compounds, azo-based polymerization initiators, solvents, reaction conditions, and polymerization rates.
- Table 2 shows the composition, Mw, PDI, and amine value of each block copolymer. The content of each structural unit in the copolymer was calculated from the charged ratio and the conversion of the monomers used in the polymerization reaction.
- Dispersant composition No. 3 is a structural unit derived from dimethylaminoethyl methacrylate in which the B block of the block copolymer as a dispersant does not have the structural unit of the general formula (1) (in the general formula (1), R 11 and R 12 has a methyl group).
- This dispersant composition No. Sample No. 3 had a high formaldehyde content of 1.7 ppm.
- the dispersant composition No. In Nos. 1 and 2 the B block of the block copolymer as a dispersant has a structural unit represented by the general formula (1).
- the amount of formaldehyde was 0.1 ppm and 0.0 ppm, which was extremely reduced.
- reaction solution was cooled to room temperature, PMA (240.0 g) was added, and a solution of an alkali-soluble resin having a nonvolatile content of 39.5% was obtained.
- the weight average molecular weight (Mw) of the alkali-soluble resin was 9,150, the molecular weight distribution (PDI) was 1.92, and the acid value was 128 mgKOH / g.
- a mixing composition was prepared so as to be 16 parts by mass, 6 parts by mass of an alkali-soluble resin, and 80 parts by mass of PMA, and 555 parts by mass of 0.3 mm zirconia beads were added, and a bead mill (trade name: DISPERMAT CA, manufactured by VMA-GETZMANN GmbH) ) For 3 hours and sufficiently dispersed. After completion of the dispersion, the beads were filtered off to obtain a colored composition.
- Pigments include C.I. I. Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) was used. The dispersibility of the obtained coloring composition was evaluated. Table 3 shows the evaluation results.
- Coloring composition No. Two three Except that the block copolymer was changed, the coloring composition No. In the same manner as in the preparation method of Colored Composition No. 1, A few were prepared. Table 3 shows the evaluation results.
- Coloring composition No. Each of 1 to 3 has good pigment dispersibility. Therefore, it can be understood that the block copolymer in which the B block has the structural unit of the general formula (1) can be used as a dispersant. Further, in particular, the coloring composition No. B using a block copolymer in which the B block has a structural unit derived from diethylaminoethyl methacrylate. No. 1 is excellent in pigment dispersibility. Therefore, by using a block copolymer in which the B block has a structural unit derived from diethylaminoethyl methacrylate, the amount of formaldehyde can be reduced, and a colored composition having excellent pigment dispersibility can be obtained. Understand.
- the present invention includes the following embodiments.
- (Embodiment 1) A dispersant composition comprising a polymer having a structure represented by the general formula (5) in a side chain. * -Y 1 -NR 11 R 12 (5)
- R 11 represents a hydrogen atom, an optionally substituted linear or cyclic hydrocarbon group having 2 or more carbon atoms.
- R 12 represents a linear or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent.
- R 11 and R 12 may combine with each other to form a cyclic structure.
- Y 1 represents a divalent hydrocarbon group. * Represents a bond. ]
- Embodiment 3 Embodiment 1 or 2 in which the polymer is a block copolymer having an A block having a structural unit derived from a (meth) acrylic monomer and a B block having a structural unit represented by the general formula (1)
- the polymer is a block copolymer having an A block having a structural unit derived from a (meth) acrylic monomer and a B block having a structural unit represented by the general formula (1)
- R 11 represents a hydrogen atom, a linear or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent.
- R 12 represents a linear or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent.
- R 11 and R 12 may combine with each other to form a cyclic structure.
- R 13 represents a hydrogen atom or a methyl group.
- X 1 represents an amide group, an ester group, or a single bond.
- Y 1 represents a divalent hydrocarbon group.
- n1 represents an integer of 1 to 10.
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents an alkylene group having 1 to 10 carbon atoms.
- R 3 represents an alkylene group having 1 to 10 carbon atoms.
- a coloring composition comprising the dispersant composition according to any one of aspects 1 to 6, a coloring material, a binder resin and a dispersion medium.
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Abstract
Description
*-Y1-N-R11R12 (5)
[一般式(5)において、R11は、水素原子、置換基を有していてもよい炭素数2以上である鎖状もしくは環状の炭化水素基を表す。R12は、置換基を有していてもよい炭素数2以上である鎖状もしくは環状の炭化水素基を表す。R11およびR12が互いに結合して環状構造を形成していてもよい。Y1は2価の炭化水素基を表す。*は結合手を表す。]
本発明の分散剤組成物は、側鎖に一般式(5)で表される構造を有する重合体を含有することを特徴とする。
*-Y1-N-R11R12 (5)
[一般式(5)において、R11は、水素原子、置換基を有していてもよい炭素数2以上である鎖状もしくは環状の炭化水素基を表す。R12は、置換基を有していてもよい炭素数2以上である鎖状もしくは環状の炭化水素基を表す。R11およびR12が互いに結合して環状構造を形成していてもよい。Y1は2価の炭化水素基を表す。*は結合手を表す。]
前記重合体は、分散性の観点から、好ましくは(メタ)アクリルモノマーに由来する構造単位を有するAブロックと、一般式(1)で表される構造単位を有するBブロックとを有するブロック共重合体が好ましい。
Aブロックは、(メタ)アクリルモノマーに由来する構造単位を含むポリマーブロックである。Aブロックにおける(メタ)アクリルモノマーに由来する構造単位は、1種のみでもあってもよいし、2種以上を有していてもよい。(メタ)アクリルモノマーに由来する構造単位を有することで、分散媒体(溶媒)、着色組成物に配合されるバインダー樹脂との高い親和性を維持できる。
芳香族ビニルモノマーとしては、スチレン、α-メチルスチレン、4-メチルスチレン、2-メチルスチレン、3-メチルスチレン、4-メトキシスチレン、2-ヒドロキシメチルスチレン、1-ビニルナフタレン等が挙げられる。
ヘテロ環を含有するビニルモノマーとしては、2-ビニルチオフェン、N-メチル-2-ビニルピロール、1-ビニル-2-ピロリドン、2-ビニルピリジン、4-ビニルピリジン、N-フェニルマレイミド、N-ベンジルマレイミド、N-シクロヘキシルマレイミド等が挙げられる。
ビニルアミドとしては、N-ビニルホルムアミド、N-ビニルアセトアミド、N-ビニル-ε-カプロラクタム等が挙げられる。
カルボン酸ビニルとしては、酢酸ビニル、ピバル酸ビニル、安息香酸ビニル等が挙げられる。
ジエン類としては、ブタジエン、イソプレン、4-メチル-1,4-ヘキサジエン、7-メチル-1,6-オクタジエン等が挙げられる。
Bブロックは下記一般式(1)で表される構造単位を含むポリマーブロックである。
一般式(1)で表される構造単位は、1種のみでもあってもよいし、2種以上を有していてもよい。一般式(1)で表される構造単位を有することで、着色材との吸着性が高く、経時的なホルムアルデヒドの発生を抑制することができる。なお、一般式(1)で表される構造単位において、X1に結合している-Y1-N-R11R12が、一般式(5)で表される構造である。
前記ハロゲンアニオンとしては、フルオロアニオン、クロロアニオン、ブロモアニオン、ヨードアニオンが挙げられる。
前記カルボキシレートアニオンとしては、酢酸アニオン、プロピオン酸アニオン等のアルキルカルボキシレートアニオン;安息香酸アニオン等の芳香族カルボキシレートアニオン等が挙げられる。
前記スルフェートアニオンとしては、メチル硫酸アニオン、エチル硫酸アニオン等のアルキルスルフェートアニオン;フェニル硫酸アニオン、ベンジル硫酸アニオン等の芳香族硫酸アニオン等が挙げられる。
前記スルホネートアニオンとしては、メタンスルホン酸アニオン、エタンスルホン酸アニオン等のアルキルスルホネートアニオン;ベンゼンスルホン酸アニオン、トルエンスルホン酸アニオン等の芳香族スルホネートアニオン等が挙げられる。
前記ホスフェートアニオンとしては、メチルホスホン酸アニオン、エチルホスホン酸アニオン等のアルキルホスフェートアニオン;フェニルホスホン酸アニオン、ベンジルホスホン酸アニオン等の芳香族ホスフェートアニオンが挙げられる。
前記ブロック共重合体の構造は、線状ブロック共重合体であることが好ましい。また、線状ブロック共重合体は、いずれの構造(配列)であっても良いが、線状ブロック共重合体の物性、または組成物の物性の観点から、AブロックをA、BブロックをBと表現したとき、(A-B)m型、(A-B)m-A型、(B-A)m-B型(mは1以上の整数、例えば1~3の整数)よりなる群から選択される少なくとも1種の構造を持つ共重合体であることが好ましい。これらの中でも、加工時の取扱い性、組成物の物性の観点から、A-B型ジブロック共重合体であることが好ましい。A-B型ジブロック共重合体を構成することで、Aブロックに有する(メタ)アクリルモノマーに由来する構造単位と、Bブロックに有する一般式(1)で表される構造単位とが局在化し、効率的に着色材と、分散媒体(溶媒)、バインダー樹脂(アルカリ可溶性樹脂)と好適に作用することができると考えられる。前記ブロック共重合体は、AブロックおよびBブロック以外の他のブロックを有していてもよい。
前記ブロック共重合体の製造方法としては、ビニルモノマーの重合反応によって、Aブロックを先に製造し、AブロックにBブロックのモノマーを重合する方法;Bブロックを先に製造し、BブロックにAブロックのモノマーを重合する方法;AブロックとBブロックとを別々に製造した後、AブロックとBブロックとをカップリングする方法等が挙げられる。
(a)ビニルモノマーを、一般式(3)で表される有機テルル化合物を用いて重合する。
(b)ビニルモノマーを、一般式(3)で表される有機テルル化合物とアゾ系重合開始剤との混合物を用いて重合する。
(c)ビニルモノマーを、一般式(3)で表される有機テルル化合物と一般式(4)で表される有機ジテルリド化合物との混合物を用いて重合する。
(d)ビニルモノマーを、一般式(3)で表される有機テルル化合物とアゾ系重合開始剤と一般式(4)で表される有機ジテルリド化合物との混合物を用いて重合する。
一般式(4)において、R31は、炭素数1~8のアルキル基、アリール基または芳香族ヘテロ環基を示す。]
炭素数1~8のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の直鎖または分岐鎖アルキル基や、シクロヘキシル基等の環状アルキル基等を挙げることができる。好ましくは炭素数1~4の直鎖または分岐鎖アルキル基であり、更に好ましくはメチル基またはエチル基である。
アリール基としては、フェニル基、ナフチル基等を挙げることができる。
芳香族ヘテロ環基としては、ピリジル基、フリル基、チエニル基等を挙げることができる。
炭素数1~8のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の直鎖または分岐鎖アルキル基や、シクロヘキシル基等の環状アルキル基等を挙げることができる。好ましくは炭素数1~4の直鎖または分岐鎖アルキル基であり、更に好ましくはメチル基またはエチル基である。
炭素数1~8のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の直鎖または分岐鎖アルキル基、シクロヘキシル基等の環状アルキル基等を挙げることができる。好ましくは炭素数1~4の直鎖または分岐鎖アルキル基であり、更に好ましくはメチル基またはエチル基である。
アリール基としては、フェニル基、ナフチル基等を挙げることができる。好ましくはフェニル基である。
置換アリール基としては、置換基を有しているフェニル基、置換基を有しているナフチル基等を挙げることができる。前記置換基を有しているアリール基の置換基としては、例えば、ハロゲン原子、ヒドロキシ基、アルコキシ基、アミノ基、ニトロ基、シアノ基、-COR341で示されるカルボニル含有基(R341は炭素数1~8のアルキル基、アリール基、炭素数1~8のアルコキシ基またはアリールオキシ基)、スルホニル基、トリフルオロメチル基等を挙げることができる。また、これらの置換基は、1個または2個置換しているのがよい。
芳香族ヘテロ環基としては、ピリジル基、フリル基、チエニル基等を挙げることができる。
アルコキシ基としては、炭素数1~8のアルキル基が酸素原子に結合した基が好ましく、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、n-ブトキシ基、sec-ブトキシ基、tert-ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基等を挙げることができる。
アシル基としては、アセチル基、プロピオニル基、ベンゾイル基等を挙げることができる。
アミド基としては、-CONR3421R3422(R3421、R3422は、それぞれ独立に水素原子、炭素数1~8のアルキル基またはアリール基)を挙げることがきる。
オキシカルボニル基としては、-COOR3431(R3431は水素原子、炭素数1~8のアルキル基またはアリール基)で表される基が好ましく、例えばカルボキシ基、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、n-ブトキシカルボニル基、sec-ブトキシカルボニル基、tert-ブトキシカルボニル基、n-ペンチルオキシカルボニル基、フェノキシカルボニル基等を挙げることができる。好ましいオキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基が挙げられる。
アリル基としては、-CR3441R3442-CR3443=CR3444R3445(R3441、R3442は、それぞれ独立に水素原子または炭素数1~8のアルキル基、R3443、R3444、R3445は、それぞれ独立に水素原子、炭素数1~8のアルキル基またはアリール基であり、それぞれの置換基が環状構造で繋がっていてもよい)等を挙げることができる。
プロパルギル基としては、-CR3451R3452-C≡CR3453(R3451、R3452は、水素原子または炭素数1~8のアルキル基、R3453は、水素原子、炭素数1~8のアルキル基、アリール基またはシリル基)等を挙げることができる。
前記分散剤組成物は、分散剤成分として、前記ブロック共重合体を含有する重合生成物を用いてもよい。前記重合生成物とは、前記ブロック共重合体を得るために重合操作(必要に応じて4級化処理)を行った際に得られる生成物を指す。前記重合生成物には、所望とするブロック共重合体と、このブロック共重合体を合成する際に副生した重合体不純物を含む。
前記分散剤組成物は、分散媒体を含有してもよい。前記分散媒体としては、ブロック共重合体を分散または溶解し、かつこれらの成分と反応せず、適度に揮発性を有するものである限り、適宜に選択して使用できる。例えば、従来公知の有機溶媒を使用することができ、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ-n-ブチルエーテル、プロピレングリコール-t-ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ-n-ブチルエーテル、メトキシメチルペンタノール、メトキシプロパノール、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、3-メチル-3-メトキシブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテル等のグリコールモノアルキルエーテル類;エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテル等のグリコールジアルキルエーテル類;エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ-n-ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、メトキシブチルアセテート、3-メトキシブチルアセテート、メトキシペンチルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ-n-ブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、3-メチル-3-メトキシブチルアセテート等のグリコールアルキルエーテルアセテート類;エチレングリコールジアセテート、1,3-ブチレングリコールジアセテート、1,6-ヘキサンジオールジアセテート等のグリコールジアセテート類;シクロヘキサノールアセテート等のアルキルアセテート類;アミルエーテル、プロピルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテル等のエーテル類;アセトン、メチルエチルケトン、メチルアミルケトン、メチルイソプロピルケトン、メチルイソアミルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチルアミルケトン、メチルブチルケトン、メチルヘキシルケトン、メチルノニルケトン、メトキシメチルペンタノン等のケトン類;エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、グリセリン、ベンジルアルコール等の1価または多価アルコール類;n-ペンタン、n-オクタン、ジイソブチレン、n-ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカン等の脂肪族炭化水素類;シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシル等の脂環式炭化水素類;ベンゼン、トルエン、キシレン、クメン等の芳香族炭化水素類;アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチル、γ-ブチロラクトン等の鎖状または環状エステル類;3-メトキシプロピオン酸、3-エトキシプロピオン酸等のアルコキシカルボン酸類;ブチルクロライド、アミルクロライド等のハロゲン化炭化水素類;メトキシメチルペンタノン等のエーテルケトン類;アセトニトリル、ベンゾニトリル等のニトリル類等が挙げられる。
本発明の着色組成物は、前記分散剤組成物、着色材、バインダー樹脂および分散媒体を含有する。
前記着色材の種類は、その用途に応じて適宜選択すればよく、例えば顔料、染料が挙げられる。前記着色組成物は、耐光性および耐熱性の観点から、着色材として顔料を含有することが好ましい。顔料としては、有機顔料および無機顔料のいずれでもよいが、有機化合物を主成分とする有機顔料が特に好ましい。顔料としては、例えば、赤色顔料、黄色顔料、橙色顔料、青色顔料、緑色顔料、紫色顔料等の各色の顔料が挙げられる。顔料の構造は、モノアゾ系顔料、ジアゾ系顔料、縮合ジアゾ系顔料等のアゾ系顔料、ジケトピロロピロール系顔料、フタロシアニン系顔料、イソインドリノン系顔料、イソインドリン系顔料、キナクリドン系顔料、インディゴ系顔料、チオインディゴ系顔料、キノフタロン系顔料、ジオキサジン系顔料、アントラキノン系顔料、ペリレン系顔料、ペリノン系顔料等の多環系顔料等が挙げられる。着色組成物に含まれる顔料は、1種類のみであってもよいし、複数種類であってもよい。
前記着色組成物は、バインダー樹脂(ただし、前記側鎖に一般式(5)で表される構造を有する重合体は除く。)を含有する。これにより、着色組成物のアルカリ現像性や基板への結着性を高めることができる。このようなバインダー樹脂としては、特に限定されるものではないが、カルボキシ基、フェノール性ヒドロキシ基等の酸性基を有する樹脂であることが好ましい。
前記着色組成物は、必要に応じて、架橋剤を含有してもよい。架橋剤とは、2個以上の重合可能な基を有する化合物をいう。重合可能な基としては、例えば、エチレン性不飽和基、オキシラニル基、オキセタニル基、N-アルコキシメチルアミノ基等を挙げることができる。前記架橋剤としては、2個以上の(メタ)アクリロイル基を有する化合物、または2個以上のN-アルコキシメチルアミノ基を有する化合物が好ましい。
前記着色組成物は、必要に応じて、光重合開始剤を含有してもよい。これにより、着色組成物に感放射線性を付与することができる。前記光重合開始剤は、可視光線、紫外線、遠赤外線、電子線、X線等の放射線の露光により、架橋剤の重合を開始し得る活性種を発生する化合物である。
前記着色組成物は、分散媒体を含有する。前記分散媒体としては、着色組成物を構成する他の成分を分散または溶解し、かつこれらの成分と反応せず、適度に揮発性を有するものである限り、適宜に選択して使用できる。例えば、従来公知の有機溶媒を使用することができ、例えば、前記分散剤組成物に使用し得る有機溶媒(分散媒体)が挙げられる。有機溶媒は、顔料等の分散性、分散剤の溶解性、顔料分散組成物の塗布性等の観点から、グリコールアルキルエーテルアセテート類、1価または多価アルコール類であることが好ましい。顔料分散組成物に含まれる溶媒は、1種類のみであってもよいし、複数種類であってもよい。
前記着色組成物には、本発明の好ましい物性を損なわない範囲であれば、前記配合剤以外に、他の配合剤を配合することができる。他の配合剤としては、増感色素、熱重合防止剤、非イオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤、可塑剤、有機カルボン酸化合物、有機カルボン酸無水物、pH調整剤、酸化防止剤、紫外線吸収剤、光安定剤、防腐剤、防カビ剤、界面活性剤、凝集防止剤、密着性改良剤、現像改良剤、保存安定剤等を挙げることができる。
アニオン系界面活性剤としては、アルキルスルホン酸塩類、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、ポリオキシエチレンアルキルエーテルスルホン酸塩類、アルキル硫酸塩類、アルキル硫酸エステル塩類、高級アルコール硫酸エステル塩類、脂肪族アルコール硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸塩類、特殊高分子系界面活性剤等が挙げられる。
カチオン系界面活性剤としては、第4級アンモニウム塩類、イミダゾリン誘導体類、アルキルアミン塩類等が挙げられる。
両性界面活性剤としては、ベタイン型化合物類、イミダゾリウム塩類、イミダゾリン類、アミノ酸類等が挙げられる。
前記着色組成物は、着色材、分散剤組成物、バインダー樹脂、分散媒体、必要に応じて、架橋剤、光重合開始剤、他の配合剤を混合することで調製できる。混合は、例えば、ペイントシェーカー、ビーズミル、ボールミル、ディゾルバー、ニーダー等の混合分散機を用いることができる。着色組成物は、混合後に濾過することが好ましい。前記着色組成物は、アルカリ現像性を有することから、カラーフィルタ用として好適に使用することができる。
本発明のカラーフィルタは、前記着色組成物を用いて形成された着色層を備えるものである。
BMA:ブチルメタクリレート
PCL5:2-ヒドロキシエチルメタクリレートの5molカプロラクトン付加物(ダイセル化学社製、プラクセル(登録商標)FM5)
DMAEMA:ジメチルアミノエチルメタクリレート
DEAEMA:ジエチルアミノエチルメタクリレート
TBAEMA:tert-ブチルアミノエチルメタクリレート
BTEE:エチル-2-メチル-2-n-ブチルテラニル-プロピオネート
DBDT:ジブチルジテルリド
AIBN:2,2’-アゾビス(イソブチロニトリル)
PMA:プロピレングリコールモノメチルエーテルアセテート
核磁気共鳴(NMR)測定装置(ブルカー・バイオスピン社製、型式:AVANCE500(周波数500MHz))を用いて、1H-NMRを測定(溶媒:CDCl3、内部標準:TMS)した。得られたNMRスペクトルについて、モノマー由来のビニル基とポリマー由来のエステル側鎖のピークの積分比を求め、モノマーの重合率を算出した。
高速液体クロマトグラフ(東ソー製、型式HLC-8320)を用いて、ゲル浸透クロマトグラフィー(GPC)より求めた。カラムはSHODEX KF-603(φ6mm×150mm)(SHODEX社製)を1本、移動相に10mmol/L臭化リチウム/10mmol/L酢酸/N-メチル―2-ピロリドン溶液、検出器に示差屈折計を使用した。測定条件は、カラム温度を40℃、試料濃度を20mg/mL、試料注入量を10μm、流速を0.2mL/minとした。標準物質としてポリスチレン(分子量427,000、190,000、96,400、37,400、10,200、2,630、906)を使用して検量線(校正曲線)を作成し、重量平均分子量(Mw)、数平均分子量(Mn)を測定した。この測定値から分子量分布(PDI=Mw/Mn)を算出した。
アミン価は、固形分1gあたりの塩基性成分と当量の水酸化カリウム(KOH)の質量を表したものである。測定試料をテトラヒドロフランに溶解し、電位差滴定装置(商品名:GT-06、三菱化学社製)を用いて、得られた溶液を0.1mol/L塩酸/2-プロパノール溶液で中和滴定した。滴定pH曲線の変曲点を滴定終点として次式によりアミン価(B)を算出した。
B=56.11×Vs×0.1×f/w
B:アミン価(mgKOH/g)
Vs:滴定に要した0.1mol/L塩酸/2-プロパノール溶液の使用量(mL)
f:0.1mol/L塩酸(2-プロパノール性)の力価
w:測定サンプルの質量(g)(固形分換算)
E型粘度計(商品名:TVE-22L、東機産業社製)を用い、コーンローター(1°34’×R24)を使用して、25℃下、ローター回転数60rpmで粘度を測定した。測定は、調製後、25℃で2時間保管した着色組成物について行った。
濃厚系粒径アナライザー(商品名:FPAR-1000、大塚電子社製)を用い、25℃下で粒径を測定した。測定は、調整後、25℃で2時間保管した着色組成物について行った。サンプルは必要に応じ、プロピレングリコールモノメチルエーテルアセテート(PGMEA)で希釈を行った。
分散剤組成物0.5gをDNPH(2,4-ジニトロフェニルヒドラジン)を含侵したシリカゲルを充填したカートリッジ(ウォーターズ社製、Sep Pak(登録商標) DNPHシリカプラスカートリッジ(商品番号:WAT037500))に注入し、室温で2時間静置させた。
アセトニトリル4mLで洗い出し、5mLにメスアップした。液体クロマトグラフ(島津製作所製、商品名:LC-10AD、カラム:Pro C18 RS(4.6×250mm,5μm(YMC社製)、移動相:アセトニトリル/超純水=65:35溶液、カラム温度:40℃、流速:1.0mL/分、検出波長:360nm)を用い、標準物質として2種アルデヒド-DNPH混合標準液(0.1μgアルデヒド/μLアセトニトリル、和光純薬製)を使用し、測定を行った。測定結果よりホルムアルデヒド量を算出した。
(ブロック共重合体No.1)
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(275.8g)、BMA(45.3g)、AIBN(1.64g)、PMA(80.3g)を仕込み、アルゴン置換後、BTEE(14.99g)、DBDT(18.47g)を加え、60℃で7時間反応させた。重合率は、98.3%であった。
ブロック共重合体No.1の製造法と同様にして、ブロック共重合体No.2、3を作製した。表1に、使用したモノマー、有機テルル化合物、有機ジテルリド化合物、アゾ系重合開始剤、溶媒、反応条件、重合率を示した。また、表2に各ブロック共重合体の組成、Mw、PDI、アミン価を示した。なお、共重合体中の各構造単位の含有率は、重合反応に用いたモノマーの仕込み比率および重合率から算出した。
各ブロック共重合体0.325gを、PMA0.675gに溶解させ、分散剤組成物を調製した。この分散剤組成物についてホルムアルデヒド量を測定し、表2に示した。
アルゴンガス導入管、撹拌機を備えたフラスコにメタクリル酸(MAA)(40.0g)、ベンジルメタクリレート(BzMA)(160.0g)、プロピレングリコールモノメチルエーテルアセテート(PMA)(580.0g)を仕込み、アルゴン置換後、2,2’-アゾビス(イソブチロニトリル)(AIBN)(4.0g)、n-ドデカンチオール(6.0g)、PMA(20.0g)を加え90℃まで昇温した。その溶液を90℃に保ちながら、その溶液にMAA(80.0g)、BzMA(320.0g)、AIBN(8.0g)、n-ドデカンチオール(12.0g)、PMA(50.0g)を1.5時間かけて滴下した。滴下が終了してから60分後、温度を110℃まで昇温し、AIBN(0.8g)、PMA(10.0g)を加えて1時間反応させ、さらにAIBN(0.8g)、PMA(10.0g)を加え1時間反応させ、さらにAIBN(0.8g)、PMA(10.0g)を加え1時間反応させた。
着色組成物No.1
顔料8質量部、ブロック共重合体No.1 6質量部、アルカリ可溶性樹脂6質量部、PMA80質量部となるように配合組成を調製し、0.3mmジルコニアビーズ555質量部を加え、ビーズミル(商品名:DISPERMAT CA、VMA-GETZMANN GmbH社製)にて3時間混合し十分に分散させた。分散終了後、ビーズをろ別して着色組成物を得た。顔料にはC.I.Pigment Red 254(商品名:BKCF、チバ・スペシャリティ・ケミカルズ社製)を用いた。得られた着色組成物の分散性を評価した。評価結果を表3に示した。
ブロック共重合体を変更したこと以外は着色組成物No.1の調製法と同様にして、着色組成物No.2、3を調製した。評価結果を表3に示した。
(実施態様1)
側鎖に一般式(5)で表される構造を有する重合体を含有することを特徴とする分散剤組成物。
*-Y1-N-R11R12 (5)
[一般式(5)において、R11は、水素原子、置換基を有していてもよい炭素数2以上である鎖状もしくは環状の炭化水素基を表す。R12は、置換基を有していてもよい炭素数2以上である鎖状もしくは環状の炭化水素基を表す。R11およびR12が互いに結合して環状構造を形成していてもよい。Y1は2価の炭化水素基を表す。*は結合手を表す。]
前記重合体のアミン価が、10mgKOH/g~200mgKOH/gである態様1に記載の分散剤組成物。
前記重合体が、(メタ)アクリルモノマーに由来する構造単位を有するAブロックと、一般式(1)で表される構造単位を有するBブロックとを有するブロック共重合体である態様1または2に記載の分散剤組成物。
前記Aブロックが、一般式(10)で表される構造単位を有する態様3に記載の分散剤組成物。
前記ブロック共重合体の分子量分布(PDI)が、2.5以下である態様3または4に記載の分散剤組成物。
前記ブロック共重合体が、リビングラジカル重合により重合されたものである態様3~5のいずれか一項に記載の分散剤組成物。
態様1~6のいずれか一項に記載の分散剤組成物、着色材、バインダー樹脂および分散媒体を含有することを特徴とする着色組成物。
カラーフィルタ用である態様7に記載の着色組成物。
態様8に記載の着色組成物を用いて形成された着色層を備えることを特徴とするカラーフィルタ。
Claims (9)
- 側鎖に一般式(5)で表される構造を有する重合体を含有することを特徴とする分散剤組成物。
*-Y1-N-R11R12 (5)
[一般式(5)において、R11は、水素原子、置換基を有していてもよい炭素数2以上である鎖状もしくは環状の炭化水素基を表す。R12は、置換基を有していてもよい炭素数2以上である鎖状もしくは環状の炭化水素基を表す。R11およびR12が互いに結合して環状構造を形成していてもよい。Y1は2価の炭化水素基を表す。*は結合手を表す。] - 前記重合体のアミン価が、10mgKOH/g~200mgKOH/gである請求項1に記載の分散剤組成物。
- 前記ブロック共重合体の分子量分布(PDI)が、2.5以下である請求項3または4に記載の分散剤組成物。
- 前記ブロック共重合体が、リビングラジカル重合により重合されたものである請求項3~5のいずれか一項に記載の分散剤組成物。
- 請求項1~6のいずれか一項に記載の分散剤組成物、着色材、バインダー樹脂および分散媒体を含有することを特徴とする着色組成物。
- カラーフィルタ用である請求項7に記載の着色組成物。
- 請求項8に記載の着色組成物を用いて形成された着色層を備えることを特徴とするカラーフィルタ。
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| JP2013214000A (ja) * | 2012-04-03 | 2013-10-17 | Dnp Fine Chemicals Co Ltd | 顔料分散組成物、カラーフィルタ用感光性着色樹脂組成物及びカラーフィルタ |
| JP2015515022A (ja) * | 2012-04-04 | 2015-05-21 | メルク パテント ゲーエムベーハー | コアとランダムコポリマーコーティングとを含む電気泳動ディスプレイ用粒子 |
| JP2018045011A (ja) * | 2016-09-13 | 2018-03-22 | 富士フイルム株式会社 | 赤外線吸収剤、組成物、膜、光学フィルタ、積層体、固体撮像素子、画像表示装置および赤外線センサ |
| JP6322837B1 (ja) * | 2017-06-13 | 2018-05-16 | 東洋インキScホールディングス株式会社 | スクアリリウム色素及びその用途 |
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| Publication number | Publication date |
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| CN112334504B (zh) | 2023-10-10 |
| TW202019995A (zh) | 2020-06-01 |
| TWI818051B (zh) | 2023-10-11 |
| KR20210040933A (ko) | 2021-04-14 |
| CN112334504A (zh) | 2021-02-05 |
| KR102791487B1 (ko) | 2025-04-08 |
| JP7299894B2 (ja) | 2023-06-28 |
| JPWO2020031633A1 (ja) | 2021-09-02 |
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