WO2013084815A1 - ブロック共重合体、分散剤及び顔料分散組成物 - Google Patents
ブロック共重合体、分散剤及び顔料分散組成物 Download PDFInfo
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- WO2013084815A1 WO2013084815A1 PCT/JP2012/081065 JP2012081065W WO2013084815A1 WO 2013084815 A1 WO2013084815 A1 WO 2013084815A1 JP 2012081065 W JP2012081065 W JP 2012081065W WO 2013084815 A1 WO2013084815 A1 WO 2013084815A1
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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
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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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/45—Anti-settling agents
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- 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
- G02F1/133509—Filters, e.g. light shielding masks
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/70—Organic dyes or pigments; Optical brightening agents
Definitions
- the present invention relates to a block copolymer, a dispersant, and a pigment dispersion composition.
- pigment dispersion methods dyeing methods, electrodeposition methods, printing methods, and the like are known as methods for producing color filters used for liquid crystal displays and the like.
- the pigment dispersion method is widely used from the viewpoints of spectral characteristics, durability, pattern shape, and accuracy.
- a coating film made of a pigment dispersion composition in which a pigment, a dispersant, and a solvent are mixed is formed on a substrate, exposed through a photomask having a desired pattern shape, and alkali developed (for example, (See Patent Document 1).
- the pigment dispersion composition may adhere to the coating device or the like, and may be dried to form a precipitate. If the solubility of the precipitate in the solvent is low, the precipitate may be mixed into the coating film, which may hinder image formation.
- the present invention when used as a dispersant, for example, has excellent dispersibility, solubility of a coating film formed from the dispersion composition in an alkaline aqueous solution (hereinafter referred to as “alkali developability”), and formed from the dispersion composition.
- alkali developability solubility of a coating film formed from the dispersion composition in an alkaline aqueous solution
- the main object of the present invention is to provide a block copolymer that can provide solubility of the dried precipitate to a solvent (hereinafter referred to as “dry re-dissolvability”).
- the gist of the present invention is as follows.
- n is an integer of 1 to 10.
- R 1 is a hydrogen atom or a methyl group.
- R 2 is an alkylene group having 1 to 10 carbon atoms.
- R 3 is an alkylene group having 1 to 10 carbon atoms.
- R 4 represents a hydrogen atom or a methyl group.
- R 5 is an alkylene group having 1 to 10 carbon atoms.
- R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- segment B including a partial structure represented by A block copolymer having an amine value of 20 mgKOH / g to 150 mgKOH / g.
- Item 2 The block copolymer according to Item 1, wherein the segment A contains 10% by mass to 100% by mass of the partial structure represented by the general formula (1).
- Item 3 The block copolymer according to Item 1 or 2, wherein the segment B contains 80% by mass to 100% by mass of the partial structure represented by the general formula (2).
- Item 4 The mass ratio of the segment A and the segment B in the block copolymer (the mass of segment A: the mass of segment B) is 50:50 to 95: 5, any one of items 1 to 3 The block copolymer described in 1.
- Item 5 The block copolymer according to any one of Items 1 to 4, wherein the block copolymer has a molecular weight distribution (PDI) of 1.05 to 2.20.
- PDI molecular weight distribution
- Item 6 The block copolymer according to any one of Items 1 to 5, which is a diblock copolymer comprising a segment A block and a segment B block.
- Item 7 A dispersant comprising the block copolymer according to any one of Items 1 to 6.
- Item 8 A pigment dispersion composition comprising the dispersant and pigment according to Item 7.
- Item 9 The pigment dispersion composition according to Item 8, which is for a color filter.
- a pigment dispersion composition having excellent dispersibility, alkali developability, and dry redissolvability can be provided.
- the block copolymer according to this embodiment has a segment A including a partial structure (monomer unit) represented by the following general formula (1).
- n is an integer of 1 to 10.
- R 1 is a hydrogen atom or a methyl group.
- R 2 is an alkylene group having 1 to 10 carbon atoms.
- R 3 is an alkylene group having 1 to 10 carbon atoms.
- n is preferably an integer of 1 to 7, and more preferably an integer of 1 to 5.
- 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, and a heptamethylene group.
- R 2 is preferably an alkylene group having 1 to 5 carbon atoms.
- 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, and a heptamethylene group.
- R 3 is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and particularly preferably an alkylene group having 3 to 8 carbon atoms.
- the partial structure represented by the general formula (1) included in the segment A may be composed of one type of monomer unit or may be composed of a plurality of types of monomer units.
- the partial structure (monomer unit) contained in the segment A may be only a partial structure represented by the general formula (1), or may be constituted by including other partial structures.
- the other partial structures may be included in any manner such as random copolymerization or block copolymerization.
- Segment A preferably contains 10% by mass to 100% by mass and more preferably 20% by mass to 80% by mass of the partial structure represented by the general formula (1). It is preferable that the segment A does not have a partial structure including a basic functional group such as the general formula (2) constituting the segment B described later.
- the proportion of the partial structure containing a basic functional group in segment A is preferably 1% by mass or less.
- segment A Another partial structure that can be included in segment A is composed of a monomer that can be copolymerized with both the monomer that constitutes the partial structure represented by the general formula (1) and the monomer that constitutes segment B described later. Is preferred.
- Specific examples of the monomer that can constitute another partial structure of the segment A include aromatic unsaturated monomers (styrene monomers), (meth) acrylic acid esters, and the like. Examples of the aromatic unsaturated monomer include styrene and ⁇ -methylstyrene.
- (meth) acrylic acid ester methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate , (Meth) acrylic acid 2-ethylhexyl, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and the like.
- (meth) acryl means “at least one of acrylic and methacryl”
- (meth) acrylate means “at least one of acrylate and methacrylate”.
- (meth) acrylic acid means “at least one of acrylic acid and methacrylic acid”.
- the other partial structure that can be contained in the segment A is preferably a partial structure (monomer unit) represented by the following general formula (3).
- R 8 represents a hydrogen atom or a methyl group.
- R 9 is an alkyl group having 1 to 10 carbon atoms which may have a substituent.
- R 9 of the general formula (3) specific examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group.
- Straight-chain or branched alkyl groups such as tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.
- R 9 is preferably an alkyl group having 1 to 5 carbon atoms which may have a substituent.
- examples of the substituent include an aryl group.
- the aryl group usually has 6 to 12 carbon atoms, preferably 6 to 9 carbon atoms.
- Specific examples of the aryl group include phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group and the like.
- the position of the substituent is not particularly limited.
- the number of substituents is usually 1 to 4, preferably 1 to 3, and more preferably 1.
- segment B In addition to the segment A, the block copolymer according to the present embodiment has a segment B including a partial structure (monomer unit) represented by the following general formula (2).
- R 4 represents a hydrogen atom or a methyl group.
- R 5 is an alkylene group having 1 to 10 carbon atoms.
- R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- alkylene group having 1 to 10 carbon atoms represented by R 5 include alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group. Can be mentioned.
- R 5 is preferably an alkylene group having 1 to 5 carbon atoms.
- alkyl group having 1 to 10 carbon atoms represented by R 6 and R 7 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Examples thereof include linear or branched alkyl groups such as tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.
- R 6 and R 7 are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- the partial structure represented by the general formula (2) contained in the segment B may be composed of one type of monomer unit or may be composed of a plurality of types of monomer units.
- the partial structure (monomer unit) contained in the segment B may be only a partial structure represented by the general formula (2), or may be constituted by including other partial structures.
- the other partial structure may be included in any mode such as random copolymerization or block copolymerization.
- Segment B preferably contains 80% by mass to 100% by mass of the partial structure represented by the general formula (2).
- the other partial structure that can be contained in the segment B is preferably composed of a monomer that can be copolymerized with both the monomer that constitutes the partial structure represented by the general formula (2) and the monomer that constitutes the segment A.
- Specific examples of the monomer that can constitute another partial structure of the segment B include aromatic unsaturated monomers (styrene monomers), heterocyclic-containing unsaturated monomers, (meth) acrylic acid esters, and the like.
- aromatic unsaturated monomer include styrene and ⁇ -methylstyrene.
- the heterocyclic-containing unsaturated monomer include 2-vinylpyridine, 4-vinylpyridine and the like.
- (meth) acrylic acid ester methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polycaprolactone (meth) acrylate, (Meth) acrylamide, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, dimethylaminopropyl (meth) acyl Ruamido and the like
- the mass ratio of segment A to segment B is preferably 50:50 to 95: 5, more preferably 60:40 to 95: 5. .
- the amine value of the block copolymer is 20 mgKOH / g to 150 mgKOH / g. It is preferable that the segment B contains a partial structure represented by the general formula (2) so that the amine value of the block copolymer falls within this range.
- the lower limit of the amine value of the block copolymer is preferably 30 mgKOH / g, and the upper limit is preferably 120 mgKOH / g.
- the lower limit of the weight average molecular weight (Mw) of the block copolymer is preferably 8,000, and more preferably 11,000.
- the upper limit of the weight average molecular weight (Mw) of the block copolymer is preferably 40,000.
- the molecular weight distribution (PDI) of the block copolymer is preferably 1.05 to 2.20, and more preferably 1.05 to 2.00.
- the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of block copolymer) / (number average molecular weight (Mn) of block copolymer).
- segment A of the block copolymer has an ester bond part and a terminal hydroxyl group in the side chain of the partial structure represented by the general formula (1), it is considered to have high affinity with the solvent and the binder resin.
- segment B has a basic functional group in the side chain of the partial structure represented by the general formula (2), it is considered to have a high affinity with the pigment.
- the partial structure represented by the general formula (1) contained in the segment A and the partial structure represented by the general formula (2) contained in the segment B are localized.
- the side chain of the partial structure represented by the general formula (1) constituting the segment A preferably interacts with the solvent and the binder resin, and independently constitutes the general formula ( Since the side chain of the partial structure represented by 2) can preferably interact with the pigment, the block copolymer is excellent in dispersibility of the pigment. Therefore, the block copolymer can be suitably used as a dispersant such as a pigment.
- the method for producing the block copolymer is not particularly limited.
- the block copolymer can be obtained, for example, by sequentially polymerizing monomers by block polymerization using a living radical polymerization method or the like. Segment A may be produced first by the polymerization reaction of the monomer, the segment B monomer may be polymerized into the segment A, the segment B may be produced first, and the segment A monomer may be polymerized into the segment B. . Moreover, in manufacture of a block copolymer, after manufacturing segment A and segment B separately by the polymerization reaction of a monomer, segment A and segment B may be coupled.
- the block copolymer is preferably a diblock copolymer comprising a block of segment A and a block of segment B.
- the living radical polymerization method is a polymerization method that enables precise control of the molecular structure while maintaining the simplicity and versatility of radical polymerization.
- the living radical polymerization method includes a method using a transition metal catalyst (ATRP), a method using a sulfur-based reversible chain transfer agent (RAFT), and a method using an organic tellurium compound depending on the method for stabilizing the polymerization growth terminal. There are methods such as (TERP).
- the pigment dispersion composition according to the present embodiment includes a dispersant composed of the above block copolymer and a pigment.
- the pigment dispersion composition may contain a binder resin, a solvent, and the like.
- the content of the dispersant is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the pigment. More preferably, it is ⁇ 50 parts by mass.
- the pigment may be either an organic pigment or an inorganic pigment, but an organic pigment mainly composed of an organic compound is particularly preferable.
- examples of the pigment include pigments of various colors such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a purple pigment.
- the structure of the pigment is azo pigments such as monoazo pigments, diazo pigments, condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo And polycyclic pigments such as pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments and perinone pigments. Only one type of pigment may be contained in the pigment dispersion composition, or a plurality of types may be used. Specific examples of the pigment include C.I. I.
- Orange pigments such as Pigment Orange 36, 38, 43;
- Blue pigments such as Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60;
- Green pigments such as Pigment Green 7, 36, 58; I. And purple pigments such as Pigment Violet 23, 32, and 50.
- the pigment content in the pigment dispersion composition is usually 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less in the total solid content of the pigment dispersion composition. .
- the pigment content in the pigment dispersion composition is usually 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more in the total solid content of the pigment dispersion composition. .
- the binder resin may be a polymer, for example.
- specific examples of monomers constituting the polymer include, for example, carboxyl groups such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, and maleic anhydride Containing unsaturated monomer: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) (Meth) acrylic such as 2-hydroxyethyl acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, cyclododecyl (meth)
- the binder resin is preferably a copolymer of a carboxyl group-containing unsaturated monomer and a (meth) acrylic acid ester.
- a copolymer include a copolymer of (meth) acrylic acid and butyl (meth) acrylate, a copolymer of (meth) acrylic acid and benzyl (meth) acrylate, And a copolymer of acrylic acid, butyl (meth) acrylate, and benzyl (meth) acrylate.
- the binder resin is particularly preferably a copolymer of (meth) acrylic acid and benzyl (meth) acrylate.
- the content of the carboxyl group-containing unsaturated monomer is usually 5% by mass to 90% by mass in all monomer components, and 10% by mass. It is preferably ⁇ 70% by mass, more preferably 20% by mass to 70% by mass.
- the weight average molecular weight (Mw) of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 20,000. preferable.
- Mw weight average molecular weight
- the weight average molecular weight (Mw) of the binder resin is 3,000 or more, the heat resistance and film strength of the coating film formed from the pigment dispersion composition are improved, and the weight average molecular weight (Mw) is 100,000 or less. If this is the case, the alkali developability of the coating film becomes good.
- the acid value of the binder resin is preferably 20 mgKOH / g to 170 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and still more preferably 90 mgKOH / g to 150 mgKOH / g.
- the acid value of the binder resin is 20 mgKOH / g or more, the alkali developability when the pigment dispersion composition is used as a coating film is good, and when it is 170 mgKOH / g or less, the heat resistance is good.
- the binder resin contained in the pigment dispersion composition may be only one type or a plurality of types.
- the content of the resin binder is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the pigment. More preferred is from 50 parts by weight to 50 parts by weight.
- the solvent is not particularly limited as long as it can dissolve, disperse, or the like a pigment, dispersion, or binder resin, and may be a known one.
- Specific examples of the solvent include 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, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3 -Methoxybutanol, triethyl Glycol monoalkyl
- the solvent is preferably glycol alkyl ether acetates, monovalent or polyhydric alcohols from the viewpoints of dispersibility of pigments, solubility of dispersants, applicability of pigment dispersion compositions, and the like.
- the solvent contained in the pigment dispersion composition may be only one type or a plurality of types.
- the content of the solvent in the pigment dispersion composition is not particularly limited and can be appropriately adjusted.
- the upper limit of the content of the solvent in the pigment dispersion composition is usually 99% by mass.
- the lower limit of the content of the solvent in the pigment dispersion composition is usually 70% by mass and preferably 80% by mass in consideration of the viscosity suitable for application of the pigment dispersion composition.
- the above solvent can be used as a solvent for dissolving and removing precipitates formed from the pigment dispersion composition.
- the pigment dispersion composition is obtained by mixing a pigment, a dispersant, a binder resin, a solvent and the like using a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, or a kneader.
- the pigment dispersion composition is preferably filtered after mixing.
- the pigment dispersion composition may contain other additives as necessary.
- additives include polyfunctional monomers, photopolymerization initiators, pigment derivatives, pH adjusters, antioxidants, ultraviolet absorbers, preservatives, and antifungal agents.
- the polyfunctional monomer is preferably a compound having at least two ethylenically unsaturated double bonds compatible with the binder resin.
- a compound having alkali solubility and having one or more acidic functional groups and two or more ethylenically unsaturated bonds in one molecule is preferable, and one or more acidic functional groups in one molecule. More preferred are compounds having a group and three or more ethylenically unsaturated bonds.
- Examples of the compound having at least two ethylenically unsaturated double bonds include polyfunctional (meth) acrylates such as bifunctional (meth) acrylates and trifunctional or higher functional (meth) acrylates.
- trifunctional or higher (meth) acrylates are preferable.
- an acidic functional group-containing polyfunctional (meth) acrylate is more preferable, and a trifunctional or higher functional functional group is contained.
- Polyfunctional (meth) acrylates are particularly preferred.
- the acidic functional group is not particularly limited as long as it is capable of alkali development, and examples thereof include a carboxy group, a sulfonic acid group, and a phosphoric acid group.
- the acidic functional group is preferably a carboxy group from the viewpoint of alkali developability and handleability of the resin composition.
- the pigment derivative examples include a sulfonic acid group, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, and a carboxyl group directly or through an alkyl group, an aryl group, a heterocyclic group, or the like in the skeleton structure of the pigment. Substituted ones are mentioned.
- the pigment and the pigment derivative in combination, the dispersibility and dispersion stability of the pigment can be improved.
- the viscosity of the pigment dispersion composition is preferably 20 mPa ⁇ s or less at 25 ° C.
- the viscosity of the pigment dispersion composition can be measured using an E-type viscometer.
- a coating film of the pigment dispersion composition can be formed on the substrate by applying the pigment dispersion composition on the substrate by a method such as spin coating, roll coating, or slit coating. After applying the pigment dispersion composition on the substrate, drying (desolvation treatment) or the like may be performed as necessary.
- the block copolymer has segment A and segment B, and the amine value of the block copolymer is 20 mgKOH / g to 150 mgKOH / g.
- the pigment dispersion composition containing such a block copolymer is excellent in alkali developability and dry redissolvability.
- the pigment dispersion composition When used as, for example, a patterning material for a color filter, the pigment dispersion composition is excellent in alkali developability, resulting in undeveloped development, resulting in a decrease in chromaticity, contrast, and dimensional accuracy of the color filter. Can be suppressed.
- the pigment dispersion composition is excellent in dry re-dissolvability, when the pigment dispersion composition adheres to a coating apparatus and is dried and a precipitate is generated, the precipitate is quickly dissolved in a solvent. In addition, the precipitate can be easily washed using a solvent or the like. Moreover, even if this precipitate is mixed into the pigment dispersion composition, the precipitate is dissolved in the pigment dispersion composition. Therefore, it can suppress that a deposit interferes with image formation.
- the details of the reason why the pigment dispersion composition according to this embodiment is excellent in alkali developability and dry redissolvability are not clear, but can be considered as follows, for example.
- the pigment dispersion composition according to this embodiment includes a dispersant composed of the above block copolymer.
- the block copolymer since the localized basic functional group of the partial structure represented by the general formula (2) is firmly adsorbed on the surface of the pigment, the pigment dispersion composition according to this embodiment is dried. Even after that, the cohesive strength of the pigment is weak, and it has an ester bond part and a terminal hydroxyl group in the side chain of the localized partial structure represented by the general formula (1), so that it interacts with the solvent and the binder resin.
- this embodiment The pigment dispersion composition according to the present invention is considered to dissolve quickly in a solvent or an alkaline aqueous solution even after drying. For the above reasons, it is considered that the pigment dispersion composition is excellent in alkali developability and dry redissolvability.
- the pigment dispersion composition can be suitably used for color filters.
- the polymerization rate, the weight average molecular weight (Mw), the molecular weight distribution (PDI), the amine value and the acid value of the dispersant and the binder resin, and the viscosity, dry redissolvability and alkali developability of the pigment dispersion composition are as follows. Evaluation was made according to the method.
- ⁇ Polymerization rate> 1 H-NMR was measured using NMR (trade name: AVANCE500, manufactured by Bruker BioSpin), and the polymerization rate was calculated from the peak area ratio of the vinyl group of the monomer and the ester side chain of the polymer.
- the amine value is represented by the weight of potassium hydroxide (KOH) equivalent to the basic component per gram of solid content.
- KOH potassium hydroxide
- the measurement sample was dissolved in tetrahydrofuran, and the obtained solution was neutralized and titrated with a 0.1 M 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 formula using the inflection point of the titration pH curve as the titration end point.
- Vs Amine value (mgKOH / g)
- Vs Amount of 0.1 M hydrochloric acid / 2-propanol solution required for titration (mL)
- f titer of 0.1M hydrochloric acid (2-propanol)
- w weight of measurement sample (g) (converted to solid content)
- the acid value represents the weight of potassium hydroxide required to neutralize acidic components per gram of solid content.
- the measurement sample was dissolved in tetrahydrofuran, and the obtained solution was subjected to neutralization titration with a 0.5 M potassium hydroxide / ethanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation).
- the acid value was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.
- A 56.11 ⁇ Vs ⁇ 0.5 ⁇ f / w
- f Potency of 0.5M potassium hydroxide / ethanol solution
- w Measurement sample weight (g) (solid content conversion)
- the pigment dispersion composition was applied to a glass plate of 50 mm ⁇ 30 mm whose surface was washed with a thickness of 25 ⁇ m and dried at 90 ° C. for 10 minutes to form a coating film.
- the glass plate was immersed in a solvent (propylene glycol monomethyl ether acetate), and the solubility of the coating film in the solvent was observed.
- the solubility was evaluated according to the following criteria.
- A The coating film is eluted from the glass plate within 5 minutes of immersion.
- ⁇ The coating film is eluted from the glass plate within 10 minutes of immersion.
- X The coating film remains on the glass plate after 10 minutes of immersion.
- a coating film of the pigment dispersion composition was formed to a thickness of 25 ⁇ m on a 50 mm ⁇ 30 mm glass plate whose surface had been cleaned, and dried at 90 ° C. for 10 minutes.
- the glass plate on which the coating film was formed was immersed in a 1% potassium hydroxide aqueous solution, and the solubility of the coating film in a 1% potassium hydroxide aqueous solution (alkali aqueous solution) was observed.
- the solubility was evaluated according to the following criteria.
- A The coating film is eluted from the glass plate within 5 minutes of immersion.
- ⁇ The coating film is eluted from the glass plate within 10 minutes of immersion.
- X The coating film remains on the glass plate after 10 minutes of immersion.
- Synthesis of polymerization initiator> Synthesis of ethyl-2-methyl-2-n-butylteranyl-propionate (hereinafter referred to as “BTEE”) Metal tellurium (trade name: Tellurium ( ⁇ 40 mesh), manufactured by Aldrich) 6.38 g (50 mmol) was suspended in 50 mL of tetrahydrofuran. To the obtained suspension, 34.4 mL (55 mmol) of n-butyllithium (manufactured by Aldrich, 1.6M hexane solution) was slowly added dropwise at room temperature (10 minutes). The resulting reaction solution was stirred until the metal tellurium disappeared completely (20 minutes).
- BTEE ethyl-2-methyl-2-n-butylteranyl-propionate
- Synthesis Example 2 Synthesis of dibutyl ditelluride (hereinafter referred to as “DBDT”) 3.19 g (25 mmol) of metal tellurium (trade name: Tellurium ( ⁇ 40 mesh), manufactured by Aldrich) was suspended in 25 mL of tetrahydrofuran, and n- Butyl lithium (manufactured by Aldrich, 1.6M hexane solution) 17.2 mL (27.5 mmol) was slowly added at 0 ° C. (10 minutes). The resulting reaction solution was stirred until the metal tellurium disappeared completely (10 minutes). Next, 20 mL of ammonium chloride solution was added at room temperature and stirred for 1 hour.
- DBDT dibutyl ditelluride
- n-butyl methacrylate (trade name: Acryester B, manufactured by Mitsubishi Rayon Co., Ltd., hereinafter referred to as “BMA”), azobisisobutyronitrile (trade name: AIBN, manufactured by Otsuka Chemical Co., Ltd.) 0.0493 g) (hereinafter referred to as “AIBN”) and 6.71 g of propylene glycol monomethyl ether acetate (hereinafter referred to as “PMA”), and after substitution with argon, BTEE (0.449 g) and DBDT (0.277 g) were added. The reaction was carried out at ° C for 22 hours. The polymerization rate was 100%.
- argon-substituted dimethylaminoethyl methacrylate (trade name: GE720 (DAM), manufactured by Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as “DMAEMA”)
- AIBN 0.0245 g
- PMA 2 0.000 g
- a mixed solution of DMAEMA (3.00 g), AIBN (0.0245 g), and PMA (2.00 g) previously substituted with argon was added to the obtained solution and reacted at 60 ° C. for 29 hours.
- the polymerization rate was 100%.
- a mixed solution of DMAEMA (347.0 g), AIBN (1.58 g), and PMA (179.0 g) previously substituted with argon was added to the obtained solution, and the mixture was reacted at 60 ° C. for 23 hours.
- the polymerization rate was 99%.
- a mixed solution of DMAEMA (101.0 g), AIBN (1.97 g), and PMA (67.2 g) previously substituted with argon was added to the obtained solution and reacted at 60 ° C. for 10 hours.
- the polymerization rate was 100%.
- a mixed solution of DMAEMA (3.00 g), AIBN (0.0245 g), and PMA (2.00 g) previously substituted with argon was added to the obtained solution and reacted at 60 ° C. for 29 hours.
- the polymerization rate was 100%.
- the obtained reaction solution was cooled to room temperature, PMA (120.0 g) was added, and a solution of binder resin A having a nonvolatile content of 40% was obtained.
- the weight average molecular weight (Mw) of the binder resin A was 9,800, the molecular weight distribution (PDI) was 1.93, and the acid value was 127 mgKOH / g.
- Examples 1 to 14 and Comparative Examples 1 to 5 The composition was adjusted to 10 parts by weight of pigment, 3 parts by weight of dispersant, 3 parts by weight of binder resin, 10 parts by weight of methoxypropanol, and 74 parts by weight of PMA, and stirred with a planetary ball mill (0.5 mm zirconia beads, 2 hours). Thus, pigment dispersion compositions of Examples 1 to 14 and Comparative Examples 1 to 5 shown in Table 1 were obtained.
- dispersant dispersants A to O obtained in Synthesis Examples 3 to 17 were used, binder resin A obtained in Synthesis Example 18 was used as the binder resin, and C.I. I. Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) and C.I. I. Pigment Green 58 (trade name: FASTOGEN Green A110, manufactured by DIC Corporation) was used.
- a dispersant comprising a block copolymer containing a partial structure represented by the general formula (1) in the segment A and a partial structure represented by the general formula (2) in the segment B.
- the coating film was excellent in alkali developability and dry redissolvability.
- Comparative Example 1 using a dispersant composed of a block copolymer not including the partial structure represented by the general formula (1) in the segment A the alkali developability of the coating film was inferior.
- Comparative Examples 2 and 4 using a dispersant composed of a block copolymer that does not include the partial structure represented by the general formula (1) in the segment A the alkaline developability and dry resolubility of the coating film are improved. It was inferior.
- Comparative Examples 3 and 5 using a dispersant composed of a random copolymer including the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) alkaline development of the coating film And poor re-dissolvability. From these results, pigment dispersion using a block copolymer containing a partial structure represented by the general formula (1) in the segment A and a partial structure represented by the general formula (2) in the segment B as a dispersant. It turns out that a composition is excellent in the alkali developability and dry re-dissolution property of a coating film.
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Abstract
Description
下記一般式(1):
で表わされる部分構造を含むセグメントAと、
下記一般式(2):
で表される部分構造を含むセグメントBとを有し、
アミン価が、20mgKOH/g~150mgKOH/gである、ブロック共重合体。
(セグメントA)
本実施形態に係るブロック共重合体は、下記一般式(1)で表わされる部分構造(モノマー単位)を含むセグメントAを有する。
本実施形態に係るブロック共重合体は、上記セグメントAに加えて、下記一般式(2)で表される部分構造(モノマー単位)を含むセグメントBを有する。
ブロック共重合体において、セグメントAとセグメントBとの質量比(セグメントA:セグメントB)は、50:50~95:5であることが好ましく、60:40~95:5であることがより好ましい。
本実施形態に係る顔料分散組成物は、上記のブロック共重合体からなる分散剤と顔料とを含む。顔料分散組成物は、バインダー樹脂、溶媒などを含んでいてもよい。
以下、本発明について、具体的な実施例に基づいて、さらに詳細に説明する。本発明は、以下の実施例に何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施することが可能である。なお、分散剤及びバインダー樹脂の重合率、重量平均分子量(Mw)、分子量分布(PDI)、アミン価及び酸価、並びに顔料分散組成物の粘度、乾燥再溶解性及びアルカリ現像性は、下記の方法に従って評価した。
NMR(商品名:AVANCE500、ブルカー・バイオスピン社製)を用いて、1H-NMRを測定し、モノマーのビニル基とポリマーのエステル側鎖のピーク面積比から重合率を算出した。
GPC(商品名:GPCV-2000、日本ウォーターズ社製、カラム:TSKgel α-3000、移動相:10mMトリエチルアミン/ジメチルホルムアミド溶液)を用い、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、440、92)を使用して検量線を作成し、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)の重量で表わしたものである。測定サンプル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0.1M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:アミン価(mgKOH/g)
Vs:滴定に要した0.1M塩酸/2-プロパノール溶液の使用量(mL)
f:0.1M塩酸(2-プロパノール性)の力価
w:測定サンプルの重量(g)(固形分換算)
酸価は、固形分1gあたりの酸性成分を中和するのに要する水酸化カリウムの重量を表わしたものである。測定サンプル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0.5M水酸化カリウム/エタ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、次式により酸価を算出した。
A:酸価(mgKOH/g)
Vs:滴定に要した0.5M水酸化カリウム/エタノール溶液の使用量(mL)
f:0.5M水酸化カリウム/エタノール溶液の力価
w:測定サンプル重量(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、1°34’×R24のコーンローターを使用して、25℃下、ローター回転数60rpmで粘度を測定した。
表面を洗浄した50mm×30mmのガラス板上に、25μmの厚さで顔料分散組成物を塗布し、90℃で10分間乾燥して塗布膜を形成した。次に、ガラス板を溶媒(プロピレングリコールモノメチルエーテルアセテート)に浸漬し、塗布膜の溶媒への溶解性を観察した。その溶解性を以下の基準により評価した。
○:浸漬10分以内に塗布膜がガラス板上から溶離している。
×:浸漬10分後に塗布膜がガラス板上に残っている。
表面を洗浄した50mm×30mmのガラス板上に、25μmの厚さで顔料分散組成物の塗布膜を形成し、90℃で10分間乾燥した。次に、塗布膜を形成したガラス板を1%水酸化カリウム水溶液に浸漬し、塗布膜の1%水酸化カリウム水溶液(アルカリ水溶液)中への溶解性を観察した。その溶解性を以下の基準により評価した。
○:浸漬10分以内に塗布膜がガラス板上から溶離している。
×:浸漬10分後に塗布膜がガラス板上に残っている。
(合成例1):エチル-2-メチル-2-n-ブチルテラニル-プロピオネート(以下「BTEE」という)の合成
金属テルル(商品名:Tellurium(-40mesh)、Aldrich社製)6.38g(50mmol)をテトラヒドロフラン50mLに懸濁させた。得られた懸濁液にn-ブチルリチウム(Aldrich社製、1.6Mヘキサン溶液)34.4mL(55mmol)を、室温下でゆっくり滴下した(10分間)。得られた反応溶液を金属テルルが完全に消失するまで撹拌した(20分間)。この反応溶液に、エチル-2-ブロモ-イソブチレート10.7g(55mmol)を室温下で加え、2時間撹拌した。反応終了後、減圧下で溶媒を濃縮し、続いて減圧蒸留して、黄色油状物8.98g(収率59.5%)のBTEEを得た。
金属テルル(商品名:Tellurium(-40mesh)、Aldrich社製)3.19g(25mmol)をテトラヒドロフラン25mLに懸濁させ、n-ブチルリチウム(Aldrich社製、1.6Mヘキサン溶液)17.2mL(27.5mmol)を0℃でゆっくり加えた(10分間)。得られた反応溶液を金属テルルが完全に消失するまで撹拌した(10分間)。次に、塩化アンモニウム溶液20mLを室温で加え、1時間撹拌した。次に、有機層を分離し、水層をジエチルエーテルで3回抽出した。集めた有機層を無水硫酸ナトリウムで乾燥後、減圧濃縮し、黒紫色油状物4.41g(11.93mmol:収率95%)のDBDTを得た。
(合成例3):分散剤Aの合成
アルゴンガス導入管、撹拌機を備えたフラスコにメタアクリル酸2-ヒドロキシエチルのカプロラクトン5mol付加物(商品名:プラクセルFM5、ダイセル化学社製、以下「PCL5」という)3.00g、メタクリル酸n-ブチル(商品名:アクリエステルB、三菱レイヨン社製、以下「BMA」という)9.00g、アゾビスイソブチニトリル(商品名:AIBN、大塚化学社製、以下「AIBN」という)0.0493g、プロピレングリコールモノメチルエーテルアセテート(以下「PMA」という)6.71gを仕込み、アルゴン置換後、BTEE(0.449g)、DBDT(0.277g)を加え、60℃で22時間反応させた。重合率は、100%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(116.0g)、BMA(84.5g)、AIBN(0.821g)、PMA(133.0g)を仕込み、アルゴン置換後、BTEE(7.49g)、DBDT(4.63g)を加え、60℃で12時間反応させた。重合率は、98%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(9.03g)、BMA(3.00g)、AIBN(0.0493g)、PMA(4.14g)を仕込み、アルゴン置換後、BTEE(0.449g)、DBDT(0.277g)を加え、60℃で22時間反応させた。重合率は、100%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(177.5g)、AIBN(0.821g)、PMA(118.3g)を仕込み、アルゴン置換後、BTEE(7.49g)、DBDT(4.63g)を加え、60℃で12時間反応させた。重合率は、99%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(359.8g)、BMA(260.0g)、AIBN(3.16g)、PMA(300.0g)を仕込み、アルゴン置換後、BTEE(31.0g)、DBDT(17.8g)を加え、60℃で19時間反応させた。重合率は、100%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(103.0g)、BMA(75.0g)、AIBN(0.821g)、PMA(88.9g)を仕込み、アルゴン置換後、BTEE(7.49g)、DBDT(4.63g)を加え、60℃で25時間反応させた。重合率は、100%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(124.0g)、BMA(90.8g)、AIBN(0.821g)、PMA(143.0g)を仕込み、アルゴン置換後、BTEE(7.49g)、DBDT(4.63g)を加え、60℃で12時間反応させた。重合率は、98%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(82.3g)、BMA(147.0g)、AIBN(0.821g)、PMA(117.0g)を仕込み、アルゴン置換後、BTEE(7.49g)、DBDT(4.63g)を加え、60℃で14時間反応させた。重合率は、99%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(634.9g)、BMA(464.0g)、AIBN(3.94g)、PMA(461.0g)を仕込み、アルゴン置換後、BTEE(36.0g)、DBDT(22.2g)を加え、60℃で14時間反応させた。重合率は、98%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(136.3g)、BMA(99.7g)、AIBN(0.547g)、PMA(98.9g)を仕込み、アルゴン置換後、BTEE(5.00g)、DBDT(3.08g)を加え、60℃で24時間反応させた。重合率は、100%であった。
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2-ヒドロキシエチルのカプロラクトン2mol付加物(商品名:プラクセルFM2D、ダイセル化学社製)6.93g、BMA(5.07g)、AIBN(0.0493g)、PMA(8.00g)を仕込み、アルゴン置換後、BTEE(0.449g)、DBDT(0.277g)を加え、60℃で22時間反応させた。重合率は、100%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにBMA(200.0g)、AIBN(0.821g)、PMA(147.8g)を仕込み、アルゴン置換後、BTEE(3.75g)、DBDT(2.30g)を加え、60℃で20時間反応させた。重合率は、99%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにDMAEMA(300g)、AIBN(2.46g)、酢酸エチル(300g)を仕込み、アルゴン置換後、BTEE(45.0g)、DBDT(27.7g)を加え、60℃で25時間反応させた。重合率は、99%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにPCL5(6.93g)、BMA(5.07g)、DMAEMA(3.00g)、AIBN(0.0493g)、PMA(7.03g)を仕込み、アルゴン置換後、BTEE(0.449g)、DBDT(0.277g)を加え、60℃で22時間反応させた。重合率は100%であった。
アルゴンガス導入管、撹拌機を備えたフラスコにトリエチレングリコールモノエチルエーテルモノメタクリレート(POLYSCIENCES社製)12.7g、BMA(34.0g)、メタクリル酸メチル(三菱レイヨン社製)70.4g、メタクリル酸2-エチルヘキシル(三菱レイヨン社製)32.0g、メタクリル酸ベンジル(三菱ガス化学社製、以下「BzMA」という)23.5g、AIBN(1.17g)、PMA(90.9g)を仕込み、アルゴン置換後、BTEE(10.7g)、DBDT(6.59g)を加え、60℃で14時間反応させた。重合率は、100%であった。
(合成例18)
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(三菱レイヨン社製、以下「MAA」という)20.0g、BzMA(80.0g)、PMA(290.0g)を仕込み、アルゴン置換後、AIBN(1.5g)、n-ドデカンチオール(2.0g)、PMA(10.0g)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(40.0g)、BzMA(160.0g)、AIBN(3.0g)、n-ドデカンチオール(4.0g)、PMA(25.0g)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(0.3g)、PMA(5.0g)を加えて1時間反応させ、さらにAIBN(0.3g)、PMA(5.0g)を加え1時間反応させ、さらにAIBN(0.3g)、PMA(5.0g)を加え1時間反応させた。
顔料10質量部、分散剤3質量部、バインダー樹脂3質量部、メトキシプロパノール10質量部、及びPMA74質量部となるように配合を調整し、遊星ボールミル(0.5mmジルコニアビーズ、2時間)で撹拌して、表1に示す実施例1~14及び比較例1~5の顔料分散組成物を得た。分散剤としては、合成例3~17で得た分散剤A~Оを用い、バインダー樹脂には合成例18で得たバインダー樹脂Aを用い、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)及びC.I.Pigment Green 58(商品名:FASTOGEN Green A110、DIC社製)を用いた。
Claims (9)
- 前記セグメントAは、前記一般式(1)で表わされる部分構造を10質量%~100質量%含む、請求項1に記載のブロック共重合体。
- 前記セグメントBは、前記一般式(2)で表わされる部分構造を80質量%~100質量%含む、請求項1または2に記載のブロック共重合体。
- 前記ブロック共重合体における前記セグメントAと前記セグメントBとの質量比(セグメントAの質量:セグメントBの質量)が、50:50~95:5である、請求項1~3のいずれか1項に記載のブロック共重合体。
- 前記ブロック共重合体の分子量分布(PDI)が、1.05~2.20である、請求項1~4のいずれか1項に記載のブロック共重合体。
- 前記セグメントAのブロックと前記セグメントBのブロックからなるジブロック共重合体である、請求項1~5のいずれか1項に記載のブロック共重合体。
- 請求項1~6のいずれか1項に記載のブロック共重合体からなる、分散剤。
- 請求項7に記載の分散剤及び顔料を含む、顔料分散組成物。
- カラーフィルタ用である、請求項8に記載の顔料分散組成物。
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US10766993B2 (en) * | 2016-02-03 | 2020-09-08 | Otsuka Chemical Co., Ltd. | ABA block copolymer, dispersant, and pigment dispersion composition |
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JP6797483B2 (ja) * | 2017-03-31 | 2020-12-09 | 大塚化学株式会社 | ブロック共重合体、分散剤、着色組成物およびカラーフィルタ |
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EP3892612A4 (en) | 2018-12-05 | 2022-09-28 | Otsuka Chemical Co., Ltd. | METHOD FOR PRODUCTION OF ORGANIC TELLURIUM COMPOUND, AND METHOD FOR PRODUCTION OF VINYL POLYMER |
US11746247B2 (en) | 2019-03-22 | 2023-09-05 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Aqueous pigment dispersion liquid |
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JP7466359B2 (ja) | 2020-04-10 | 2024-04-12 | 大塚化学株式会社 | 着色組成物、および、カラーフィルタ |
JP7079835B2 (ja) * | 2020-12-10 | 2022-06-02 | 株式会社Dnpファインケミカル | カラーフィルタ用顔料分散液、カラーフィルタ用着色組成物、カラーフィルタ及び表示装置 |
WO2024116875A1 (ja) * | 2022-12-02 | 2024-06-06 | 大塚化学株式会社 | ブロック共重合体、分散剤、および、着色組成物 |
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JP2013119568A (ja) | 2013-06-17 |
CN103974987B (zh) | 2015-12-02 |
EP2789635B1 (en) | 2017-08-30 |
US20150152212A1 (en) | 2015-06-04 |
KR20140099256A (ko) | 2014-08-11 |
EP2789635A4 (en) | 2015-08-12 |
TWI553027B (zh) | 2016-10-11 |
EP2789635A1 (en) | 2014-10-15 |
TW201331244A (zh) | 2013-08-01 |
CN103974987A (zh) | 2014-08-06 |
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US9260557B2 (en) | 2016-02-16 |
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