CN112334504B - Dispersing agent composition, coloring composition and color filter - Google Patents

Dispersing agent composition, coloring composition and color filter Download PDF

Info

Publication number
CN112334504B
CN112334504B CN201980039848.6A CN201980039848A CN112334504B CN 112334504 B CN112334504 B CN 112334504B CN 201980039848 A CN201980039848 A CN 201980039848A CN 112334504 B CN112334504 B CN 112334504B
Authority
CN
China
Prior art keywords
meth
group
block
general formula
acrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201980039848.6A
Other languages
Chinese (zh)
Other versions
CN112334504A (en
Inventor
清水达彦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Otsuka Chemical Co Ltd
Original Assignee
Otsuka Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Otsuka Chemical Co Ltd filed Critical Otsuka Chemical Co Ltd
Publication of CN112334504A publication Critical patent/CN112334504A/en
Application granted granted Critical
Publication of CN112334504B publication Critical patent/CN112334504B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Optical Filters (AREA)
  • Graft Or Block Polymers (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

Technical problems: a dispersant composition which generates little formaldehyde over time is provided. The solution is as follows: a dispersant composition comprising a polymer having a structure represented by the general formula (5) in a side chain. * -Y 1 ‑N‑R 11 R 12 (5) [ in the general formula (5), R 11 Represents a hydrogen atom, a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 12 Represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 11 And R is 12 Can be mutually bonded to form a ring structure, Y 1 Represents a divalent hydrocarbon group and represents a bonding site.]

Description

Dispersing agent composition, coloring composition and color filter
Technical Field
The present invention relates to a dispersant composition containing a polymer.
Background
Conventionally, in the production of color filters used in liquid crystal displays and the like, dyeing methods, printing methods, inkjet methods, electrodeposition methods, pigment dispersion methods, and the like have been known as methods for imparting a coloring material to a substrate. Among them, the pigment dispersion method is the mainstream from the viewpoints of spectroscopic characteristics, durability, pattern shape and accuracy. In this pigment dispersion method, a coating film formed 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 is cured by irradiation of radiation through a photomask having a desired pattern shape, and is subjected to alkali development.
In recent years, in order to obtain good color reproducibility and high contrast of a color filter, a high concentration of pigment in a coloring composition has been studied. In the case of increasing the pigment concentration, the proportion of the dispersant is relatively reduced, and therefore, the dispersant is required to have high dispersibility (for example, refer to paragraph 0004 of patent document 1). In addition, in alkali development, a binder resin having alkali solubility plays a great role. However, in the case of a pigment dispersion composition in which pigment is concentrated, the proportion of the binder resin as a developing component is reduced, and the alkali developability is lowered. Therefore, alkali developability originally required for the binder resin is also required for the dispersant. As such a dispersant, patent document 2 describes the use of an a-B block copolymer as pigment dispersion, wherein the a-B block copolymer is composed of an a block having a polylactone chain in a side chain and a B block having a tertiary amine group in a side chain (see paragraphs 0023 to 0045 of patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2009-265515
Patent document 2: japanese patent application laid-open No. 2013-119568
Disclosure of Invention
Problems to be solved by the invention
In order to improve dispersibility of the coloring material in the resin-type dispersant, it is proposed to introduce a tertiary amine group into a side chain (refer to patent document 2). However, it is considered that the tertiary amine group-containing resin-type dispersant generates formaldehyde with the passage of time due to the tertiary amine group. Therefore, if such a resin-type dispersant is used in the coloring composition, formaldehyde becomes contained in the coloring composition. In recent years, since environmental standards have become more stringent, the amount of formaldehyde in the coloring composition will not meet the environmental standards if a conventional resin-type dispersant is used.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a dispersant composition which generates a small amount of formaldehyde over time.
Solution to the problem
The dispersant composition of the present invention capable of solving the above-mentioned problems is characterized by comprising a polymer having a structure represented by the general formula (5) in a side chain.
*-Y 1 -N-R 11 R 12 (5)
[ in the general formula (5), R 11 Represents a hydrogen atom, a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 12 Represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 11 And R is 12 Can be mutually bonded to form a ring structure, Y 1 Represents a divalent hydrocarbon group and represents a bonding site.]
It is considered that if a polymer having an amino group is used as a dispersant, formaldehyde is generated over time due to the amino group. In the present invention, it is surprising that the formaldehyde generation with time can be suppressed and the formaldehyde in the dispersant composition can be reduced by setting the amino group to a specific structure (structure represented by the general formula (5)). Excellent dispersibility of the coloring material can also be obtained.
The present invention also includes a coloring composition characterized by containing the above-described dispersant composition, a coloring material, a binder resin, and a dispersion medium. The present invention also provides a color filter including a colored layer formed using the above-described coloring composition.
Effects of the invention
According to the present invention, a dispersant composition with a small formaldehyde generation amount with the lapse of time can be obtained.
Detailed Description
An example of a preferred embodiment of the present invention will be described below. The following embodiments are merely examples. The present invention is not limited to the following embodiments.
In the present invention, "(meth) acrylic group" means "at least one of acrylic group and methacrylic group". "(meth) acrylic-based monomer" means a monomer having a "(meth) acryl group" in the molecule. "(meth) acryl" means "at least one of acryl and methacryl". "vinyl monomer" refers to a monomer having a carbon-carbon double bond in the molecule that can undergo free radical polymerization. "structural unit derived from a (meth) acrylic acid based monomer" means a structural unit in which a radical polymerizable carbon-carbon double bond of a (meth) acrylic acid based monomer is polymerized to form a carbon-carbon single bond. "structural unit derived from a vinyl monomer" refers to a structural unit of a vinyl monomer in which a free-radically polymerizable carbon-carbon double bond is polymerized to form a carbon-carbon single bond.
< dispersant composition >
The dispersant composition of the present invention is characterized by comprising a polymer having a structure represented by the general formula (5) in a side chain.
*-Y 1 -N-R 11 R 12 (5)
[ in the general formula (5), R 11 Represents a hydrogen atom, a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 12 Represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 11 And R is 12 Can be mutually bonded to form a ring structure, Y 1 Represents a divalent hydrocarbon group and represents a bonding site.]
It is considered that if a polymer having an amino group is used as a dispersant, formaldehyde is generated over time due to the amino group. In the present invention, it is surprising that the formaldehyde generation with time can be suppressed and the formaldehyde in the dispersant composition can be reduced by setting the amino group to a specific structure (structure represented by the general formula (5)). Excellent dispersibility of the coloring material can also be obtained.
The R is 11 And R is 12 Examples of the chain hydrocarbon group include a linear alkyl group and a branched alkyl group. The number of carbon atoms of the linear alkyl group is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 5. The straight-chain alkyl group includes ethyl group, n-propyl group N-butyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-lauryl, etc. The branched 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 isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, neopentyl, and isooctyl.
The R is 11 And R is 12 Examples of the substituent of the chain hydrocarbon group include a halogen group, an alkoxy group and a benzoyl group (-COC) 6 H 5 ) Hydroxyl, etc.
The R is 11 And R is 12 Examples of the cyclic hydrocarbon group 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 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The number of carbon atoms of the aromatic group is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6 to 8. Examples of the aromatic group include phenyl, tolyl, xylyl, and mesityl. Examples of 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 an alkylene group having 1 to 3 carbon atoms.
The R is 11 And R is 12 Examples of the substituent of the cyclic hydrocarbon group include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxyl group.
The R is 11 And R is 12 Examples of the cyclic structure formed by bonding to each other include a five-membered to seven-membered nitrogen-containing heterocyclic ring or a condensed ring formed by condensing two nitrogen-containing heterocyclic rings. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring.
The Y is 1 Examples of the divalent hydrocarbon group include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, and an arene diyl group having 6 to 10 carbon atoms. Of which carbon atoms are preferredAn alkylene group having a number of 1 to 10. The alkylene group may be either a straight chain or a branched chain, but is preferably a straight chain. Y is Y 1 Alkylene groups having 1 to 5 carbon atoms are preferable.
The structure represented by the general formula (5) -N-R 11 R 12 Examples of the moiety include monoalkylamino groups such as ethylamino, propylamino and t-butylamino; dialkylamino groups such as diethylamino, dipropylamino, and bis (2-hydroxyethyl) amino.
Examples of the polymer having a structure represented by the general formula (5) in the side chain include (meth) acrylic polymers, polyurethane polymers, polyester polymers, polyallylamine polymers, and carbodiimide polymers.
From the viewpoints of adsorptivity to a coloring material and dispersibility of a coloring material, the amine value of a polymer having a structure represented by the general formula (5) in a side chain is preferably 10mgKOH/g or more, more preferably 50mgKOH/g or more, still more preferably 80mgKOH/g or more, preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 120mgKOH/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, further preferably 5,000 or more, particularly preferably 6,000 or more, preferably 40,000 or less, more preferably 30,000 or less, further preferably 25,000 or less, and particularly preferably 20,000 or less. If the weight average molecular weight is within the above range, the dispersibility when used as a dispersant is more excellent.
(Block copolymer)
From the standpoint of dispersibility, the polymer is preferably a block copolymer having an a block having a structural unit derived from a (meth) acrylic acid based monomer and a B block having a structural unit represented by the general formula (1).
[ in the general formula (1), R 11 Represents a hydrogen atom, optionally substituted Chain or cyclic hydrocarbon group of 2 or more carbon atoms of the radical, R 12 Represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 11 And R is 12 Can be mutually bonded to form a ring 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 various components and the like of the block copolymer are described below.
(A block)
The a block is a polymer block comprising structural units derived from (meth) acrylic-based monomers. The structural units derived from the (meth) acrylic acid based monomer in the a block may be one kind only, or may be two or more kinds. By having a structural unit derived from a (meth) acrylic acid based monomer, high affinity with a dispersion medium (solvent) and a binder resin incorporated in the coloring composition can be maintained.
In 100% by mass of the a block, the content of the structural unit derived from the (meth) acrylic acid based monomer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.
Examples of the (meth) acrylic acid based monomer include (meth) acrylic acid esters having a chain alkyl group (straight chain alkyl group or branched chain alkyl group), (meth) acrylic acid esters having a cyclic alkyl group, (meth) acrylic acid esters having a polycyclic structure, (meth) acrylic acid esters having an aromatic group, (meth) acrylic acid esters having a polyalkylene glycol structural unit, (meth) acrylic acid esters having a hydroxyl group, (meth) acrylic acid esters having a lactone-modified hydroxyl group, (meth) acrylic acid esters having an alkoxy group, (meth) acrylic acid esters having an oxygen-containing heterocyclic group, and (meth) acrylic acid esters having an acidic group, and the like, and one or two or more of them may be used in combination.
The (meth) acrylate having a linear alkyl group is preferably a (meth) acrylate having a linear alkyl group and having 1 to 20 carbon atoms in the linear alkyl group, and more preferably a (meth) acrylate having a linear alkyl group and having 1 to 10 carbon atoms in the linear alkyl group. Examples of the (meth) acrylic acid ester having a linear alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, decyl (meth) acrylate, n-lauryl (meth) acrylate, and n-stearyl (meth) acrylate.
The branched alkyl (meth) acrylate is preferably a branched alkyl (meth) acrylate having 3 to 20 carbon atoms in a branched alkyl group, and preferably a branched alkyl (meth) acrylate having 3 to 10 carbon atoms in a branched alkyl group. Examples of the (meth) acrylic acid ester having a branched alkyl group include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, and the like.
The (meth) acrylate having a cyclic alkyl group is preferably a (meth) acrylate having a cyclic alkyl group and having 6 to 12 carbon atoms. Examples of the cyclic alkyl group include cyclic alkyl groups having a monocyclic structure (e.g., cycloalkyl groups). Specific examples of the (meth) acrylic acid ester having a cyclic alkyl group with a monocyclic structure include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, and the like.
The (meth) acrylate having a polycyclic structure is preferably a (meth) acrylate having a polycyclic structure and having 6 to 12 carbon atoms. Examples of the polycyclic structure include cyclic alkyl groups having a bridged ring structure (e.g., adamantyl, norbornyl, isobornyl). Specific examples of the (meth) acrylic acid ester having a polycyclic structure include isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, and 2-ethyl-2-adamantyl (meth) acrylate.
The aromatic group-containing (meth) acrylate is preferably an aromatic group-containing (meth) acrylate having 6 to 12 carbon atoms as an aromatic group. Examples of the aryl group include aryl groups, and may have a chain portion such as alkylaryl groups, arylalkyl groups, and aryloxyalkyl groups. Specific examples of the (meth) acrylic acid ester having an aromatic group include benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.
Examples of the (meth) acrylic acid ester having a polyalkylene glycol structural unit include polyethylene glycol (polymerization degree=2 to 10) methyl ether (meth) acrylic acid ester, polyethylene glycol (polymerization degree=2 to 10) ethyl ether (meth) acrylic acid ester, polyethylene glycol (polymerization degree=2 to 10) propyl ether (meth) acrylic acid ester, polyethylene glycol (polymerization degree=2 to 10) phenyl ether (meth) acrylic acid ester and the like (meth) acrylic acid esters having a polyethylene glycol structural unit; (meth) acrylates having a polypropylene glycol structural unit such as polypropylene glycol (polymerization degree=2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree=2 to 10) ethyl ether (meth) acrylate, polypropylene glycol (polymerization degree=2 to 10) propyl ether (meth) acrylate, and polypropylene glycol (polymerization degree=2 to 10) phenyl ether (meth) acrylate.
Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate. Among them, (meth) acrylic esters having a hydroxyalkyl group having 1 to 5 carbon atoms are more preferable.
Examples of the (meth) acrylate having a lactone-modified hydroxyl group include those obtained by adding a lactone to the above-mentioned (meth) acrylate having a hydroxyl group, and those obtained by adding caprolactone are preferable. The addition amount of caprolactone is preferably 1 to 10 moles, more preferably 1 to 5 moles. Examples of the (meth) acrylic acid ester having a lactone-modified hydroxyl group include 1 mole of caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 2 mole of caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 3 mole of caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 4 mole of caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 5 mole of caprolactone adduct of 2-hydroxyethyl (meth) acrylate, and 10 mole of caprolactone adduct of 2-hydroxyethyl (meth) acrylate.
Examples of the (meth) acrylate having an alkoxy group include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.
The (meth) acrylate having an oxygen-containing heterocyclic group is preferably an oxygen-containing heterocyclic group having a four-membered to six-membered ring. Specific examples of the (meth) acrylate having an oxygen-containing heterocyclic group include glycidyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, methyl (3-ethyloxetan-3-yl) acrylate, (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2- [ (2-tetrahydropyranyl) oxy) ] ethyl (meth) acrylate, and 1, 3-dioxane- (meth) acrylate.
Examples of the acidic group include a carboxyl group (-COOH) and a sulfonic acid group (-SO) 3 H) Phosphate group (-OPO) 3 H 2 ) Phosphonic acid groups (-PO) 3 H 2 ) Phosphinic acid groups (-PO) 2 H 2 ). Examples of the (meth) acrylate having an acidic group include (meth) acrylate having a carboxyl group, (meth) acrylate having a phosphate group, and (meth) acrylate having a sulfonate group.
Examples of the (meth) acrylate having a carboxyl group include carboxyethyl (meth) acrylate; carboxypentyl (meth) acrylate; and monomers obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride, and phthalic anhydride with a (meth) acrylate having a hydroxyl group, such as 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, and 2- (meth) acryloyloxyethyl phthalate. Examples of the (meth) acrylic acid ester having a sulfonic acid group include ethyl (meth) acrylate sulfonate. Examples of the (meth) acrylate having a phosphate group include 2- (phosphoryloxy) ethyl (meth) acrylate.
The a block may also have structural units other than those derived from (meth) acrylic acid based monomers. The other structural unit that may be contained in the a block is not particularly limited as long as it is formed of a vinyl monomer copolymerizable with both the (meth) acrylic acid based monomer and a vinyl monomer forming the B block described later. The vinyl monomers capable of forming the other structural units of the A block may be used alone or in combination of two or more.
Specific examples of the vinyl monomer capable of forming the other structural unit of the a block include α -olefin, aromatic vinyl monomer, heterocyclic vinyl monomer, vinyl amide, vinyl carboxylate, diene, and the like. These vinyl monomers may also have hydroxyl groups, epoxy groups.
Examples of the α -olefin include 1-hexene, 1-octene, and 1-decene.
Examples of the aromatic vinyl monomer include styrene, α -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, and 1-vinylnaphthalene.
Examples of the heterocyclic vinyl monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine, N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide.
Examples of the vinylamide include N-vinylformamide, N-vinylacetamide, N-vinyl-. Epsilon. -caprolactam, and the like.
Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, and vinyl benzoate.
Examples of the dienes include butadiene, isoprene, 4-methyl-1, 4-hexadiene, and 7-methyl-1, 6-octadiene.
The a block preferably contains a structural unit represented by the general formula (10), i.e., a structural unit derived from a (meth) acrylate having the lactone-modified hydroxyl group. The structural unit represented by the general formula (10) has an ester bond moiety and a terminal hydroxyl group in a side chain, and therefore has high affinity with a dispersion medium and a binder resin, and improves the alkali developability of the block copolymer.
[ in the general formula (10), 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.]
N1 in the formula (10) is preferably an integer of 1 to 7, more preferably an integer of 1 to 5.
The R is 2 The alkylene group having 1 to 10 carbon atoms may be either a straight chain or a branched chain, but is preferably a straight chain. The R is 2 Specific examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, and 1-methylethylene. R is R 2 Alkylene groups having 1 to 5 carbon atoms are preferable.
The R is 3 The alkylene group having 1 to 10 carbon atoms may be either a straight chain or a branched chain, but is preferably a straight chain. The R is 3 Specific examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene and the like. R is R 3 An alkylene group having 1 to 8 carbon atoms is preferable, and an alkylene group having 3 to 8 carbon atoms is more preferable.
When the a block contains a structural unit represented by the general formula (10), the content of the structural unit in 100 mass% of the a block is preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 30 mass% or more, particularly preferably 60 mass% or more, preferably 95 mass% or less, more preferably 90 mass% or less, further preferably 85 mass% or less. By setting the content of the structural unit derived from the (meth) acrylate having a lactone-modified hydroxyl group within the above range, the alkali developability of the block copolymer can be improved.
The a block preferably has structural units derived from a vinyl monomer having an acidic group, preferably a (meth) acrylate ester having an acidic group, (meth) acrylic acid. By having a structural unit derived from a vinyl monomer having an acidic group, the solubility in an alkali developer is improved, and the alkali developability can be improved. However, if the ratio is increased, there is a possibility that the affinity with the solvent or the alkali-soluble resin is lowered. Therefore, the proportion of the structural unit derived from the vinyl monomer having an acidic group is preferably set so that the acid value of the whole block copolymer is lower than the amine value.
When the structural unit derived from the vinyl monomer having an acidic group is contained, the content of the structural unit is preferably 2% by mass or more, and more preferably 20% by mass or less, based on 100% by mass of the A block. If the content of the structural unit derived from the vinyl monomer having an acidic group is 2 mass% or more, the dissolution rate in alkali neutralization in alkali development is high, and if it is 20 mass% or less, the hydrophilicity is not excessively high, and the formation of pixels can be suppressed from becoming disordered.
In the A block, the content of the structural unit represented by the general formula (1) described later is less than 10% by mass, preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and most preferably no structural unit represented by the general formula (1). The lower the content of the structural unit represented by the general formula (1) in the a block, the more the dispersibility of the coloring material improves.
Preferably the a block does not have amino groups. That is, it is preferable that the vinyl monomer constituting the a block does not contain a vinyl monomer having an amino group. If amino groups are present in a large amount in the A block, the coloring material is adsorbed on both the A block and the B block when used as a dispersant, and the dispersibility of the coloring material is lowered. The content of the structural unit (including the structural unit in which the amino group is quaternized) 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, further preferably 0.1% by mass or less, and most preferably 0% by mass.
When two or more structural units are contained in the a block, the various structural units contained in the a block may be contained in the a block in any form, such as random copolymerization and block copolymerization, and from the viewpoint of uniformity, random copolymerization is preferable. For example, the a block may be formed from a copolymer of: the copolymer has structural units composed of a1 block and structural units composed of a2 block.
(B Block)
The B block is a polymer block comprising structural units represented by the following general formula (1).
(structural unit represented by the general formula (1))
The structural unit represented by the general formula (1) may be one kind or two or more kinds. By having the structural unit represented by the general formula (1), the adsorption property with the coloring material is high, and the generation of formaldehyde with the lapse of time can be suppressed. In the structural unit represented by the general formula (1), X is bonded to 1 on-Y 1 -N-R 11 R 12 Is of a structure shown in a general formula (5).
[ in the general formula (1), R 11 Represents a hydrogen atom, a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 12 Represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 11 And R is 12 Can be mutually bonded to form a ring 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 in the general formula (1) 11 And R is 12 R is the same as R in the above general formula (5) 11 And R is 12 The meaning is the same. R in the general formula (1) 11 And R is 12 Examples of the chain hydrocarbon group and the cyclic hydrocarbon group include R of the above general formula (5) 11 And R is 12 The illustrated groups. R in the general formula (1) 11 And R is 12 The number of carbon atoms of the straight-chain alkyl group is preferably 2 to 20, more preferably 2 to 10, still more preferably 2 to 5, and the number of carbon atoms of the branched alkyl group is preferably 3 to 20, more preferably 3 to 10, still more preferably 3 to 5.
The R is 11 And R is 12 The ring structure formed by bonding to each other may be, for example, five-membered ringA nitrogen-containing heterocycle having a ring to a seven-membered ring or a condensed ring obtained by condensing two nitrogen-containing heterocycles. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the structures represented by the following formulas (1-1), (1-2) and (1-3) are exemplified.
[ in the general formulae (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, and x represents a bonding site, and when l is 2 to 5, m is 2 to 4, n is 2 to 4, a plurality of R's are present 14 Can be the same or different.]
The X is 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 method of the amide group include C-CO-NH-Y 1 Or C-NH-CO-Y 1 Preferably C-CO-NH-Y 1 . Examples of the bonding method of the ester group include C-CO-O-Y 1 Or C-O-CO-Y 1 Preferably C-CO-O-Y 1 。
Y in the general formula (1) 1 And Y in the general formula (5) 1 The meaning is the same. The Y is 1 Alkylene groups having 1 to 10 carbon atoms are preferable. The alkylene group may be either a straight chain or a branched chain, but is preferably a straight chain. Y is Y 1 Alkylene groups having 1 to 5 carbon atoms are preferable.
Specific examples of the vinyl monomer forming the structural unit represented by the general formula (1) include ethylaminoethyl (meth) acrylate, ethylaminopropyl (meth) acrylate, ethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, propylaminoethyl (meth) acrylate, propylaminopropyl (meth) acrylate, propylaminobutyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dipropylaminopropyl (meth) acrylate, dipropylaminobutyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, and the like.
The content of the structural unit represented by the general formula (1) in 100 mass% of the B block is preferably 10 mass% or more, more preferably 30 mass% or more, further preferably 50 mass% or more, preferably 98 mass% or less, more preferably 80 mass% or less, further preferably 70 mass% or less. By setting the content of the structural unit represented by the general formula (1) within this range, it is considered that the coloring material has high affinity.
The B block may also have structural units of the formula (2). The structural units represented by the general formula (2) in the B block may be one kind or two or more kinds. If the B block has a structural unit represented by the general formula (2), the strong adsorptivity to the surface of the coloring material can be maintained for a long period of time, and the storage stability can be further improved.
[ in the general formula (2), R 21 Represents a hydrogen atom, a chain or cyclic hydrocarbon group which may have a substituent, R 22 And R is 23 Each independently represents a chain or cyclic hydrocarbon group which may have a substituent, R 22 And R is 23 Can be mutually bonded to form a ring 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.]
The R is 21 ～R 23 Examples of the chain hydrocarbon group include a linear alkyl group and a branched alkyl group. The number of carbon atoms of the straight-chain alkyl group is preferably 1 to 20, more preferably 2 to 20, still more preferably 2 to 10, particularly preferably 2 to 5. Examples of the straight-chain alkyl group include ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-nonyl, n-decyl, and n-lauryl. The branched 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 isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, neopentyl, and isooctyl.
The R is 21 ～R 23 Examples of the substituent of the chain hydrocarbon group include a halogen group, an alkoxy group and a benzoyl group (-COC) 6 H 5 ) Hydroxyl, etc.
The R is 21 ～R 23 Examples of the cyclic hydrocarbon group 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 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The number of carbon atoms of the aromatic group is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6 to 8. Examples of the aromatic group include phenyl, tolyl, xylyl, and mesityl. Examples of 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 an alkylene group having 1 to 3 carbon atoms.
The R is 21 ～R 23 Examples of the substituent of the cyclic hydrocarbon group include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxyl group.
The R is 22 And R is 23 Examples of the cyclic structure formed by bonding to each other include a five-membered to seven-membered nitrogen-containing heterocyclic ring or a condensed ring formed by condensing two nitrogen-containing heterocyclic rings. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the structures represented by the following formulas (2-1), (2-2) and (2-3) are exemplified.
[ in the general formulae (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, and x represents a bonding site, and when l is 2 to 5, m is 2 to 4, n is 2 to 4, a plurality of R's are present 26 May or may not be the sameThe same applies.]
The X is 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 method of the amide group include C-CO-NH-Y 2 Or C-NH-CO-Y 2 Preferably C-CO-NH-Y 2 . Examples of the bonding method of the ester group include C-CO-O-Y 2 Or C-O-CO-Y 2 Preferably C-CO-O-Y 2 。
The Y is 2 Examples of the divalent hydrocarbon group include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, and an arene diyl group having 6 to 10 carbon atoms. Among them, an alkylene group having 1 to 10 carbon atoms is preferable. The alkylene group may be either a straight chain or a branched chain, but is preferably a straight chain. Y is Y 2 Alkylene groups having 1 to 5 carbon atoms are preferable.
Z - Examples thereof include halogen anions, carboxylate anions, sulfate anions, sulfonate anions, phosphate anions, and oxynitride anions (nitroxide anion).
Examples of the halogen anions include fluoride anions, chloride anions, bromide anions, and iodide anions.
Examples of the carboxylate anions include alkylcarboxylate anions such as acetate anions and propionate anions; aromatic carboxylate anions such as benzoic acid anions, and the like.
Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; aromatic sulfate anions such as phenylsulfate anions and benzylsulfate anions.
Examples of the sulfonate anions include alkylsulfonate anions such as methanesulfonate anions and ethanesulfonate anions; aromatic sulfonate anions such as benzenesulfonic acid anion and toluenesulfonic acid anion.
Examples of the phosphate anions include alkyl phosphate anions such as methyl phosphate anions and ethyl phosphate anions; aromatic phosphate anions such as phenyl phosphate anions and benzyl phosphate anions.
Specific examples of the vinyl monomer forming the structural unit represented by the above formula (2) include (meth) acryloyloxyethyl benzyl diethyl ammonium chloride, (meth) acryloyloxypropyl benzyl diethyl ammonium chloride, (meth) acryloyloxybutyl benzyl diethyl ammonium chloride, (meth) acryloyloxyethyl benzyl diethyl ammonium bromide, (meth) acryloyloxypropyl benzyl diethyl ammonium bromide, (meth) acryloyloxybutyl benzyl diethyl ammonium bromide, (meth) acryloyloxyethyl benzyl diethyl ammonium iodide, (meth) acryloyloxypropyl benzyl diethyl ammonium iodide, (meth) acryloyloxybutyl benzyl diethyl ammonium iodide, (meth) acryloyloxyethyl benzyl diethyl ammonium fluoride, (meth) acryloyloxypropyl benzyl diethyl ammonium fluoride, and (meth) acryloyloxybutyl benzyl diethyl ammonium fluoride.
When the structural unit represented by the general formula (2) is contained, the content of the structural unit is preferably 2% by mass or more, more preferably 20% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, based on 100% by mass of the B block. By setting the content of the structural unit represented by the general formula (2) within this range, the coloring material has high affinity.
The B block may be a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), or may contain other structural units. From the viewpoint of maintaining 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 preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, in 100% by mass of the B block. In addition, it is preferable that the B block contains substantially no 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 in 100% by mass of the B block is preferably 5% by mass or less, more preferably 2% by mass or less.
Specific examples of the vinyl monomer capable of forming the other structural unit of the B block include the same monomers as those exemplified as the specific examples of the vinyl monomer capable of forming the other structural unit of the a block.
When the B block contains 2 or more structural units, the various structural units contained in the B block may be contained in the B block in any form, such as random copolymerization and block copolymerization, and from the viewpoint of uniformity, random copolymerization is preferable. For example, the B block may be formed from a copolymer having structural units composed of the B1 block and structural units composed of the B2 block.
(Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. Further, the linear block copolymer may have any structure (arrangement), but from the viewpoint of physical properties of the linear block copolymer or physical properties of the composition, when the A block is represented as A and the B block is represented as B, it is preferable to have a structure selected from (A-B) m Type (A-B) m type-A, (B-A) m Copolymers of at least 1 structure of type B (m is an integer greater than 1, for example an integer from 1 to 3). Among them, a-B type diblock copolymer is preferable from the viewpoints of workability at the time of processing and physical properties of the composition. It is considered that the structural units derived from the (meth) acrylic acid based monomer in the a block and the structural units represented by the general formula (1) in the B block are concentrated by constituting the a-B type diblock copolymer, and thus they can effectively act on the coloring material, and suitably act on the dispersion medium (solvent) and the binder resin (alkali-soluble resin). The block copolymer may also comprise blocks other than the a block and the B block.
The content of the a block in 100 mass% of the whole block copolymer is preferably 35 mass% or more, more preferably 40 mass% or more, further preferably 45 mass% or more, preferably 85 mass% or less, more preferably 80 mass% or less, further preferably 75 mass% or less. The content of the B block in 100 mass% of the whole block copolymer is preferably 15 mass% or more, more preferably 20 mass% or more, further preferably 25 mass% or more, preferably 65 mass% or less, more preferably 60 mass% or less, further preferably 55 mass% or less. By adjusting the content of the A block and the B block within the above range, the dispersibility when used as a dispersant is further improved.
The mass ratio of the A block to the B block (A block/B block) in the block copolymer is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, preferably 95/5 or less, more preferably 90/10 or less, still more preferably 80/20 or less. If the mass ratio of the A block to the B block is within the above range, the dispersibility when used as a dispersant is further improved.
When the block copolymer contains a structural unit having an acidic group, 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.
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 or more, further preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, further 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, further preferably 5,000 or more, particularly preferably 6,000 or more, preferably 40,000 or less, more preferably 30,000 or less, further preferably 25,000 or less, and particularly preferably 20,000 or less. If the weight average molecular weight is within the above range, the dispersibility when used as a dispersant is more excellent.
The molecular weight distribution (PDI) of the block copolymer is preferably 2.5 or less, more preferably 2.0 or less, and further preferably 1.6 or less. In the present invention, the molecular weight distribution (PDI) is a value obtained from (the weight average molecular weight (Mw) of the block copolymer)/(the number average molecular weight (Mn) of the block copolymer). The smaller the PDI, the narrower the molecular weight distribution, and the copolymer having a uniform molecular weight, the narrowest the molecular weight distribution when the value is 1.0. That is, the lower limit value of PDI is 1.0. If the molecular weight distribution (PDI) of the block copolymer exceeds 2.5, the block copolymer becomes a copolymer having a small molecular weight or a copolymer having a large molecular weight.
The amine value of the block copolymer is preferably 10mgKOH/g or more, more preferably 50mgKOH/g or more, still more preferably 80mgKOH/g or more, preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 120mgKOH/g or less, from the viewpoints of adsorptivity to a coloring material and dispersibility of a coloring material.
When the block copolymer contains a structural unit having an acidic group, the acid value of the block copolymer is preferably 5mgKOH/g or more, and preferably 50mgKOH/g or less. By setting the acid value in this range, the block copolymer can be properly reacted with the binder resin (alkali-soluble resin) without impairing the affinity of the block copolymer with the coloring material.
(method for producing Block copolymer)
The method for producing the block copolymer includes the following methods: a method of preparing an A block and then polymerizing a monomer of a B block on the A block by polymerization of vinyl monomers; a method of preparing a B block and then polymerizing a monomer of an A block on the B block; and (3) preparing an A block and a B block respectively, and then coupling the A block and the B block.
Although the polymerization method is not particularly limited, living radical polymerization is preferred. That is, the block copolymer is preferably a polymer polymerized by living radical polymerization. The conventional radical polymerization method tends to cause deactivation of the growth end not only in the initiation reaction and the growth reaction but also in the termination reaction and the chain transfer reaction, and thus a polymer mixture having various molecular weights and a non-uniform composition tends to be formed. In contrast, living radical polymerization is preferable in that it is not easy to cause termination reaction and chain transfer while maintaining the simplicity and versatility of conventional radical polymerization, and it is possible to grow without inactivating the growth end, and therefore it is easy to prepare a polymer having a uniform composition by precisely controlling the molecular weight distribution.
In living radical polymerization, there are the following methods depending on the method of stabilizing the polymerization growth end: a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); a method using an organic tellurium compound (TERP method), and the like. Since the ATRP method uses an amine complex, the acid group of the vinyl monomer having an acid group may not be protected. When a plurality of monomers are used in the RAFT method, there are cases where it is difficult to form a low molecular weight distribution and there are problems such as sulfur odor and coloration. Among these methods, the TERP method is preferably used from the viewpoints of diversity of monomers that can be used, molecular weight control in a high molecular region, composition uniformity, or coloration.
The TERP method is a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent, and is described in, for example, international publication No. 2004/14848, international publication No. 2004/14962, international publication No. 2004/072126, and International publication No. 2004/096870.
Specific polymerization methods of the TERP method include the following (a) to (d).
(a) The vinyl monomer is polymerized using the organic tellurium compound represented by the general formula (3).
(b) The 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) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (3) and an organic ditellurium compound represented by the general formula (4).
(d) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (3), an azo-based polymerization initiator and an organic ditellurium compound represented by the general formula (4).
R 31 -Te-Te-R 31 (4)
[ in the general formula (3), R 31 Represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group, R 32 And R is 33 Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 34 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.
In the general formula (4), R 31 An alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group.]
R 31 The group shown is alkyl, aryl or aromatic heterocyclic group with 1-8 carbon atoms, and is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and the like, and cyclic alkyl groups such as cyclohexyl and the like. The straight-chain or branched alkyl group having 1 to 4 carbon atoms is preferable, and methyl or ethyl is more preferable.
Examples of the aryl group include phenyl and naphthyl.
Examples of the aromatic heterocyclic group include pyridyl, furyl and thienyl.
R 32 And R is 33 The groups shown 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 straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and the like, and cyclic alkyl groups such as cyclohexyl and the like. The straight-chain or branched alkyl group having 1 to 4 carbon atoms is preferable, and methyl or ethyl is more preferable.
R 34 The group shown is alkyl, aryl, substituted aryl, aromatic heterocyclic group, alkoxy, acyl, amido, oxo-carbonyl, cyano, allyl or propargyl with 1-8 carbon atoms, and is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and the like, and cyclic alkyl groups such as cyclohexyl and the like. The straight-chain or branched alkyl group having 1 to 4 carbon atoms is preferable, and methyl or ethyl is more preferable.
Examples of the aryl group include phenyl and naphthyl. Phenyl is preferred.
Examples of the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent. Examples of the substituent of the substituted aryl group include a halogen atom, a hydroxyl group, an alkoxy group and an amino groupNitro, cyano, -COR 341 The carbonyl-containing group (R) 341 Is 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, a trifluoromethyl group or the like. In addition, these substituents may be substituted for one or two.
Examples of the aromatic heterocyclic group include pyridyl, furyl and thienyl.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
Examples of the acyl group include acetyl, propionyl, and benzoyl.
The amide group may be-CONR 3421 R 3422 (R 3421 、R 3422 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
Oxycarbonyl is preferably-COOR 3431 (R 3431 Hydrogen atom, alkyl group having 1 to 8 carbon atoms, or aryl group), for example, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, phenoxycarbonyl group, etc. Preferred examples of the oxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.
Allyl groups, for example-CR 3441 R 3442 -CR 3443 ＝CR 3444 R 3445 (R 3441 、R 3442 Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 3443 、R 3444 、R 3445 Independently of each other, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and each substituent may be bonded in a cyclic structure).
Propargyl groups include-CR 3451 R 3452 -C≡CR 3453 (R 3451 、R 3452 Is hydrogen atom or alkyl with 1-8 carbon atoms, R 3453 Hydrogen atom, alkyl group having 1 to 8 carbon atoms, aryl group, or silyl group), and the like.
Specific examples of the organic tellurium compound represented by the general formula (3) include (methyltellulmethyl) benzene, (methyltellulmethyl) naphthalene, ethyl-2-methyl-2-methyltellusection-propionate, ethyl-2-methyl-2-n-butyltellurium-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methyltellusection-propionate, (2-hydroxyethyl) -2-methyl-2-methyltellusection-propionate, and (3-trimethylsilylpropargyl) -2-methyl-2-methyltellusection-propionate, and all of the organic tellurium compounds described in International publication Nos. 2004/14848, 2004/14962, 2004/072126, and 2004/096870.
Specific examples of the organic ditellurium compound represented by the general formula (4) include dimethyl ditellurium, diethyl ditellurium, di-n-propyl ditellurium, diisopropyl ditellurium, dicyclohexyl ditellurium, di-n-butyl ditellurium, di-sec-butyl ditellurium, dicyclohexyl ditellurium, diphenyl ditellurium, bis (p-methoxyphenyl) ditellurium, bis (p-aminophenyl) ditellurium, bis (p-nitrophenyl) ditellurium, bis (p-cyanophenyl) ditellurium, bis (p-sulfonylphenyl) ditellurium, dinaphthyl ditellurium, and bipyridyl ditellurium.
The azo-based polymerization initiator is not particularly limited as long as it is an azo-based polymerization initiator used in usual radical polymerization. Examples thereof include 2,2' -azobis (isobutyronitrile) (AIBN), 2' -azobis (2-methylbutyronitrile) (AMBN), 2' -azobis (2, 4-dimethylvaleronitrile) (VNN), 1' -azobis (1-cyclohexanecarbonitrile) (ACHN), and 2,2' -azobisisobutyric acid dimethyl ester (MAIB), 4' -azobis (4-cyanovaleric acid) (ACVA), 1' -azobis (1-acetoxy-1-phenylethane), 2' -azobis (2-methylbutanamide) 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile) (V-70), 2' -azobis (2-methylamidinopropane) dihydrochloride, 2' -azobis [2- (2-imidazolin-2-yl) propane ], 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 2,2' -azobis (2, 4-trimethylpentane), 2-cyano-2-propylazocarboxamide, 2' -azobis (N-butyl-2-methylpropionamide), 2' -azobis (N-cyclohexyl-2-methylpropionamide), or the like.
In the polymerization step, an azo polymerization initiator and/or an organic ditelluride compound of the general formula (4) are further mixed with the vinyl monomer and the organic tellurium compound of the general formula (3) in the vessel after the substitution with the inert gas for the purpose of promoting the reaction, controlling the molecular weight and the molecular weight distribution, etc., depending on the kind of the vinyl monomer. In this case, examples of the inert gas include nitrogen, argon, helium, and the like. Argon and nitrogen are preferred.
The amount of the vinyl monomer used in the above-mentioned (a), (b), (c) and (d) may be appropriately adjusted depending on the physical properties of the objective copolymer. The vinyl monomer is preferably 5 to 10000 moles per 1 mole of the organic tellurium compound of the general formula (3).
When the organic tellurium compound of the general formula (3) and the azo-based polymerization initiator are used together in the above-mentioned (b), the azo-based polymerization initiator is preferably set to 0.01 to 10 mol based on 1 mol of the organic tellurium compound of the general formula (3).
When the organic tellurium compound of the general formula (3) and the organic tellurium compound of the general formula (4) are used together in the above-mentioned (c), the organic tellurium compound of the general formula (4) is preferably set to 0.01 to 100 mol based on 1 mol of the organic tellurium compound of the general formula (3).
When the organic tellurium compound of the general formula (3), the organic ditellurium compound of the general formula (4) and the azo polymerization initiator are used together in the above-mentioned (d), the organic ditellurium compound of the general formula (4) is preferably used in an amount of 0.01 to 100 mol based on 1 mol of the organic tellurium compound of the general formula (3), and the azo polymerization initiator is preferably used in an amount of 0.01 to 10 mol based on 1 mol of the organic tellurium compound of the general formula (3).
The polymerization reaction may be carried out in the absence of a solvent, but it may also be carried out using an aprotic solvent or a protic solvent which is generally used in radical polymerization and stirring the mixture. Examples of aprotic solvents that can be used include anisole, benzene, toluene, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, and trifluoromethylbenzene. Examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethylcellosolve, butylcellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, and diacetone alcohol.
The amount of the solvent to be used may be appropriately adjusted, for example, preferably 0.01ml or more, more preferably 0.05ml or more, still more preferably 0.1ml or more, preferably 50ml or less, more preferably 10ml or less, still more preferably 1ml or less, relative to 1g of the vinyl monomer.
The reaction temperature and reaction time may be appropriately adjusted according to the molecular weight or molecular weight distribution of the copolymer obtained, but are usually stirred at 0℃to 150℃for 1 minute to 100 hours. The TERP process can obtain high yields and precise molecular weight distribution even at low polymerization temperatures and short polymerization times. In this case, the pressure is usually normal pressure, but may be increased or decreased.
After completion of the polymerization reaction, the target copolymer can be isolated by removing the solvent, residual vinyl monomer, and the like used from the resulting reaction mixture by a usual separation and purification means.
The growing end of the copolymer obtained by polymerization is-Ter derived from tellurium compound 31 (wherein R is 31 The same as above), tellurium atoms are deactivated by the operation in the air after the completion of the polymerization reaction, but may remain. Since the copolymer having tellurium atoms remaining at the terminal thereof is colored or has poor thermal stability, it is preferable to remove the tellurium atoms.
The method for removing tellurium atoms may be used as follows: a radical reduction method using tributylstannane, a thiol compound, or the like; adsorption with active carbon, silica gel, active alumina, active clay, molecular sieve, polymer adsorbent, etc.; a method of adsorbing a metal with an ion exchange resin or the like; liquid-liquid extraction or solid-liquid extraction in which residual tellurium compounds are removed by adding peroxide such as hydrogen peroxide water or benzoyl peroxide or oxidizing tellurium atoms at the copolymer terminals by blowing air or oxygen into the system and washing with water or a suitable solvent; a purification method in a solution state such as ultrafiltration in which only substances having a specific molecular weight or less are extracted and removed. Furthermore, these methods may also be used in combination.
By polymerization, the reaction mixture was polymerizedThe other end (the end opposite to the growth end) of the copolymer obtained by the reaction is-CR from tellurium compound 32 R 33 R 34 (wherein R is 32 、R 33 And R is 34 R in the formula (3) 32 、R 33 And R is 34 The same) morphology.
When the tertiary amino group of the structural unit represented by the formula (1) is quaternized, examples of the quaternizing agent include haloalkanes such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide; halogenated aralkyl compounds such as benzyl chloride, benzyl bromide, and benzyl iodide; dimethyl sulfate; dialkyl sulfates such as diethyl sulfate and di-n-propyl sulfate. Among them, halogenated aralkyl such as benzyl chloride, benzyl bromide and benzyl iodide are preferable, and benzyl chloride is more preferable. The quaternized structure is introduced with alkyl groups and aralkyl groups derived from the quaternizing agent. Therefore, by measuring the amounts of alkyl groups and aralkyl groups introduced by 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 may be a method of contacting the polymer with a quaternizing agent. Specifically, a method in which a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (1) is polymerized, and then a quaternizing agent is added to the reaction solution and stirred is mentioned. The temperature of the reaction solution to which the quaternizing agent is added is preferably 55 to 65 ℃, and the stirring time is preferably 5 to 20 hours. When the quaternizing agent is added, the reaction liquid after polymerization is preferably diluted. The solvent to be added for dilution may be a solvent usable in the polymerization reaction, and is preferably a protic solvent, and more preferably methanol.
(polymerization product)
The dispersant composition may use a polymerization product containing the block copolymer as a dispersant component. The polymerization product is a product obtained when a polymerization operation (quaternization treatment as needed) is performed to obtain the block copolymer. The polymerization product contains the desired block copolymer and polymer impurities produced as by-products in the synthesis of the block copolymer.
The polymeric impurities are other polymers that are inevitably produced as by-products in the synthesis of the desired block copolymers. Examples of the polymer impurities produced as by-products in the synthesis of the A-B diblock copolymer include random polymers having the same composition as the A block and random polymers having the same composition as the B block. The polymer impurities are polymers produced as by-products in synthesizing the desired block copolymer, and do not include the additional polymer added.
The content of the block copolymer in the polymerization product is preferably 50 mass% or more of 100 mass% of the polymerization product. If the content of the block copolymer in the polymerization product is 50 mass% or more, the dispersibility improves when the polymerization product is used as a dispersant.
(dispersion medium)
The dispersant composition may contain a dispersing medium. The dispersion medium may be appropriately selected for use as long as it can disperse or dissolve the block copolymer, does not react with these components, and has moderate volatility. Examples of the conventionally known organic solvents include glycol monoalkyl ethers such as 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, methoxypropanol, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, and the like; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; glycol diacetates such as ethylene glycol diacetate, 1, 3-butanediol diacetate and 1, 6-hexanediol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, dipentyl ether, ethylisobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxy methyl amyl ketone; monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, and benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane, etc.; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; chain or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and gamma-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butane chloride and pentane chloride; ether ketones such as methoxy methyl pentanone; nitriles such as acetonitrile and benzonitrile.
The content of the dispersion medium in the dispersant composition is not particularly limited and may be appropriately adjusted. The upper limit value of the content of the dispersion medium in the dispersant composition is usually 99 mass%. In addition, the lower limit value of the content of the dispersion medium in the dispersant composition is usually 10% by mass, preferably 30% by mass, in view of the viscosity suitable for the preparation of the coloring composition to be described later.
< coloring composition >
The coloring composition of the present invention contains the above-mentioned dispersant composition, coloring material, binder resin and dispersion medium.
(coloring Material)
The type of the coloring material may be appropriately selected depending on the application thereof, and examples thereof include pigments and dyes. From the viewpoints of light resistance and heat resistance, the coloring composition preferably contains a pigment as a coloring material. The pigment may be any of an organic pigment and 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 various colors such as red pigment, yellow pigment, orange pigment, blue pigment, green pigment, and violet pigment. Examples of the structure of the pigment include azo pigments such as monoazo pigments, diazo pigments and condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and polycyclic pigments such as pyrene pigments. The pigment contained in the coloring composition may be one kind or plural kinds.
Specific examples of pigments include Red pigments such as c.i. pigment Red (c.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, 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264, 269; yellow pigments such as c.i. pigment Yellow (c.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, 150, 151, 154, 155, 166, 167, 168, 170, 180, 185, 188, 193, 194, 213; orange pigments such as c.i. pigment Orange (c.i. pigment Orange) 36, 38, 43; c.i. pigment Blue (c.i. pigment Blue) 15, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, etc.; green pigment such as c.i. pigment Green (c.i. pigment Green) 7, 36, 58, 59, 62, 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum hydroxide phthalocyanine, diphenoxyphosphinyloxy aluminum phthalocyanine, diphenylphosphinyloxy aluminum phthalocyanine, polyhalogenated diphenoxyphosphinyloxy aluminum phthalocyanine, polyhalogenated diphenylphosphinyloxy aluminum phthalocyanine, etc.; violet pigments such as c.i. pigment Violet (c.i. pigment Violet) 23, 32, 50, and the like. Pigments, preferably c.i. pigment red 254, c.i. pigment red 255, c.i. pigment red 264, c.i. pigment blue 15, c.i. pigment blue 15:2, c.i. pigment blue 15:3, c.i. pigment blue 15:4, c.i. pigment blue 15:6, c.i. pigment blue 16, c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 58, c.i. pigment green 59, and the like.
When the coloring composition of the present invention is used to form a light-shielding material such as a black matrix of a color filter, a black pigment may be used. The black pigment may be used alone or in combination with the red pigment, the green pigment, the blue pigment, or the like. Examples of the black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among them, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.
The average particle diameter of the coloring material is appropriately selected depending on the use thereof, and is not particularly limited. From the viewpoint of high transparency and high contrast, the coloring composition preferably contains a coloring material having an average particle diameter of 10nm to 150 nm.
The coloring material may contain a pigment derivative as a dispersing aid. The pigment derivative preferably contains an acidic pigment derivative having an acidic group for ionic bonding with and adsorption of an amino group in a polymer contained in the dispersant composition. The dye derivative is a substance in which an acidic functional group is introduced into a dye skeleton. The pigment skeleton is preferably the same or similar skeleton as the coloring material constituting the coloring composition, or the same or similar skeleton as the compound serving as the pigment raw material. Specific examples of the dye skeleton include azo dye skeleton, phthalocyanine dye skeleton, anthraquinone dye skeleton, triazine dye skeleton, acridine dye skeleton, perylene dye skeleton, and the like. The acidic groups introduced into the pigment skeleton are preferably carboxyl groups, phosphate groups, or sulfonate groups. The sulfonic acid group is preferable from the viewpoint of the convenience of synthesis and the strength of acidity. The acidic group may be directly bonded to the pigment skeleton, but may be bonded to the pigment 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 pigment derivative is not particularly limited, and is preferably, for example, 4 parts by mass to 17 parts by mass relative to 100 parts by mass of the coloring material.
From the viewpoint of brightness, the upper limit value of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 75% by mass, and more preferably 60% by mass, of the total solid content of the coloring composition. The lower limit value 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, based on the total solid content of the coloring composition. The solid component herein means a component other than a dispersion medium described later.
The content of the dispersant component (block copolymer and polymerization product) in the coloring composition is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 10 to 80 parts by mass, relative to 100 parts by mass of the coloring material.
(adhesive resin)
The coloring composition contains a binder resin (the binder resin does not include the polymer having the structure represented by the general formula (5) in the side chain. This improves the alkali developability of the coloring composition and the adhesion to the substrate. Such a binder resin is not particularly limited, but a resin having an acidic group such as a carboxyl group or a phenolic hydroxyl group is preferable.
The binder resin preferably comprises a random copolymer of structural units derived from a carboxyl group-containing vinyl monomer and structural units derived from a (meth) acrylate. The carboxyl group-containing vinyl monomer is preferably (meth) acrylic acid. Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and the like.
In the binder resin, the total content of the structural unit derived from the carboxyl group-containing vinyl monomer and the structural unit derived from the (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. In the binder resin, the content of the structural unit derived from the carboxyl group-containing vinyl monomer is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, preferably 90% by mass or less, and more preferably 70% by mass or less.
Among them, random copolymers of carboxyl group-containing vinyl monomers and (meth) acrylic esters are preferable. Specific examples of such copolymers include random copolymers of (meth) acrylic acid and butyl (meth) acrylate, random copolymers of (meth) acrylic acid and benzyl (meth) acrylate, random copolymers of (meth) acrylic acid and butyl (meth) acrylate and benzyl (meth) acrylate, and the like. From the viewpoint of affinity of the binder resin for the coloring material, a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate is particularly preferable.
The content of (meth) acrylic acid in the copolymer of the carboxyl group-containing vinyl monomer and the (meth) acrylic acid ester is usually 5 to 90% by mass, preferably 10 to 70% by mass, more preferably 20 to 70% by mass, based on the total monomer component.
The binder resin may be a resin having a carbon-carbon double bond capable of undergoing radical polymerization in a side chain. Since the side chain has a double bond, the photocurable property of the coloring composition of the present invention is improved, and thus resolution and adhesion can be further improved. Examples of the method for introducing a carbon-carbon double bond capable of undergoing radical polymerization into a side chain include a method in which a compound such as glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, o (or m) vinylbenzyl glycidyl ether, or the like is reacted with an acidic group of the binder resin.
The Mw of the binder resin is preferably 3,000 ～ 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 20,000. If the Mw of the binder resin is 3,000 or more, the heat resistance, film strength, etc. of the colored layer formed from the colored composition are good, and if the Mw is 100,000 or less, the alkali developability of the coated film is better.
The acid value of the binder resin is preferably 20mgKOH/g to 170mgKOH/g, more preferably 50mgKOH/g to 150mgKOH/g, still more preferably 90mgKOH/g to 150mgKOH/g. The acid value of the binder resin is 20mgKOH/g or more, and the alkali developability when the coloring composition is used as a coloring layer is better, and if it is 170mgKOH/g or less, the heat resistance is good.
The binder resin contained in the coloring composition may be one or more. The content of the binder resin in the coloring composition is preferably 3 to 200 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 20 to 80 parts by mass, based on 100 parts by mass of the coloring material.
(crosslinking agent)
The coloring composition may contain a crosslinking agent as needed. The crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an ethylene oxide group, an oxetane group, and an N-alkoxymethylamino group. The crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups. The crosslinking agent may be used singly or in combination of two or more.
Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, a caprolactone-modified polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride, and the like.
Examples of the aliphatic polyhydroxy compound include binary aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and aliphatic polyhydroxy compounds having three or more members such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerol di (meth) acrylate. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; tetrabasic acid dianhydrides such as pyromellitic anhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, and the like.
In the coloring composition, the content of the crosslinking agent is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass, based on 100 parts by mass of the coloring material. If the content of the crosslinking agent is too small, sufficient curability may not be obtained. If the amount of the crosslinking agent is too large, the alkali developability of the coloring composition of the present invention tends to be low, and the substrate on the unexposed portion or the light shielding layer tends to be stained with a base or remain on a film.
(photopolymerization initiator)
The coloring composition may contain a photopolymerization initiator as needed. Radiation sensitivity can thereby be imparted to the color composition. The photopolymerization initiator is a compound that can generate an active material that initiates polymerization of the crosslinking agent by exposure to radiation such as visible light, ultraviolet rays, far infrared rays, electron rays, X-rays, and the like.
Examples of the photopolymerization initiator include thioxanthone compounds, acetophenone compounds, bisimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -diketone compounds, polynuclear quinone compounds, diazonium compounds, imide sulfonate compounds, and aminoketone compounds. The photopolymerization initiator may be used singly or in combination of two or more.
In the coloring composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, based on 100 parts by mass of the crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, the exposure curing may be insufficient, and if the content is too large, the colored layer formed may be easily detached from the substrate at the time of development.
(dispersion medium)
The coloring composition contains a dispersion medium. The dispersion medium may be appropriately selected and used as long as it can disperse or dissolve other components constituting the coloring composition, does not react with these components, and has moderate volatility. For example, conventionally known organic solvents can be used, and examples thereof include the organic solvents (dispersion media) 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 a pigment or the like, solubility of a dispersant, coatability of a pigment dispersion composition, and the like. The solvent contained in the pigment-dispersion composition may be one or more.
When pixels of a color filter are formed by photolithography, the boiling point of the dispersion medium (under the conditions of pressure 1013.25 hPa. Under the conditions of boiling points are all described below) is preferably 100℃to 200 ℃. Among the above dispersion media, glycol alkyl ether acetates are preferred in terms of good balance of coatability, surface tension, and the like, and relatively high solubility of constituent components in the coloring composition. In addition, a dispersion medium having a boiling point of 150℃or higher is preferably used. By using a dispersion medium having a high boiling point, the destruction of the relationship between the coloring compositions due to rapid drying of the coloring compositions can be suppressed. The dispersion medium having a boiling point of 150℃or higher may be glycol alkyl ether acetate. The content of the dispersion medium having a boiling point of 150 ℃ or higher is preferably 3 to 50 mass% based on 100 mass% of the entire dispersion medium.
The content of the dispersion medium in the coloring composition is not particularly limited, and may be appropriately adjusted. The upper limit value of the content of the dispersion medium in the coloring composition is usually 99 mass%. Further, the lower limit value of the content of the dispersion medium in the coloring composition is usually 70% by mass, preferably 80% by mass, in view of the viscosity suitable for coating the coloring composition. The dispersion medium described above can be used as a solvent for dissolving and removing the precipitate formed from the coloring composition.
(other additives)
Other additives may be added to the coloring composition in addition to the above additives within a range that does not impair the preferable physical properties of the present invention. Examples of the other additives include sensitizing dye, thermal polymerization inhibitor, nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, plasticizer, organic carboxylic acid compound, organic carboxylic acid anhydride, pH adjuster, antioxidant, ultraviolet absorber, light stabilizer, preservative, mildew inhibitor, surfactant, anticoagulant, adhesion improver, development improver, and storage stabilizer.
Examples of the sensitizing dye include 4,4 '-dimethylaminobenzophenone, 4' -diethylaminobenzophenone, 2-aminobenzophenone, 4 '-diaminobenzophenone, 3' -diaminobenzophenone, 3, 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-oxazol, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2, 5-bis (p-diethylaminophenyl) 1,3, 4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, and (p-diethylaminophenyl) pyrimidine.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2, 6-t-butyl-p-cresol, and beta-naphthol.
Examples of the nonionic surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a polyoxyethylene-type surfactant.
Examples of the anionic surfactant include alkyl sulfonates, alkylbenzenesulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, higher alcohol sulfates, fatty alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and special polymer surfactants.
Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.
The amphoteric surfactant includes betaine type compounds, imidazolium salts, imidazolines, amino acids, and the like.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dioctanoate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and glyceryl triacetate.
Examples of the organic carboxylic acid compound include monocarboxylic acids, carboxylic acids having a carboxyl group directly bonded to a phenyl group, carboxylic acids having a carboxyl group bonded from a phenyl group through a carbon bond, and the like.
Examples of the organic carboxylic acid anhydride include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1, 2-cyclohexene dicarboxylic anhydride, n-octadecylsuccinic anhydride, 5-norbornene-2, 3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalene dicarboxylic anhydride.
< method for producing coloring composition >
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 additives. As the mixing, for example, a paint stirrer, a bead mill, a ball mill, a dissolver, a kneader, or a mixing and dispersing machine can be used. The coloring composition is preferably filtered after mixing. Since the coloring composition has alkali developability, it can be suitably used for a color filter.
In addition, a coloring material which has been subjected to a surface treatment in advance with the dispersant composition of the present invention may also be used. The surface treatment method may use the following method: a dry method of adding a mixed dispersant while stirring a coloring material by using a henschel mixer, a ball mill, an atomizing colloid mill, a banbury mixer, or the like; and a wet method of removing the solvent after the treatment in the solvent. Thus, by surface-treating with the dispersant composition of the present invention, the dispersibility of the coloring material can be improved and aggregation can be prevented.
< color Filter >
The color filter of the present invention includes a colored layer formed using the above-described coloring composition.
The method for producing the color filter includes, for example, the following methods. First, a thermoplastic resin sheet such as a polyester resin, a polyolefin resin, a polycarbonate resin, or a polymethyl methacrylate resin; thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly (meth) acrylic resins; the transparent substrate such as various glasses is preferably provided with a black matrix formed of the coloring composition, and color pixels for passing light of three primary colors of red (R), green (G) and blue (B) are provided on the transparent substrate. As a method for producing a color filter, a black colored composition is applied, and then soft baking (pre-bak) is performed to evaporate a solvent (dispersion medium) and form a coating film. Then, after exposing the coating film to light through a photomask, the coating film is developed with an alkali developer (an aqueous solution containing an organic solvent, a surfactant, an alkali compound, or the like), and the unexposed portion of the coating film is dissolved and removed to form a black pattern (black matrix). Then, after hard baking (post-baking) as needed, the same operation is sequentially repeated for red (R), green (G), and blue (B), thereby obtaining a color filter having three primary color pixel arrays of red, green, and blue disposed on a substrate. However, the order of forming the pixels of each color in the present invention is not limited to the above.
When the coloring composition is applied to the substrate, a suitable coating method such as a spray coating method, a roll coating method, a spin coating method, a slot die coating method, or a bar coating method may be used, but a spin coating method or a slot die coating method is particularly preferable.
After a protective film is formed on the pixel pattern thus obtained as needed, a transparent conductive film (indium tin oxide (ITO) or the like) is formed by sputtering. After the transparent conductive film is formed, a separator may be further formed to manufacture a color filter.
The color filter of the present invention has a uniform dimensional accuracy, and can be suitably used for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic papers, and the like.
Further, since the coloring composition has low viscosity and excellent dispersibility of the coloring material, it can be suitably used as a colored pillar spacer supported on a Thin Film Transistor (TFT) substrate and a color filter substrate sandwiching a liquid crystal layer. For example, a composition having a high Optical Density (OD) as described in Japanese patent application laid-open No. 2015-191234 is mentioned.
Examples
The present invention will be described in further detail based on specific examples. The present invention is not limited to the following examples, and can be carried out with appropriate modifications within the scope not changing the gist thereof. The polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), amine number, formaldehyde content of the dispersant composition, and dispersibility (viscosity, particle diameter) of the coloring composition of the block copolymer and the binder resin were evaluated by the following methods.
The abbreviations have the following meanings.
BMA: butyl methacrylate
PCL5: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (PLACCEL (registered trademark) FM5, manufactured by Dacellosolve chemical Co., ltd.)
DMAEMA: dimethylaminoethyl methacrylate
DEAEMA: diethylaminoethyl methacrylate
TBAEMA: tert-butylaminoethyl methacrylate
BTEE: ethyl-2-methyl-2-n-butyltellurium-propionate
DBDT: dibutyl ditelluride
AIBN:2,2' -azobis (isobutyronitrile)
PMA: propylene glycol monomethyl ether acetate
(polymerization Rate) measurement using a Nuclear Magnetic Resonance (NMR) measurement apparatus (model: AVANCE500 (frequency 500 MHz)) manufactured by Bruker Biospin Co., ltd.) 1 H-NMR (solvent: CDCl) 3 Internal standard: TMS). The integral ratio of the vinyl group of the monomer to the peak of the ester side chain derived from the polymer was obtained from the obtained NMR spectrum, and the polymerization rate of the monomer was calculated.
(weight average molecular weight (Mw) and molecular weight distribution (PDI)) were determined by Gel Permeation Chromatography (GPC) using a high performance liquid chromatograph (model HLC-8320, manufactured by Tosoh Co., ltd.). The column used was SHODEX KF-603 (. Phi.6.0 mm. Times.150 mm) (SHODEX Co., ltd.) as a mobile phase, 10 mmol/L lithium bromide/10 mmol/L acetic acid/N-methyl-2-pyrrolidone, and a differential refractometer as a detector. The measurement conditions were as follows: the column temperature was 40℃and the sample concentration was 20mg/mL, the sample injection amount was 10. Mu.L, and the flow rate was 0.2 mL/min. Using polystyrene (molecular weights 427,000, 190,000, 96,400, 37,400, 10,200, 2,630, 906) as a standard substance, a standard curve (calibration curve) was prepared, and a weight average molecular weight (Mw) and a number average molecular weight (Mn) were measured. From this measurement value, the molecular weight distribution (pdi=mw/Mn) was calculated.
(amine number) amine number represents the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of solid component. The measurement sample was dissolved in tetrahydrofuran, and the resulting solution was neutralized with a 0.1 mol/L hydrochloric acid/2-propanol solution using a potential difference titration apparatus (trade name: GT-06, mitsubishi chemical Co., ltd.). The amine value (B) was calculated according to the following formula, with the inflection point of the titration pH curve as the titration end point.
B＝56.11×Vs×0.1×f/w
B: amine number (mgKOH/g)
Vs: the amount of 0.1 mole/L hydrochloric acid/2-propanol solution (mL) required for titration
f: titre of 0.1 mol/L hydrochloric acid (2-propanol)
w: measuring the mass (g) of the sample (solid content conversion value)
Viscosity was measured at 25℃using an E-type viscometer (trade name: TVE-22L, manufactured by Tokyo Co., ltd.) using a conical rotor (1℃34'. Times.R24) at a rotor rotation speed of 60 rpm. The color composition after preparation was stored at 25℃for 2 hours and was subjected to viscosity measurement.
(particle size) the particle size was measured at 25℃using a dense particle size analyzer (trade name: FPAR-1000, manufactured by Otsuka electronics Co., ltd.). The measurement was performed on the coloring composition stored at 25℃for 2 hours after the preparation. Samples can be diluted with Propylene Glycol Monomethyl Ether Acetate (PGMEA) as needed.
(amount of formaldehyde) 0.5g of the dispersant composition was poured into a cartridge (manufactured by Waters Co., ltd., sep Pak (registered trademark) DNPH-Silica Plus Cartridge (trade name: WAT 037500)) filled with DNPH (2, 4-dinitrophenylhydrazine) -impregnated silica gel, and allowed to stand at room temperature for 2 hours.
Eluting with 4mL of acetonitrile, and fixing the volume to 5mL. The measurement was performed using a liquid chromatograph (trade name: LC-10AD, manufactured by Shimadzu corporation, column: proC18 RS (4.6X108 mm, manufactured by YMC corporation), mobile phase: acetonitrile/ultrapure water=65:35 solution, column temperature: 40 ℃, flow rate: 1.0 mL/min, detection wavelength: 360 nm) and two kinds of aldehyde-DNPH mixed standard solutions (0.1. Mu.g of aldehyde/. Mu.L of acetonitrile, manufactured by Wako pure chemical industries, ltd.) as standard substances. The formaldehyde content was calculated from the measurement results.
< preparation of Block copolymer >
(Block copolymer No. 1)
PCL5 (275.8 g), BMA (45.3 g), AIBN (1.64 g) and PMA (80.3 g) were placed in a flask equipped with an argon gas tube and a stirrer, and after argon gas substitution, BTEE (14.99 g) and DBDT (18.47 g) were added and reacted at 60℃for 7 hours. The polymerization rate was 98.3%.
To the resulting solution was added a mixed solution of DEAEMA (191.4 g) and PMA (47.9 g) which had been replaced with argon gas, and the mixture was reacted at 60℃for 13.5 hours. The polymerization rate was 99.4%.
After the completion of the reaction, the reaction solution was poured into n-heptane under stirring. The precipitated polymer was suction-filtered and dried to obtain a block copolymer No.1. The Mw of the resulting block copolymer No.1 was 16,301, the PDI was 1.44 and the amine value was 108mgKOH/g. Further, the composition of the block copolymer No.1 is given in Table 2. The content of each structural unit in the copolymer was calculated based on the addition ratio of the monomer used in the polymerization reaction and the polymerization rate.
(Block copolymer No.2, 3)
Block copolymers No.2 and 3 were prepared in the same manner as the block copolymer No.1. The monomers, organic tellurium compounds, organic ditellurium compounds, azo polymerization initiators, solvents, reaction conditions, and polymerization rates used are shown in Table 1. In addition, the composition, mw, PDI, amine number of each block copolymer are given in Table 2. The content of each structural unit in the copolymer was calculated based on the addition ratio of the monomer used in the polymerization reaction and the polymerization rate.
TABLE 1
< dispersant composition >
A dispersant composition was prepared by dissolving 0.325g of each block copolymer in 0.675g of PMA. The formaldehyde content of the dispersant composition was measured as shown in table 2.
TABLE 2
The B block of the block copolymer as a dispersant of dispersant composition No.3 does not have a structural unit of the formula (1) but has a structural unit derived from dimethylaminoethyl methacrylate (R in the formula (1)) 11 And R is 12 Methyl). The formaldehyde content of the dispersant composition No.3 was as high as 1.7ppm. In contrast, the B block of the block copolymer as a dispersant of dispersant compositions No.1 and 2 has a structural unit of the general formula (1). The formaldehyde content of these dispersant compositions No.1 and 2 was 0.1ppm and 0.0ppm, which were very low.
< Synthesis of alkali-soluble resin (Binder resin) ]
To a flask equipped with an argon line and a stirrer were added methacrylic acid (MAA) (40.0 g), benzyl methacrylate (BzMA) (160.0 g), propylene glycol monomethyl ether acetate (PMA) (580.0 g), and after argon substitution, 2' -azobis (isobutyronitrile) (AIBN) (4.0 g), n-dodecyl mercaptan (6.0 g), and PMA (20.0 g) were added and the temperature was raised to 90 ℃. To this solution was added dropwise MAA (80.0 g), bzMA (320.0 g), AIBN (8.0 g), n-dodecyl mercaptan (12.0 g) and PMA (50.0 g) over 1.5 hours while maintaining the solution at 90 ℃. After 60 minutes from the end of the addition, the temperature was raised to 110℃and AIBN (0.8 g) and PMA (10.0 g) were added to react for 1 hour, AIBN (0.8 g) and PMA (10.0 g) were further added to react for 1 hour, and AIBN (0.8 g) and PMA (10.0 g) were further added to react for 1 hour.
The resulting reaction solution was cooled to room temperature, and PMA (240.0 g) was added to give a solution of an alkali-soluble resin having a nonvolatile content of 39.5%. The alkali-soluble resin had a weight average molecular weight (Mw) of 9,150, a molecular weight distribution (PDI) of 1.92 and an acid value of 128mgKOH/g.
< preparation of coloring composition >
Coloring composition No.1
A pigment was prepared according to a preparation composition of 8 parts by mass of a pigment, 1 6 parts by mass of a block copolymer No.1 6 parts by mass of an alkali-soluble resin, and 80 parts by mass of PMA, 555 parts by mass of 0.3mm zirconia beads were added, and the mixture was mixed with a bead mill (trade name: DISPERMAT CA, VMA-manufactured by GETZMANN GmbH) for 3 hours to sufficiently disperse the beads. After the completion of the dispersion, the beads were filtered off to obtain a colored composition. As the pigment, C.I. pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemie Co., ltd.) was used. The dispersibility of the obtained coloring composition was evaluated. The evaluation results are shown in Table 3.
Coloring composition No.2, 3
Coloring compositions No.2 and 3 were prepared in the same manner as the preparation method of coloring composition No.1, except that the block copolymer was changed. The evaluation results are shown in Table 3.
TABLE 3
Pigment dispersibility of the coloring compositions No.1 to 3 was good. Thus, it is understood that a block copolymer having a structural unit of the general formula (1) in the B block can be used as a dispersant. In addition, pigment dispersibility of the coloring composition No.1 using a block copolymer having a B block having a structural unit derived from diethylaminoethyl methacrylate is particularly excellent. Therefore, it is found that when a block copolymer having a structural unit derived from diethylaminoethyl methacrylate as the B block is used, a coloring composition having a reduced formaldehyde content and excellent pigment dispersibility can be obtained.
The present invention includes the following embodiments.
Embodiment 1A dispersant composition comprising a polymer having a structure represented by general formula (5) in a side chain.
*-Y 1 -N-R 11 R 12 (5)
[ in the general formula (5), R 11 Represents a hydrogen atom, a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 12 Represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 11 And R is 12 Can be mutually bonded to form a ring structure, Y 1 Represents a divalent hydrocarbon group and represents a bonding site.]
The dispersant composition according to embodiment 1, wherein the amine value of the polymer is 10mgKOH/g to 200mgKOH/g.
(embodiment 3) the dispersant composition according to embodiment 1 or 2, wherein the polymer is a block copolymer having an a block having structural units derived from a (meth) acrylic acid based monomer and a B block having structural units represented by the general formula (1).
[ in the general formula (1), R 11 Represents a hydrogen atom, a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 12 Represents a carbon atom which may have a substituentChain or cyclic hydrocarbon group having a sub-number of 2 or more, R 11 And R is 12 Can be mutually bonded to form a ring 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.]
(embodiment 4) the dispersant composition according to embodiment 3, wherein the A block has a structural unit represented by the general formula (10).
[ in the general formula (10), 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.]
Embodiment 5 the dispersant composition according to embodiment 3 or 4, wherein the molecular weight distribution (PDI) of the block copolymer is 2.5 or less.
The dispersant composition according to any one of embodiments 3 to 5, wherein the block copolymer is a polymer polymerized by living radical polymerization.
Embodiment 7 is a coloring composition comprising the dispersant composition according to any one of embodiments 1 to 6, a coloring material, a binder resin, and a dispersion medium.
(embodiment 8) the coloring composition according to embodiment 7, which is used for a color filter.
Embodiment 9 is a color filter comprising a colored layer formed using the colored composition described in embodiment 8.

Claims (8)

1. A dispersant composition comprising only one block copolymer having an A block and a B block as a dispersant component, or only a polymerization product comprising the block copolymer as a dispersant component,
the A block has structural units represented by the general formula (10) and structural units derived from other (meth) acrylic acid based monomers:
in the general formula (10), 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,
the structural unit derived from the other (meth) acrylic acid based monomer is a structural unit derived from the following (meth) acrylic acid based monomer:
one or more of (meth) acrylic acid esters having a chain alkyl group, (meth) acrylic acid esters having a cyclic alkyl group, (meth) acrylic acid esters having a polycyclic structure, (meth) acrylic acid esters having an aromatic group, (meth) acrylic acid esters having a polyalkylene glycol structural unit, (meth) acrylic acid esters having a hydroxyl group, (meth) acrylic acid esters having an alkoxy group, and (meth) acrylic acid esters having an oxygen-containing heterocyclic group,
the A block does not contain a structural unit represented by the general formula (1), or contains less than 10 mass% of a structural unit represented by the general formula (1);
The B block has a structural unit represented by the general formula (1):
in the general formula (1), R 11 Represents a hydrogen atom, a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 12 Represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent, R 11 And R is 12 Can be mutually bonded to form a ring 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 hydrocarbon group having a divalent state,
the B block is substantially free of structural units derived from vinyl monomers having acidic groups.
2. The dispersant composition of claim 1, wherein the block copolymer has an amine value of 10mgKOH/g to 200mgKOH/g.
3. The dispersant composition of claim 1, wherein the a block does not contain a structural unit represented by the general formula (1).
4. The dispersant composition of claim 1, wherein the block copolymer has a molecular weight distribution PDI of 2.5 or less.
5. The dispersant composition as claimed in any one of claims 1 to 4, wherein the block copolymer is a polymer polymerized by living radical polymerization.
6. A coloring composition comprising the dispersant composition according to any one of claims 1 to 5, a coloring material, a binder resin and a dispersion medium.
7. The coloring composition according to claim 6, which is used for a color filter.
8. A color filter comprising a colored layer formed using the colored composition according to claim 7.
CN201980039848.6A 2018-08-07 2019-07-17 Dispersing agent composition, coloring composition and color filter Active CN112334504B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2018-148512 2018-08-07
JP2018148512 2018-08-07
PCT/JP2019/028051 WO2020031633A1 (en) 2018-08-07 2019-07-17 Dispersant composition, coloring composition and color filter

Publications (2)

Publication Number Publication Date
CN112334504A CN112334504A (en) 2021-02-05
CN112334504B true CN112334504B (en) 2023-10-10

Family

ID=69414745

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980039848.6A Active CN112334504B (en) 2018-08-07 2019-07-17 Dispersing agent composition, coloring composition and color filter

Country Status (5)

Country Link
JP (1) JP7299894B2 (en)
KR (1) KR20210040933A (en)
CN (1) CN112334504B (en)
TW (1) TWI818051B (en)
WO (1) WO2020031633A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6605783B1 (en) * 2018-04-26 2019-11-13 大塚化学株式会社 Dispersant composition, coloring composition and color filter

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07228786A (en) * 1994-02-18 1995-08-29 Nippon Carbide Ind Co Inc Aqueous dispersion
JP2001279139A (en) * 2000-03-30 2001-10-10 Matsushita Electric Ind Co Ltd Black ink for electrostatic ink jet recording device and method for manufacturing the same
JP2002146260A (en) * 2000-11-16 2002-05-22 Daicel Chem Ind Ltd Water-based resin dispersion for dispersing pigment, pigment dispersion and water-based coating material composition
CN102213916A (en) * 2010-04-08 2011-10-12 Jsr株式会社 Coloring composition, color filter and color liquid crystal display element
CN102736414A (en) * 2011-03-31 2012-10-17 东洋油墨Sc控股株式会社 Dyeing composition and color filter using same
JP2012207159A (en) * 2011-03-30 2012-10-25 Dainippon Printing Co Ltd Dye dispersion, photosensitive resin composition for color filter, color filter, liquid crystal display device, and organic light-emitting display device
CN102981364A (en) * 2011-09-05 2013-03-20 Jsr株式会社 Coloring composition used for color filter, color filter and display element
JP2013178460A (en) * 2012-02-03 2013-09-09 Toyo Ink Sc Holdings Co Ltd Colored composition and color filter using the same
JP2013214000A (en) * 2012-04-03 2013-10-17 Dnp Fine Chemicals Co Ltd Pigment dispersion composition, photosensitive color resin composition for color filter, and color filter
CN103974987A (en) * 2011-12-06 2014-08-06 大塚化学株式会社 Block copolymer, dispersing agent, and pigment dispersion composition
JP2015515022A (en) * 2012-04-04 2015-05-21 メルク パテント ゲーエムベーハー Particles for electrophoretic display comprising a core and a random copolymer coating
JP2017025305A (en) * 2015-07-21 2017-02-02 Jsr株式会社 Colorant and method for producing the same, coloring composition, colored cured film and display element
JP6322837B1 (en) * 2017-06-13 2018-05-16 東洋インキＳｃホールディングス株式会社 SQUARYLIUM DYE AND USE THEREOF

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009265515A (en) 2008-04-28 2009-11-12 The Inctec Inc Colored photosensitive composition for color filter
JP6760805B2 (en) * 2016-09-13 2020-09-23 富士フイルム株式会社 Infrared absorbers, compositions, films, optical filters, laminates, solid-state image sensors, image displays and infrared sensors

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07228786A (en) * 1994-02-18 1995-08-29 Nippon Carbide Ind Co Inc Aqueous dispersion
JP2001279139A (en) * 2000-03-30 2001-10-10 Matsushita Electric Ind Co Ltd Black ink for electrostatic ink jet recording device and method for manufacturing the same
JP2002146260A (en) * 2000-11-16 2002-05-22 Daicel Chem Ind Ltd Water-based resin dispersion for dispersing pigment, pigment dispersion and water-based coating material composition
CN102213916A (en) * 2010-04-08 2011-10-12 Jsr株式会社 Coloring composition, color filter and color liquid crystal display element
JP2012207159A (en) * 2011-03-30 2012-10-25 Dainippon Printing Co Ltd Dye dispersion, photosensitive resin composition for color filter, color filter, liquid crystal display device, and organic light-emitting display device
CN102736414A (en) * 2011-03-31 2012-10-17 东洋油墨Sc控股株式会社 Dyeing composition and color filter using same
CN102981364A (en) * 2011-09-05 2013-03-20 Jsr株式会社 Coloring composition used for color filter, color filter and display element
CN103974987A (en) * 2011-12-06 2014-08-06 大塚化学株式会社 Block copolymer, dispersing agent, and pigment dispersion composition
JP2013178460A (en) * 2012-02-03 2013-09-09 Toyo Ink Sc Holdings Co Ltd Colored composition and color filter using the same
JP2013214000A (en) * 2012-04-03 2013-10-17 Dnp Fine Chemicals Co Ltd Pigment dispersion composition, photosensitive color resin composition for color filter, and color filter
JP2015515022A (en) * 2012-04-04 2015-05-21 メルク パテント ゲーエムベーハー Particles for electrophoretic display comprising a core and a random copolymer coating
JP2017025305A (en) * 2015-07-21 2017-02-02 Jsr株式会社 Colorant and method for producing the same, coloring composition, colored cured film and display element
JP6322837B1 (en) * 2017-06-13 2018-05-16 東洋インキＳｃホールディングス株式会社 SQUARYLIUM DYE AND USE THEREOF

Also Published As

Publication number Publication date
CN112334504A (en) 2021-02-05
KR20210040933A (en) 2021-04-14
TW202019995A (en) 2020-06-01
JP7299894B2 (en) 2023-06-28
WO2020031633A1 (en) 2020-02-13
TWI818051B (en) 2023-10-11
JPWO2020031633A1 (en) 2021-09-02

Similar Documents

Publication Publication Date Title
CN111971116B (en) Dispersant composition, coloring composition and color filter
JP7235474B2 (en) Coloring composition and color filter
JP7348998B2 (en) Polymerization products containing block copolymers
JP7235475B2 (en) Coloring composition and color filter
CN112334504B (en) Dispersing agent composition, coloring composition and color filter
CN112334505B (en) Dispersing agent composition, coloring composition and color filter
CN111247182B (en) Block copolymer, dispersant, coloring composition, and color filter
JP7344106B2 (en) Colored compositions and color filters
JP7348804B2 (en) Dispersant compositions, coloring compositions and color filters
JP7324623B2 (en) Block copolymer, dispersant, coloring composition, and color filter
WO2024116876A1 (en) Block copolymer, dispersant, and coloring composition
JP6797483B2 (en) Block copolymers, dispersants, coloring compositions and color filters
JP2023085227A (en) Dispersant, coloring composition, and color filter
TW202428659A (en) Block copolymer, dispersing agent, and colored composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant