WO2007007685A1 - Dispersing agent, method for producing same, and pigment dispersion and ink containing such dispersing agent - Google Patents

Dispersing agent, method for producing same, and pigment dispersion and ink containing such dispersing agent Download PDF

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Publication number
WO2007007685A1
WO2007007685A1 PCT/JP2006/313605 JP2006313605W WO2007007685A1 WO 2007007685 A1 WO2007007685 A1 WO 2007007685A1 JP 2006313605 W JP2006313605 W JP 2006313605W WO 2007007685 A1 WO2007007685 A1 WO 2007007685A1
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WIPO (PCT)
Prior art keywords
group
pigment
carbon atoms
general formula
dispersant
Prior art date
Application number
PCT/JP2006/313605
Other languages
French (fr)
Japanese (ja)
Inventor
Yasushi Ariyoshi
Joji Mikami
Tomoko Tachibana
Yoshiko Takabatake
Tsutomu Hiroshima
Hiroshi Chosokabe
Mayumi Ogura
Tomonori Ikegami
Toshiharu Yoshizawa
Original Assignee
Toyo Ink Manufacturing 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
Priority claimed from JP2006185611A external-priority patent/JP4020150B1/en
Application filed by Toyo Ink Manufacturing Co., Ltd. filed Critical Toyo Ink Manufacturing Co., Ltd.
Priority to CN2006800248922A priority Critical patent/CN101218017B/en
Priority to KR1020087002884A priority patent/KR101249574B1/en
Publication of WO2007007685A1 publication Critical patent/WO2007007685A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters

Definitions

  • Dispersant method for producing the same, and pigment dispersion and ink containing the dispersant
  • the present invention includes a dispersant capable of producing a dispersion excellent in dispersibility, fluidity, and storage stability, a method for producing the same, a pigment dispersion containing the dispersant, and the dispersant. It relates to various inks. Examples of the ink using the dispersant include color filter ink, photosensitive black ink, inkjet ink, and color filter inkjet ink.
  • a dispersant is used to maintain a good dispersion state.
  • the dispersant combines the structure of the part that adsorbs to the pigment and the part that has a high affinity for the solvent that is the dispersion medium, and the balance of these two parts determines the performance of the dispersant.
  • Various dispersants are used according to the surface condition of the pigment to be dispersed.
  • an acidic dispersant is used for a pigment having a surface that is biased toward basicity. In this case, the acidic functional group becomes the pigment adsorption site.
  • various dispersants having carboxylic acid as an acidic functional group have been proposed (for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and the like).
  • a synergist is a compound that has a structure similar to the chemical structure of the whole or a part of the compound forming the pigment and can be strongly adsorbed to the pigment by ⁇ - ⁇ interaction.
  • Synergists use a ionic functional group contained in the synergist itself to make the surface of the pigment acidic or basic so that a dispersant or pigment carrier (pigment
  • Patent Document 8 exemplifies a pigment composition containing a synergist having a basic group as a substituent and a dispersant having a phosphate group.
  • a dispersant having a phosphate group has a certain degree of pigment dispersion ability when used in combination with a synergist having a basic group as a substituent, but it has poor storage stability, or has defects due to phosphate groups such as heat resistance. There were cases where problems were caused by lowness, poor chemical resistance, and poor compatibility. The same applies to the dispersant having a sulfonic acid group.
  • Dispersants having such phosphoric acid groups or sulfonic acid groups are poor in developability to applied inks and paints, while conventional dispersants using carboxylic acids and basic groups as substituents. Even if it is combined with the synergist it has, there is no problem in terms of heat resistance, chemical resistance, and compatibility, but it has a high ability as a dispersant such as high viscosity, poor stability, and poor pigment fine dispersion. When it was inferior, it was hard.
  • color filter inks black matrix photosensitive black inks, and inkjet inks that use very fine pigments at high concentrations, as well as pigment dispersibility, coating properties, ejection properties, Solubility and adhesion to the substrate are required, and it has been difficult to satisfy all with conventional dispersants.
  • Patent Document 1 Japanese Patent Laid-Open No. 61-61623
  • Patent Document 2 JP-A-1-141968
  • Patent Document 3 JP-A-2-219866
  • Patent Document 4 Japanese Patent Laid-Open No. 11-439842
  • Patent Document 5 Japanese Patent Laid-Open No. 63-305137
  • Patent Document 6 JP-A-1-247468
  • Patent Document 7 JP-A-3-26767
  • Patent Document 8 Japanese Patent Laid-Open No. 63-248864
  • Patent Document 9 Japanese Patent Laid-Open No. 9-176511
  • An object of the present invention is to provide a dispersant capable of producing a dispersion excellent in dispersibility, fluidity, and storage stability at a low use amount, and a pigment dispersion containing the dispersant.
  • the present invention provides a color filter ink, a photosensitive black ink, an inkjet ink, and a color filter ink that are excellent in stability, dry re-dissolvability, and in some cases, printing stability using the dispersant.
  • P monovalent polymer part
  • R a is an alkyl group having 1 to 18 carbon atoms, 2 to 18 alkenyl groups, cycloalkyl groups having 3 to 18 carbon atoms, and aryl group forces having 6 to 18 carbon atoms are selected groups
  • R a2 is a hydrogen atom or 1 to 18 alkyl groups, alkenyl groups having 2 to 18 carbon atoms, cycloalkyl groups having 3 to 18 carbon atoms, and group forces that also include aryl groups having 6 to 18 carbon atoms).
  • X 1 is a tetravalent group represented by the following general formula (2), general formula (3), or general formula (4):
  • the total number of carbon atoms of the group X 1 represented by the general formula (4) is 4 to 20, and in the general formula (4), R 3 is a direct bond, —O—, or 1 to 8 carbon atoms.
  • R 4 , R 5 , R 6 and R 9 are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, or R 4 and R 6 and / or R 5 and R 9. May be directly bonded to form an unsaturated double bond.
  • R 7 and R 8 are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, or a direct bond between R 7 and R 8 or a divalent hydrocarbon group having 1 to 8 carbon atoms.
  • R 3 , R 7 and R 8 may form a tetravalent hydrocarbon group having 1 to 8 carbon atoms to form a polycyclic group X 1 . It can be solved by a dispersant represented by
  • the monovalent polymer portion (P) is selected from the group consisting of a polyester chain group, a polyester chain group, and a vinyl copolymer chain group.
  • the monovalent polymer portion (P) is a monovalent polyether chain group represented by the following general formula (5) and a Z or polyester chain group:
  • the polymer part (Pe) consists of:
  • Y 1 is a monovalent terminal group containing 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms,
  • X 2 is O—, —S—, or —N (R b ) — (where R b is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms),
  • G 1 scale 11 . It is a repeating unit indicated by —
  • G 2 is a repeating unit represented by —C ( ⁇ O) R 12 0 —
  • R 12 is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms,
  • R 13 is a linear or branched alkylene group having 2 to 6 carbon atoms, a linear or branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, Or a C 6-20 arylene group,
  • R 14 is represented by —CH (R 15 ) —CH (R 16 ) —
  • R 15 and R 16 is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms.
  • nl is an integer from 0 to 100
  • m2 is an integer from 0 to 60
  • m3 is an integer from 0 to 30, provided that ml + m2 + m3 is 1 or more and 100 or less
  • the arrangement of the repeating unit GG 3 in the general formula (5) is not intended to limit the order thereof.
  • the group X 2 and the group R 17 Repeat units ( ⁇ ⁇ ( ⁇ indicate that they are included in any order, and
  • G′-G 3 ⁇ may be either a random type or a block type.
  • Y 1 is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, and Y 1 preferably has an ethylenically unsaturated double bond.
  • m2 is preferably an integer of 3 to 15.
  • the dispersant may be a waxy solid at 25 ° C or a liquid at 25 ° C.
  • Y 2 is a polymerization termination group of the vinyl polymer
  • R 21 and R 22 are each independently a hydrogen atom or a methyl group
  • R 25 (where X 6 is O or —N (R 26 ) —, and R 25 and R 26 may have a hydrogen atom or an aromatic group as a substituent. Number of atoms] '18 linear or branched alkyl group,
  • X 4 is O—R 27 or —S—R 27 ,
  • R is a linear or branched alkylene group having 1 to 18 carbon atoms
  • n 2-50.
  • the present invention also relates to a pigment dispersion containing a pigment and a dispersant represented by the general formula (1).
  • the pigment dispersion is in the form of a paste or a chip.
  • the pigment dispersion according to the present invention in addition to the pigment and the dispersant represented by the general formula (1), the pigment derivative having a basic group, the basic An anthraquinone derivative having a group, an attaridone derivative having a basic group, and a triazine derivative having a basic group [0018]
  • the present invention also relates to an inkjet ink comprising a pigment, a dispersant represented by the general formula (1), and a pigment carrier.
  • the present invention also relates to a color filter ink comprising a pigment, a pigment carrier containing a monomer, and a dispersant represented by the general formula (1).
  • thermosetting inkjet ink comprising a pigment, a thermosetting compound, an organic solvent, and a dispersing agent represented by the general formula (1).
  • the present invention also relates to an inkjet ink for a color filter, comprising a pigment, a thermosetting compound, an organic solvent, and a dispersant represented by the general formula (1).
  • the present invention relates to carbon black, a photopolymerization initiator, a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an attaridone derivative having a basic group, and a triazine derivative having a basic group.
  • a photosensitive black ink characterized by comprising at least one basic synergist selected, an ethylenically unsaturated monomer, and a dispersant represented by the general formula (1).
  • the present invention provides a first step of producing a polymer having a hydroxyl group at one end (POH) or a polymer having a primary amino group at one end (PNH), and the polymer. (POH)
  • the present invention also relates to a method for producing a dispersant.
  • a monoalcohol, a primary monoamine, a secondary monoamine, and a compound that also has a group power of monothiol power are selected as an initiator.
  • the selected cyclic compound is ring-opening polymerized to form a polyether having hydroxyl group at one end and Z or polyester.
  • Another preferred embodiment of the production method according to the present invention is that, in the first step, a monoalcohol, a primary monoamine, a secondary monoamine, and a group force that also has a monothiol force are selected.
  • a compound as an initiator ring-opening polymerization of alkylene oxide to obtain a polymer having a hydroxyl group at one end, a reductive amination of the hydroxyl group to a polyether having an amino group at one end (PeNH 3) is produced.
  • an ethylenically unsaturated monomer is used in the first step using a compound having a hydroxyl group and a thiol group in the molecule as a chain transfer agent.
  • a compound having a hydroxyl group and a thiol group in the molecule as a chain transfer agent.
  • PvOH butyl copolymer
  • An unsaturated monomer is polymerized to produce a vinyl copolymer (PvNH) having a hydroxyl group at one end.
  • the dispersant of the present invention By using the dispersant of the present invention, a pigment dispersion excellent in dispersibility, fluidity and storage stability can be obtained at a low use amount.
  • a color filter ink, a photosensitive black ink, an inkjet ink, and an inkjet ink for a color filter which are excellent in stability, dry re-dissolvability, and in some cases, excellent printing stability using the dispersant.
  • a high-quality color filter substrate having strong adhesion between the coating film and the substrate can be provided using the pigment dispersion or the ink.
  • FIG. 1 is an infrared absorption spectrum of the dispersant according to the present invention obtained in Example 1.
  • FIG. 2 is a 13 C-NMR spectrum (in a heavy chloroform solvent) of the dispersant according to the present invention obtained in Example 1.
  • a dispersant (dispersant
  • the dispersing agent has a structure of a part adsorbing on the particulate material and a part having a high affinity for the solvent as the dispersion medium, the performance of the dispersing agent is determined by the balance of these two parts. In other words, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important.
  • the compound represented by the general formula (1) has a specific structure having two or three carboxyl groups. This specific structure containing a plurality of carboxyl groups serves as a pigment adsorption site and is suitable as a dispersant. However, in the compounds similar to the general formula (1), for example - eight 4 In other words, the case having only one carboxyl group (outside the scope of the present invention) is not preferable because high dispersibility, fluidity and storage stability are not exhibited.
  • the dispersant according to the present invention represented by the general formula (1), as represented by the structural formula, includes a tetravalent group X 1 and groups A to A 4 as its four substituents.
  • Have The tetravalent group X 1 is represented by the general formula (2), the general formula (3), or the general formula (4).
  • Preferable embodiments of the tetravalent group X 1 represented by the general formula (4) include the following groups.
  • R 3 , R 7 and R 8 represent a tetravalent hydrocarbon group [> CH—CH—CH]].
  • R 3 is a trivalent hydrocarbon group [> CH—CH—], and R 8 is a divalent carbon.
  • R 3 , R 7 and R 8 represent a tetravalent hydrocarbon group [> CH
  • R 3 , R 7 and R 8 represent a tetravalent hydrocarbon group [(-CH-) CH-CH (-
  • the tetravalent group X 1 contains an aromatic ring from the viewpoint of low viscosity and storage stability of the pigment dispersion or ink.
  • the group X 1 represented by the formula (3) is preferred.
  • k is 1.
  • dispersing agent according to the present invention represented by the general formula (1) is, as represented by the structural formula, and a group A ⁇ A 4 as tetravalent four substituents of group X 1
  • one or two monovalent polymer moieties (P) [polymer moiety (P)] contained as groups A to A 4 have a molecular weight of 00 to This part is an affinity part for the solvent as a dispersion medium, and aggregation of the pigment can be suppressed by steric repulsion.
  • the molecular weight of the monovalent polymer part (P) is more preferably 500 to 400, and most preferably 800 to 3500.
  • the molecular weight of the polymer part (P) in the present invention means the polystyrene conversion average molecular weight in GPC.
  • the molecular weight of the polymer part (P) is less than 200, the effect of steric repulsion by the solvent affinity part is reduced, making it difficult to prevent pigment aggregation and insufficient dispersion stability. Dispersions with insufficient dispersion stability are not preferred because the pigment will settle down over time and the viscosity of the dispersion will increase.
  • the molecular weight exceeds 5000, the absolute amount of the solvent affinity part increases, which is not preferable because the dispersibility effect itself is lowered and the viscosity of the dispersion is increased.
  • the polymer portion (P) is selected from a group force that can be a polyether, polyester, and bulule copolymer. These are easy to adjust the molecular weight within the above range, and also have good affinity for the solvent. More preferably, the polymer part (P) is substantially free of a hydroxyl group, a primary amino group, a secondary amino group, and a thiol group.
  • One preferable structure of these monovalent polymer portions (P) is a polyvalent polyether represented by the general formula (5) and a polymer portion (Pe) having Z or polyester strength. it can.
  • Y 1 is a linear or branched alkyl group having 1 to 18 carbon atoms to reduce viscosity and storage stability of the pigment dispersion and various inks. The viewpoint power is also preferable.
  • Y 1 in the general formula (5) preferably has an ethylenically unsaturated double bond.
  • active energy ray curability can be imparted to the dispersant of the present invention.
  • m2 is preferably an integer of 3 to 15, from the viewpoint of low viscosity and storage stability of the pigment dispersion and various inks.
  • Y 1 is a force that is a linear or branched alkyl group having 1 to 7 carbon atoms, or ethylenic It preferably has an unsaturated double bond.
  • the dispersant of the present invention is a waxy solid at 25 ° C from the viewpoint of storage stability of the high-concentration pigment dispersion and various inks.
  • liquid at 25 ° C is preferable in terms of ease of handling.
  • the waxy solid means a solid that changes to a transparent liquid by force heating (for example, heating to about 40 ° C to 100 ° C), which is an opaque solid at room temperature.
  • Another preferred structure of the monovalent polymer portion (P) is a monovalent bulle copolymer portion (Pv) represented by the general formula (6).
  • the part of the repeating unit of the polymer part (Pv) represented by the general formula (6) that is, ⁇ [C (R 21 ) (R 23 ) -C (R 21 ) (R 23 )] ⁇ is It can be the same force (homopolymer) or different (copolymer).
  • R 21 and R 22 are either one of a hydrogen atom and the other one of a cation group
  • Y 2 in the general formula (6) that is, the polymerization termination group of the vinyl polymer is any known one introduced when the polymerization of a normal ethylenically unsaturated monomer is carried out by a normal method. It is a polymerization terminator and is obvious to those skilled in the art. Specifically, for example, it can be a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer. Whichever of these chemical structures is used, the dispersant of the present invention is The effect can be exhibited without being affected by the polymerization termination group Y 2 .
  • the dispersant of the present invention can be produced by the production method of the present invention.
  • the production method of the present invention produces "a polymer having a hydroxyl group at one end ( ⁇ )” or "a polymer having a primary amino group at one end ( ⁇ )”.
  • the hydrogen atom or the site obtained by removing one hydrogen atom from the primary amino group is one or two of ⁇ to A 4 , It constitutes the coalescence part ( ⁇ ), and the tetracarboxylic dianhydride constitutes X 1 in the general formula (1).
  • the first step for producing a “polymer having a hydroxyl group at one end (POH)” will be described.
  • the polymer (POH) obtained in the first step a compound selected from the group of monoalcohol, primary monoamine, secondary monoamine, and monothiol is used as an initiator.
  • the polymer (PeOH) comprising the above polyether and Z or polyester can be produced by a known method, and the group power of monoalcohol, primary monoamine, secondary monoamine, and monothiol is selected. It can be easily obtained by ring-opening polymerization of a cyclic compound selected from the group consisting of alkylene oxide, rataton, lactide, dicarboxylic anhydride, and epoxide using the compound as an initiator.
  • the monoalcohol may be any compound as long as it is a compound having one hydroxyl group.
  • Tetraethyleneglycol-mono-hexenorehexenole ether Tetraethyleneglycol-mono-hexenorehexenole ether, tetrapropylene glycolenomonomethinoleether, tetrapropyleneglycolenomonoethylenoether, tetrapropyleneglycolmonopropylether, tetrapropyleneglycolenobutinoreether
  • alkylene glycol monoalkyl ethers such as tetrapropylene glycol monohexenole ether, tetrapropylene glycol mono-2-ethyl hexyl ether, tetradiethylene glycol monomethyl ether, and the like.
  • a monoalcohol having an ethylenically unsaturated double bond may be used as the monoalcohol.
  • active energy ray curing performance can be imparted to the produced dispersant.
  • Examples of the group having an ethylenically unsaturated double bond include a buyl group or a (meth) atallyloyl group (in the case of “(meth) atallyloyl group”, an attaloyl group and Z or methacryloyl). The following are the same.)
  • the preferred is a (meth) atallyloyl group.
  • the type of the group having a double bond may be one type or a plurality of types.
  • the monoalcohol having an ethylenically unsaturated double bond a compound containing one, two, or three or more ethylenically unsaturated double bonds can be used.
  • monoalcohols having one ethylenically unsaturated double bond include 2-hydroxyethyl (meth) acrylate (in the case of “(meth) acrylate”, And Z or metatalylate, the same shall apply hereinafter), 3-hydroxypropyl (meth) ataryl
  • monoalcohols having two ethylenically unsaturated double bonds include 2-hydroxy-1-3-allyloyloxypropyl methacrylate.
  • Examples include glycerin di (meth) acrylate.
  • monoalcohols having 3 ethylenically unsaturated double bonds include pentaerythritol tritalylate, and monoalcohols having 5 ethylenically unsaturated double bonds include, for example, dipentaerythritol.
  • One rupenta acrylate is mentioned.
  • pentaerythritol triatalylate and dipentaerythritol pentaatalylate can be obtained as a mixture of pentaerythritol tetraatalylate and dipentaerythritol hexaatalylate, respectively.
  • HPLC High Performance Liquid Chromatography
  • those having two or more ethylenically unsaturated double bonds are preferred because they are excellent in curability when used as an active energy ray-curable ink.
  • Examples of primary monoamines include methylamine, ethylamine, 1-propylamine, isopropylamine, 1-butylamine, isobutylamine, tert-butylamine, 1-pentylamine, isopentylamine, 3-pentylamine, 1-hexylamine, cyclohexanamine, Hexylamine, 4-methyl-2-pentylamine, 1-heptylamine, 1-octylamine, isooctylamine, 2-ethylhexylamine, 1-nonylamine, isononylamine, 1 decinoreamine, 1 dodecinoreamine, 1 myristinoleamine, Aliphatic primary monoamines such as cetinoleamine, 1-stearylamine, isostearylamine, 2-octyldecylamine, 2-octyldodecylamine, 2-hexyldecylamine, beherylamine, oleylamine,
  • Secondary monoamines include, for example, dimethylamine, jetylamine, di-1-propylamine, diisopropylamine, di-1-butylamine, diisopropylamine, di-1-pentylamine, diisopentylamine, di1-1hexylamine, di-1-amine.
  • Cyclohexylamine di (4-methyl-2-pentyl) amine, di1-1heptylamine, di-1-octylamine, isooctylamine, di (2-ethylhexyl) amine, di-1-noramine, diisono- Luamine, di-1-decylamine, di-1-dodecylamine, di-1 myristylamine, dicetylamine, di-1-stearylamine, diisosterylamine, di (2-octyldecyl) amine, di (2-octyldodecyl) amine , G- (2-hexyldecyl) amine, N-methylethylamine, N-methylbutylamine, N-methylisobutyramine, N-methylpropylamine, N-methylhexylamine, piperazine, alkyl substitution Aliphatic secondary monoamines such as piperazine.
  • Examples of monothiols include methyl thiol, ethyl thiol, 1 propyl thiol, isopropyl thiol, 1-butyl thiol, isobutyl thiol, tert-butyl thiol, 1 pentyl thiol, isopentyl thiol, 3 pentyl thio monoole, 1 monohexino Retinore, cyclohexenoreinore, 4-methinoreole 2 pentinore canonole, 1-heptinoretinoreol, 1-octinorenore, isooctinoretinore, 2-ethylhexylthiol 1-nonyl thiol, isononyl thiol, 1 decyl thiol, 1 dodecyl thiol, 1 myristyl thiol, cetyl thiol
  • Group power of monoalcohol, primary monoamine, secondary monoamine, and monothiol used in the production method of the present invention The compound selected is not limited to the above examples, but is a hydroxyl group, primary amino group, secondary Any compound can be used as long as it is a compound having one amino group or thiol group, and these compounds may be used alone or in combination of two or more. Of these, monoalcohol is preferably used, and aliphatic monoalcohol is more preferable.
  • a moiety other than a hydroxyl group, a primary amino group, a secondary amino group, or a thiol group of a compound selected from the group of monoalcohol, primary monoamine, secondary monoamine, and monothiol has a general formula ( 5) Construct Y 1 inside.
  • the combined force of alkylene oxide, rataton, lactide, and dicarboxylic anhydride and epoxide is a group force.
  • the reaction sequence of the selected cyclic compound may be any, for example, It is also possible to polymerize alkylene oxide on the initiator as the first step, polymerize rataton in the second step, and alternately polymerize dicarboxylic acid anhydride and epoxide in the third step.
  • the initiator for polymerizing ratatones in the second stage is an “alkylene oxide polymer having a hydroxyl group at one end” polymerized in the first stage.
  • the initiator for alternately polymerizing the dicarboxylic acid anhydride and the epoxide in the third stage is polymerized by the second stage, so that “an alkylene oxide polymer having a hydroxyl group at one end and a rataton polymer”.
  • Block copolymer ".
  • the production method of the present invention includes such a “polymer having a hydroxyl group at one end” as an initiator for producing a polymer (PeOH) described below. Similarly, a polymer (PeNH 2) described later,
  • Polymer (PvOH) and polymer (PvNH 3) can also be initiators.
  • the reaction sequence of the cyclic compound is not limited to the combination of the first-stage alkylene oxide, the second-stage ratatotone, and the third-stage dicarboxylic acid anhydride and epoxide, but the alkylene oxide.
  • Latatones (and z or lattides), and combinations of dicarboxylic anhydrides and epoxides can be performed in any order, each one and several times.
  • any cyclic compound can be selected from them.
  • a product can also be selected to carry out ring-opening polymerization.
  • alkylene oxide for example, ethylene oxide, propylene oxide, 1,2-, 1,4-1,2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used.
  • the bond type may be random or Z or block.
  • the number of moles of alkylene oxide per mole of initiator is preferably 0-100.
  • the polymerization of the alkylene oxide is carried out by a known method, for example, in the presence of an alkali catalyst.
  • Polymers (PeOH) obtained by polymerizing alkylene oxide on the hydroxyl group of monoalcohol are commercially available, such as the Nippon Oil & Fats Ox series and the Nippon Oil & Fats Bremer series. In this production method, it can be used as a polymer (PeOH).
  • the alkylene group of the alkylene oxide constitutes R 11 in the repeating unit G 1 in the general formula (5).
  • rataton examples include 13-buchi mouth rataton, ⁇ -buchi mouth rataton, ⁇ -valerolataton, ⁇ -valerolataton, ⁇ -force prolataton, ⁇ -force prolataton, alkyl-substituted ⁇ -force
  • ⁇ -valerolataton, ⁇ -force prolatatone, and alkyl-substituted ⁇ -force prolatatone are preferred from the viewpoint of ring-opening polymerization. It can be used without being limited to these, and may be used alone or in combination of two or more.
  • R 31 and R 32 are each independently a hydrogen atom, a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms,
  • R 33 and R 34 are each independently a hydrogen atom, a halogen atom, or a saturated or unsaturated linear or branched lower alkyl group having 1 to 9 carbon atoms.
  • lactides are lactide (3,6 dimethyl-1,1,4 dioxane 2,5 dione) and glycolide (1,4 dioxane 2,5 dione).
  • lactide 3,6 dimethyl-1,1,4 dioxane 2,5 dione
  • glycolide 1,4 dioxane 2,5 dione
  • Ring-opening polymerization of rataton and Z or lactide is a known method, for example, a reactor connected with a dehydrating tube and a condenser is charged with an initiator, rataton and Z or lactide, and a polymerization catalyst in a nitrogen stream. Can be done.
  • a low-boiling monoalcohol is used, the reaction can be carried out under pressure using an autoclave.
  • the number of moles of polymerization of ratatone and Z or lactide with respect to 1 mole of initiator is preferably in the range of 1 to 60 moles, more preferably 2 to 20 moles, and most preferably 3 to 15 moles.
  • known catalysts can be used without limitation, and examples thereof include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium chloride bromide, tetraptylammonium chloride bromide, and tetramethyl ester.
  • Ammo Mudd, Tetrab Quaternary ammonia salts such as tilammomud, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium bromide, tetramethylphosphomum chloride, tetrabutylphosphomum chloride, tetramethylphosphomum mouthmide, Tetrabutylphosphomubromide, tetramethylphosphomudomide, tetrabutylphosphomudomide, benzyltrimethylphosphomumuchloride, benzyltrimethylphosphomubromide, benzyltrimethylphosphomubromide, tetraphenylphosphomumuchloride, tetraphenolphosphomubromide, tetraphenol
  • quaternary phosphonium salts such as norephospho-mu-mode
  • phosphorus compounds such as triphenylphosphine, potassium acetate, sodium
  • the amount of catalyst used is 0.1 ppm to 30 OO ppm, preferably 1 ppm to 1000 ppm. If the amount of catalyst exceeds 3000 ppm, the coloring of the resin may become severe. On the other hand, if the amount of the catalyst used is less than 0.1 ppm, the rate of ring-opening polymerization of rataton and Z or lactide becomes extremely slow, which is not preferable.
  • the polymerization temperature of Rataton and Z or lactide is 100 ° C to 220 ° C, preferably 110 ° C to 210 ° C.
  • the reaction rate is very slow when the reaction temperature is less than 100 ° C.
  • side reactions other than the addition reaction of rataton and Z or lactide for example, depolymerization of the rataton adduct to the rataton monomer, cyclic rataton Dimer and trimmer formation is likely to occur.
  • the partial force other than the ester group of latathone or lactide constitutes R 12 in the repeating unit G 2 in the general formula (5).
  • dicarboxylic acid anhydride examples include succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, itaconic acid anhydride, glutaric acid anhydride, dodecenyl succinic acid anhydride, and chlorendec acid anhydride. It is done.
  • Examples of the epoxide include methyl daricidyl ether, ethyl daricidyl ether, butyl daricidyl ether, 2-ethyl hexyl glycidyl ether, dodecyl glycidyl ether, phenyl daricidyl ether, p-tertiary butyl.
  • the dicarboxylic acid anhydride and the epoxide are used simultaneously with the initiator and react alternately.
  • the hydroxyl group, primary amino group, secondary amino group, or thiol group of the initiator first reacts with the acid anhydride group of the dicarboxylic acid anhydride to form a carboxyl group.
  • the epoxide epoxy group reacts with the group to form a hydroxyl group.
  • the reaction similar to the above can be sequentially proceeded so that the acid anhydride group of the dicarboxylic acid anhydride reacts with this hydroxyl group.
  • the number of moles of polymerization of dicarboxylic anhydride and epoxide with respect to 1 mole of initiator is preferably 0 to 30 moles.
  • the reaction ratio of dicarboxylic anhydride and epoxide ([D] Z [E]) is
  • the alternating polymerization of the dicarboxylic acid anhydride and the epoxide is preferably performed in the range of 50 ° C to 180 ° C, more preferably in the range of 60 ° C to 150 ° C.
  • the reaction rate is very slow when the reaction temperature is below 50 ° C or above 180 ° C.
  • the portion other than the dicarboxylic acid anhydride group of the dicarboxylic acid anhydride constitutes R 13 in the repeating unit G 3 in the general formula (5), and forms a cyclic ether of epoxide.
  • the portion constitutes R 14 in the repeating unit G 3 in the general formula (5)
  • a monoalcohol having an ethylenically unsaturated double bond when producing a "polyether and polymer having Z or polyester strength (PeOH)" When using a dicarboxylic acid anhydride or epoxide, it is preferable to use a polymerization inhibitor.
  • a polymerization inhibitor for example, hydroquinone, methylneuroquinone, hydroquinone monomethyl ether, p-benzozoquinone, 2,4 dimethyl-6-t-butylphenol, phenothiazine, etc., which are preferred alone or in combination, are used.
  • % To 6% preferably in the range of 0.05% to 1.0%.
  • the vinyl copolymer (PvOH) can be obtained by polymerizing an ethylenically unsaturated monomer using a compound having a hydroxyl group and a thiol group in the molecule as a chain transfer agent.
  • Examples of the compound having a hydroxyl group and a thiol group in the molecule include mercapto methanol, 2 mercaptoethanol, 3 mercapto 1 propanol, 1 mercapto 2 butanol, 2 mercapto 3 butanol and the like.
  • a vinyl copolymer (PvOH) can be obtained by mixing a compound having a hydroxyl group and a thiol group and an ethylenically unsaturated monomer and heating the mixture.
  • bulk polymerization or solution polymerization is performed using a compound having 1 to 30 parts by weight of a hydroxyl group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer.
  • the reaction temperature is preferably 40 to 150 ° C, more preferably 50 to 110 ° C, and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.
  • the thiol group becomes a radical generating group for polymerizing the ethylenically unsaturated monomer
  • another polymerization initiator is not necessarily required for the polymerization, but it can also be used.
  • the polymerization initiator 0.005 to 5 parts by weight is preferable with respect to 100 parts by weight of the ethylenically unsaturated monomer.
  • the polymerization initiator for example, an azo compound and an organic peroxide can be used.
  • azo compounds examples include 2, 2'-azobisisobutyro-tolyl, 2, 2, 1-azobis (2-methylbutyoxy-tolyl), 1, 1, 1-azobis (cyclohexane 1-carbo-tolyl) 2,2, -azobis (2,4 dimethylvale-tolyl), 2,2, -azobis (2,4 dimethyl-4-methoxyvalero-tolyl), dimethyl 2,2'-azobis (2 methylpropionate) ), 4, 4, azobis (4 cyanovaleric acid), 2, 2, 1 azobis (2-hydroxymethylpropio-tolyl), 2, 2, azobis [2- (2-imidazoline-2] Yl) propane] and the like.
  • organic peroxides examples include benzoyl peroxide, t-butyl perbenzoate, tamen hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) Examples thereof include peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl baroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropio-rubberoxide, dicetylba one-year-old oxide.
  • These polymerization initiators can be used alone or in combination of two or more.
  • Examples of the ethylenically unsaturated monomer include acrylic monomers and monomers other than acrylic monomers.
  • acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) Atarylate, t-Butyl (Meth) Atalylate, 2-Ethylhexyl (Meth) Atalylate, Cyclohexyl (Meth) Atalylate, Stearyl (Meth) Atalylate, Lauryl (Meth) Atalylate, Tetrahydroful Furyl (meth) acrylate, isobornyl (meth) acrylate, phenol (meth) acrylate, benzyl (meth) acrylate, methoxy polypropylene glycol (meth) acrylate,
  • (meth) acrylamides such as atalyloylmorpholine, N, N dimethylaminoethyl (meth) acrylate, N, N (meth) acrylates containing amino group such as dimethylaminoethyl (meth) acrylate Is mentioned.
  • Examples of monomers other than the acrylic monomer include styrenes such as styrene and ⁇ -methylstyrene, ethyl vinyl ether, ⁇ -propyl vinyl ether, isopropyl vinyl ether, ⁇ -butyl vinyl ether, Examples include butyl ethers such as isobutyl vinyl ether, and fatty acid butyls such as vinyl acetate and propionate.
  • the monomer other than the acrylic monomer can be used in combination with the acrylic monomer.
  • carboxyl group-containing ethylenically unsaturated monomer alone or in combination with the above-described monomer can also be used.
  • carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ⁇ -coupler loratatone-added acrylic acid, ⁇ -force pralatatatone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • One type or two or more types can be selected.
  • the polymer ( ⁇ ) is a monoalcohol.
  • a compound having an all group or a compound having a primary amino group and a hydroxyl group in the molecule is used as a chain transfer agent, and an ethylenically unsaturated monomer is polymerized. It is preferable to have a vinyl copolymer (PvNH 2) ”.
  • polyether having a hydroxyl group (PeOH)” has already been described with respect to the production method of the polymer (PeOH), and the conditions and raw materials are also as described above.
  • this ⁇ polyether having a hydroxyl group at one end (PeOH) '' for example, in the presence of ammonia, hydrogen and a catalyst, at a pressure of 5 to 30 MPa, at a high temperature of 170 to 250 ° C., 0.15 to 2 hours Obtained by reaction.
  • “polyether having an amino group at one end (PeNH 2)” can be obtained.
  • Raney nickel Z aluminum catalyst is preferred.
  • Polyether having an amino group at one end (PeNH 3) is commercially available, for example,
  • the “Vinyl copolymer having a primary amino group at one end (PvNH)” has a primary amino group and a thio group.
  • a compound having an alkyl group as a chain transfer agent and mixing and heating an ethylenically unsaturated monomer and a polymerization initiator in accordance with the target molecular weight.
  • bulk polymerization or solution polymerization is performed using 1 to 30 parts by weight of a compound having a primary amino group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer.
  • the types of ethylenically unsaturated monomers, polymerization initiators and solvents that can be used, the amounts used, and the polymerization conditions are the same as those described for the vinyl copolymer (PvOH) having a hydroxyl group at one end.
  • Examples of the compound having a primary amino group and a thiol group in the molecule include 2 aminoethanethiol, 6 amino-2 mercaptobenzothiazole, 3 amino-5 mercapto-1, 2, 4 triazole, 4 amino 3— Mercapto—4H—1, 2, 4 Triazole, 4 Amino 3—Menolecapto 5—Methinole 4H— 1, 2, 4 Triazolene, 4 Amino-2 Mercaptopyrimidine, 2 Amino-5 Mercapto 1,3,4 Thiadiazole, 3—Amino-5 Mercapto 1, 2, 4 thiazole, 5 amino-2 mercaptobenzoimidazole and the like. Of these, 2-aminoethanethiol is preferably used.
  • Examples of the compound having a primary amino group and a hydroxyl group in the molecule include 2-aminoethanol, 3-aminopropanol, and 4-aminobutanol.
  • the primary monoamine and secondary monoamine are composed of a primary or secondary amino group and an alkyl group, and the alkyl group portion has 1 to 18 carbon atoms.
  • a certain monoamine is preferred!
  • no solvent or a solvent can be used in some cases.
  • the solvent for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, and the like can be used. Two or more kinds of these polymerization solvents may be mixed and used.
  • the used solvent can be removed by an operation such as distillation after the completion of the reaction, or can be used as it is as a part of the product of the dispersant.
  • a primary amino group is reacted with an anhydride group of tetracarboxylic dianhydride.
  • the dispersant represented by the general formula (1) according to the present invention can be obtained.
  • tetracarboxylic dianhydride examples include aliphatic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and polycyclic tetracarboxylic dianhydrides.
  • Examples of the aliphatic tetracarboxylic dianhydride include 1, 2, 3, 4 butanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 3 Dimethyl 1, 2, 3, 4 Cyclobutane tetracarboxylic dianhydride, 1, 2, 3, 4 Cyclopentane tetracarboxylic dianhydride, 2, 3, 5 Tricarboxycyclopentyl acetic dianhydride, 2, 3 , 5, 6-Tetracarboxycyclohexane dianhydride, 2, 3, 5, 6-tetracarbo Xynorbornanani anhydride, 3, 5, 6 Tricarboxynorbornane 2 acetic acid dianhydride, 2, 3, 4, 5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5 dioxotetrahydrofural) 3-methyl 3
  • Examples include cyclohexene mono 1,2 dicarboxylic dian
  • aromatic tetracarboxylic anhydride examples include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3, 3 ', 4, 4, monobenzophenone tetracarboxylic dianhydride, 2, 2', 3, 3, monobenzophenone tetracarboxylic dianhydride, 3, 3, 4, 4, 4, 4, Biphenylsulfonetetracarboxylic dianhydride, 2, 2 ', 3, 3,-Biphenylsulfonetetracarboxylic dianhydride, 1, 4, 5, 8 Naphthalenetetracarboxylic dianhydride, 2, 3 , 6, 7 Naphthalene tetracarboxylic dianhydride, 3, 3 ', 4, 4, -biphenyl ether tetracarboxylic dianhydride, 3, 3'
  • polycyclic tetracarboxylic acid anhydrides examples include 3,4-dicarboxy 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4 dicarboxy 1,2,3, 4-tetrahydro 6-methyl-1 naphthalene succinic dianhydride wear.
  • the tetracarboxylic dianhydride used in the production method of the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. It doesn't matter. These can be used alone or in combination. What is preferably used in the present invention is an aromatic tetracarboxylic dianhydride, which has a viewpoint of reducing the viscosity of a pigment dispersion or various inks.
  • pyromellitic dianhydride 3, 3 ', 4, 4' monobenzophenone tetracarboxylic dianhydride, ethylene glycol ditrimellitic anhydride ester, 3, 3 ', 4, 4' monoben Zophenone tetracarboxylic dianhydride, 9, 9 bis (3,4-dicarboxyphenyl) fluorene dianhydride, 3, 3 ', 4, 4, biphenylsulfone tetracarboxylic dianhydride, 2,3,6,7 naphthalenetetracarboxylic dianhydride and 3,3 ', 4,4, -biphenyltetracarboxylic dianhydride are preferred.
  • the reaction ratio in the second step is the hydroxyl group of the polymer (POH) or the first grade of the polymer (PNH).
  • a catalyst for example, a tertiary amine compound can be used, for example, triethylamine, triethylenediamine, N, N dimethylbenzilamine, N-methylmorpholine, 1,8 diazabicyclo- [5.4.0] — 7undesen, 1, 5 diazabicyclo [4. 3. 0] —5 Nonene.
  • a tertiary amine compound for example, triethylamine, triethylenediamine, N, N dimethylbenzilamine, N-methylmorpholine, 1,8 diazabicyclo- [5.4.0] — 7undesen, 1, 5 diazabicyclo [4. 3. 0] —5 Nonene.
  • the second step may be performed without a solvent, or an appropriate dehydrated organic solvent may be used.
  • the solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as part of the product of the dispersant as it is.
  • the reaction temperature in the second step is preferably 80 ° C to 180 ° C, more preferably 90 ° C to 160 ° C when a "polymer having a hydroxyl group at one end (POH)" is used. Perform in the range. When the reaction temperature is less than 80 ° C, the reaction rate is slow. When the reaction temperature exceeds 180 ° C, the acid anhydride that has reacted and opened the ring forms a cyclic anhydride again, and the reaction may be terminated.
  • PNH primary amino group at one end
  • it is preferably 0 to 150 ° C. Preferably, it is performed in the range of 10 ° C to 100 ° C. The reaction may not proceed below 0 ° C. 1
  • a pigment can be favorably dispersed.
  • the pigment that can be dispersed by the dispersant of the present invention include various pigments used in inks and the like.
  • Organic pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinatalidone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinol pigments, anthraquinone pigments.
  • the dispersant of the present invention is composed of metal oxides such as titanium dioxide, iron oxide, pentamonium antimony, zinc oxide, silica, cadmium sulfate, calcium carbonate, barium carbonate, and barium sulfate. It can also be used to disperse inorganic pigments such as clay, talc, yellow lead and carbon black.
  • the dispersant of the present invention is a solid fine particle containing fine particles other than pigment, for example, fine metal particles such as gold, silver, copper, platinum, iron, cobalt, nickel, titanium and Z or alloys thereof. Can be used for dispersion.
  • the dispersant of the present invention is not limited to the pigments exemplified above, and may be applied to any fine powders.
  • the dispersant of the present invention has a carboxyl group. Therefore, since the interaction with solid fine particles (particularly pigments) whose surface is neutral to basic is strong, it is preferable to use such solid fine particles (particularly pigments) for dispersion.
  • a pigment whose surface is biased to basicity is preferable.
  • the pigment whose surface is biased to basic is a calculation formula:
  • [P] means a pigment having a [P] value of molZg or more.
  • the surface base amount and the surface acid amount of the pigment can be determined, for example, by the method described in the literature (Coloring Materials, 61 [12], 692-698, 1988).
  • the dispersion includes at least a pigment and a dispersant represented by the general formula (1).
  • the pigment dispersion according to the present invention is, for example, a paste (pigment).
  • It can be a force that is a paste) or a solid pigment chip.
  • various inks for final use can be prepared.
  • pigment dispersion of the present invention is blended with various additives in the process of preparing the ink, which is its final application.
  • the type of additive to be blended varies depending on the viscosity and dispersion stability required for the pigment dispersion and the type of ink used as the final application. Therefore, for the purposes of this specification, “pigment dispersion” refers to a pigment and a dispersion of the general formula (1) that are substantially composed only of the pigment and the dispersant represented by the general formula (1). In addition to the dispersant represented by the formula (1), it means a dispersion in a state further containing various compounding components, and includes a dispersion in an arbitrary state until just before the ink is formed.
  • the pigment dispersion according to the present invention preferably contains a synergist, particularly a basic synergist.
  • a synergist particularly a basic synergist.
  • a basic synergist it is possible to satisfactorily disperse pigments that are difficult to disperse with only the dispersant of the present invention, particularly pigments whose surface is not neutral to basic.
  • the amount of the dispersant represented by the general formula (1) is as follows.
  • the amount is preferably 0.1 to: LOO parts by weight, more preferably 0.5 to 75 parts by weight, and most preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the material. If the blending amount of the dispersant is less than 0.1 part by weight with respect to 100 parts by weight of the pigment, the dispersibility may be deteriorated. May be worse.
  • the basic synergists that can be contained in the pigment dispersion of the present invention include “pigment derivatives having basic groups”, “anthraquinone derivatives having basic groups”, “ataridon derivatives having basic groups” And “a triazine derivative having a basic group”.
  • Equation (8)
  • J is independently SO 2 in the general formula (8) and the general formula (11).
  • f represents an integer of 1 to 10
  • R 35 and R 36 are each independently an alkyl group which may be substituted, an alkyl group which may be substituted, or a group which may be substituted, in the general formula (8) to the general formula (11).
  • a good phenyl group, or R 35 and R 36 together with a nitrogen atom in the formula, together with an additional nitrogen, oxygen or sulfur atom, optionally substituted heterocyclic residue Represents
  • R 37 represents an alkyl group which may be substituted, an alkyl group which may be substituted, or a phenyl group which may be substituted;
  • R 38 , R 39 , R 4 °, and R 41 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted group. Represents a group of radicals,
  • K represents NR 42 — Z— NR 43 or a direct bond
  • R 42 and R 43 are each independently a hydrogen atom, an optionally substituted alkyl group, a substituted! /, May! /, A alkenyl group, or a substituted! Y! / Represents a phenyl group, Z represents an optionally substituted alkylene group, an optionally substituted alkylene group, or a substituted, optionally substituted phenyl group. ,
  • W represents a substituent represented by the general formula (8) or a substituent represented by the general formula (10). Represent, and
  • Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (8), or a substituent represented by the general formula (10).
  • Examples of the amine compound used to form the substituents represented by the general formula (8) to the general formula (11) include secondary or tertiary monoamines, diamines, cyclic amines, strong loxyl groups. Examples thereof include a cyclic amine, a hydroxyl group-containing cyclic amine, and a cyclic diamine. Specific examples include dimethylamine, jetylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutyramine, N, N-methylisobutylamine, N, N.
  • the pigment moiety constituting the "pigment derivative having a basic group” includes, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo and polyazo, phthalocyanine dyes, Anthraquinone dyes such as diaminodianthraquinone, anthrapyrimidine, flavantron, anthrone, indanthrone, pyranthrone, violanthrone, quinatalidine dye, dioxazine dye, perinone dye, perylene dye, thioindigo dye, isoindoline dye It is derived from organic dyes such as dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, and metal complex dyes.
  • anthraquinone derivative having a basic group or the “ataridon derivative having a basic group” includes an alkyl group such as a methyl group or an ethyl group on the anthraquinone ring or the acridone ring in addition to the basic group.
  • Amino group such as a methyl group or an ethyl group on the anthraquinone ring or the acridone ring in addition to the basic group.
  • It may have a substituent such as a nitro group, a hydroxyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a halogen such as chlorine.
  • a substituent such as a nitro group, a hydroxyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a halogen such as chlorine.
  • the triazine moiety constituting the "triazine derivative having a basic group” includes, in addition to the basic group, an alkyl group (for example, a methyl group, an ethyl group, a butyl group), an amino group, and an alkylamino group.
  • a group eg, dimethylamino group, jetylamino group, dibutylamino group, etc.
  • nitro group hydroxyl group, alkoxy group (eg, methoxy group, ethoxy group, butoxy group, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.)
  • a phenyl group for example, an alkyl group, an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen atom, etc.
  • a phenylamino group for example, an alkyl group, an amino group
  • Group an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen atom, etc.
  • the preferred triazine moiety is induced by 1, 3, 5 triazine forces.
  • the "pigment derivative having a basic group”, “anthraquinone derivative having a basic group”, and “ataridon derivative having a basic group” used in the present invention are known by various synthetic routes. It can be synthesized by the method of For example, after introducing a substituent represented by the following formula (14) to the following formula (17) into an organic dye, anthraquinone or attaridone, the above general formula (8) to the above general formula reacts with these substituents.
  • Amine compounds capable of forming the substituent represented by (11), for example, N, N dimethylaminopropylamine, N-methylbiperazine, jetylamine or 4- [4-hydroxy-6- [3- (dibutylamino) Propylamino] -1,3,5 triazin-2-ylamino] aline and the like can be obtained.
  • the organic dye is a azo dye
  • the substituents represented by the general formula (8) to the general formula (11) are arranged in advance to obtain a diazo component (for example, having a diazo group).
  • the azo pigment derivative can also be produced by introducing it into a compound) or a coupling component (for example, a compound having a acetoamide group) and then performing a coupling reaction.
  • the "triazine derivative having a basic group" used in the present invention can be synthesized by a known method through various synthetic routes.
  • the amount of the basic synergist is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 25 parts by weight with respect to 100 parts by weight of the pigment. It is. If the basic synergist is less than 1 part by weight with respect to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and if it exceeds 50 parts by weight, the heat resistance and Z or light resistance may be deteriorated.
  • the pigment dispersion according to the present invention may contain various pigment carriers in addition to the dispersant and the synergist.
  • Typical examples of pigment carriers are solvents (especially organic Solvent).
  • solvents especially organic Solvent
  • a known solvent which is usually used as a solvent for the pigment dispersion can be used for the pigment dispersion according to the present invention.
  • Examples of the solvent include methanol, ethanol, isopropyl alcohol, butanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, cyclohexanol, benzyl alcohol, alcohol alcohols such as amyl alcohol, ethylene glycol Noremonomethylenoateolene, Ethylene glycol monoethyl etherolate, Ethylene glycol monoisopropyl ether, Ethylene glycol monobutenoyl ether, Ethylene glycol monohexyl ether, Methoxymethoxyethanol, Diethylene glycol nole monomethyl Noleyatenore, Diethyleneglycolenomonochinenoatenore, Diethyleneglycolenobutinolenoatenore, Diethylene glycol monomethyl ether Tercetate, diethyleneglycolenomethinoreethenoreacetate, diethyleneglycolen
  • the pigment dispersion of the present invention may contain a thermosetting compound as a pigment carrier.
  • thermosetting compounds include melamine resin, benzoguanamine resin, phenol resin, blocked isocyanate, silane coupling compound, epoxy resin, alicyclic epoxy resin, oxetane resin, ethylene An unsaturated monomer, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, or urea resin. These thermosetting compounds react easily by heating to form a cross-linked structure (cross In order to form a linkage structure), it is preferable to include the thermosetting compound in a pigment dispersion for preparing a thermosetting ink.
  • Examples of the melamine resin include those having an imino group, a methylol group, and Z or an alkoxymethyl group, and a melamine resin containing only an alkoxymethyl group is particularly preferable.
  • Specific examples of the alkoxymethyl group-containing melamine resin include hexamethoxymethylol melamine, hexasuboxymethylol melamine and the like, but are not necessarily limited thereto.
  • melamine rosin commercially available rosin can be used, and specific examples of the commercially available products include the following. However, it is not necessarily limited to these. Specific examples of the commercial products are Sanwa Chemical Co., Ltd.-Power rack MW-30M, MW-30, MW-22, MS-21, MX-45, MX-500, MX-520, MX-43, MX-302, Nippon Cytex Industries' Cymel 300, 301, 303, 350, 285, 232, 235, 236, 238, My Coat 506, 508, etc.
  • benzoguanamine resin examples include those having an imino group, a methylol group, and Z or an alkoxymethyl group, and an alkoxymethyl group-containing benzoguanamine resin is particularly preferable.
  • Commercially available resin can be used as benzoguanamine resin. Specific examples of commercially available products include Sanwa Chemical Co., Ltd.-Power Rack BX-4000, SB-401, Nippon Cytex Industries, Ltd. For example, Cymel 1123 made by the company.
  • phenolic resin for example, either a novolac-type phenolic resin obtained by reacting phenols and aldehydes in the presence of an acidic catalyst or a resol-type phenolic resin prepared by reacting in the presence of a basic catalyst may be used.
  • phenols include ortho-cresol, paracresol, para-phenol, para-phenol, 2,3-xylenol, phenol, metacresanol, 3,5-xylenol, resorino, and tecnore.
  • neutroquinone bisphenol A, bisphenol F, bisphenol B, bisphenol E, bisphenol H, and bisphenol S.
  • aldehydes include formaldehyde and acetoaldehyde.
  • the phenols and aldehydes may be used alone or in combination of two or more.
  • Examples of the isocyanate compound used as a raw material for the blocked isocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, tonoridine resin isocyanate, diphenol methane 4, 4'- Diisocyanates, diphenylmethane 2,4'-diisocyanate, bis (4-isocyanate cyclohexyl) methane, tetramethylxylylene diisocyanate, etc., isocyanurates of these diisocyanates, trimethylolpropane adduct Forces that can include molds, biuret types, prepolymers having isocyanate groups (dipolymers and low polymers obtained with polyol strength), urethane diones having isocyanate residues, and the like are
  • Examples of the blocking agent for the isocyanate compound include phenol (dissociation temperature of 180 ° C or higher), ⁇ -prolactam (dissociation temperature of 160 to 180 ° C), oxime (dissociation temperature of 130 to 160 ° C). ), Or an active methylene (100 to 120 ° C.), and the like.
  • One type can be used alone, or two or more types can be used in combination.
  • silane coupling agent examples include bursilanes such as butyrris (/ 3-methoxyethoxy) silane, butylethoxysilane, butyltrimethoxysilane , and (meth) acrylic such as ⁇ -methacryloxypropyltrimethoxysilane.
  • Silanes ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mono (3,4-epoxycyclohexyl) methyltrimethoxysilane, 13- (3,4-epoxycyclohexyl) ethylyltri Epoxy silanes such as ethoxysilane, j8 (3, 4-epoxycyclohexyl) methyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropinoletriethoxysilane, ⁇ - ⁇ (amino Ethyl) - ⁇ -aminopropyltrimethoxysilane, ⁇ - ⁇ (aminoethyl) - ⁇ -aminop Pills triethoxysilane, N-j8 (aminoethyl) .gamma.
  • Aminopuropiru Examples thereof include aminosilanes such as trimethoxysilane and ⁇ -phenol ⁇ aminopropyltriethoxysilane, and thiosilanes such as y-mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane.
  • Examples of the epoxy resin include bisphenol full orange glycidyl ether and vinyl. Cresol fluoric acid glycidyl ether, bisphenoxyethanol fluoric acid glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol Polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, diglycidyl terephthalate, diglycidyl o-phthalate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. Polyglycolyl ether, polyglycol
  • unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenol (meth) acrylate, benzyl (meth) acrylate,
  • Alkyl (meth) acrylates such as;
  • Alkoxypolyalkylene glycol (meth) acrylates such as methoxy polypropylene glycol (meth) acrylate and ethoxy polyethylene glycol (meth) acrylate; acrylic acid, methacrylic acid, 2-carboxyethyl (meth) acrylate, ⁇ — Carboxy— (meth) acrylates containing carboxyl groups such as poly force prolatatone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, and tetrahydroxyphthalate monohydroxyethyl (meth) acrylate.
  • carboxyl groups such as poly force prolatatone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, and tetrahydroxyphthalate monohydroxyethyl (meth) acrylate.
  • Carboxyl group-containing ethylenically unsaturated monomers other than the above-mentioned carboxyl group-containing (meth) atalylates such as crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc .; 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 2- Hydroxyl-containing (meth) acrylates such as hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, poly (ethylene) acrylate (meth) acrylate, polypropylene glycol (meth) acrylate.
  • Amino group-containing (meth) acrylates such as N, N dimethylaminoethyl (meth) acrylate, N, N jetylaminoethyl (meth) acrylate;
  • Styrenes such as styrene and ⁇ -methylstyrene
  • Butyl ethers such as ethino levinino le etherenole, ⁇ propino levinino le etherenole, isopropino levinino le etherenole, ⁇ butyl vinyl ether, isobutyl vinyl ether; fatty acid vinyls such as vinyl acetate and vinyl propionate;
  • polyester (meth) acrylate polyurethane (meta ) Acrylate, epoxy (meth) acrylate, (meth) acrylic maleic acid-modified polybutadiene and the like.
  • (meth) acrylate refers to methacrylate or acrylate
  • (meth) acrylamide refers to methacrylamide or acrylamide
  • (meth) acrylonitrile refers to methacrylo-tolyl or acrylonitrile.
  • pigment dispersion of the present invention as a pigment carrier, vinyl resin (acrylic resin, polystyrene resin, styrene monomaleic acid resin, etc.), polyurethane resin, polyester resin, polyimide Resin, Petitral Resin, Chlorinated Polyethylene, Chlorinated Polypropylene, Polysalt Bull, Salt Butyl Acetate Bull Copolymer, Polyacetate Bull, Alkyd Resin, Polyamide Resin, Rubber Resin, Cyclized Rubber A systemic resin, celluloses, polyethylene, and a polybutadiene force can be selected. By containing these rosins, the dispersibility of the pigment is improved and the stability over time can be improved.
  • strength of a colored film, etc. can be improved.
  • the bull resin is particularly preferable because of its excellent transparency, light resistance, and heat resistance.
  • the vinyl-based resin means a resin obtained by copolymerizing at least the ethylenically unsaturated monomer exemplified above.
  • the vinyl-based resin used in the present invention may contain an ethylenically unsaturated monomer having a phosphoric acid group or a sulfonic acid group as a polymerization component in addition to the ethylenically unsaturated monomer exemplified above. it can.
  • the ethylenically unsaturated monomer having a phosphoric acid group is represented by the following general formula (18) as typified by ethylene glycol (meth) acrylate phosphate and propylene glycol (meth) acrylate phosphate.
  • An ethylenically unsaturated monomer is mentioned.
  • R 44 is a hydrogen atom or a methyl group
  • R 45 is an alkylene group
  • u represents an integer of 1 to 20.
  • ethylenically unsaturated monomer having a phosphoric acid group are as follows.
  • These ethylenically unsaturated monomers having a phosphoric acid group can be produced, for example, by the method described in JP-B-50-22536 or JP-A-58-128393.
  • Commercial products include, for example, Phosmer M, Phosmer CL, Phosmer PE, Phosmer MH (manufactured by Yu-Chemical), Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.), JAMP-514 (Johoku Chemical Co., Ltd. KAYAMER PM-2, KAYAMER PM—21 (or above) Nippon Kayaku Co., Ltd.).
  • Examples of the ethylenically unsaturated monomer having a sulfonic acid group include 2-acrylamido 2-methylpropane sulfonic acid, vinyl sulfonic acid, 3 aryloxy-2-hydroxy propane sulfonic acid, and p-styrene sulfonic acid. , Methallyl sulfonic acid, allyl sulfonic acid, methallyl benzene sulfonic acid, allyloxy benzene sulfonic acid, 2-sulfo butyl metatalylate, 4-sulfo butyl metatalylate and the like.
  • the vinyl-based resin it is preferable to use an ethylenically unsaturated monomer represented by the following general formula (19) or general formula (20).
  • a bull-based resin co-polymerized with these ethylenically unsaturated monomers as a pigment carrier, the dispersibility of the pigment and the stability over time can be improved, and the pigment paste can be made to have a low viscosity. it can.
  • R 4b and R 48 represent a hydrogen atom or a methyl group
  • 'and R represent an alkylene group having 1 to 4 carbon atoms
  • V and w are 1 ⁇ : Represents an integer of L00.
  • Examples of the ethylenically unsaturated monomer represented by the general formula (19) and the general formula (20) include, for example, paracumylphenol ethylene oxide-modified acrylate, ethylene oxide-modified bisphenol A dimethacrylate, Ethylene oxide modified bisphenol A ditalylate, propylene oxide modified bisphenol A dimethacrylate, propylene oxide modified bisphenol A ditalylate, ethylene oxide propylene oxide Modified bisphenol A dimethacrylate, ethylene oxide Propylene oxide modified bisphenol A diatalylate, propylene oxide ethylene oxide (block type) modified bisphenol A dimethacrylate, propylene oxide tetramethylene oxide modified bisphenol A dimethacrylate, propylene And oxide tetramethylene oxide-modified bisphenol A diatalylate.
  • These are commercially available as, for example, the Blemmer series from Nippon Oil & Fats Co., Ltd. and the Aronix series from Toa Gosei Co.
  • bur-based rosin can be carried out, for example, in the presence of an initiator, under an inert gas stream at 50-150 ° C for 2 to LO time. If necessary, the reaction may be performed in the presence of the solvent.
  • Initiators include organic peroxides such as benzoyl peroxide, tamen hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-tert-butyl peroxide, and t-butyl peroxybenzoate. And 2, 2, and azo compounds such as azobisisobuty-mouth-tolyl.
  • the initiator is preferably used in an amount of 1 to 20 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer.
  • additives that can be added to the pigment dispersion of the present invention include, for example, photopolymerization initiators, chain transfer agents, plasticizers, surface conditioners, ultraviolet inhibitors, light stabilizers, acids. Examples thereof include antistatic agents, antistatic agents, antiblocking agents, antifoaming agents, viscosity modifiers, waxes, surfactants, and leveling agents.
  • the photopolymerization initiator will be described.
  • the epoxy resin, the alicyclic epoxy resin, the oxetane resin, and the ethylenically unsaturated monomer are active energy ray-curable compounds, and a coloring composition containing the compound
  • the coated film can be cured by irradiating with active energy lines.
  • the active energy ray-curable compounds the ethylenically unsaturated monomer is cured by radical polymerization, and epoxy resin, cycloaliphatic epoxy resin, oxetane resin, and ethylenically unsaturated monomer. Vinyl ethers contained in the polymer are cured by cationic polymerization.
  • active energy rays indicate ionizing radiation such as electron beams and ultraviolet rays.
  • Examples of the photopolymerization initiator that can be used in the radical polymerization system include, Initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thixoxane photopolymerization initiator, triazine photopolymerization initiator, phosphine photopolymerization initiator, oxime photopolymerization initiator, imidazole Photopolymerization initiator, borate photopolymerization initiator, rubazole photopolymerization initiator, quinone photopolymerization initiator, titanocene photopolymerization initiator, and the like.
  • acetophenone photopolymerization initiator for example, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1 (4 isopropylpyrethane- 2) 2-hydroxy-1,2-methylpropane 1-one, 1-hydroxycyclohexyl phenyl ketone, 2 benzyl 1-2 dimethylamino 1- (4 morpholinophenyl) butane 1-on, and the like.
  • benzoin photopolymerization initiator examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal.
  • Benzophenone-based photopolymerization initiators include, for example, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenolpenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl 4'-methyldiphenol. Such as sulfide.
  • thixanthone photopolymerization initiator examples include thixanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthixanthone, 2,4 diisopropylthioxanthone, and the like.
  • Examples of the triazine-based photopolymerization initiator include 2, 4, 6 trichlorine s triazine, 2—phenol 1, 6 bis (trichloromethyl) s triazine, 2— (p-methoxyphenol).
  • Examples of the phosphine photopolymerization initiator include bis (2,4,6 trimethylbenzoyl) phenol phosphine oxide, 2,4,6 trimethylbenzoyl diphenylphosphine oxide, and the like.
  • Examples of the quinone-based photopolymerization initiator include 9, 10 phenanthrenequinone, camphor quinone, and ethyl anthraquinone.
  • Examples of the oxime-based photopolymerization initiator include compounds represented by the following formula (21): 1 [9-ethyl 6- (2-methylbenzoyl) -9H-power rubazole-3-yl] — (O —acetyloxime), 1, 2-octanedione, 1— [4— (phenylthio) one, 2 (O —benzoyloxime)], O (acetyl) N— (1—phenol 1 2-Oxo 2— (4
  • imidazole-based photopolymerization initiator examples include 2,2'bis (o black-mouthed phenol) -4,5,4 ', 5, -tetraphenyl-1,2, -biimidazole.
  • borate photopolymerization initiator examples include compounds represented by the following formulas (22) to (25).
  • the photopolymerization initiator is not necessarily required.
  • the cationic photopolymerization initiator is an essential component regardless of the active energy ray type.
  • Specific examples of cationic photopolymerization initiators include arylsulphum salt derivatives (for example, Cyracure UVI-6990 manufactured by Union Carbide, Silacure UVI-6974, Adekaoptomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd., Adeka optomer SP-152, Adeka optomer SP-170, Adeka optomer SP-172), Allyodonium salt derivatives (eg RP-2074 made by Rhodia), Allen ion complex derivatives (eg Irgacure 261 made by Ciba-Gigi Co., Ltd.) ), Diazo-um salt derivatives, triazine-based initiators and other halogenated compounds.
  • arylsulphum salt derivatives for example, Cyracure UVI-6990 manufactured by Union Carbide, Silacure UVI-6974, Adekaoptomer
  • Examples of the photopolymerization accelerator used in combination with the cationic photopolymerization initiator include anthracene and anthracene derivatives (for example, Adekaobomer SP-100, manufactured by Asahi Denki Kogyo Co., Ltd., 9, 10 dibutoxyanthracene, 9, 10 ethoxyanthracene, 9, 10 dipropoxyanthracene). These cationic photopolymerization initiators or cationic photopolymerization accelerators can be used alone or in combination.
  • the chain transfer agent will be described.
  • Examples of the chain transfer agent that can be used in the pigment dispersion of the present invention include thiol compounds, and polyfunctional thiols having two or more thiol groups are particularly preferable.
  • thiol compounds and polyfunctional thiols having two or more thiol groups are particularly preferable.
  • trimethylolpropane tristipropionate trimethylolpropane tris (3-mercaptobutyrate)
  • trimethylolpropane tris (3 mercaptoisoptylate) can be preferably used.
  • these polyfunctional wheels are particularly preferable when combined with an imidazole photopolymerization initiator because the sensitivity is increased and the active energy ray curability is improved.
  • the pigment dispersion of the present invention essentially includes the pigment and the dispersant represented by the general formula (1), and the basic synergist, the solvent, the pigment carrier other than the dispersant, and other additives.
  • the mixture thus mixed can be prepared by dispersing the pigment in a pigment carrier by dispersing it with a shaker, horizontal sand mill, vertical sand mill, Ryura Yura type bead mill, or attritor.
  • the pigment, the basic synergist, the dispersant represented by the general formula (1), the pigment carrier other than the dispersant, and other additives may mix all the components to disperse the force. And only the basic synergist, or only the basic synergist and the dispersing agent, or only the pigment, the basic synergist and the dispersing agent, and then add another component and perform dispersion again. May be.
  • a kneader or a kneader mixer such as a three-roll mill Dispersion, solid dispersion by a two-roll mill or the like, or basic synergist and Z or treatment of the dispersant may be performed on the pigment.
  • any disperser or mixer such as a high speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic disperser can be used to produce the pigment dispersion of the present invention.
  • the viscosity can be adjusted by changing the ratio of various blending components and pigments.
  • a pigment dispersion chip by performing a coating treatment of the pigment in advance using a two-roll mill.
  • the compounding amount of the raw material when coating the pigment is 1 to 30 parts by weight of a basic synergist with respect to 100 parts by weight of the pigment, the dispersant represented by the general formula (1) and other than the dispersant.
  • the range is preferably 20 to 200 parts by weight of the pigment carrier and 4 to 200 parts by weight of the solvent. If the amount of basic synergist is less than 1 part by weight, the paste-like pigment dispersion (pigment)
  • the effect of reducing the viscosity of the paste-like pigment dispersion is over 30 parts by weight. If the amount exceeds 30 parts by weight, the basic synergists become excessive and the unadsorbed basic synergists aggregate.
  • the paste-like pigment dispersion which also has a chip-like pigment dispersion strength, thickens. Further, when the total amount of the dispersant and the pigment carrier other than the dispersant is less than 20 parts by weight, the pigment surface cannot be sufficiently covered, and the dispersion stability of the pigment is lowered, and the amount exceeds 200 parts by weight.
  • the viscosity of the paste-like pigment dispersion prepared from the chip-like pigment dispersion is increased by the free dispersant that is not adsorbed on the pigment and the pigment carrier other than the dispersant.
  • the amount of the solvent is less than 4 parts by weight, the initial coating on the pigment of the basic carrier and the pigment carrier other than the dispersant and the dispersant is insufficient, and the pigment is not sufficiently covered.
  • the viscosity of the paste-like pigment dispersion prepared from the chip-like pigment dispersion may not be stable, and when it exceeds 200 parts by weight, it is difficult to cover the pigment.
  • the coating treatment of the pigment can be performed by the following two-stage process.
  • the composition containing the pigment, the dispersant represented by the general formula (1), the pigment carrier other than the dispersant, and the solvent is passed through the two rolls about 20 times to obtain the pigment.
  • This is a chip forming process in which wetting and adsorption of the rosin component proceed. In this chipping process, about 80% by weight of the blended solvent is volatilized. Further, a kneaded product is obtained in which the dispersant and a pigment carrier other than the dispersant are adsorbed on the pigment.
  • the dispersant and the pigment carrier other than the dispersant are converted into the chip forming step (1).
  • the resin component is crosslinked in the coating treatment step (2). It occurs, and part of the oil is cut. This reaction is the result of excessive mechanical pressure and grinding, and further heating, and is a mechanochemical reaction. Only the pigment, the dispersant and the pigment carrier other than the dispersant are used. Then, it is difficult for the cross-linking reaction of the resin component to occur.
  • the basic synergist, the dispersant and the pigment carrier other than the dispersant are firmly adsorbed on the pigment surface, and further heated and pressurized By kneading, it is presumed that crosslinking of the dispersant and a pigment carrier other than the dispersant occurs.
  • the heating temperature in the coating treatment step (2) is preferably in the range of 80 ° C to 120 ° C.
  • the dispersant represented by the general formula (1) and the pigment carrier other than the dispersant may not be sufficiently crosslinked, and when the temperature exceeds 120 ° C, the dispersant and the Deterioration of the pigment carrier other than the dispersant may occur.
  • the surplus dispersant that has not been adsorbed on the pigment surface and the pigment carrier other than the dispersant may affect physical properties such as the viscosity of the paste-like pigment dispersion prepared from the chip-like pigment dispersion. Therefore, it may be removed by washing or filtration.
  • the coated pigment may be dried after washing if it does not agglomerate after drying, but it is not necessary to dry it if the solvent used in the coating treatment is satisfactory for the intended use. .
  • compositions can be prepared and the type of ink is not limited.
  • Typical inks include, for example, non-aqueous inks, water-based inks, or solvent-free paints, gravure inks, offset inks, and color filter inks (inks).
  • composition for color filter black ink composition for color filter
  • ink composition for inkjet printing ink for anthalpe
  • colorants for plastics ink for anthalpe
  • color filter inks that require the use of fine pigments, photosensitive black ink compositions, ink-jet inks, and ink jet inks for color finalizers (inkjet
  • ink for color filter it is preferable to filter by a filter or centrifugal method for the purpose of removing coarse particles and foreign matters after being dispersed by a disperser.
  • the color filter ink of the present invention can be suitably used for the production of a color filter substrate of a liquid crystal display panel used for, for example, a thin television.
  • the color filter ink of the present invention essentially comprises a pigment, the dispersant represented by the general formula (1), and the ethylenically unsaturated monomer, and other pigment carriers and other additives as necessary. It is composed of
  • a photosensitive resin can be blended.
  • a resin having a reactive substituent such as a hydroxyl group, a carboxyl group, and a Z or amino group has a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group.
  • a resin obtained by reacting a (meth) acrylic compound or keihynoic acid to introduce a photocrosslinkable group such as a (meth) atallyloyl group or a styryl group into the polymer is used.
  • polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and ⁇ -olefin-maleic anhydride copolymer are used as (meth) acrylic compounds having a hydroxyl group such as hydroxyalkyl (meth) acrylate.
  • acid anhydrides such as styrene-maleic anhydride copolymer and ⁇ -olefin-maleic anhydride copolymer
  • the pigment carrier preferably contains an alkali-soluble non-photosensitive resin.
  • Alkali-soluble non-photosensitive resin is a resin that dissolves in an alkaline aqueous solution and does not crosslink with radicals, and has a weight average molecular weight of 1,000 to 500,000 having an acidic functional group such as a carboxyl group or a sulfone group, preferably Examples include 5000 to 100000 resins.
  • an alkali-soluble non-photosensitive resin specifically, an acidic functional group Vinyl having ⁇ , one year old Refuin Z (anhydride) maleic acid copolymers a, styrene Z (anhydrous) maleic acid copolymers, styrene Z styrene sulfonic acid copolymer, ethylene Z (meth) acrylic acid copolymerization And an isobutylene Z (anhydrous) maleic acid copolymer.
  • bur resin having an acidic functional group bur resin having an acidic functional group, ⁇ -year-old refin Z (anhydrous) maleic acid copolymer, styrene ⁇ (anhydrous) maleic acid copolymer, and styrene-styrene sulfonic acid copolymer power at least 1 selected
  • a seed resin, especially a vinyl resin having an acidic functional group is preferably used because of its high heat resistance and transparency.
  • the beer-based resin having an acidic functional group is a copolymer of ethylenically unsaturated monomers having a carboxyl group, a phosphoric acid group, or a sulfonic acid group among the ethylenically unsaturated monomers by the above method. This can be easily obtained.
  • the color filter ink of the present invention preferably contains "a compound having a basic group".
  • a “compound having a basic group” excellent in pigment dispersion has a great effect of suppressing reaggregation of the pigment after dispersion. Therefore, when using the dispersant of the present invention represented by the general formula (1) and utilizing its excellent dispersibility to prepare an ink containing a pigment well dispersed in a pigment carrier, In order to suppress reaggregation of the pigment and obtain a color filter having excellent transparency, it is preferable to use a “compound having a basic group”.
  • a compound having a basic group is added to the ink for a power filter according to the present invention, because the dispersant can form a better adsorption / alignment surface with respect to the pigment.
  • the amount of the “compound having a basic group” is preferably 1 to 40 parts by weight, and more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the pigment. If the amount of the “compound having a basic group” is less than 1 part by weight, the dispersion effect is insufficient, and if it is more than 40 parts by weight, this may also affect the dispersion.
  • Examples of the “compound having a basic group” include a basic linseed basic surfactant and the above-mentioned basic synergist. Of these, basic synergists that form better adsorption and orientation of pigments are preferred.
  • Examples of the basic rosin include aliphatic polyamines and polyester graft polymers.
  • Examples of basic surfactants include lauryl sulfate monoethanolamine, lauryl sulfate.
  • Key-on surfactants such as triethanolamine acid, ammonium lauryl sulfate, monoethanolamine stearate, or monoethanolamine of styrene acrylic acid copolymer, alkyldimethylaminoacetic acid betaine
  • amphoteric surfactants such as alkylbetaines and alkylimidazolines. These can be used alone or in combination of two or more.
  • the pigment is sufficiently dispersed in a pigment carrier and applied to a transparent substrate such as glass so that the dry film thickness is 0.2 to 5 m.
  • the solvent can be included.
  • the photopolymerization initiator is added to the ink.
  • the color filter ink of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the ink over time.
  • storage stabilizers include benzyltrimethyl chloride or quaternary ammonium chloride such as jetylhydroxyamine, organic acids such as lactic acid or oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, Alternatively, organic phosphines such as tetraphenylphosphine, phosphites, and the like can be given.
  • the pigment is contained in the color filter ink in a proportion of 1.5 to 15% by weight. It is preferred that in addition, when the color filter ink of the present invention is used to form a filter segment by a printing method, a pigment is contained in the color filter ink in a proportion of 1.5 to 45% by weight. It is preferable. Further, the pigment is preferably contained in the final filter segment in a proportion of 10 to 50% by weight, more preferably 20 to 45% by weight, and the remainder is provided by a pigment carrier containing a dispersant. Is preferred!
  • the color filter ink of the present invention can be prepared as a gravure offset printing ink, a waterless offset printing ink, a silk screen printing ink, a solvent developing type or an alkali developing type colored resist material.
  • a gravure offset printing ink a waterless offset printing ink
  • a silk screen printing ink a solvent developing type or an alkali developing type colored resist material.
  • an alkali development type colored resist material is preferable.
  • the photosensitive black ink of the present invention comprises carbon black, a photopolymerization initiator, a basic synergist, an ethylenically unsaturated monomer, and a dispersant.
  • the photosensitive black ink of the present invention is particularly used in black matrix applications for color filters.
  • the content of the dispersant represented by the general formula (1) is preferably 0 on the basis of the total solid weight of the photosensitive black ink (100% by weight). .01 to 30 parts by weight, more preferably 0.1 to 30 parts by weight, still more preferably 0.5 to 20 parts by weight.
  • the content of the dispersant is less than 0.01 parts by weight, the adhesion to glass and the photosensitive black ink are insufficient, and when it exceeds 30 parts by weight, the adhesion to glass and the photosensitive black ink are insufficient. The stability effect may be worse.
  • the photosensitive black ink of the present invention may contain a pigment carrier other than the dispersant represented by the general formula (1).
  • the ratio [M1ZP1] of the weight [P1] of the resin and the weight [Ml] of the ethylenically unsaturated monomer is from 0.10 to 0.70. In particular, 0.15 to 0.65 is more preferable, and 0.20 to 60.60 is particularly preferable.
  • [M1 / P 1] is less than 0.10, the sensitivity is low, and when [M1ZP1] is more than 0.70, the black matrix pattern shape is poor in linearity, cross-sectional shape, or tack.
  • the ratio [II Z Ml] between the weight [Ml] of the ethylenically unsaturated monomer and the weight [II] of the photopolymerization initiator is preferably 0.15-0.62. This is because if the [I1ZM1] force is less than 0.15, the sensitivity becomes low and the progress of photopolymerization becomes difficult. In addition, when [I1ZM1] exceeds 0.62, the black matrix pattern shape may have poor linearity, cross-sectional shape failure, or tack.
  • carbon black is used as a light shielding component.
  • the one-bon black those described above as the pigment can be used, but in particular, carbon having an average primary particle diameter of 20 to 40 nm, a specific surface area of 70 to 180 m 2 Zg, and an oil absorption of 100 cm 3 Zl00 g or less Black can be preferably used.
  • the oil absorption amount of the present invention refers to the oil absorption amount of dibutyl phthalate.
  • a photosensitive black ink using carbon black having an average primary particle size of less than 20 nm alone is advantageous in terms of light shielding properties because it has a large number of carbon black particles per unit volume. Photocurability is inferior due to light-shielding properties. Further, it is difficult to stably disperse carbon black, and there is a problem that a phenomenon that a part of the black composition remains on a glass substrate after development or a phenomenon of residue (also called background stain) occurs.
  • the photosensitive black ink containing carbon black having an average primary particle size exceeding 0 nm has a small number of carbon black particles per unit volume, which is advantageous in terms of photocuring properties.
  • the matrix pattern shape, especially linearity, is insufficient.
  • Carbon black having an average primary particle size of 20 to 40 nm, a specific surface area of 70 to 180 m 2 Zg, and an oil absorption of 100 cm 3 Zl00 g or less is, for example, MOGUL L, BLACK PEARLS (L, 520, 450, 430 manufactured by CABOT) ), REGAL (660R, 660, 500R, 330R, 330, 300R, 250R, 250, 99R, 991), MA (77, 7, 8, 11, 100, 100R, 100S, 200RB, manufactured by Mitsubishi Chemical) , 14), # (52, 50, 47, 45, 45L, 44, 33, 32, 95, 85, 260), CF 9, Special Black550 from DEGUSSA, Printex (55, 45, 300, ES23, 35) , 3 50, Asahi Carbon's Asahi # 70L N- 326, Colombian 'Carbon RAVEN (125 5, 1250, 1200, 1170, 1040, 1035, 1030, 1020, 1000
  • REGAL (250R, 250) manufactured by CABOT, # 47 manufactured by Mitsubishi Kagaku, and particularly preferably # 47 manufactured by Mitsubishi Kagaku can be used.
  • a method of increasing the optical density (OD value) by combining two kinds of light-shielding materials that is, carbon black having a small average particle size and an average particle size It has been proposed to improve the OD value by forming a close-packed structure in a black matrix in combination with carbon black (for example, JP-A-9 133806 and JP-A-9 279082). No., JP-A-11-80584).
  • the average primary particle size difference is 5nm or more
  • the photosensitive black ink using the first carbon black (al) having an average primary particle diameter of 8 to 20 nm alone the number of carbon black particles per unit volume is large, and from the viewpoint of light shielding properties. Although advantageous, it is inferior in photocurability because of its high light shielding properties. In addition, it is difficult to stably disperse carbon black, and if a phenomenon occurs in which a part of the black composition remains on the glass substrate after development, or a residue (also called background stain), or a phenomenon that occurs, is there.
  • the photosensitive black ink using the second carbon black (a2) having an average primary particle diameter of 21 to 40 nm alone has a small number of carbon black particles per unit volume, and is photocurable. Is advantageous, but the light shielding property is insufficient.
  • the number of carbon black particles per unit volume is small, and photocurability is advantageous.
  • the pattern shape, particularly the linearity, is insufficient.
  • the first carbon black (al) is preferably one having an average primary particle size of 10 to 18 nm.
  • Carbon black which is ⁇ 600 m 2 Zg can be preferably used.
  • the black matrix pattern When carbon black larger than 600m 2 Zg, which tends to cause shape deterioration and adhesion deterioration, is used, it becomes difficult to stably disperse carbon black.
  • Carbon black having an average primary particle size of less than 8 nm is difficult to produce and is not suitable as the first carbon black (al).
  • the second carbon black (a2) preferably has an average primary particle diameter of 22 to 37 nm, and carbon black having a specific surface area force of 0 to 600 m 2 / g is preferably used. Can do. When using carbon black with a specific surface area of less than 0 m 2 / g, it tends to cause deterioration of the pattern shape and adhesion of the black matrix. When using carbon black larger than 600 m 2 Z g, Stable dispersion becomes difficult.
  • the first carbon black (al) having an average primary particle diameter of 8 to 20 nm for example, MONARCH made by CABOT or BLACK PERLS (1400, 1300, 1100, 1000, 900, 880, 800, 700), VULCAN (P, 9A32), # (2700B, 2650, 2600, 2450B, 2400B, 2350, 2300, 1000, 990, 980, 970, 960, 9 50, 900, 850), Color Black (FW2000, FW2, FW2V, FWl, FW18, S170, S 160), Special Black (6, 5), Printex (95, 90, 85, 80, 75, 40, 60) from MCF88, MA600, DEGUSSA , Tokai Carbon sheath ⁇ (9H SAF-HS, 9 S AF), Asahi Carbon's Asahi # 80, Colombian 'Carbon ROYAL SPECTRA, NEO SPECTRA MARK (I and II), NEO SPECTRA AG, SUPER
  • CABOT MONARCH (1 100, 800), BLACK PERLS (1100, 800), Mitsubishi Igaku # 850, DEGUSS A Printex95, CABOT MONARCH1100, DEGUSSA Printex95 are used. be able to. 3 ⁇ 4 ⁇ ⁇ — ⁇ 3 ⁇ 4 A: KOSO]
  • the total solid weight of the photosensitive black ink is preferably 40 to 65% by weight in total, more preferably 45% in total. It can be used in an amount of ⁇ 60% by weight.
  • the polyfunctional thiol can be used.
  • the polyfunctional thiol can be used in an amount of preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the total solid weight of the photosensitive black ink (100% by weight). . If the amount is less than 1% by weight, the effect of adding a polyfunctional thiol is insufficient. If the amount exceeds 30% by weight, the sensitivity is too high and the resolution is lowered, or the stability of the photosensitive black ink is lowered.
  • the solvent used in the photosensitive black ink of the present invention is preferably 150 to 3500 parts by weight, more preferably 250 to 2000 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive black ink. Can be used in quantities.
  • the pigment carrier used in the photosensitive black ink of the present invention may be the same as the color filter ink.
  • the inkjet ink of the present invention includes a pigment, a dispersant represented by the general formula (1), and the pigment carrier other than the dispersant.
  • the inkjet ink of the present invention contains an ethylenically unsaturated monomer as the pigment carrier other than the dispersant, and is an active energy ray curable ink jet ink that is cured with ultraviolet rays or an electron beam.
  • -ray Hardening ink composition for inkjet printing The polymerization method may be either radical polymerization or cationic polymerization.
  • the ink jet ink of the present invention may contain the thermosetting compound as the pigment carrier other than the dispersant, and may be used as a thermosetting ink composition for inkjet printing. it can.
  • thermosetting inkjet ink Is suitable as an ink-jet ink for a color filter, and in particular, a thermosetting ink jet ink is suitable because it does not require an active energy ray irradiation facility.
  • the number average molecular weight of the thermosetting compound that can be used in the inkjet ink for a color filter of the present invention is not particularly limited, but is preferably 50 to 2000, more preferably 100 to L000. It is.
  • thermosetting compounds it is preferable that the melamine resin or benzoguanamine resin is contained in the ink for a color filter of the present invention in an amount of 1 wt% to 40 wt%.
  • epoxy resin, phenol resin, blocked isocyanate compound, or ethylenically unsaturated monomer is contained in an amount of 1% to 40% by weight in the ink jet ink for color filter of the present invention. It is preferably contained.
  • the silane coupling agent is preferably contained in the ink composition of the present invention in an amount of 0.1 wt% to 40 wt%. If the content of the thermosetting compound is insufficient, the heat resistance or chemical resistance may be poor. On the other hand, when the content exceeds 40%, the viscosity of the inkjet ink for color filter may increase, or the storage stability may decrease.
  • the inkjet ink for a color filter of the present invention preferably contains a solvent.
  • the solvent is highly soluble in the pigment carrier, and the non-drying property of the ink at the printer nozzles is low.
  • the solvent is less swelled with the printer member in contact with the ink.
  • the solvent viscosity is as low as possible. Is preferred. From these viewpoints, among the solvents described above, it is preferable to use one of alcohols, glycol derivatives, esters, and Z or ketones alone or in combination of two or more. .
  • the pigment carrier other than the dispersant can be used in the inkjet ink for a color filter.
  • these pigment carriers those having a crosslinkable functional group can also be used.
  • the crosslinkable functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and an alkoxyl group.
  • the resin having a crosslinkable functional group is preferably a bull resin having a hydroxyl group or a carboxyl group because the resin is slowly crosslinked by an esterification reaction.
  • the bull resin having a hydroxyl group or a carboxyl group is composed of an ethylenically unsaturated monomer having a hydroxyl group or an ethylenically unsaturated monomer having a carboxyl group, a hydroxyl group and And a resin obtained by copolymerizing an ethylenically unsaturated monomer having no carboxyl group.
  • Examples of the ethylenically unsaturated monomer having a hydroxyl group include the above-mentioned hydroxyl group-containing (meth) acrylates, and examples of the ethylenically unsaturated monomer having a carboxyl group include those described above.
  • Examples of the ethylenically unsaturated monomer having no hydroxyl group and carboxyl group include those having no hydroxyl group and carboxyl group among the above ethylenically unsaturated monomers.
  • the pigment carrier having a crosslinkable functional group the pigment carrier having a phosphate group or a sulfonic acid group is improved because the dispersibility of the pigment and the stability over time are improved and the ink has a low viscosity. Is preferred.
  • the phosphate group and the sulfonate group are alkali metals such as sodium, potassium and lithium, polyvalent metals such as calcium, magnesium, aluminum and zinc, ammonia, or ethylamine, dibutylamine, triethanolamine and ethylamine.
  • a salt may be formed with an organic amine such as propylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, stearylamine, oleylamine, distearylamine and the like.
  • the pigment carrier having a phosphoric acid group or a sulfonic acid group the ethylenic unsaturated monomer having a phosphoric acid group or the ethylenic unsaturated monomer having a sulfonic acid group was copolymerized.
  • a vinyl polymer is preferred.
  • these ethylenically unsaturated monomers having a phosphoric acid group or the ethylenically unsaturated monomers having a sulfonic acid group can be used alone or in combination of two or more.
  • the copolymerization ratio of the ethylenically unsaturated monomer having a phosphoric acid group or the ethylenically unsaturated monomer having a sulfonic acid group is 100% by weight of the total ethylenically unsaturated monomer.
  • the amount is preferably 0.1 to 30 parts by weight or less, more preferably 0.1 to 5 parts by weight or less.
  • the weight-average molecular weight (Mw) of the vinyl-based resin having a phosphoric acid group or a sulfonic acid group is preferably ⁇ 1000 to 50000, and more preferably ⁇ 2000 to 30000.
  • a vinyl resin containing the ethylenically unsaturated monomer represented by the general formula (19) or the general formula (20) is preferable to use as a polysynthetic component.
  • the ethylenically unsaturated monomer represented by the general formula (19) or the general formula (20) may be used alone or in combination of two or more.
  • the copolymerization ratio of the ethylenically unsaturated monomer represented by the general formula (19) or the general formula (20) is 100 parts by weight of the total ethylenically unsaturated monomer. 0.1 to 50 parts by weight is preferred.
  • the weight average molecular weight (Mw) of the vinyl-based resin containing the ethylenically unsaturated monomer represented by the general formula (19) or the general formula (20) as a polysynthesis component is preferably 5000 to 100. 000, more preferably ⁇ is 10000-50000.
  • the pigment used in the inkjet ink for a color filter according to the present invention is preferably coated with the above method.
  • the solid content is preferably 3 to 60 wt%, more preferably 4 to 40 wt%, based on the total weight of the ink composition. If the solid content is less than 3% by weight, the concentration and resistance of the ink film will be insufficient, exceeding 60% by weight. As a result, the viscosity of the ink increases and the stability over time may decrease.
  • the viscosity of the inkjet ink of the present invention is preferably 2 mPa's or more and 40 mPa's or less, more preferably 3 mPa's or more and 30 mPa's or less, and further preferably 4 mPa's or more and 20 mPa's or less. -Layer is preferred. If the viscosity is too large, stable discharge cannot be achieved when discharging continuously.
  • the average dispersed particle size of the inkjet ink of the present invention is preferably 5 nm or more and 200 nm or less, more preferably lOnm or more and 150 nm or less. If the average dispersed particle size is too large, the nozzles may become clogged and stable ejection cannot be performed immediately. On the other hand, if the average dispersed particle size is too small, reaggregation is likely to occur, and the stability over time deteriorates.
  • the surface tension of the inkjet ink of the present invention is preferably 20 mNZm or more and 40 mNZm or less, more preferably 24 mNZm or more and 35 mNZm or less. If the surface tension is too high, the ink cannot be stably ejected from the nozzle. Conversely, if the surface tension is too low, the ink cannot form droplets after ejection from the nozzle.
  • the ink jet ink may contain the above-mentioned other additives in the range where the viscosity of the ink becomes 3 to 50 mPa's at 25 ° C.
  • the inkjet ink of the present invention has a low viscosity even when the pigment concentration is high, it is excellent in ejection stability, and the pigment content can be increased as compared with a normal inkjet ink, so that the ejection amount is reduced. be able to. Therefore, it is possible to improve the productivity and quality of printed matter for which a high print density is desired, including for color filter substrates.
  • the ink-jet ink of the present invention is suitable for production of a color filter substrate that requires high productivity and quality.
  • the ink-jet ink of the present invention has a high pigment concentration, the printing density can be increased even with paper in which the ink permeates in the depth direction or plastic, glass, and metal that spreads in the lateral direction. it can. Further, since the discharge amount can be suppressed, it is possible to avoid the phenomenon that ink flows out and mixes when the ink receiving amount of the receiving layer is exceeded, and the phenomenon that the dot shape does not become a perfect circle can be avoided. It can also be used for limited applications in printing.
  • the color filter includes a black matrix and at least two color filter segments other than black on a transparent substrate such as a glass plate.
  • the color of the filter segment is selected from about 2 to 6 colors from blue, green, red, cyan, yellow, magenta, orange or purple. Filter segments with the same color and different densities may be formed.
  • the color filter substrate can be used for, for example, a liquid crystal display panel used for a thin television.
  • the black matrix is, for example, a photolithographic method in which a photosensitive black ink of radical polymerization type is applied, exposed, developed, and patterned, a printing method for printing a black ink, or a metal is deposited. It can be formed on a transparent substrate by an evaporation method or the like to be etched later.
  • One photolithography method is to apply the photosensitive black ink of the present invention on a transparent substrate by a coating method such as spin coating, slit coating, or roll coating, and then through a photomask.
  • the active surface is irradiated with active energy rays from the coating surface side, and the developer is sprayed with a force immersed in a solvent or alkaline developer, spraying, etc., and the unirradiated part (that is, the uncured part) is removed for development.
  • This is a method for forming a target image (that is, a black matrix).
  • the photosensitive black ink of the present invention can be used for forming the black matrix, but other than the usual photosensitive black ink and other multilayer films of black chromium and chromium Z chromium oxide, titanium nitride, etc.
  • An inorganic film or a resin film in which a light shielding agent is dispersed may be used.
  • a preferred embodiment is when the photosensitive black ink of the present invention is used.
  • the coating thickness of the photosensitive black ink is preferably in the range of 0.2 to 5 ⁇ m (when dry), and it is easy to balance coating properties and light shielding properties. 0.5 to 2 A range of m is more preferable.
  • the optical density (OD value) per 1 ⁇ m dry film thickness of the black matrix is highly light-shielding. In view of the above, it is particularly preferably 3.0 or more, more preferably 3.5 or more, and still more preferably 3.8 or more. The higher the optical density, the better. However, in the case of ultraviolet rays or visible light, it is generally desirable that the optical density is 3.0 or more and 4.7 or less because a cured coating film can be obtained.
  • an aqueous solution such as sodium carbonate or sodium hydroxide is used, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used.
  • an antifoamer and surfactant can also be added to a developing solution.
  • an electron beam, ultraviolet rays, or visible light of 400 to 500 nm can be used.
  • a thermionic emission gun, a field emission gun, or the like can be used as the electron beam source irradiated from the ink application surface side.
  • a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, or a carbon arc lamp can be used as a source (light source) of ultraviolet light and visible light of 400 to 500 nm.
  • an ultra-high pressure mercury lamp or a xenon mercury lamp is often used because it is a point light source and the brightness is stable.
  • Force applied to the composition surface side The active energy dose to be irradiated is preferably in the range of 5 to: LOOOmJ, which can be set in a timely manner.
  • the combination of filter segments of the color filter includes a red filter segment, a green filter segment, and a blue filter segment, or includes a magenta filter segment, a cyan filter segment, and a yellow filter segment. Is mentioned.
  • These filter segments can be formed using the color filter ink or the color filter ink jet ink of the present invention.
  • an active energy ray irradiation device is not necessarily required.
  • soda-lime glass low alkali borosilicate glass, or non-alkali alloy
  • Glass plates such as luminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate are used.
  • a transparent electrode with intensities such as indium oxide or oxide tin is formed on the surface of the glass plate and the resin plate to drive the liquid crystal after the panel is turned on! Well! /
  • a thin film transistor may be formed in advance on the reflective substrate, and a filter segment may be formed thereafter.
  • the filter segment By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.
  • a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate can be used.
  • Methods for forming each color filter segment include a photolithography method, an ink jet method, a printing method, an electrodeposition method, and a transfer method.
  • each color filter segment by a photolithography method can be performed, for example, by the following method. That is, the color filter ink of the present invention prepared as a solvent development type or alkali development type colored resist material is applied to a transparent substrate such as glass by a coating method such as spray coating, spin coating, slit coating or roll coating. The coating is applied so that the dry film thickness is 0.2 to: LO / zm, more preferably 0.2 to 5 / ⁇ ⁇ . When drying the coating film, a vacuum dryer, a competition oven, an IR oven, a hot plate, or the like may be used.
  • the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or not in contact with the film.
  • the color filter can be manufactured by forming the desired pattern by spraying the developer with a spray immersed in a solvent or an alkaline developer, or spraying to remove the uncured portion.
  • an alkali developer similar to the formation of the black matrix can be used.
  • a film for preventing polymerization inhibition by oxygen can be formed, and then the ultraviolet exposure can be performed.
  • a color filter is formed by ejecting the inkjet ink for the color filter of the present invention into an area divided by the black matrix of the substrate on which the black matrix is formed using an inkjet ink ejection device. It is. When using the color filter inkjet ink of the present invention, it is preferable to heat it.
  • the electrodeposition method uses a transparent conductive film formed on a transparent substrate to form a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoretic colloidal particles. It is a manufacturing method.
  • the transfer method is a method in which a filter segment is preliminarily formed on the surface of a peelable transfer base sheet or transfer cylinder, and the filter segment is transferred to a desired transparent substrate.
  • an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, or the like is formed as necessary.
  • the liquid crystal display panel for example, bonds the color filter manufactured as described above to a counter substrate using a sealing agent, injects liquid crystal from the injection port provided in the seal portion, and then seals the injection port. If necessary, it can be manufactured by laminating a polarizing film or a retardation film on the outside of the substrate.
  • the liquid crystal display panels thus manufactured are Twisted Nematic (TN), Super Twisted Nematic (STN), In-Placed Switching (IPS). ), Vaticari ⁇ ⁇ Alaimen HVA: Vertical
  • the present invention will be specifically described with reference to examples, but the present invention is not particularly limited to the examples.
  • “parts” represents “parts by weight” and “%” represents “% by weight”.
  • the number average molecular weight and the weight average molecular weight are obtained from Tosoichi Co., Ltd. Gel Permeation Chromatography HLC-8120GPC! / Four separation columns are connected in series, and TSK-GEL SUPER H5000, H4000, H3000, and H2000 manufactured by Tosoh Corporation are used as packing materials in order. Polystyrene measured using mobile hydrolyzer It is a converted molecular weight.
  • the acid value, hydroxyl value, and amine value are values measured by the following methods.
  • the obtained dispersant was a waxy solid at 25 ° C., and had a number average molecular weight of 2430, a weight average molecular weight of 3590, and an acid value of 49 mg KOHZg.
  • the waxy solid means a solid that is opaque at room temperature but changes to a transparent liquid upon heating.
  • the dispersant obtained in Example 1 is a transparent liquid at about 50 ° C. It was to become.
  • Example 1 The infrared absorption spectrum of the dispersant obtained in Example 1 is shown in FIG. 1, and the 13 C-NMR ⁇ petatre (in a heavy chloroform solvent) is shown in FIG.
  • Example 2 The same apparatus, catalyst, and reaction procedure as in Example 1 were used, but each dispersant was obtained using the compounds shown in Tables 1 and 2 as starting materials in the amounts used in Tables 1 and 2. However, in Examples 4, 5, 9, 12, 13, and 15, the inside of the reaction vessel was replaced with dry air instead of nitrogen gas. In addition, “water” described in Example 7 and Example 13 is added after confirming the completion of the reaction between tetracarboxylic dianhydride and the hydroxyl group of the polyester having a hydroxyl group at one end by an acid value, Water used to hydrolyze the remaining acid anhydride.
  • Methoxy PEG400 ' ⁇ ' One-end methoxy polyethylene glycol (Number average molecular weight 395, Hydroxyl value: 142mgKOHZg)
  • Example 17 was carried out at 100 ° C for 5 hours, and Examples 18 and 19 were carried out at 50 ° C for 3 hours.
  • Methoxy PEGIOOO ' ⁇ ' One-end methoxy polyethylene glycol (number average molecular weight 960, hydroxyl value: 58mgKOHZg)
  • TMEG- ⁇ 'Ethylene glycol ditrimellitic anhydride manufactured by Nippon Nippon Chemical Co., Ltd .: trade name Ricacid TMEG-100
  • the obtained dispersant was a waxy solid at 25 ° C., and had a number average molecular weight of 3640, a weight average molecular weight of 5460, and an acid value of 40 mgKOHZg.
  • the dispersants obtained in Examples 2, 9, 12, 14, 15, 17, 18, and 19 were 25 ° C. Even if it does not contain a solvent, it is liquid and is excellent in handling.
  • a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 200 parts of n-butyl metatalylate and 10 parts of 2-mercaptoethanol and replaced with nitrogen gas.
  • the reaction vessel was heated to 80 ° C and reacted for 12 hours.
  • a solid content measurement confirmed that 95% had reacted.
  • the number average molecular weight of the obtained reaction product (polymer) was 2460, and the weight average molecular weight was 4530.
  • Example 16 Using the same apparatus and reaction procedure as in Example 16, the ethylenically unsaturated monomer, chain transfer agent, polymerization initiator, and tetracarboxylic dianhydride listed in Table 4 were used in the dosages listed in Table 4. To obtain each dispersant.
  • a mixture of 39.0 parts of 2-ethylhexyl alcohol, 21.8 parts of pyromellitic anhydride and 50 parts of methoxypropyl acetate was reacted at the boiling point in a nitrogen stream for 5 hours.
  • the generated water was separated with a gene stark trap.
  • the non-volatile content was adjusted to 50% with methoxypropyl acetate to obtain a comparative dispersant.
  • the acid value per nonvolatile content of the reaction product was 96 mgKOHZg.
  • a reaction vessel equipped with a gas inlet tube, a thermometer, a stirrer, and a condenser is charged with 17.8 parts neopentyl glycol, 31.9 parts pyromellitic anhydride, and 75.0 parts methoxypropyl acetate, and 150-160 The temperature was raised to ° C and the reaction was carried out in a nitrogen stream for 5 hours. When the acid value became 3 34 mgKOHZg or less, the mixture was cooled to 50 ° C, and ⁇ 1-strength prolatatone (249.7 parts) and tetrabutyl titanate (0.6 parts) were added and reacted at 150 ° C for 5 hours.
  • the mixture was cooled and methoxypropyl acetate was added to adjust the non-volatile content to 50% to obtain a comparative dispersant.
  • the acid value per nonvolatile content of the reaction product was 55 mg KOHZg.
  • BLEMMER 55PET-800 [manufactured by NOF Corporation: poly (ethylene glycol-tetramethylene glycol) monometatalylate; number average molecular weight: 840, Hydroxyl value: 67mgKOHZg] 49. 5 parts, epsilon prolatathone 50.5 parts, monobutyltin (IV) oxide 0.04 parts as catalyst and methylhydroquinone as polymerization inhibitor were charged and dried air at 120 ° C for 5 hours. The reaction was carried out while introducing.
  • BLEMMER 55PET-800 manufactured by NOF Corporation: poly (ethylene glycol-tetramethylene glycol) monometatalylate; number average molecular weight: 840, Hydroxyl value: 67 mg KOHZg] 49.5 parts, epsilon prolatathone 50.5 parts, monobutyltin (IV) oxide 0.04 parts as catalyst Methylhydroquinone was charged as a polymerization inhibitor and reacted while introducing dry air at 120 ° C for 5 hours.
  • the obtained dispersant was a waxy solid at 25 ° C., and had a number average molecular weight of 10 860, a weight average molecular weight of 17700, and an acid value of 1 mgKOHZg.
  • Example 27 In the same manner as in Example 27, the initial viscosity, the viscosity with time, and the rate of change in viscosity of the dispersion obtained using the dispersant obtained in the above Example were measured. However, in Examples 37 to 41, dispersions were prepared by changing the solvent to be used from n-octanol to methoxypropyl acetate in Example 27. The results are shown in Tables 5-7.
  • Example 16 Example 17 Example 18 Example 18 Example 19 Example 20 What was obtained What was obtained What was obtained What was obtained Initial viscosity 35 45 38 48 55 Viscosity over time 35 42 39 50 55 Rate of change 100% 93% 103% 104% 100%
  • Example 27 Dispersion Production Example
  • each of the dispersants obtained in Examples 21 to 26 (nonvolatile content: 50% by weight)
  • a dispersion was produced by the operation and evaluation method described in Example 27. The rate of change in viscosity was measured and evaluated. The results are shown in Table 8.
  • Example 27 Dispersion Production Example
  • the initial viscosity, the time-dependent viscosity and the rate of change of the viscosity of the dispersion produced using the dispersants obtained in Reference Examples 1, 2, 5 and 6 was measured.
  • Comparative Example 3 a dispersion was prepared by changing the solvent used to n-octanol instead of the methoxypropyl acetate used in Example 27. The results are shown in Table 9.
  • F is the surface excess functionality of the pigment molZg
  • B is the surface base amount of the pigment molZg
  • A is the surface acid amount of the pigment molZg
  • F value (excess surface functionality of pigment) calculated from: 9 g of copper phthalocyanine pigment having a basic surface of 140 ⁇ molZg, 3 g of the dispersant obtained in Example 1, 48 g of methoxypropyl acetate, and 60 g of glass beads (0.8 mm in diameter) were placed in a 140 mL mayonnaise bottle, placed in a scandetta and dispersed for 3 hours. The obtained dispersion liquid glass beads were removed to obtain a dispersion.
  • Example 52 when the operation described in Example 48 was repeated, instead of “3 g of the dispersant obtained in Example 1”, the “dispersant obtained in Example 22 (nonvolatile content) was replaced. 50%) 6 g ”was used, and“ Methoxypropyl acetate 45 g ”was used instead of“ Methoxypropyl acetate 48 g ”to obtain a dispersion.
  • Table 10 Table 10
  • Comparative Examples 5 to 8 With respect to the dispersions obtained by the same method as in Example 27 except that the dispersants obtained in Reference Examples 1 to 4 were used, their initial viscosity, time-dependent viscosity, and rate of change in viscosity were measured. The results are shown in Table 11.
  • Comparative Examples 1 and 5 using the comparative dispersant obtained by the method described in Example 5 of Patent Document 1 since the polymer part (P) does not exist in the dispersant, the dispersibility is extremely low. Gelling occurred during spraying or storage at 40 ° C.
  • Comparative Examples 2 and 6 in which the comparative dispersant obtained by the method described in Example 1 of Patent Document 2 was used, a compound containing two or more tetracarboxylic dianhydride moieties in one molecule was obtained. As a result, the initial viscosity was high, and the storage stability with time was bad. Further, the molecular weight of the polymer part (P) is 168, and the molecular weight of Comparative Example 3 using a dispersant lower than the range 200 of the present invention, or the polymer part (P) is 5570, which is within the scope of the present invention. In Comparative Example 4 where the dispersant was used, the viscosity of the dispersion was higher than 5000 and V was higher than 5000.
  • Comparative Examples 7 and 8 using a dispersion that did not contain two or more carboxyl groups as a substituent of the group X 1 had high viscosity and poor storage stability. As described above, the comparative dispersants have drawbacks.
  • the basic derivatives ⁇ 1 to 14 used in the following Examples and Comparative Examples relating to the use of the dispersant are shown in Tables 12 to 14 below.
  • the basic derivatives a 1 to a 14 were produced by reacting an amine compound with a dye as a raw material by a known production method. [0290] [Table 12]
  • paste pigment dispersions are shown in Examples 53-70.
  • pigment basic synergist, dispersant, alkyd resin (Hitachi Chemical Co., Ltd. “Phtalkid 133-60”), melamine resin (Hitachi Chemical Co., Ltd.
  • V6 is the viscosity at 6 rpm and V60 is the viscosity at 60 rpm
  • the obtained pigment paste paste-like pigment dispersion was stored in a thermostat at 50 ° C for 1 week to accelerate the change over time, and the change in viscosity (%) before and after the change over time was measured. Stability was evaluated in the following two steps. The results are shown in Table 16.
  • Viscosity change rate before and after storage at 50 ° C for 1 week is within ⁇ 10%.
  • Example 53 Example 59, Example 60, Example 62, and Example 63 were applied to an aluminum plate with bar coater # 5, respectively. Then, after baking at 180 ° C for 1 hour and then immersing in a 5% strength saline solution for 24 hours, no paint film prestar was formed.
  • Comparative Example 12 Comparative Example 16, Comparative Example 20, Comparative Example 22, and Comparative Example 23 were each coated on an aluminum plate with bar coater # 5. Then, after baking at 180 ° C for 1 hour, when immersed in a 5% strength saline solution for 24 hours, blisters were formed on all coating films.
  • Examples 71-75 show the preparation of paste pigment dispersions for non-aqueous inkjet inks.
  • the pigment, pigment derivative, and dispersing agent were added to the organic solvent and stirred with a high-speed mixer, etc. until uniform, and then the resulting mill base was mixed with a horizontal sand mill. And dispersed for about 1 hour.
  • a comparative paste-like pigment dispersion was produced in the same manner.
  • the inkjet ink was diluted 200-1000 times with ethyl acetate and measured with a particle size distribution meter [Microtrac UPA150 (Nikkiso Co., Ltd.)].
  • Ink-jet ink was printed with a large-format ink-jet printer [IP-6500 (manufactured by Seiko I Infotech)], and the printing state of the nozzle check pattern was observed and evaluated in the following three stages:
  • Print defects such as missing nozzles and bending are less than 1%;
  • the mixture was further reacted at 80 ° C for 3 hours, and then a solution prepared by dissolving 1.0 part of azobisisobutyor-tolyl in 50 parts of hexanone was added, and further at 80 ° C for 1 hour.
  • the reaction was continued to obtain an acrylic resin solution.
  • the weight average molecular weight of the acrylic resin was about 40000.
  • sample approximately 2 g of the acrylic resin solution heat at 180 ° C for 20 minutes and dry to measure the nonvolatile content, so that the nonvolatile content of the acrylic resin solution is 20% by weight.
  • cyclohexanone was added to the previously synthesized acrylic resin solution to prepare an acrylic resin solution I.
  • a resist-coated substrate is sandwiched between two polarizing plates, and light is irradiated using a backlight unit for a liquid crystal display from the side of one polarizing plate.
  • the light emitted from the knock light 'unit passes through the first polarizing plate and is then polarized, and then passes through the resist-coated substrate. To reach the polarizing plate. If the planes of polarization of the first and second polarizers are parallel, light will pass through the second polarizer, but if the plane of polarization is perpendicular! It is blocked by the second polarizing plate.
  • the luminance meter used was a color luminance meter BM-5A manufactured by Topcon Corporation, and the polarizing film used was a polarizing film LLC2-92-18 manufactured by Sanritsu. In the measurement, in order to block unnecessary light, the measurement was carried out by applying a black mask with lcm square holes in the measurement area.
  • Example 81- The color filter inks of LOO and Comparative Examples 32-37 were produced according to the blending ratio (weight ratio) shown in Table 20. First, a pigment, a dispersant, a part of an acrylic resin solution, and a part of cyclohexanone are stirred and mixed uniformly, and then a Eiger mill ("Eger Japan" Dispersion was carried out for 2 hours using model M-250 mm and filtered through a 5 m filter to prepare a pigment dispersion. The dispersant was added in advance dissolved in cyclohexanone.
  • the pigment dispersion, the remainder of the acrylic resin solution, the monomer, the photopolymerization initiator, the sensitizer, and the remaining mixture of cyclohexanone were stirred and mixed uniformly, and then 1 m of Filtration through a filter produced a color filter ink.
  • the blending ratio (weight ratio) shown in Table 20 is finally maintained and dispersion can be performed, the pigment dispersion can be produced.
  • the amount of the acrylic resin solution and cycloxanone added in the stage and the color filter ink manufacturing stage can be freely determined.
  • Green Green pigment ⁇ ⁇ ⁇ 'By mixing the following pigments.
  • Red :: Red pigment ⁇ ⁇ ⁇ 'By mixing the following pigments.
  • Yellow ' Yellow pigment ⁇ ⁇ ⁇ ⁇ C. I. Pigment Yellow 139
  • Trimethylolpropane tritalylate (“NK ester ATM PTJ” manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Photopolymerization initiator "Irgacure 907" manufactured by Ciba-Gaigi
  • Sensitizer ⁇ FJ manufactured by Hodogaya Co., Ltd.
  • Disperbyk- 111 Phosphoric acid group-containing pigment dispersant manufactured by Big Chemi
  • Solspers 41000 Phosphate group-containing pigment dispersant manufactured by Nippon Lubrizol
  • PB-821 Axillary dispersant with basic group manufactured by Ajinomoto Fine Techno Co., Ltd.
  • the initial viscosity value (VI) measured the day after the color filter ink was prepared, and the time-dependent viscosity value (V2) that was allowed to stand for one week at 40 ° C and accelerated over time.
  • V2 time-dependent viscosity value
  • ELD viscometer manufactured by the company, measurement was performed at 25 ° C under the condition of a rotation speed of 20 rpm. From this initial viscosity value and the viscosity value with time, the rate of change in viscosity (Vr) with time is calculated using the following formula (4):
  • Vr is the rate of change in viscosity over time
  • VI is the initial viscosity value
  • V2 is the viscosity value over time
  • Color filter ink was applied onto a glass substrate (100mm X 100mm; 1.1mm thickness) using a spin coater at 500rpm, 1000rpm, or 1500rpm, and three types of coated substrates with different film thicknesses were obtained. .
  • a spin coater at 500rpm, 1000rpm, or 1500rpm, and three types of coated substrates with different film thicknesses were obtained.
  • the resist material coating the substrate and dried at 70 ° C 20 minutes, subjected to ultraviolet exposure in integrated light intensity 150MjZcm 2 using an ultra-high pressure mercury lamp, heated at 230 ° C, After cooling, the contrast ratios It was measured.
  • the chromaticity ( ⁇ , X, y) of the coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).
  • OSP-SP100 microspectrophotometer
  • the color filter ink was applied on a glass substrate (100 mm X 100 mm; 1.1 mm thickness) using a spin coater at a rotational speed of 2.0 m after drying. after drying for 20 minutes at ° C, subjected to ultraviolet exposure in integrated light intensity 150MjZcm 2 using an ultra-high pressure mercury lamp through a photo mask having a stripe-shaped opening having a width 100 m, with 5% aqueous sodium carbonate The unexposed area was washed away and beta-patterned with a hot air oven at 230 ° C for 30 minutes to form a 100 m wide stripe pattern on the substrate.
  • the chemical resistance of the obtained coating film was evaluated.
  • the sample was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C for 30 minutes, and the adhesion to the glass before and after immersion was visually observed and evaluated in three stages.
  • the presence or absence of the vertical streaks of the dried coating and the resist material solidified from the head tip force was evaluated. Specifically, the color filter ink was applied onto a glass substrate (lOOmmX 100mm; 1.1mm thickness) using a die coat type coating device, and the resulting coated substrate was 70%. After drying at 20 ° C. for 20 minutes, a dry coating film was formed, and vertical stripes (vertical coating stripes in the coating direction) of the dried coating film obtained by the following method were evaluated in three stages by visual observation. In addition, the presence or absence of the resist material solidified from the head tip force separation on the dry coating film was evaluated in three stages by visual observation.
  • thermosetting inkjet ink the production of the thermosetting inkjet ink will be described.
  • the dispersant was placed in a sand mill and dispersed for 4 hours.
  • Melamine compound MX-43 alkoxyalkyl group-containing melamine compound; manufactured by Sanwa Chemical Co., Ltd.
  • Example 102 epoxy compound EPPN-201 (manufactured by Honka Pharmaceutical Co., Ltd.), and Solvent (CBAc) was mixed in a mixer, and pressure filtered with a membrane filter to produce an inkjet ink with a pigment concentration (PC) of 13%.
  • the green pigment, the basic synergist, the pigment carrier, and the dispersants of Examples 103 to 104 were uniformly stirred to obtain a mixture.
  • the solvent volatilized to form a sheet.
  • a solvent PGMAc: propylene glycol monomethyl ether acetate
  • PGMAc propylene glycol monomethyl ether acetate
  • Coated pigment and solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, for melamine compound MX-43 and Examples 103 to 104, benzoguanamine compound-power rack SB-401 (Alkoxyalkyl group-containing benzoguanamine compound manufactured by Sanwa Chemical Co., Ltd.) and a solvent (CBAc) were added and mixed. The coarse particles were filtered and an ink jet ink having a pigment concentration of 18% was obtained.
  • the yellow pigment, the basic synergist, the pigment carrier, and the dispersant for Example 105 were uniformly stirred to obtain a mixture. 60 When the mixture was put into a two-roll roll heated to ° C and kneaded for 10 minutes, the solvent was volatilized to form a sheet.
  • the solvent (PGMAc) was added and the two rolls were heated to 80 ° C. and kneaded. During the dispersion operation, the solvent was volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a pigment chip.
  • the coated pigment and solvent (CBAc) were mixed in a mixer, and further dispersed in a sand mill, and melamine compound MX-43 and solvent (CBAc) were further added and mixed.
  • the dust was coarse filtered and a thermosetting inkjet ink with a pigment concentration of 19% was obtained.
  • the blue pigment, the basic synergist, the pigment carrier, and the dispersant for Example 106 were uniformly stirred to obtain a mixture.
  • the solvent volatilized to form a sheet.
  • the solvent was added and the two rolls were heated to 80 ° C. and kneaded.
  • the solvent volatilized, and the heated kneaded product became an elastic solid.
  • the obtained solid was cooled and pulverized to obtain a pigment chip.
  • the coated pigment and solvent (CBAc) were mixed in a mixer, and further dispersed in a sand mill, and melamine compound MX-43 and solvent (CBAc) were further added and mixed. Waste and coarse substances were filtered and a thermosetting inkjet ink with a pigment concentration of 12% was obtained.
  • the blue pigment, basic synergist, pigment carrier, and dispersant were uniformly stirred at the blending ratio (weight ratio) shown in Table 23 to obtain a mixture.
  • the solvent was volatilized to form a sheet.
  • a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C and kneaded.
  • the solvent volatilized and the heated kneaded product became an elastic solid.
  • the obtained solid was cooled and pulverized to obtain a pigment chip.
  • Coated pigment and solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, melamine compound MX-43, acrylic monomer (Karaad TPA) 330; Nippon Gyaku Co., Ltd.) and solvent (CBAc) were added and mixed. The coarse particles were filtered and a thermosetting inkjet ink having a pigment concentration of 12% was obtained.
  • Example 109 Magenta pigment, basic synergist, pigment carrier, and solvent (BuCBAc).
  • the dispersant was placed in a sand mill and dispersed for 4 hours. Further, Melamine compound MX-43 and solvent (BuCBAc) Were mixed in a mixer and pressure filtered through a membrane filter to obtain a thermosetting inkjet ink having a pigment concentration (PC) of 15%.
  • PC pigment concentration
  • thermosetting inkjet ink The viscosity, fluidity, and storage stability of the thermosetting inkjet ink were evaluated by the following methods. Moreover, the thermosetting inkjet ink was ejected by an inkjet printer having a piezo head capable of changing the frequency of 4 to 10 KHz, and the ejection stability was evaluated by the following method. The results are shown in Table 23 and Table 24.
  • the dynamic viscoelasticity measuring apparatus the viscosity of the shear rate 10 (lZs) (r a: ? MPa and 'S) was measured, the viscosity of the shear rate 100 measured earlier (lZs) (r ?: mPa' s)
  • the ratio rj aZ r? was calculated and the fluidity was evaluated according to the following criteria.
  • the printing state was visually observed, and the ejection stability was evaluated according to the following criteria.
  • ⁇ Nozzle missing after intermittent 15 minutes is 5% or less.
  • ⁇ Nozzle drop after 5 minutes intermittently exceeds 5% and 10% or less.
  • Cyclohexanone was added to the dispersant of Example 1 so that the non-volatile content was 30% to prepare a resin solution ⁇ 2.
  • Methyl meta whale bowl 10.0 parts
  • Carbon black (Mitsubishi Chemical # 47, average primary particle size 23nm, specific surface area 132m 2 Z g, oil absorption cm 3 / 100g) 100 parts, basic synergist (a 14) 4 parts, oil solution B1 14 And 56 parts of rosin solution B2 were mixed and diluted with cyclohexanone to a final solid content of 20%. This was dispersed in a paint shaker for 2 hours using glass beads having a diameter of 0.8 mm to prepare a carbon black dispersion A. Dispersion A had a viscosity of 8.70 mPa's at 25 ° C.
  • carbon black was mixed with CABOT REG AL250R (average primary particle size 35 nm, specific surface area 50 m 2 Zg, oil absorption 46 cm 3 Zl00 g) 80 g and DEGUSSA Printex95 (average primary particle size 15 nm)
  • Carbon black dispersion B was prepared in the same manner as in the preparation of carbon black dispersion A, except that the specific surface area was 250 m 2 Zg and the oil absorption was 52 g / 100 g.
  • the obtained carbon black dispersion B had a viscosity of 6.27 mPa's at 25 ° C.
  • CABOT average primary particle size 7511111, specific surface area 25 m 2 Zg, oil absorption 72 cm 3 Zl00 g
  • Carbon black dispersion D was prepared in the same manner as in preparation of carbon black dispersion A, except that 70 parts of rosin solution B2 alone was used instead of mixing 6 parts.
  • the viscosity of Dispersion D obtained was 10.82 mPa ⁇ s at 25 ° C.
  • the mixture was stirred and mixed so that the mixture became uniform at the blending ratio (weight ratio) shown in Table 25, and then filtered through a 2 ⁇ m filter, and the photosensitive black inks of Examples 110 to 117 and Comparative Example 44 were used. Obtained.
  • the resulting photosensitive black ink was evaluated for sensitivity, stability, light-shielding property (OD value per unit film thickness), black matrix pattern shape, and adhesion to glass by the following methods. The results obtained are also shown in Table 25.
  • a photosensitive black ink is applied to a glass substrate (lOOmm X 100mm; 1. lm m thickness) by spin coating, and then dried at 70 ° C for 15 minutes to form a coating film with a dry film thickness of about 1 ⁇ m. Prepared and measured film thickness. Then, using an ultra-high pressure mercury lamp, various exposure amounts (mjZcm 2 ) of ultraviolet rays were exposed through a photomask. After developing with an aqueous sodium carbonate solution, the unexposed portion was removed by washing with ion exchanged water.
  • the film thickness of the exposed portion after development and washing with water was measured, and the minimum exposure amount (mjZcm 2 ) at which a film thickness of 95% or more with respect to the film thickness before development was obtained was taken as the sensitivity. Sensitivity was evaluated in the following two steps.
  • a 10-micrometer mask pattern was used for the photomask, and a striped black matrix pattern was formed.
  • the developing speed was measured by the following method. That is, photosensitive black ink is applied to a glass substrate (lOOmm X 100mm; 1.1 mm thickness) by spin coating, and then dried at 70 ° C for 15 minutes to form a coating film with a dry film thickness of about 1 ⁇ m. Prepared and measured the film thickness. This was spray-developed using an aqueous sodium carbonate solution, and the time for the photosensitive black ink to disappear was measured. The measurement time was divided by the measured film thickness, and the time per unit film thickness (second Zm) was taken as the development speed.
  • Comparative Example 44 the photosensitive black ink after storage for 7 days at 40 ° C. had a viscosity of more than lOOmPa's at 25 ° C. and further became a gel. For this reason, the coating process necessary for developing speed evaluation cannot be performed, and it is not suitable as the photosensitive black ink of the present invention. Therefore, in Comparative Example 44, the evaluation was “X J” without evaluating the developing speed after the photosensitive black ink was stored at 40 ° C. for 7 days.
  • a photosensitive black ink was applied to a glass substrate, and the film thickness was measured after heating at 230 ° C. for 1 hour without performing an exposure step.
  • the optical density (OD value) of the photosensitive black ink coated substrate thus obtained was measured with a Macbeth densitometer (GRE TAG D200-II), and the measured optical density (OD value) was divided by the measured film thickness. Then, the optical density (ODZ ⁇ m) per unit film thickness was determined.
  • the black matrix pattern shape was evaluated by the following method. In other words, in the same method as the “sensitivity” measurement in the previous section (a), a striped black matrix was formed by forming a striped black matrix pattern with an exposure dose of 70 miZcm 2. The pattern shape of the dust was observed with an optical microscope or an electron beam scanning microscope, and the cross-sectional shape of the linearity was observed. However, since the photosensitive black ink of Example 112 had low sensitivity, 3
  • the linearity was evaluated in the following three stages.
  • the cross-sectional shape was evaluated in the following two stages.
  • ⁇ When the cross-sectional shape is a forward taper (the bottom which is the surface in contact with the glass is wider than the top), when the force is vertical;
  • a photosensitive black ink was applied to a glass substrate and heated at 230 ° C. for 1 hour without performing an exposure step.
  • a high-performance epoxy rapid-curing adhesive (cured at room temperature for 1 hour) is attached to the photosensitive black ink coated surface of the resulting photosensitive black ink coated substrate, and a cross-cut adhesion test method according to JIS K5400 Thus, the glass adhesion of the coating film was evaluated.
  • To peel off attach a high-performance epoxy quick-curing adhesive (cured at room temperature for 1 hour) to the head of the M6 bolt, bond (self-weight) on the grid, heat at 90 ° C for 5 minutes, and then bolt by hand. I peeled it off. Since the bolts were smaller than the 1 mm x 1 mm x 100 grids, the initial adhesion was expressed by the ratio of the non-peeled area of the coating film to the bolt adhesion area.
  • the adhesion (%) is calculated by the following formula (5) for both initial adhesion and post-PCT adhesion:
  • Ad (%) [(Nr-Nt) / Nt] X 100 (5)
  • Ad adhesion
  • Nr is the number of grids on the bonding surface
  • Nt is the number of grids on the bolt bonding surface
  • Ethylenically unsaturated compound Dipentaerythritol hexaatalylate (DPHA)
  • Photoinitiator A Etanone, 1 [9-ethyl-6- (2 methylbenzoyl) -9H-force [Luvazole-3-yl] 1, 1- (O-acetyloxyme), Chinoku “Specialty” Chemicals “Irgacure OXE02”
  • Photoinitiator B 2, 2, Bis (o-black mouth) 1, 4, 5, 4, 5, Tetraphenol 1, 2, 2-biimidazole
  • Photopolymerization initiator C borate-based photopolymerization initiator represented by the formula (22)
  • Photopolymerization initiator D 2-Benzyl-2-dimethylamino-1 (4-morpholinophenol)
  • the dispersant of the present invention By using the dispersant of the present invention, a pigment dispersion excellent in dispersibility, fluidity and storage stability can be obtained at a low use amount. Therefore, it is possible to provide a color filter ink, a photosensitive black ink, an inkjet ink, and an inkjet ink for a color filter, which are excellent in stability, drying re-dissolution property, and in some cases, printing stability, using the dispersant of the present invention. it can. Furthermore, a high-quality color filter substrate having strong adhesion between the coating film and the substrate can be provided using the pigment dispersion of the present invention or the ink. As mentioned above, although this invention was demonstrated along the specific aspect, the deformation

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Abstract

Disclosed is a dispersing agent represented by the following general formula (1). Regarding A1-A4, two of them respectively represent a monovalent polymer moiety (P) and the other two respectively represent -C(=O)OH or -CH2C(=O)OH; one of them represents a monovalent polymer moiety (P) and the other three respectively represent -C(=O)OH or -CH2C(=O)OH; or one of them represents a monovalent polymer moiety (P), two of the other three respectively represent -C(=O)OH or -CH2C(=O)OH and the other one represents -C(=O)-Xa-Ra. X1 represents a tetravalent group represented by the following general formula (2), (3) or (4).

Description

明 細 書  Specification
分散剤、その製造方法、並びに該分散剤を含む顔料分散体及びインク 技術分野  Dispersant, method for producing the same, and pigment dispersion and ink containing the dispersant
[0001] 本発明は、分散性、流動性、及び保存安定性に優れた分散体を製造することので きる分散剤、その製造方法、該分散剤を含む顔料分散体、及び該分散剤を含む各 種インクに関する。該分散剤を用いたインクとしては、例えば、カラーフィルタ用インク 、感光性黒色インク、インクジェットインク及びカラーフィルタ用インクジェットインクを 挙げることができる。  [0001] The present invention includes a dispersant capable of producing a dispersion excellent in dispersibility, fluidity, and storage stability, a method for producing the same, a pigment dispersion containing the dispersant, and the dispersant. It relates to various inks. Examples of the ink using the dispersant include color filter ink, photosensitive black ink, inkjet ink, and color filter inkjet ink.
背景技術  Background art
[0002] 一般に、インク等を製造する場合、顔料を安定に高濃度で分散することが難しぐ 製造工程や製品そのものに対して種々の問題を引き起こすことが知られている。 例えば、微細な粒子からなる顔料を含む分散体は往々にして高粘度を示し、製品 の分散機力 の取り出しや輸送が困難となるば力りでなぐ分散性が悪い場合は保 存中にゲルィ匕を起こし、使用困難となることさえある。更に展色物の表面に関しては 光沢の低下、レべリング不良等の状態不良を生じる。また、異種の顔料を混合して使 用する場合、凝集による色別れや、沈降などの現象により展色物に色むらや著しい 着色力の低下が現れることがある。  In general, when manufacturing ink or the like, it is known that it is difficult to stably disperse the pigment at a high concentration, which causes various problems to the manufacturing process and the product itself. For example, dispersions containing pigments composed of fine particles often exhibit high viscosity, and if the dispersibility of the product is poor if the dispersibility of the product is difficult to remove or transport, It can cause habits and even make it difficult to use. In addition, on the surface of the color-exhibited object, poor gloss and poor leveling will occur. In addition, when different types of pigments are used in combination, color unevenness due to agglomeration, precipitation, and other phenomena may cause color unevenness and a marked decrease in coloring power.
[0003] そこで一般的には分散状態を良好に保っために分散剤が利用されている。分散剤 は顔料に吸着する部位と、分散媒である溶剤に親和性の高い部位との構造を持ち合 わせ、この 2つの部位のバランスで分散剤の性能は決まる。分散剤は被分散物であ る顔料の表面状態に合わせ種々のものが使用されている力 塩基性に偏った表面を 有する顔料には酸性の分散剤が使用されるのが一般的である。この場合、酸性官能 基が顔料の吸着部位となる。このように、酸性の官能基としてカルボン酸を有する分 散剤は、種々提案されている (例えば特許文献 1、特許文献 2、特許文献 3、特許文 献 4など)。  [0003] Therefore, in general, a dispersant is used to maintain a good dispersion state. The dispersant combines the structure of the part that adsorbs to the pigment and the part that has a high affinity for the solvent that is the dispersion medium, and the balance of these two parts determines the performance of the dispersant. Various dispersants are used according to the surface condition of the pigment to be dispersed. In general, an acidic dispersant is used for a pigment having a surface that is biased toward basicity. In this case, the acidic functional group becomes the pigment adsorption site. As described above, various dispersants having carboxylic acid as an acidic functional group have been proposed (for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and the like).
しかし、これらの公知の分散剤は、ある程度の分散能力は持ち合わせるが、低粘度 で安定な分散体をつくるには使用量を多くする必要があった。しかし、使用量を多く することは、インク、塗料等への展開を考える上で、塗膜の耐性が落ちる場合がある など好まし 、ものではなかった。 However, although these known dispersants have a certain degree of dispersion ability, it is necessary to increase the amount of use in order to produce a stable dispersion with low viscosity. But use a lot It was not preferable to consider the development of inks, paints, etc. because the resistance of the coating film might be reduced.
[0004] 一方で、種々のワニスに対して顔料を母体骨格として側鎖に酸性基や塩基性基を 置換基として有するシナジストを混合する方法も提案されて!ゝる (例えば、特許文献 5 、特許文献 6、及び特許文献 7等)。しかし、これだけでは必ずしも満足な効果が得ら れず、前記のような酸性基や塩基性基を置換基として有するシナジストに対して、更 にその対イオンを有する分散剤を使用することが提案されている（例えば、特許文献 8及び特許文献 9)。ここで、シナジスト（synergist)とは、顔料を形成する化合物の全 体又は部分の化学構造に似た構造を有し、顔料に対して π— π相互作用で強固に 吸着することのできるものをいう。シナジストは、シナジストそれ自体が含有するイオン 性官能基によって顔料の表面を酸性若しくは塩基性にして、対イオンを有する分散 剤若しくは顔料担体 (pigment  [0004] On the other hand, a method has been proposed in which various varnishes are mixed with a synergist having an acidic group or a basic group as a substituent in the side chain using a pigment as a base skeleton (for example, Patent Document 5, Patent Document 6, Patent Document 7, etc.). However, this alone does not necessarily provide a satisfactory effect, and it has been proposed to use a dispersant having a counter ion for synergists having acidic groups or basic groups as substituents as described above. (For example, Patent Document 8 and Patent Document 9). Here, a synergist is a compound that has a structure similar to the chemical structure of the whole or a part of the compound forming the pigment and can be strongly adsorbed to the pigment by π-π interaction. Say. Synergists use a ionic functional group contained in the synergist itself to make the surface of the pigment acidic or basic so that a dispersant or pigment carrier (pigment
carrier)の効果を大きくする機能を有する。  It has a function to increase the effect of carrier).
[0005] 特許文献 8には、塩基性基を置換基として有するシナジストと、リン酸基を有する分 散剤とを含む顔料組成物の例示がある。リン酸基を有する分散剤は塩基性基を置換 基として有するシナジストとの併用により、ある程度の顔料分散能力を有するが、保存 安定性が悪い場合や、リン酸基由来の欠点、例えば耐熱性の低さ、耐薬品性の低さ 、相溶性の悪さなどで問題を生じる場合があった。これは、スルホン酸基を有する分 散剤も同様である。このようなリン酸基や、スルホン酸基を有する分散剤は、応用する インクや塗料などへの展開性に乏しぐ一方、従来のカルボン酸を用いた分散剤と、 塩基性基を置換基として有するシナジストとの組合せでも、耐熱性、耐薬品性、相溶 性の点については問題がないが、粘度が高いこと、安定性が悪いこと、顔料微分散 化不良など、分散剤としての能力に劣る場合が多力つた。  [0005] Patent Document 8 exemplifies a pigment composition containing a synergist having a basic group as a substituent and a dispersant having a phosphate group. A dispersant having a phosphate group has a certain degree of pigment dispersion ability when used in combination with a synergist having a basic group as a substituent, but it has poor storage stability, or has defects due to phosphate groups such as heat resistance. There were cases where problems were caused by lowness, poor chemical resistance, and poor compatibility. The same applies to the dispersant having a sulfonic acid group. Dispersants having such phosphoric acid groups or sulfonic acid groups are poor in developability to applied inks and paints, while conventional dispersants using carboxylic acids and basic groups as substituents. Even if it is combined with the synergist it has, there is no problem in terms of heat resistance, chemical resistance, and compatibility, but it has a high ability as a dispersant such as high viscosity, poor stability, and poor pigment fine dispersion. When it was inferior, it was hard.
[0006] 特に、非常に微細な顔料を高い濃度で用いるカラーフィルタ用インク、ブラックマトリ ックス用感光性黒色インク、及びインクジェットインクなどに関しては顔料の分散能力 とともに、塗工性、吐出性、乾燥再溶解性、及び基材への密着性などが求められ、従 来の分散剤では全てを満足することが難しかった。  [0006] In particular, color filter inks, black matrix photosensitive black inks, and inkjet inks that use very fine pigments at high concentrations, as well as pigment dispersibility, coating properties, ejection properties, Solubility and adhesion to the substrate are required, and it has been difficult to satisfy all with conventional dispersants.
[0007] 特許文献 1 :特開昭 61— 61623号公報 特許文献 2：特開平 1― 141968号公報 [0007] Patent Document 1: Japanese Patent Laid-Open No. 61-61623 Patent Document 2: JP-A-1-141968
特許文献 3 :特開平 2— 219866号公報  Patent Document 3: JP-A-2-219866
特許文献 4：特開平 11—439842号公報  Patent Document 4: Japanese Patent Laid-Open No. 11-439842
特許文献 5：特開昭 63 - 305137号公報  Patent Document 5: Japanese Patent Laid-Open No. 63-305137
特許文献 6：特開平 1― 247468号公報  Patent Document 6: JP-A-1-247468
特許文献 7：特開平 3 - 26767号公報  Patent Document 7: JP-A-3-26767
特許文献 8：特開昭 63— 248864号公報  Patent Document 8: Japanese Patent Laid-Open No. 63-248864
特許文献 9：特開平 9 - 176511号公報  Patent Document 9: Japanese Patent Laid-Open No. 9-176511
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0008] 本発明は、低使用量で分散性、流動性、及び保存安定性に優れる分散体を製造 することのできる分散剤、及び該分散剤を含む顔料分散体の提供を目的とする。 また、該分散剤を用いて安定性及び乾燥再溶解性、場合により印字安定性に優れ たカラーフィルタ用インク、感光性黒色インク、インクジェットインク及びカラーフィルタ 用インクを提供する。 [0008] An object of the present invention is to provide a dispersant capable of producing a dispersion excellent in dispersibility, fluidity, and storage stability at a low use amount, and a pigment dispersion containing the dispersant. In addition, the present invention provides a color filter ink, a photosensitive black ink, an inkjet ink, and a color filter ink that are excellent in stability, dry re-dissolvability, and in some cases, printing stability using the dispersant.
更に、該顔料分散体又は該インクを用いて塗膜と基材との間で強固な密着性を有 する、高品質なカラーフィルタ基盤を提供することを目的とする。  It is another object of the present invention to provide a high-quality color filter substrate having strong adhesion between a coating film and a substrate using the pigment dispersion or the ink.
課題を解決するための手段  Means for solving the problem
[0009] 前記の課題は、本発明による下記一般式（1)で示される分散剤によって解決するこ とができる。すなわち、一般式（1)： [0009] The above-described problems can be solved by a dispersant represented by the following general formula (1) according to the present invention. That is, general formula (1):
[化 1]  [Chemical 1]
Al\ メ Al \ me
(1)  (1)
A2 ヽ A4 A 2ヽ A 4
一般式（1)中、 A〜A4は、 In the general formula (1), A to A 4 are
2つ力 相互に同じか若しくは異なる分子量 200〜5000の一価の重合体部分 (P)で あり、他の 2つが、相互に同じか若しくは異なる— C ( = 0) OH又は—CH C ( = 0) 0  Two forces are monovalent polymer parts (P) having the same or different molecular weights of 200 to 5000, and the other two are the same or different from each other — C (= 0) OH or —CH C (= 0) 0
2  2
Hである糸且合せであるか、 1つが分子量 200〜5000の一価の重合体部分（P)であり、他の 3つが、相互に同じ か若しくは異なる— C( = 0)OH又は— CH C( = 0)OHである組合せである力、又 Whether the thread is H One is a monovalent polymer part (P) having a molecular weight of 200 to 5000, and the other three are combinations that are the same or different from each other — C (= 0) OH or —CHC (= 0) OH. A force, also
2  2
は、 Is
1つが分子量 200〜5000の一価の重合体部分（P)であり、他の 2つが、相互に同じ か若しくは異なる— C( = 0)OH又は— CH C( = 0)OHであり、他のもう 1つが— C(  One is a monovalent polymer part (P) with a molecular weight of 200-5000, and the other two are the same or different from each other — C (= 0) OH or —CH C (= 0) OH, the other Another one is — C (
2  2
=0)— Xa— Ra (但し、 Xaは、— 0-、又は— N(Ra2)—であり、 Raは、炭素原子数 1 〜18のアルキル基、炭素原子数 2〜18のァルケ-ル基、炭素原子数 3〜18のシクロ アルキル基及び炭素原子数 6〜18のァリール基力 なる群力 選択される基であり、 Ra2は、水素原子又は炭素原子数 1〜18のアルキル基、炭素原子数 2〜18のァルケ -ル基、炭素原子数 3〜 18のシクロアルキル基及び炭素原子数 6〜 18のァリール基 力もなる群力も選択される基である）である組合せであって、 = 0) —X a — R a (where X a is —0—or —N (R a2 ) —, R a is an alkyl group having 1 to 18 carbon atoms, 2 to 18 alkenyl groups, cycloalkyl groups having 3 to 18 carbon atoms, and aryl group forces having 6 to 18 carbon atoms are selected groups, and R a2 is a hydrogen atom or 1 to 18 alkyl groups, alkenyl groups having 2 to 18 carbon atoms, cycloalkyl groups having 3 to 18 carbon atoms, and group forces that also include aryl groups having 6 to 18 carbon atoms). A combination of:
X1は、下記一般式（2)、一般式（3)又は一般式 (4)で示される四価の基である： 一般式 (2): X 1 is a tetravalent group represented by the following general formula (2), general formula (3), or general formula (4): General formula (2):
[化 2] [Chemical 2]
Figure imgf000007_0001
Figure imgf000007_0001
〔一般式（2)中、 kは 1又は 2を示す。〕；  [In general formula (2), k represents 1 or 2. ];
一般式 (3): General formula (3):
[化 3] [Chemical 3]
Figure imgf000007_0002
Figure imgf000007_0002
〔一般式 (3)中、 R2は、直接結合、 CH O c(=o) c(=o)oc[In general formula (3), R 2 is a direct bond, CH O c (= o) c (= o) oc
H CH OC( = 0)—、一 C( = 0)OCH(OC( = 0)CH )CH OC( soH CH OC (= 0) —, one C (= 0) OCH (OC (= 0) CH) CH OC (so
2 2 3 2 2 2 3 2
一、 C(CF ) —、式： [化 4] 1, C (CF) —, formula: [Chemical 4]
Figure imgf000008_0001
Figure imgf000008_0001
〔一般式 (4)で示される基 X1が有する合計炭素原子数は 4〜20であって 一般式 (4)中、 R3は、直接結合、— O—、又は炭素原子数 1〜8の二価又は三価の 炭化水素基であり、 [The total number of carbon atoms of the group X 1 represented by the general formula (4) is 4 to 20, and in the general formula (4), R 3 is a direct bond, —O—, or 1 to 8 carbon atoms. A divalent or trivalent hydrocarbon group of
R4、 R5、 R6、及び R9はそれぞれ独立に水素原子、若しくは炭素原子数 1〜8の炭化 水素基であるか、又は、 R4と R6と及び/又は R5と R9とで直接結合して不飽和二重結 合を形成してもよぐ R7及び R8はそれぞれ独立に水素原子、若しくは炭素原子数 1〜8の炭化水素基で あるか、又は R7と R8とで直接結合又は炭素原子数 1〜8の二価炭化水素基を形成し て環状基 X1を形成してもよぐあるいは R3と R7と又は R3と R8とで炭素原子数 1〜8の 三価炭化水素基を形成して環状基 X1を形成してもよぐあるいは R3と R7と R8とで炭素 原子数 1〜8の四価炭化水素基を形成して多環状基 X1を形成してもよい。〕 で示される分散剤によって解決することができる。 R 4 , R 5 , R 6 and R 9 are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, or R 4 and R 6 and / or R 5 and R 9. May be directly bonded to form an unsaturated double bond. R 7 and R 8 are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, or a direct bond between R 7 and R 8 or a divalent hydrocarbon group having 1 to 8 carbon atoms. To form a cyclic group X 1 or R 3 and R 7 or R 3 and R 8 to form a trivalent hydrocarbon group having 1 to 8 carbon atoms to form a cyclic group X 1 Alternatively, R 3 , R 7 and R 8 may form a tetravalent hydrocarbon group having 1 to 8 carbon atoms to form a polycyclic group X 1 . It can be solved by a dispersant represented by
[0010] 本発明による分散剤の好ま 、態様にぉ 、ては、一価の重合体部分 (P)が、ポリエ 一テル鎖基、ポリエステル鎖基、及びビニル共重合体鎖基からなる群から選択される [0010] In a preferred embodiment of the dispersant according to the present invention, the monovalent polymer portion (P) is selected from the group consisting of a polyester chain group, a polyester chain group, and a vinyl copolymer chain group. Selected
[0011] 本発明による分散剤の別の好ましい態様においては、一価の重合体部分 (P)が、 下記一般式（5)で示される一価のポリエーテル鎖基及び Z又はポリエステル鎖基か らなる重合体部分 (Pe)である： In another preferred embodiment of the dispersant according to the present invention, the monovalent polymer portion (P) is a monovalent polyether chain group represented by the following general formula (5) and a Z or polyester chain group: The polymer part (Pe) consists of:
一般式 (5) :  General formula (5):
[化 7]  [Chemical 7]
Y1— X"- (5)
Figure imgf000009_0001
Y 1 — X "-(5)
Figure imgf000009_0001
〔一般式 (5)中、  [In general formula (5),
Y1は、炭素原子数 1〜20、酸素原子数 0〜12、及び窒素原子数 0〜3を含む 1価の 末端基、 Y 1 is a monovalent terminal group containing 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms,
X2は、 O—、— S—、又は— N (Rb)—(但し、 Rbは水素原子又は炭素原子数 1〜1 8の直鎖状若しくは分岐状のアルキル基)であり、 X 2 is O—, —S—, or —N (R b ) — (where R b is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms),
X3は、 OC ( = 0) OC ( = 0) CH -N (Rc) C ( = 0) 又は一 N (RC) C X 3 is OC (= 0) OC (= 0) CH -N (R c ) C (= 0) or one N (R C ) C
2  2
( = 0) CH （但し、 Reは水素原子又は炭素原子数 1〜18の直鎖状若しくは分岐状 (= 0) CH (where R e is a hydrogen atom or a straight or branched chain having 1 to 18 carbon atoms)
2  2
のアルキル基）であり、  An alkyl group of
G1は、—尺11。—で示される繰り返し単位であり、 G 1— scale 11 . It is a repeating unit indicated by —
G2は、— C ( = O) R120 -で示される繰り返し単位であり、 G 2 is a repeating unit represented by —C (═O) R 12 0 —
G3は、 C ( = 0)R13C ( = 0)— OR140—で示される繰り返し単位であり、 R は炭素原子数 2〜8の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数 3 〜8のシクロアルキレン基であり、 G 3 is a repeating unit represented by C (= 0) R 13 C (= 0) —OR 14 0— R is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms,
R12は炭素原子数 1〜8の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数 4 〜8のシクロアルキレン基であり、 R 12 is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms,
R13は炭素原子数 2〜6の直鎖状若しくは分岐状のアルキレン基、炭素原子数 2〜6 の直鎖状若しくは分岐状のァルケ-レン基、炭素原子数 3〜20のシクロアルキレン 基、又は炭素原子数 6〜20ァリーレン基であり、 R 13 is a linear or branched alkylene group having 2 to 6 carbon atoms, a linear or branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, Or a C 6-20 arylene group,
R14は、—CH (R15)—CH (R16)—で示され、 R 14 is represented by —CH (R 15 ) —CH (R 16 ) —
R15と R16は、どちらか一方が水素原子であり、もう一方が炭素原子数 1〜20のアルキ ル基、炭素原子数 2〜20のァルケ-ル基、炭素原子数 6〜20のァリール基、アルキ ル部分の炭素原子数 1〜20のアルキルォキシメチレン基、アルケニル部分の炭素原 子数 2〜20のァルケ-ルォキシメチレン基、ァリール部分の炭素原子数 6〜20でァリ ール部分が場合によりハロゲン原子で置換されていることのあるァリールォキシメチレ ン基、 N—メチレン フタルイミド基であって、 One of R 15 and R 16 is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. Group, alkyloxymethylene group having 1 to 20 carbon atoms in the alkyl moiety, alkoxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety, and aryl moiety having 6 to 20 carbon atoms in the aryl moiety. Is an aryloxymethylene group, an N-methylene phthalimide group, optionally substituted with a halogen atom,
R17は、前記尺11、前記一 C ( = 0)R12—、又は一 C ( = 0)R13C ( = 0)—OR14—であ り、 R 17 is the scale 11 , the one C (= 0) R 12 —, or one C (= 0) R 13 C (= 0) — OR 14 —,
mlは 0〜100の整数であり、 m2は 0〜60の整数であり、 m3は 0〜30の整数であり、 但し ml +m2+m3は 1以上 100以下であり、  ml is an integer from 0 to 100, m2 is an integer from 0 to 60, m3 is an integer from 0 to 30, provided that ml + m2 + m3 is 1 or more and 100 or less,
一般式（5)における前記繰り返し単位 G G3の配置は、その順序を限定するもので はなぐ一般式 (5)で表される重合体部分 (P)において、基 X2と基 R17との間に繰り返 し単位 (^〜(^が任意の順序で含まれていることを示し、更に、それらの繰り返し単位The arrangement of the repeating unit GG 3 in the general formula (5) is not intended to limit the order thereof. In the polymer part (P) represented by the general formula (5), the group X 2 and the group R 17 Repeat units (^ ~ (^ indicate that they are included in any order, and
G'-G3^,それぞれランダム型又はブロック型のどちらでもよい。〕 G′-G 3 ^ may be either a random type or a block type. ]
[0012] 前記一般式（5)において、 Y1は炭素原子数 1〜18の直鎖状若しくは分岐状のアル キル基である力、 Y1はエチレン性不飽和二重結合を有することが好ましい。また、前 記一般式（5)において、 m2が 3〜 15の整数であることが好ましい。 In the general formula (5), Y 1 is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, and Y 1 preferably has an ethylenically unsaturated double bond. . In the general formula (5), m2 is preferably an integer of 3 to 15.
[0013] 本発明による更に別の好ましい態様においては、前記分散剤が、 25°Cでロウ状固 体であるか、ある 、は 25°Cで液状であることができる。 [0013] In still another preferred embodiment according to the present invention, the dispersant may be a waxy solid at 25 ° C or a liquid at 25 ° C.
[0014] 本発明による分散剤の更に別の好ましい態様においては、一価の重合体部分 (P) 力 下記一般式 (6)で示される一価のビニル共重合体 (Pv)である： 一般式 (6) [0014] In still another preferred embodiment of the dispersant according to the present invention, the monovalent polymer moiety (P) Force A monovalent vinyl copolymer (Pv) represented by the following general formula (6): General formula (6)
[化 8]  [Chemical 8]
Figure imgf000011_0001
Figure imgf000011_0001
〔一般式 (6)中、 Y2は、ビニル重合体の重合停止基であり、 [In general formula (6), Y 2 is a polymerization termination group of the vinyl polymer,
R21及び R22は、それぞれ独立に水素原子又はメチル基であり、 R 21 and R 22 are each independently a hydrogen atom or a methyl group,
R23及び R24は、いずれか一方が水素原子、他の一方が芳香族基、又は C ( = 0)One of R 23 and R 24 is a hydrogen atom, the other is an aromatic group, or C (= 0)
— X6— R25 (但し、 X6は、 O 若しくは— N (R26)—であり、 R25及び R26は水素原子 又は置換基として芳香族基を有して ヽてもよ ヽ炭素原子数] '18の直鎖状若しくは 分岐状のアルキル基であり、 — X 6 — R 25 (where X 6 is O or —N (R 26 ) —, and R 25 and R 26 may have a hydrogen atom or an aromatic group as a substituent. Number of atoms] '18 linear or branched alkyl group,
X4は、 O— R27 又は— S— R27 であり、 X 4 is O—R 27 or —S—R 27 ,
R は炭素原子数 1- ' 18の直鎖状若しくは分岐状のアルキレン基であり、  R is a linear or branched alkylene group having 1 to 18 carbon atoms,
X5は、 oc ( = o) OC ( = 0) CH N (Rd) C ( = 0)—、又は N (Ra) CX 5 is oc (= o) OC (= 0) CH N (R d ) C (= 0) —, or N (R a ) C
( = 0) CH （但し、 Rdは水素原子又は炭素原子数 1〜18の直鎖状若しくは分岐状 (= 0) CH (where R d is a hydrogen atom or a straight or branched chain having 1 to 18 carbon atoms)
2  2
のアルキル基）であり、  An alkyl group of
nは 2〜50である。〕  n is 2-50. ]
[0015] 本発明は、顔料と前記一般式 (1)で表される分散剤とを含む顔料分散体にも関す る。  [0015] The present invention also relates to a pigment dispersion containing a pigment and a dispersant represented by the general formula (1).
[0016] 本発明による好ま 、態様にぉ 、ては、前記顔料分散体がペースト状又はチップ 状である。  [0016] Preferably, according to the present invention, the pigment dispersion is in the form of a paste or a chip.
[0017] 本発明による顔料分散体の別の好ま 、態様にぉ 、ては、顔料と前記一般式（1) で表される分散剤とに加えて、塩基性基を有する顔料誘導体、塩基性基を有するァ ントラキノン誘導体、塩基性基を有するアタリドン誘導体、及び塩基性基を有するトリ ァジン誘導体力 なる群力 選ばれる少なくとも一種の塩基性シナジストを更に含む [0018] 本発明は、顔料と、前記一般式 (1)で表される分散剤と、顔料担体とを含むことを 特徴とするインクジェットインクにも関する。 In another preferred embodiment of the pigment dispersion according to the present invention, in addition to the pigment and the dispersant represented by the general formula (1), the pigment derivative having a basic group, the basic An anthraquinone derivative having a group, an attaridone derivative having a basic group, and a triazine derivative having a basic group [0018] The present invention also relates to an inkjet ink comprising a pigment, a dispersant represented by the general formula (1), and a pigment carrier.
[0019] 本発明は、顔料と、モノマーを含む顔料担体と、前記一般式（1)で表される分散剤 とを含有することを特徴とするカラーフィルタ用インクにも関する。 The present invention also relates to a color filter ink comprising a pigment, a pigment carrier containing a monomer, and a dispersant represented by the general formula (1).
[0020] 本発明は、顔料、熱硬化性化合物、有機溶剤、及び前記一般式 (1)で表される分 散剤を含むことを特徴とする熱硬化性インクジェットインクにも関する。 [0020] The present invention also relates to a thermosetting inkjet ink comprising a pigment, a thermosetting compound, an organic solvent, and a dispersing agent represented by the general formula (1).
[0021] 本発明は、顔料、熱硬化性化合物、有機溶剤、及び前記一般式 (1)で表される分 散剤を含むことを特徴とするカラーフィルタ用インクジェットインクにも関する。 [0021] The present invention also relates to an inkjet ink for a color filter, comprising a pigment, a thermosetting compound, an organic solvent, and a dispersant represented by the general formula (1).
[0022] 本発明は、カーボンブラックと、光重合開始剤と、塩基性基を有する顔料誘導体、 塩基性基を有するアントラキノン誘導体、塩基性基を有するアタリドン誘導体、及び 塩基性基を有するトリァジン誘導体力 なる群力 選ばれる少なくとも一種の塩基性 シナジストと、エチレン性不飽和単量体と、前記一般式（1)で表される分散剤とを含 むことを特徴とする、感光性黒色インクにも関する。 [0022] The present invention relates to carbon black, a photopolymerization initiator, a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an attaridone derivative having a basic group, and a triazine derivative having a basic group. A photosensitive black ink characterized by comprising at least one basic synergist selected, an ethylenically unsaturated monomer, and a dispersant represented by the general formula (1). Related.
[0023] 本発明は、片末端に水酸基を有する重合体 (POH)を製造するか、若しくは片末端 に 1級アミノ基を有する重合体 (PNH )を製造する第一の工程と、該重合体 (POH) [0023] The present invention provides a first step of producing a polymer having a hydroxyl group at one end (POH) or a polymer having a primary amino group at one end (PNH), and the polymer. (POH)
2  2
若しくは重合体 (PNH )とテトラカルボン酸二無水物とを反応させる第二の工程とを  Or a second step of reacting the polymer (PNH) with tetracarboxylic dianhydride.
2  2
含む、分散剤の製造方法にも関する。  The present invention also relates to a method for producing a dispersant.
[0024] 本発明による製造方法の好ましい態様においては、第一の工程で、モノアルコー ル、 1級モノアミン、 2級モノアミン、及びモノチオール力もなる群力も選択される化合 物を開始剤として、アルキレンオキサイド、ラタトン、ラクチド、及びジカルボン酸無水 物とエポキシドとの組合せ力 なる群力 選択される環状ィ匕合物を開環重合して片末 端に水酸基を有するポリエーテル及び Z又はポリエステル力もなる重合体 (PeOH) を製造する。 [0024] In a preferred embodiment of the production method according to the present invention, in the first step, a monoalcohol, a primary monoamine, a secondary monoamine, and a compound that also has a group power of monothiol power are selected as an initiator. Oxide, Rataton, Lactide, and the combined force of dicarboxylic anhydride and epoxide. Group force. The selected cyclic compound is ring-opening polymerized to form a polyether having hydroxyl group at one end and Z or polyester. Produce coalescence (PeOH).
[0025] 本発明による製造方法の別の好ま 、態様にぉ 、ては、第一の工程で、モノアルコ ール、 1級モノアミン、 2級モノアミン、及びモノチオール力もなる群力も選択されるィ匕 合物を開始剤として、アルキレンオキサイドを開環重合して片末端に水酸基を有する 重合体を得た後、該水酸基を還元アミノ化して片末端にアミノ基を有するポリエーテ ル (PeNH )を製造する。 [0025] Another preferred embodiment of the production method according to the present invention is that, in the first step, a monoalcohol, a primary monoamine, a secondary monoamine, and a group force that also has a monothiol force are selected. Using a compound as an initiator, ring-opening polymerization of alkylene oxide to obtain a polymer having a hydroxyl group at one end, a reductive amination of the hydroxyl group to a polyether having an amino group at one end (PeNH 3) is produced.
2  2
[0026] 本発明による製造方法の更に別の好ましい態様においては、第一の工程で、分子 内に水酸基とチオール基とを有する化合物を連鎖移動剤として使用して、エチレン 性不飽和単量体を重合して、片末端に水酸基を有するビュル共重合体 (PvOH)を 製造するか、若しくは分子内に 1級ァミノ基とチオール基とを有する化合物を連鎖移 動剤として使用して、エチレン性不飽和単量体を重合して、片末端に水酸基を有す るビニル共重合体 (PvNH )を製造する。  [0026] In still another preferred embodiment of the production method according to the present invention, an ethylenically unsaturated monomer is used in the first step using a compound having a hydroxyl group and a thiol group in the molecule as a chain transfer agent. To produce a butyl copolymer (PvOH) having a hydroxyl group at one end, or using a compound having a primary amino group and a thiol group in the molecule as a chain transfer agent. An unsaturated monomer is polymerized to produce a vinyl copolymer (PvNH) having a hydroxyl group at one end.
2  2
発明の効果  The invention's effect
[0027] 本発明の分散剤を用いることにより、低使用量で、分散性、流動性、及び保存安定 性に優れる顔料分散体を得ることができる。  [0027] By using the dispersant of the present invention, a pigment dispersion excellent in dispersibility, fluidity and storage stability can be obtained at a low use amount.
また、該分散剤を用いて安定性及び乾燥再溶解性、場合により印字安定性に優れ たカラーフィルタ用インク、感光性黒色インク、インクジェットインク及びカラーフィルタ 用インクジェットインクを提供することができる。  In addition, it is possible to provide a color filter ink, a photosensitive black ink, an inkjet ink, and an inkjet ink for a color filter, which are excellent in stability, dry re-dissolvability, and in some cases, excellent printing stability using the dispersant.
更に、該顔料分散体又は該インキを用いて塗膜と基材との間で強固な密着性を有 する、高品質なカラーフィルタ基盤を提供することができる。  Furthermore, a high-quality color filter substrate having strong adhesion between the coating film and the substrate can be provided using the pigment dispersion or the ink.
図面の簡単な説明  Brief Description of Drawings
[0028] [図 1]実施例 1で得られた本発明による分散剤の赤外線吸収スペクトルである。 FIG. 1 is an infrared absorption spectrum of the dispersant according to the present invention obtained in Example 1.
[図 2]実施例 1で得られた本発明による分散剤の13 C—NMRスペクトル (重クロ口ホル ム溶媒中）である。 FIG. 2 is a 13 C-NMR spectrum (in a heavy chloroform solvent) of the dispersant according to the present invention obtained in Example 1.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0029] 一般に、分散剤（dispersant; [0029] Generally, a dispersant (dispersant;
dispersing agent)は粒状物質に吸着する部位と、分散媒である溶剤に親和性の高い 部位との構造を持ち合わせて 、るため、この 2つの部位のバランスで分散剤の性能 が決まる。つまり、分散性を発現させるためには、分散剤の顔料 (pigment)に吸着す る性能と分散媒である溶剤への親和性がともに非常に重要である。前記一般式（1) で表される化合物は、カルボキシル基を 2個又は 3個を有する特定の構造を有して 、 る。この複数のカルボキシル基を含む特定の構造が顔料の吸着部位となり分散剤と して好適である。しかしながら、前記一般式（1)に似た化合物で、例えば 〜八4のう ちカルボキシル基が 1個のみ有する場合 (本発明の範囲外)では、高い分散性、流動 性、及び保存安定性を発現せず好ましくない。 Since the dispersing agent) has a structure of a part adsorbing on the particulate material and a part having a high affinity for the solvent as the dispersion medium, the performance of the dispersing agent is determined by the balance of these two parts. In other words, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important. The compound represented by the general formula (1) has a specific structure having two or three carboxyl groups. This specific structure containing a plurality of carboxyl groups serves as a pigment adsorption site and is suitable as a dispersant. However, in the compounds similar to the general formula (1), for example - eight 4 In other words, the case having only one carboxyl group (outside the scope of the present invention) is not preferable because high dispersibility, fluidity and storage stability are not exhibited.
[0030] 前記一般式（1)で表される本発明による分散剤は、構造式で表されている通り、四 価の基 X1と、その 4つの置換基としての基 A〜A4とを有する。四価の基 X1は、前記 一般式 (2)、一般式 (3)又は一般式 (4)で表される。 The dispersant according to the present invention represented by the general formula (1), as represented by the structural formula, includes a tetravalent group X 1 and groups A to A 4 as its four substituents. Have The tetravalent group X 1 is represented by the general formula (2), the general formula (3), or the general formula (4).
[0031] 前記一般式 (4)で示される四価の基 X1の好ましい態様としては、例えば、以下の基 を挙げることができる。 [0031] Preferable embodiments of the tetravalent group X 1 represented by the general formula (4) include the following groups.
[化 9]  [Chemical 9]
CH CHCH CH
CH2 H2C、 CH 2 H 2 C,
[化 10] [Chemical 10]
CH CHCH CH
C CH C CH
[化 11] [Chemical 11]
Figure imgf000014_0001
Figure imgf000014_0001
[化 12] H[Chemical 12] H
Figure imgf000015_0001
Figure imgf000015_0001
[化 13]  [Chemical 13]
Figure imgf000015_0002
Figure imgf000015_0002
[化 14]  [Chemical 14]
Figure imgf000015_0003
Figure imgf000015_0003
[化 15]  [Chemical 15]
Figure imgf000015_0004
Figure imgf000015_0004
〔一般式 (4)にお ヽて、 R3と R7と R8とで四価炭化水素基〔 > CH— CH— CHく〕を [In the general formula (4), R 3 , R 7 and R 8 represent a tetravalent hydrocarbon group [> CH—CH—CH]].
2 形成して多環状基 X1を形成した場合である。〕 2 is a case where the polycyclic group X 1 is formed. ]
[化 16] \ CH八 CH， [Chemical 16] \ CH 8 CH,
CH- -CH  CH- -CH
[化 17]
Figure imgf000016_0001
[Chemical 17]
Figure imgf000016_0001
〔一般式 (4)において、 R3が三価炭化水素基〔>CH— CH―〕であり、 R8が二価炭 [In the general formula (4), R 3 is a trivalent hydrocarbon group [> CH—CH—], and R 8 is a divalent carbon.
2  2
化水素基〔- CH = C (CH ) -〕である場合である。〕 This is the case when it is a hydrogen fluoride group [—CH═C (CH 3) —]. ]
[化 18] [Chemical 18]
Figure imgf000016_0002
Figure imgf000016_0002
〔一般式 (4)において、 R3と R7と R8とで四価炭化水素基〔>CH [In the general formula (4), R 3 , R 7 and R 8 represent a tetravalent hydrocarbon group [> CH
<〕を形成して多環状基 X1を形成した場合である。〕 This is a case where <> is formed to form a polycyclic group X 1 . ]
[化 19][Chemical 19]
Figure imgf000016_0003
〔一般式 (4)において、 R3と R7と R8とで四価炭化水素基〔>CH— CH = CH— CHく 〕 /を 成して多環状基 X1を形成した場合である。〕
Figure imgf000016_0003
[In the general formula (4), R 3 , R 7 and R 8 form a tetravalent hydrocarbon group [> CH—CH = CH—CH]] / to form a polycyclic group X 1 . ]
[化 20] H [Chemical 20] H
\  \
H C  H C
H  H
\  \
H C  H C
H H
Figure imgf000017_0001
Figure imgf000017_0001
[化 21] [Chemical 21]
CH CH CH CH CH CH
Z ヽ  Z ヽ
H2 H2 H 2 H 2
〔一般式 (4)において、 R3と R7と R8とで四価炭化水素基〔（― CH -) CH-CH (-[In the general formula (4), R 3 , R 7 and R 8 represent a tetravalent hydrocarbon group [(-CH-) CH-CH (-
2 2 twenty two
CH一）〕を形成して多環状基 X1を形成した場合である。〕 CH 1)] is formed to form a polycyclic group X 1 . ]
2 2  twenty two
前記一般式（1)中で、顔料分散体又はインクの低粘度化及び保存安定性の観点 から、四価の基 X1が芳香環を含むのが好ましぐ前記一般式 (2)又は一般式 (3)で 示される基 X1が好ましい。更に、前記一般式（2)においては、 kが 1の場合が好ましく 、前記一般式（3)においては、 R2が直接結合、— C ( = 0)— — C ( = 0) OCH CH In the general formula (1), it is preferable that the tetravalent group X 1 contains an aromatic ring from the viewpoint of low viscosity and storage stability of the pigment dispersion or ink. The group X 1 represented by the formula (3) is preferred. Further, in the general formula (2), it is preferable that k is 1. In the general formula (3), R 2 is a direct bond, —C (= 0) —— C (= 0) OCH CH
2 oc(=o) SO 又は式: 2 oc (= o) SO or formula:
[化 22]  [Chemical 22]
Figure imgf000017_0002
で表される基である場合が好ま U [0033] 前記一般式（1)で表される本発明による分散剤は、構造式で表されている通り、四 価の基 X1の 4つの置換基として基 A〜A4とを有し、基 A〜A4として、カルボキシル 基〔一 C ( = 0) OH又は—CH C ( = 0) OH〕の 2個又は 3個を有する。
Figure imgf000017_0002
Is preferred to be a group represented by U [0033] dispersing agent according to the present invention represented by the general formula (1) is, as represented by the structural formula, and a group A～A 4 as tetravalent four substituents of group X 1 As the groups A to A 4, there are two or three carboxyl groups [one C (= 0) OH or —CH 2 C (= 0) OH].
2  2
基 A〜A4の組合せとしては、 2つが分子量 200〜5000の一価の重合体部分（P) であり、他の 2つが— C ( = 0) OH又は— CH C ( = 0) OHの組合せであることが好ま As the combination of groups A to A 4 , two are monovalent polymer parts (P) having a molecular weight of 200 to 5000, and the other two are —C (= 0) OH or —CH C (= 0) OH Preferred to be a combination
2  2
しい。最も好ましくは、基 A〜A4は、 2つが分子量 200〜5000の一価の重合体部分 (P)であり、他の 2つが— C ( = 0) OHの組合せである場合である。 That's right. Most preferably, the groups A to A 4 are where two are monovalent polymer moieties (P) having a molecular weight of 200 to 5000 and the other two are combinations of —C (= 0) OH.
[0034] また、前記一般式（1)において、基 A〜A4として含まれている 1つ又は 2つの一価 の重合体部分（P) [polymer moiety (P)〕は、分子量力 00〜5000であり、この部位 が分散媒である溶剤への親和性部分となり、顔料の凝集を立体反発によって抑制す ることができる。前記一価の重合体部分 (P)の分子量は、更に好ましくは 500〜400 0であり、最も好ましくは 800〜3500である。ここで、重合体部分 (P)に分子量分布 が存在する場合、本発明で 、う重合体部分 (P)の分子量は GPCでのポリスチレン換 算数平均分子量を意味する。重合体部分 (P)の分子量が 200未満の場合、溶媒親 和部による立体反発の効果が少なくなるため、顔料の凝集を防ぐことが困難となり、 分散安定性が不十分となる。分散安定性の不十分な分散体は時間と共に顔料が沈 降したり、また分散体の粘度が上昇したりするため好ましくない。また、分子量が 500 0を超える場合、溶媒親和部の絶対量が増えてしまい、分散性の効果自体が低下し たり、分散体の粘度が高くなつたりするため好ましくない。 [0034] In the general formula (1), one or two monovalent polymer moieties (P) [polymer moiety (P)] contained as groups A to A 4 have a molecular weight of 00 to This part is an affinity part for the solvent as a dispersion medium, and aggregation of the pigment can be suppressed by steric repulsion. The molecular weight of the monovalent polymer part (P) is more preferably 500 to 400, and most preferably 800 to 3500. Here, when the molecular weight distribution exists in the polymer part (P), the molecular weight of the polymer part (P) in the present invention means the polystyrene conversion average molecular weight in GPC. When the molecular weight of the polymer part (P) is less than 200, the effect of steric repulsion by the solvent affinity part is reduced, making it difficult to prevent pigment aggregation and insufficient dispersion stability. Dispersions with insufficient dispersion stability are not preferred because the pigment will settle down over time and the viscosity of the dispersion will increase. On the other hand, when the molecular weight exceeds 5000, the absolute amount of the solvent affinity part increases, which is not preferable because the dispersibility effect itself is lowered and the viscosity of the dispersion is increased.
[0035] ここで、重合体部分 (P)はポリエーテル、ポリエステル、及びビュル共重合体力 な る群力 選択されることが好ましい。これらは、分子量を前記範囲に調整することが容 易であり、かつ、溶剤への親和性も良好である。更に好ましくは、重合体部分 (P)は 水酸基、 1級ァミノ基、 2級ァミノ基、及びチオール基を実質的に含まないものである  [0035] Here, it is preferable that the polymer portion (P) is selected from a group force that can be a polyether, polyester, and bulule copolymer. These are easy to adjust the molecular weight within the above range, and also have good affinity for the solvent. More preferably, the polymer part (P) is substantially free of a hydroxyl group, a primary amino group, a secondary amino group, and a thiol group.
[0036] これら一価の重合体部分 (P)の好ましい 1つの構造として、前記一般式（5)で示さ れるー価のポリエーテル及び Z又はポリエステル力 なる重合体部分 (Pe)を挙げる ことができる。前記一般式 (5)の中で、 Y1が炭素数 1〜18の直鎖状若しくは分岐状 のアルキル基であることが、顔料分散体及び各種インクの低粘度化及び保存安定性 の観点力も好ましい。 [0036] One preferable structure of these monovalent polymer portions (P) is a polyvalent polyether represented by the general formula (5) and a polymer portion (Pe) having Z or polyester strength. it can. In the general formula (5), it is preferable that Y 1 is a linear or branched alkyl group having 1 to 18 carbon atoms to reduce viscosity and storage stability of the pigment dispersion and various inks. The viewpoint power is also preferable.
[0037] また別の形態として、前記一般式（5)の中で Y1がエチレン性不飽和二重結合を有 することが好ましい。この場合、本発明の分散剤に活性エネルギー線硬化性を付与 することができる。 [0037] In another form, Y 1 in the general formula (5) preferably has an ethylenically unsaturated double bond. In this case, active energy ray curability can be imparted to the dispersant of the present invention.
[0038] また、前記一般式（5)の中で、 m2が 3〜 15の整数であることが、顔料分散体及び 各種インクの低粘度化及び保存安定性の観点カゝら好ましい。  [0038] In the general formula (5), m2 is preferably an integer of 3 to 15, from the viewpoint of low viscosity and storage stability of the pigment dispersion and various inks.
[0039] また、前記一般式（5)の中で、 m2 = 0、 m3 = 0の場合、 Y1は炭素数 1〜7の直鎖 状若しくは分岐状のアルキル基である力、若しくはエチレン性不飽和二重結合を有 することが好ましい。 [0039] In the general formula (5), when m2 = 0 and m3 = 0, Y 1 is a force that is a linear or branched alkyl group having 1 to 7 carbon atoms, or ethylenic It preferably has an unsaturated double bond.
[0040] 本発明の分散剤は、 25°Cでロウ状固体であることが、高濃度顔料分散体及び各種 インクの保存安定性の観点力 好ましい。また、 25°Cで液状のものは扱いやすさの 点で好ましい。ここで、ロウ状固体とは、常温では不透明の固体である力 加熱 (例え ば、 40°C〜100°C程度への加熱）により透明な液体に変化するものを意味する。  [0040] It is preferable that the dispersant of the present invention is a waxy solid at 25 ° C from the viewpoint of storage stability of the high-concentration pigment dispersion and various inks. In addition, liquid at 25 ° C is preferable in terms of ease of handling. Here, the waxy solid means a solid that changes to a transparent liquid by force heating (for example, heating to about 40 ° C to 100 ° C), which is an opaque solid at room temperature.
[0041] 前記の一価の重合体部分 (P)の好ましい別の 1つの構造として、前記一般式 (6)で 示される一価のビュル共重合体部分 (Pv)を挙げることもできる。  [0041] Another preferred structure of the monovalent polymer portion (P) is a monovalent bulle copolymer portion (Pv) represented by the general formula (6).
前記一般式 (6)で示される重合体部分 (Pv)の繰り返し単位の部分、すなわち、 { 〔C (R21) (R23) -C (R21) (R23)〕 }は、相互に同一もの力もなる（ホモポリマー）で あっても、異なるものからなる（コポリマー）でもよい。一般式 (6)で示される重合体部 分 (Pv)の好ましい形態は、 R21及び R22が、いずれか一方が水素原子、他の一方カ チル基であり、 R23及び R24は、いずれか一方が水素原子、他の一方が— C ( = 0) - O— (CH ) CH及び The part of the repeating unit of the polymer part (Pv) represented by the general formula (6), that is, {[C (R 21 ) (R 23 ) -C (R 21 ) (R 23 )]} is It can be the same force (homopolymer) or different (copolymer). In a preferred form of the polymer part (Pv) represented by the general formula (6), R 21 and R 22 are either one of a hydrogen atom and the other one of a cation group, and R 23 and R 24 are One is a hydrogen atom and the other is — C (= 0)-O— (CH) CH and
2 3 3 Z又は— C ( = 0)— O— CH— Ar (Arは芳香族基）であり、 X  2 3 3 Z or — C (= 0) —O—CH—Ar (Ar is an aromatic group), X
2  2
4が— S— CH CH—であり、 X5が— OC ( = 0)—又は— NHC ( = 0)—の場合であ 4 is — S— CH CH— and X 5 is — OC (= 0) — or — NHC (= 0) —.
2 2  twenty two
る。  The
[0042] 一般式 (6)中の Y2、すなわち、ビニル重合体の重合停止基は、通常のエチレン性 不飽和単量体の重合を通常の方法で実施した場合に導入される任意の公知重合停 止基であり、当業者には自明である。具体的には、例えば、重合開始剤由来の基、 連鎖移動剤由来の基、溶剤由来の基、又はエチレン性不飽和単量体由来の基であ ることができる。 これらのいずれの化学構造を有していても、本発明の分散剤は 、重合停止基 Y2の影響を受けずに、その効果を発揮することができる。 [0042] Y 2 in the general formula (6), that is, the polymerization termination group of the vinyl polymer is any known one introduced when the polymerization of a normal ethylenically unsaturated monomer is carried out by a normal method. It is a polymerization terminator and is obvious to those skilled in the art. Specifically, for example, it can be a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer. Whichever of these chemical structures is used, the dispersant of the present invention is The effect can be exhibited without being affected by the polymerization termination group Y 2 .
[0043] 次に、本発明による分散剤製造方法を説明する。本発明の製造方法によって、本 発明の前記分散剤を製造することができる。 [0043] Next, the method for producing a dispersant according to the present invention will be described. The dispersant of the present invention can be produced by the production method of the present invention.
[0044] 本発明の製造方法は、前記の通り、「片末端に水酸基を有する重合体 (ΡΟΗ)」を 製造するか、若しくは「片末端に 1級アミノ基を有する重合体 (ΡΝΗ )」を製造する第 [0044] As described above, the production method of the present invention produces "a polymer having a hydroxyl group at one end (ΡΟΗ)" or "a polymer having a primary amino group at one end (ΡΝΗ)". First to manufacture
2  2
一の工程と、該重合体 (ΡΟΗ)若しくは重合体 (ΡΝΗ )とテトラカルボン酸二無水物  One step, the polymer (ΡΟΗ) or polymer (ΡΝΗ) and tetracarboxylic dianhydride
2  2
とを反応させる第二の工程とを含む。ここで、「片末端に水酸基を有する重合体 (ΡΟ Η)」若しくは「片末端に 1級アミノ基を有する重合体 (ΡΝΗ )」からそれぞれ水酸基の  And a second step of reacting. Here, from each of “polymer having a hydroxyl group at one end (ΡΟ Η)” or “polymer having a primary amino group at one end (ΡΝΗ)”,
2  2
水素原子、又は 1級ァミノ基の水素原子を 1つ取り除いた部位が、前記一般式（1)で 表される分散剤において、 ^〜A4中の 1つ又は 2つである一価の重合体部分 (Ρ)を 構成し、テトラカルボン酸二無水物は、前記一般式（1)における X1を構成する。 In the dispersant represented by the general formula (1), the hydrogen atom or the site obtained by removing one hydrogen atom from the primary amino group is one or two of ^ to A 4 , It constitutes the coalescence part (Ρ), and the tetracarboxylic dianhydride constitutes X 1 in the general formula (1).
[0045] まず、「片末端に水酸基を有する重合体 (POH)」を製造する第一の工程につ!ヽて 説明する。本発明の製造方法において、第一の工程で得られる重合体 (POH)とし ては、モノアルコール、 1級モノアミン、 2級モノアミン、及びモノチオールの群から選 択される化合物を開始剤として、アルキレンオキサイド、ラタトン、ラクチド、ジカルボン 酸無水物、及びエポキシドの群力 選択される環状ィ匕合物を開環重合して得られる「 片末端に水酸基を有するポリエーテル及び Z又はポリエステル力 なる重合体 (Pe 0 」であるか、又は、分子内に水酸基とチオール基とを有する化合物を連鎖移動 剤として使用し、エチレン性不飽和単量体を重合して得られる「片末端に水酸基を有 するビニル共重合体 (PvOH)」であることがより好ま U、。  First, the first step for producing a “polymer having a hydroxyl group at one end (POH)” will be described. In the production method of the present invention, as the polymer (POH) obtained in the first step, a compound selected from the group of monoalcohol, primary monoamine, secondary monoamine, and monothiol is used as an initiator. Group power of alkylene oxide, rataton, lactide, dicarboxylic acid anhydride, and epoxide “Polyether having a hydroxyl group at one end and a polymer having Z or polyester strength” obtained by ring-opening polymerization of a selected cyclic compound (Pe 0 ”or“ a compound having a hydroxyl group at one end ”obtained by polymerizing an ethylenically unsaturated monomer using a compound having a hydroxyl group and a thiol group in the molecule as a chain transfer agent. U, more preferred to be a vinyl copolymer (PvOH).
[0046] 前記のポリエーテル及び Z又はポリエステルからなる重合体（PeOH)は、公知の 方法で製造することができ、モノアルコール、 1級モノアミン、 2級モノアミン、及びモノ チオールの群力 選択される化合物を開始剤として、アルキレンオキサイド、ラタトン 、ラクチド、ジカルボン酸無水物、及びエポキシドの群から選択される環状化合物を 開環重合することで容易に得ることができる。  [0046] The polymer (PeOH) comprising the above polyether and Z or polyester can be produced by a known method, and the group power of monoalcohol, primary monoamine, secondary monoamine, and monothiol is selected. It can be easily obtained by ring-opening polymerization of a cyclic compound selected from the group consisting of alkylene oxide, rataton, lactide, dicarboxylic anhydride, and epoxide using the compound as an initiator.
[0047] モノアルコールとしては、水酸基を一つ有する化合物であればいかなる化合物でも 構わない。例示すると、メタノール、エタノール、 1 プロパノール、イソプロパノール、 1ーブタノール、イソブタノール、 tert ブタノール、 1 ペンタノール、イソペンタノ一 ノレ、 1一へキサノーノレ、シクロへキサノーノレ、 4ーメチノレー 2 ペンタノ一ノレ、 1 ヘプ タノール、 1ーォクタノール、イソォクタノール、 2—ェチルへキサノール、 1ーノナノ一 ル、イソノナノール、 1ーデカノール、 1 ドデカノール、 1 ミリスチルアルコール、セ チルアルコール、 1ーステアリルアルコール、イソステアリルアルコール、 2—ォクチル デカノール、 2—オタチルドデカノール、 2—へキシルデカノール、ベへ-ルアルコー ル、ォレイルアルコールなどの脂肪族モノアルコール、ベンジルアルコール、フエノキ シエチルアルコール、パラクミルフエノキシエチルアルコールなどの芳香環含有モノ ァノレコーノレ、エチレングリコーノレモノメチノレエーテノレ、エチレングリコーノレモノェチノレ エーテノレ、エチレングリコーノレモノプロピノレエーテノレ、エチレングリコーノレモノブチノレ エーテノレ、エチレングリコーノレモノへキシノレエーテノレ、エチレングリコーノレモノー 2— ェチルへキシルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリ コーノレモノェチノレエーテノレ、プロピレングリコーノレモノプロピノレエーテノレ、プロピレン グリコーノレモノブチノレエーテノレ、プロピレングリコーノレモノへキシノレエーテノレ、プロピ レングリコールモノー 2—ェチルへキシルエーテル、ジエチレングリコールモノメチル エーテノレ、ジエチレングリコーノレモノェチノレエーテノレ、ジエチレングリコーノレモノプロ ピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコーノレモノ へキシノレエーテノレ、ジエチレングリコーノレモノー 2—ェチノレへキシノレエーテノレ、ジプ ロピレングリコーノレモノメチノレエーテノレ、ジプロピレングリコーノレモノェチノレエーテノレ、 ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコーノレモノブチノレエ 一テル、ジプロピレングリコーノレモノへキシノレエーテル、ジプロピレングリコーノレモノー 2—ェチルへキシルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレ ングリコールモノェチルエーテル、トリエチレングリコールモノプロピルエーテル、トリ エチレングリコーノレモノブチノレエーテノレ、トリエチレングリコーノレモノへキシノレエーテ ル、トリエチレングリコールモノー 2—ェチルへキシルエーテル、トリプロピレングリコー ルモノメチルエーテル、トリプロピレングリコールモノェチルエーテル、トリプロピレング リコールモノプロピルエーテル、トリプロピレングリコールモノブチルエーテル、トリプロ ピレングリコーノレモノへキシノレエーテル、トリプロピレングリコーノレモノー 2—ェチノレへ キシノレエーテル、テトラエチレングリコーノレモノメチノレエーテル、テトラエチレングリコ 一ノレモノェチノレエーテノレ、テトラエチレングリコーノレモノプロピノレエーテノレ、テトラェチ レングリコーノレモノブチノレエーテノレ、テトラエチレングリコーノレモノへキシノレエーテノレ[0047] The monoalcohol may be any compound as long as it is a compound having one hydroxyl group. For example, methanol, ethanol, 1 propanol, isopropanol, 1-butanol, isobutanol, tert butanol, 1 pentanol, isopentanol 1-hexanol, 1-hexanol, 1-hexanol, 1-hexanol, 1-octanol, 1-octanol, 2-ethyl hexanol, 1-nonanol, isononanol, 1-decanol, 1 dodecanol, 1 myristyl alcohol, Aliphatic monoalcohols such as cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyl decanol, 2-octyldodecanol, 2-hexyl decanol, behexyl alcohol, oleyl alcohol, benzyl alcohol , Phenoxy ethyl alcohol, paracumyl phenoxy ethyl alcohol, etc., aromatic ring-containing monophenolate, ethyleneglycololemonomethinoleatenore, ethyleneglycolenomonoethylenole ethenore, ethyle Glycolol Monopropenoleetenore, Ethylene Glycolol Monobutinole Ethenore, Ethylene Glycolanol Monohexenoleetenole, Ethylene Glyconore Mono-2-ethyl Hexyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycole Monomethenole Etherol, propylene glycol monomonopropenore etherenole, propylene glycol monomono butinore etherenole, propylene glycol monomonohexenore etherenole, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl etherenole, diethylene glycolenomono Ethenole etherol, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomono Hexinoreethenole, diethyleneglycolenomonomono 2-ethylenohexenoleetenore, dipropyleneglycololemonomethinoleatenore, dipropyleneglycolenomonotenenoreatenore, dipropyleneglycolmonopropylenoate, dipropyleneglycol Noremonobutynole ether, dipropylene glycol monohexenole ether, dipropylene glycol nolemono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether , Triethylene glycol monobutino oleate, triethylene glycol mono hexenoate, triethylene glycol mono 2-ethylhexyl ether, tripro Lenglycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexenole ether, tripropylene glycol monoremono-2-ethylenohexenoleether, Tetraethyleneglycolenomonomethylenoether, tetraethyleneglycol Monoremonoechinoleatenore, Tetraethyleneglycolenomonopropinoreateenore, Tetraethyleneglycolenomonobutinoreatenore, Tetraethyleneglycolenomonomonohexenoreatenore
、テトラエチレングリコーノレモノー 2—ェチノレへキシノレエーテル、テトラプロピレングリ コーノレモノメチノレエーテル、テトラプロピレングリコーノレモノェチノレエーテル、テトラプ ロピレングリコールモノプロピルエーテル、テトラプロピレングリコーノレモノブチノレエー テル、テトラプロピレングリコーノレモノへキシノレエーテル、テトラプロピレングリコーノレモ ノー 2—ェチルへキシルエーテル、テトラジエチレングリコールモノメチルエーテル等 のアルキレングリコールモノアルキルエーテルなどが挙げられる。 , Tetraethyleneglycol-mono-hexenorehexenole ether, tetrapropylene glycolenomonomethinoleether, tetrapropyleneglycolenomonoethylenoether, tetrapropyleneglycolmonopropylether, tetrapropyleneglycolenobutinoreether And alkylene glycol monoalkyl ethers such as tetrapropylene glycol monohexenole ether, tetrapropylene glycol mono-2-ethyl hexyl ether, tetradiethylene glycol monomethyl ether, and the like.
[0048] 更に、本発明の製造方法において、モノアルコールとしてエチレン性不飽和二重結 合を有するモノアルコールを使用してもよい。この場合、生成される分散剤に、活性 エネルギー線硬化性能を付与することができる。 [0048] Furthermore, in the production method of the present invention, a monoalcohol having an ethylenically unsaturated double bond may be used as the monoalcohol. In this case, active energy ray curing performance can be imparted to the produced dispersant.
前記のエチレン性不飽和二重結合を有する基の例としては、ビュル基、又は (メタ） アタリロイル基 (なお、「(メタ)アタリロイル基」と表記する場合には、アタリロイル基及 び Z又はメタクリロイル基を示すものとする。以下同じ。）が挙げられる力 好ましいの は (メタ)アタリロイル基である。これら二重結合を有する基の種類は、一種類でもよい し、複数種類でもよい。  Examples of the group having an ethylenically unsaturated double bond include a buyl group or a (meth) atallyloyl group (in the case of “(meth) atallyloyl group”, an attaloyl group and Z or methacryloyl). The following are the same.) The preferred is a (meth) atallyloyl group. The type of the group having a double bond may be one type or a plurality of types.
[0049] エチレン性不飽和二重結合を有するモノアルコールとしては、エチレン性不飽和二 重結合を 1個、 2個、及び 3個以上含む化合物を用いることができる。エチレン性不飽 和二重結合の数が 1個のモノアルコールとしては、例えば、 2—ヒドロキシェチル (メタ )アタリレート（なお、「(メタ)アタリレート」と表記する場合には、アタリレート及び Z又 はメタタリレートを示すものとする。以下同じ。）、 3—ヒドロキシプロピル (メタ)アタリレ  [0049] As the monoalcohol having an ethylenically unsaturated double bond, a compound containing one, two, or three or more ethylenically unsaturated double bonds can be used. Examples of monoalcohols having one ethylenically unsaturated double bond include 2-hydroxyethyl (meth) acrylate (in the case of “(meth) acrylate”, And Z or metatalylate, the same shall apply hereinafter), 3-hydroxypropyl (meth) ataryl
チル 2— (ヒドロキシメチル）アタリレート、 2—ヒドロキシ一 3—フエノキシプロピルアタリ レート、 1, 4—シクロへキサンジメタノールモノ（メタ）アタリレート、 2—ヒドロキシェチ ルビニルエーテル、ジエチレングリコールモノビニルエーテル、 4ーヒドロキシブチノレ ビュルエーテル等が挙げられる。エチレン性不飽和二重結合の数が 2個のモノアル コールとしては、例えば、 2—ヒドロキシ一 3—アタリロイロキシプロピルメタタリレート、 グリセリンジ (メタ)アタリレート等が挙げられる。エチレン性不飽和二重結合の数が 3 個のモノアルコールとしては、例えば、ペンタエリスリトールトリアタリレート、エチレン 性不飽和二重結合の数が 5個のモノアルコールとしては、例えば、ジペンタエリスリト 一ルペンタアタリレートが挙げられる。 Cyl 2- (hydroxymethyl) acrylate, 2-hydroxy-1-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4 -Hydroxybutynole butyl ether and the like. Examples of monoalcohols having two ethylenically unsaturated double bonds include 2-hydroxy-1-3-allyloyloxypropyl methacrylate. Examples include glycerin di (meth) acrylate. Examples of monoalcohols having 3 ethylenically unsaturated double bonds include pentaerythritol tritalylate, and monoalcohols having 5 ethylenically unsaturated double bonds include, for example, dipentaerythritol. One rupenta acrylate is mentioned.
[0050] このうち、ペンタエリスリトールトリアタリレート及びジペンタエリスリトールペンタアタリ レートは、それぞれ、ペンタエリスリトールテトラアタリレート及びジペンタエリスリトール へキサアタリレートの混合物として得られるので、生成される分散剤の分子量を制御 するためには HPLC (高速液体クロマトグラフィ）法や水酸基価の測定によりモノアル コール体の比率を決定する必要がある。モノアルコール体の数と G1〜G3を形成す る原料の比率により、分散剤の分子量が決まるからである。 [0050] Of these, pentaerythritol triatalylate and dipentaerythritol pentaatalylate can be obtained as a mixture of pentaerythritol tetraatalylate and dipentaerythritol hexaatalylate, respectively. In order to control it, it is necessary to determine the ratio of monoalcohols by HPLC (High Performance Liquid Chromatography) method or hydroxyl value measurement. This is because the molecular weight of the dispersant is determined by the number of monoalcohols and the ratio of the raw materials forming G1 to G3.
前記のモノアルコールのうち、エチレン性不飽和二重結合の数が 2個以上のものを 使用すると活性エネルギー線硬化型インクとしたときの硬化性に優れる分散剤となり 好ましい。  Among the above monoalcohols, those having two or more ethylenically unsaturated double bonds are preferred because they are excellent in curability when used as an active energy ray-curable ink.
[0051] 1級モノアミンとしては、例えば、メチルァミン、ェチルァミン、 1 プロピルァミン、ィ ソプロピルァミン、 1ーブチルァミン、イソブチルァミン、 tert—ブチルァミン、 1 ペン チルァミン、イソペンチルァミン、 3 ペンチルァミン、 1一へキシルァミン、シクロへキ シルァミン、 4ーメチルー 2 ペンチルァミン、 1一へプチルァミン、 1ーォクチルァミン 、イソォクチルァミン、 2—ェチルへキシルァミン、 1ーノニルァミン、イソノニルァミン、 1 デシノレアミン、 1ードデシノレアミン、 1 ミリスチノレアミン、セチノレアミン、 1ーステア リルァミン、イソステアリルァミン、 2—ォクチルデシルァミン、 2—オタチルドデシルアミ ン、 2—へキシルデシルァミン、ベへ-ルァミン、ォレイルァミンなどの脂肪族 1級モノ ァミン、 3—メトキシプロピルァミン、 3—エトキシプロピルァミン、 3—プロポキシプロピ ルァミン、 3 ブトキシプロピルァミン、 2 ェチルへキシロキシプロピルァミン、 3—ィ ソブチロキシプロピルァミン、 3—デシロキシプロピルァミン、 3—ミリスチロキシプロピ ルァミンなどのアルコキシアルキル 1級モノアミン、ベンジルァミンなどの芳香族 1級モ ノアミンが挙げられる。 2級モノアミンとしては、例えば、ジメチルァミン、ジェチルアミ ン、ジ 1 プロピルァミン、ジイソプロピルァミン、ジ 1ーブチルァミン、ジイソプチ ルァミン、ジ 1 ペンチルァミン、ジイソペンチルァミン、ジ 1一へキシルァミン、ジ シクロへキシルァミン、ジー（4ーメチルー 2 ペンチル）ァミン、ジ 1一へプチルアミ ン、ジ 1ーォクチルァミン、イソォクチルァミン、ジー（2—ェチルへキシル）ァミン、 ジ一 1—ノ-ルァミン、ジイソノ-ルァミン、ジ一 1—デシルァミン、ジ一 1—ドデシルァ ミン、ジ 1 ミリスチルァミン、ジセチルァミン、ジ 1ーステアリルァミン、ジイソステ ァリルァミン、ジー（2—ォクチルデシル）アミン、ジー（2—オタチルドデシル）ァミン、 ジー（2—へキシルデシル）ァミン、 N—メチルェチルァミン、 N—メチルブチルァミン、 N—メチルイソブチルァミン、 N—メチルプロピルアミン、 N—メチルへキシルァミン、 ピぺラジン、アルキル置換ピぺラジンなどの脂肪族 2級モノアミンが挙げられる。 [0051] Examples of primary monoamines include methylamine, ethylamine, 1-propylamine, isopropylamine, 1-butylamine, isobutylamine, tert-butylamine, 1-pentylamine, isopentylamine, 3-pentylamine, 1-hexylamine, cyclohexanamine, Hexylamine, 4-methyl-2-pentylamine, 1-heptylamine, 1-octylamine, isooctylamine, 2-ethylhexylamine, 1-nonylamine, isononylamine, 1 decinoreamine, 1 dodecinoreamine, 1 myristinoleamine, Aliphatic primary monoamines such as cetinoleamine, 1-stearylamine, isostearylamine, 2-octyldecylamine, 2-octyldodecylamine, 2-hexyldecylamine, beherylamine, oleylamine, 3—Me Toxipropylamine, 3-Ethoxypropylamine, 3-Propoxypropylamine, 3-Butoxypropylamine, 2-Ethylhexyloxypropylamine, 3-Debutoxypropylamine, 3-Desiloxypropylamine And alkoxyalkyl primary monoamines such as 3-myristoxypropylamine and aromatic primary monoamines such as benzylamine. Secondary monoamines include, for example, dimethylamine, jetylamine, di-1-propylamine, diisopropylamine, di-1-butylamine, diisopropylamine, di-1-pentylamine, diisopentylamine, di1-1hexylamine, di-1-amine. Cyclohexylamine, di (4-methyl-2-pentyl) amine, di1-1heptylamine, di-1-octylamine, isooctylamine, di (2-ethylhexyl) amine, di-1-noramine, diisono- Luamine, di-1-decylamine, di-1-dodecylamine, di-1 myristylamine, dicetylamine, di-1-stearylamine, diisosterylamine, di (2-octyldecyl) amine, di (2-octyldodecyl) amine , G- (2-hexyldecyl) amine, N-methylethylamine, N-methylbutylamine, N-methylisobutyramine, N-methylpropylamine, N-methylhexylamine, piperazine, alkyl substitution Aliphatic secondary monoamines such as piperazine.
[0052] モノチオールとしては、例えば、メチルチオール、ェチルチオール、 1 プロピルチ オール、イソプロピルチオール、 1ーブチルチオール、イソブチルチオール、 tert— ブチルチオール、 1 ペンチルチオール、イソペンチルチオール、 3 ペンチルチオ 一ノレ、 1一へキシノレチォーノレ、シクロへキシノレチォーノレ、 4ーメチノレー 2 ペンチノレ チォーノレ、 1一へプチノレチォーノレ、 1ーォクチノレチォーノレ、イソォクチノレチォーノレ、 2 ェチルへキシルチオール、 1ーノニルチオール、イソノニルチオール、 1 デシル チオール、 1ードデシルチオール、 1 ミリスチルチオール、セチルチオール、 1ース テアリルチオール、イソステアリルチオール、 2—ォクチルデシルチオール、 2—オタ チノレドデシノレチォーノレ、 2—へキシノレデシノレチォーノレ、ベへニノレチォ一ノレ、ォレイノレ チオールなどの脂肪族モノチオール、チォグリコール酸メチル、チォグリコール酸ォ クチル、チォグリコール酸メトキシブチルなどのチォグリコール酸アルキルエステル、 メルカプトプロピオン酸メチル、メルカプトプロピオン酸ォクチル、メルカプトプロピオン 酸メトキシブチル、メルカプトプロピオン酸トリデシルなどのメルカプトプロピオン酸ァ ルキルエステルが挙げられる。 [0052] Examples of monothiols include methyl thiol, ethyl thiol, 1 propyl thiol, isopropyl thiol, 1-butyl thiol, isobutyl thiol, tert-butyl thiol, 1 pentyl thiol, isopentyl thiol, 3 pentyl thio monoole, 1 monohexino Retinore, cyclohexenoreinore, 4-methinoreole 2 pentinore canonole, 1-heptinoretinoreol, 1-octinorenore, isooctinoretinore, 2-ethylhexylthiol 1-nonyl thiol, isononyl thiol, 1 decyl thiol, 1 dodecyl thiol, 1 myristyl thiol, cetyl thiol, 1 stearyl thiol, isostearyl thiol, 2-octyl decyl thiol, 2-ota chinoredo decino regio -Nore, 2—heki Aliphatic monothiols such as Noredecino Reino, Behenino Reino, Oleinole Thiol, methyl thioglycolate, octyl thioglycolate, alkyl thioglycolate such as methoxybutyl thioglycolate, methyl mercaptopropionate And mercaptopropionate alkyl esters such as octyl mercaptopropionate, methoxybutyl mercaptopropionate and tridecyl mercaptopropionate.
[0053] 本発明の製造方法で用いるモノアルコール、 1級モノアミン、 2級モノアミン、及びモ ノチオールの群力 選択される化合物は、前記例示に限定されることなぐ水酸基、 1 級ァミノ基、 2級ァミノ基、又はチオール基を一つ有する化合物であればいかなるィ匕 合物も用いることができ、また単独で用いても、 2種類以上を併用して用いても構わな い。このうち、好ましくはモノアルコールが用いられ、更には脂肪族モノアルコールを 用いる場合が好ましい。 ここで、モノアルコール、 1級モノアミン、 2級モノアミン、及びモノチオールの群から 選択される化合物のそれぞれ水酸基、 1級ァミノ基、 2級ァミノ基、又はチオール基以 外の部分が、一般式 (5)中の Y1を構成する。 [0053] Group power of monoalcohol, primary monoamine, secondary monoamine, and monothiol used in the production method of the present invention The compound selected is not limited to the above examples, but is a hydroxyl group, primary amino group, secondary Any compound can be used as long as it is a compound having one amino group or thiol group, and these compounds may be used alone or in combination of two or more. Of these, monoalcohol is preferably used, and aliphatic monoalcohol is more preferable. Here, a moiety other than a hydroxyl group, a primary amino group, a secondary amino group, or a thiol group of a compound selected from the group of monoalcohol, primary monoamine, secondary monoamine, and monothiol has a general formula ( 5) Construct Y 1 inside.
[0054] 前記例示したモノアルコール、 1級モノアミン、 2級モノアミン、及びモノチオールの 群から選択される化合物を開始剤として、アルキレンオキサイド、ラタトン、ラクチド、 及びジカルボン酸無水物とエポキシドとの組合せ力 なる群力 選択される環状ィ匕合 物を開環重合して、「片末端に水酸基を有するポリエーテル及び Z又はポリエステル 力 なる重合体 (PeOH)」を製造することができる。但し、ジカルボン酸無水物とェポ キシドとは必ず同時に用いられ、交互に重合させる。  [0054] Combining force of alkylene oxide, rataton, lactide, and dicarboxylic acid anhydride and epoxide using a compound selected from the group of monoalcohol, primary monoamine, secondary monoamine, and monothiol exemplified above as an initiator The ring-like compound selected from the group force can be subjected to ring-opening polymerization to produce a “polyether having a hydroxyl group at one end and a polymer having Z or polyester strength (PeOH)”. However, dicarboxylic anhydride and epoxide are always used at the same time and are polymerized alternately.
[0055] ここで、アルキレンオキサイド、ラタトン、ラクチド、及びジカルボン酸無水物とェポキ シドとの組合せ力 なる群力 選択される環状ィ匕合物の反応順序は、どのようなもの でもよぐ例えば、一段階目として前記開始剤にアルキレンオキサイドを重合した後、 二段階目にラタトンを重合し、更に三段階目にジカルボン酸無水物とエポキシドとを 交互に重合することもできる。この例では、二段階目にラタトンを重合するときの開始 剤は、一段階目に重合されている「片末端に水酸基を有するアルキレンオキサイド重 合体」となる。また、三段階目にジカルボン酸無水物とエポキシドとを交互に重合する ときの開始剤は、二段階目までに重合されて 、る「片末端に水酸基を有するアルキレ ンオキサイド重合体とラタトン重合体のブロック共重合体」となる。本発明の製造方法 では、以降に説明する重合体 (PeOH)を製造する場合の開始剤として、このような「 片末端に水酸基を有する重合体」も含む。また、同様に後述する重合体 (PeNH )、  [0055] Here, the combined force of alkylene oxide, rataton, lactide, and dicarboxylic anhydride and epoxide is a group force. The reaction sequence of the selected cyclic compound may be any, for example, It is also possible to polymerize alkylene oxide on the initiator as the first step, polymerize rataton in the second step, and alternately polymerize dicarboxylic acid anhydride and epoxide in the third step. In this example, the initiator for polymerizing ratatones in the second stage is an “alkylene oxide polymer having a hydroxyl group at one end” polymerized in the first stage. The initiator for alternately polymerizing the dicarboxylic acid anhydride and the epoxide in the third stage is polymerized by the second stage, so that “an alkylene oxide polymer having a hydroxyl group at one end and a rataton polymer”. Block copolymer ". The production method of the present invention includes such a “polymer having a hydroxyl group at one end” as an initiator for producing a polymer (PeOH) described below. Similarly, a polymer (PeNH 2) described later,
2 重合体 (PvOH)、及び重合体 (PvNH )も開始剤となりうる。  2 Polymer (PvOH) and polymer (PvNH 3) can also be initiators.
2  2
[0056] 前記の環状ィ匕合物の反応順序は、一段階目のアルキレンオキサイド、二段階目の ラタトン、三段階目のジカルボン酸無水物とエポキシドとの組合せに限定されず、ァ ルキレンオキサイド、ラタトン (及び z又はラタチド）、及びジカルボン酸無水物とェポ キシドとの組合せを任意の順序で、それぞれ 1な!、し複数回に亘つて実施することが できる。あるいは、アルキレンオキサイド、ラタトン (及び Z又はラタチド）、及びジカル ボン酸無水物とエポキシドとの組合せについて、全ての開環重合を実施せずに、そ れらの内から、任意の環状ィ匕合物を選択して、開環重合を実施することもできる。 [0057] アルキレンオキサイドとしては、例えば、エチレンオキサイド、プロピレンオキサイド、 1, 2—、 1, 4一、 2, 3—又は 1, 3—ブチレンオキサイド及びこれらの 2種以上の併用 系が用いられる。 2種以上のアルキレンオキサイドを併用するときの結合形式はラン ダム及び Z又はブロックの 、ずれでもよ 、。開始剤 1モルに対するアルキレンォキサ イドの重合モル数は、 0〜 100が好ましい。 [0056] The reaction sequence of the cyclic compound is not limited to the combination of the first-stage alkylene oxide, the second-stage ratatotone, and the third-stage dicarboxylic acid anhydride and epoxide, but the alkylene oxide. , Latatones (and z or lattides), and combinations of dicarboxylic anhydrides and epoxides can be performed in any order, each one and several times. Alternatively, for any combination of alkylene oxides, latatones (and Z or lattides), and dicarboxylic acid anhydrides and epoxides, without any ring-opening polymerization, any cyclic compound can be selected from them. A product can also be selected to carry out ring-opening polymerization. As the alkylene oxide, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-1,2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more alkylene oxides are used in combination, the bond type may be random or Z or block. The number of moles of alkylene oxide per mole of initiator is preferably 0-100.
[0058] アルキレンオキサイドの重合は、公知方法、例えばアルカリ触媒の存在下、 100〜  [0058] The polymerization of the alkylene oxide is carried out by a known method, for example, in the presence of an alkali catalyst.
200°Cの温度で、加圧状態で行うことができる。モノアルコールの水酸基にアルキレ ンオキサイドを重合して得られる重合体 (PeOH)は市販されており、例えば、 日本油 脂社製ュ-オックスシリーズ、 日本油脂社製ブレンマーシリーズなどがあり、本発明 の製造方法において、重合体 (PeOH)として使用することができる。市販品を具体的 に例示すると、ュ-オックス M— 400、 M— 550、 M— 2000、ブレンマー PE— 90、 P E— 200、 PE— 350、 AE— 90、 AE— 200、 AE— 400、 PP— 1000、 PP— 500、 P P— 800、 AP— 150、 AP— 400、 AP— 550、 AP— 800、 50PEP— 300、 70PEP — 350B、 AEPシリーズ、 55PET— 400、 30PET— 800、 55PET— 800、 AETシリ ーズ、 30PPT— 800、 50PPT— 800、 70PPT— 800、 APTシリーズ、 10PPB— 50 0B、 10APB— 500Bなどがある。これらの市販品を用いて第一の工程を省略しても よい。  It can be performed in a pressurized state at a temperature of 200 ° C. Polymers (PeOH) obtained by polymerizing alkylene oxide on the hydroxyl group of monoalcohol are commercially available, such as the Nippon Oil & Fats Ox series and the Nippon Oil & Fats Bremer series. In this production method, it can be used as a polymer (PeOH). Specific examples of commercial products are: Duox M-400, M-550, M-2000, Bremmer PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP — 1000, PP—500, PP—800, AP—150, AP—400, AP—550, AP—800, 50PEP—300, 70PEP—350B, AEP series, 55PET—400, 30PET—800, 55PET—800, There are AET series, 30PPT-800, 50PPT-800, 70PPT-800, APT series, 10PPB-500B, 10APB-500B. The first step may be omitted using these commercially available products.
[0059] ここで、アルキレンオキサイドのアルキレン基が、前記一般式（5)における繰り返し 単位 G1中の R11を構成する。 Here, the alkylene group of the alkylene oxide constitutes R 11 in the repeating unit G 1 in the general formula (5).
[0060] ラタトンとしては、具体的には 13—ブチ口ラタトン、 γ—ブチ口ラタトン、 γ—バレロラ タトン、 δ—バレロラタトン、 δ—力プロラタトン、 ε—力プロラタトン、アルキル置換さ れた ε—力プロラタトン、が挙げられ、このうち δ—バレロラタトン、 ε—力プロラタトン 、アルキル置換された ε—力プロラタトンを使用するのが開環重合性の点で好ましい 本発明の製造方法において、ラタトンは、前記例示に限定されることなく用いること ができ、また単独で用いても、 2種類以上を併用して用いても構わない。 2種類以上 を併用して用いることで結晶性が低下し室温で液状になる場合があるので、作業性 の点と、他の樹脂との相溶性の点で好まし 、。 ラクチドとしては、下記一般式 (7)で示されるものが好ましい (グリコリドを含む)。 一般式 (7) : [0060] Specific examples of the rataton include 13-buchi mouth rataton, γ-buchi mouth rataton, γ-valerolataton, δ-valerolataton, δ-force prolataton, ε-force prolataton, alkyl-substituted ε-force Of these, δ-valerolataton, ε-force prolatatone, and alkyl-substituted ε-force prolatatone are preferred from the viewpoint of ring-opening polymerization. It can be used without being limited to these, and may be used alone or in combination of two or more. Use in combination of two or more types is preferable in terms of workability and compatibility with other resins, as the crystallinity may decrease and become liquid at room temperature. As the lactide, those represented by the following general formula (7) are preferable (including glycolide). General formula (7):
[化 23]  [Chemical 23]
Figure imgf000027_0001
Figure imgf000027_0001
〔一般式 (7)中、 [In general formula (7),
R31及び R32は、それぞれ独立して、水素原子、飽和若しくは不飽和の直鎖若しくは 分枝の炭素原子数 1〜20のアルキル基であり、 R 31 and R 32 are each independently a hydrogen atom, a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms,
R33及び R34は、それぞれ独立して、水素原子、ハロゲン原子、並びに飽和若しくは不 飽和の直鎖若しくは分枝の炭素原子数 1〜9の低級アルキル基である。〕 R 33 and R 34 are each independently a hydrogen atom, a halogen atom, or a saturated or unsaturated linear or branched lower alkyl group having 1 to 9 carbon atoms. ]
[0062] 本発明の製造方法において、特に好適なラクチドはラクチド（3, 6 ジメチル一 1, 4 ジォキサン 2, 5 ジオン）及びグリコリド（1, 4 ジォキサン 2, 5 ジオン）で ある。前記ラタトン又はラクチドのうち、ラタトンが用いられるのが好ましい。  In the production method of the present invention, particularly preferred lactides are lactide (3,6 dimethyl-1,1,4 dioxane 2,5 dione) and glycolide (1,4 dioxane 2,5 dione). Of the ratatones or lactides, it is preferable to use ratatanes.
[0063] ラタトン及び Z又はラクチドの開環重合は、公知方法、例えば、脱水管、コンデンサ 一を接続した反応器に、開始剤、ラタトン及び Z又はラクチド、及び重合触媒を仕込 み、窒素気流下で行うことができる。低沸点のモノアルコールを用いる場合には、ォ 一トクレーブを用いて加圧下で反応させることができる。また、モノアルコールにェチ レン性不飽和二重結合を有するものを使用する場合は、重合禁止剤を添加し、乾燥 空気流下で反応を行うことが好ま 、。  [0063] Ring-opening polymerization of rataton and Z or lactide is a known method, for example, a reactor connected with a dehydrating tube and a condenser is charged with an initiator, rataton and Z or lactide, and a polymerization catalyst in a nitrogen stream. Can be done. When a low-boiling monoalcohol is used, the reaction can be carried out under pressure using an autoclave. In addition, when using a monoalcohol having an ethylenically unsaturated double bond, it is preferable to add a polymerization inhibitor and perform the reaction under a dry air flow.
[0064] 開始剤 1モルに対するラタトン及び Z又はラクチドの重合モル数は、 1〜60モルの 範囲が好ましぐ更には 2〜20モルが好ましぐ最も好ましくは 3〜 15モルである。  [0064] The number of moles of polymerization of ratatone and Z or lactide with respect to 1 mole of initiator is preferably in the range of 1 to 60 moles, more preferably 2 to 20 moles, and most preferably 3 to 15 moles.
[0065] 重合触媒としては、公知のものを制限なく使用することができるが、例えば、テトラメ チルアンモ -ゥムクロリド、テトラプチルアンモ -ゥムクロリド、テトラメチルアンモ -ゥム ブロミド、テトラプチルアンモ-ゥムブロミド、テトラメチルアンモ-ゥムョード、テトラブ チルアンモ-ゥムョード、ベンジルトリメチルアンモ -ゥムクロリド、ベンジルトリメチル アンモ-ゥムブロミド、ベンジルトリメチルアンモ -ゥムョードなどの四級アンモ-ゥム 塩、テトラメチルホスホ-ゥムクロリド、テトラブチルホスホ-ゥムクロリド、テトラメチルホ スホ-ゥムブ口ミド、テトラブチルホスホ-ゥムブロミド、テトラメチルホスホ-ゥムョード 、テトラブチルホスホ-ゥムョード、ベンジルトリメチルホスホ-ゥムクロリド、ベンジルト リメチルホスホ-ゥムブロミド、ベンジルトリメチルホスホ-ゥムョード、テトラフエ-ルホ スホ -ゥムクロリド、テトラフエ-ノレホスホ-ゥムブロミド、テトラフエ-ノレホスホ-ゥムョ ードなどの四級ホスホ-ゥム塩の他、トリフエ-ルフォスフィンなどのリン化合物、酢酸 カリウム、酢酸ナトリウム、安息香酸カリウム、安息香酸ナトリウムなどの有機カルボン 酸塩、ナトリウムアルコラート、カリウムアルコラートなどのアルカリ金属アルコラートの 他、三級アミン類、有機錫化合物、有機アルミニウム化合物、有機チタネート化合物[0065] As the polymerization catalyst, known catalysts can be used without limitation, and examples thereof include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium chloride bromide, tetraptylammonium chloride bromide, and tetramethyl ester. Ammo Mudd, Tetrab Quaternary ammonia salts such as tilammomud, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium bromide, tetramethylphosphomum chloride, tetrabutylphosphomum chloride, tetramethylphosphomum mouthmide, Tetrabutylphosphomubromide, tetramethylphosphomudomide, tetrabutylphosphomudomide, benzyltrimethylphosphomumuchloride, benzyltrimethylphosphomubromide, benzyltrimethylphosphomubromide, tetraphenylphosphomumuchloride, tetraphenolphosphomubromide, tetraphenol In addition to quaternary phosphonium salts such as norephospho-mu-mode, phosphorus compounds such as triphenylphosphine, potassium acetate, sodium acetate Arm, potassium benzoate, organic carboxylic acid salts such as sodium benzoate, sodium alcoholate, other alkali metal alcoholates such as potassium alcoholate, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds
、及び塩ィ匕亜鉛などの亜鉛ィ匕合物等が挙げられる。触媒の使用量は 0. lppm〜30 OOppm、好ましくは lppm〜1000ppmである。触媒量が 3000ppmを超えると、榭脂 の着色が激しくなる場合がある。逆に、触媒の使用量が 0. lppm未満ではラタトン及 び Z又はラクチドの開環重合速度が極めて遅くなるので好ましくない。 And zinc compounds such as salt and zinc. The amount of catalyst used is 0.1 ppm to 30 OO ppm, preferably 1 ppm to 1000 ppm. If the amount of catalyst exceeds 3000 ppm, the coloring of the resin may become severe. On the other hand, if the amount of the catalyst used is less than 0.1 ppm, the rate of ring-opening polymerization of rataton and Z or lactide becomes extremely slow, which is not preferable.
[0066] ラタトン及び Z又はラクチドの重合温度は 100°C〜220°C、好ましくは、 110°C〜2 10°Cの範囲で行う。反応温度が 100°C未満では反応速度がきわめて遅ぐ 220°Cを 超えるとラタトン及び Z又はラクチドの付加反応以外の副反応、例えばラタトン付加体 のラタトンモノマーへの解重合、環状のラタトンダイマーやトリマーの生成等が起こり やすい。 [0066] The polymerization temperature of Rataton and Z or lactide is 100 ° C to 220 ° C, preferably 110 ° C to 210 ° C. The reaction rate is very slow when the reaction temperature is less than 100 ° C. When the reaction temperature exceeds 220 ° C, side reactions other than the addition reaction of rataton and Z or lactide, for example, depolymerization of the rataton adduct to the rataton monomer, cyclic rataton Dimer and trimmer formation is likely to occur.
[0067] ここで、ラタトン又はラクチドのエステル基以外の部分力 前記一般式（5)における 繰り返し単位 G2中の R12を構成する。 Here, the partial force other than the ester group of latathone or lactide constitutes R 12 in the repeating unit G 2 in the general formula (5).
[0068] ジカルボン酸無水物としては、例えば、コハク酸無水物、マレイン酸無水物、フタル 酸無水物、ィタコン酸無水物、グルタル酸無水物、ドデセニルコハク酸無水物、及び クロレンデック酸無水物などが挙げられる。 [0068] Examples of the dicarboxylic acid anhydride include succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, itaconic acid anhydride, glutaric acid anhydride, dodecenyl succinic acid anhydride, and chlorendec acid anhydride. It is done.
[0069] エポキシドとしては、例えば、メチルダリシジルエーテル、ェチルダリシジルエーテ ル、ブチルダリシジルエーテル、 2—ェチルへキシルグリシジルエーテル、ドデシルグ リシジルエーテル、フエニルダリシジルエーテル、 p—ターシャリーブチルフエ二ルグリ シジルエーテル、 2, 4—ジブロモフエ-ルグリシジルエーテル、 3—メチルージブロモ フエ-ルグリシジルエーテル（但し、ブロモの置換位置は任意である）、ァリルグリシジ ルエーテル、エトキシフエ-ルグリシジルエーテル、グリシジル (メタ）アタリレート、グリ シジルフタルイミド、及びスチレンォキシドなどが挙げられる。 [0069] Examples of the epoxide include methyl daricidyl ether, ethyl daricidyl ether, butyl daricidyl ether, 2-ethyl hexyl glycidyl ether, dodecyl glycidyl ether, phenyl daricidyl ether, p-tertiary butyl. Feniruri Sidyl ether, 2, 4-dibromophenol glycidyl ether, 3-methyl-dibromophenol glycidyl ether (however, the substitution position of bromo is arbitrary), aryl glycidyl ether, ethoxyphenol glycidyl ether, glycidyl (meth) atari Examples include rate, glycidyl phthalimide, and styrene oxide.
[0070] 本発明の製造方法においては、ジカルボン酸無水物とエポキシドとは開始剤に対 して同時に使用され、交互に反応する。このとき、開始剤の水酸基、 1級ァミノ基、 2 級ァミノ基、又はチオール基に対して、まずジカルボン酸無水物の酸無水物基が反 応しカルボキシル基を生じ、次!、でこのカルボキシル基にエポキシドのエポキシ基が 反応して水酸基を生じる。更に、この水酸基にジカルボン酸無水物の酸無水物基が 反応するというように、以下、順次、前記と同様の反応を進行させることができる。開 始剤 1モルに対するジカルボン酸無水物及びエポキシドの重合モル数はそれぞれ 0 〜30モルが好ましい。また、ジカルボン酸無水物とエポキシドとの反応比率（[D]Z[ E])は、 [0070] In the production method of the present invention, the dicarboxylic acid anhydride and the epoxide are used simultaneously with the initiator and react alternately. At this time, the hydroxyl group, primary amino group, secondary amino group, or thiol group of the initiator first reacts with the acid anhydride group of the dicarboxylic acid anhydride to form a carboxyl group. The epoxide epoxy group reacts with the group to form a hydroxyl group. Further, the reaction similar to the above can be sequentially proceeded so that the acid anhydride group of the dicarboxylic acid anhydride reacts with this hydroxyl group. The number of moles of polymerization of dicarboxylic anhydride and epoxide with respect to 1 mole of initiator is preferably 0 to 30 moles. The reaction ratio of dicarboxylic anhydride and epoxide ([D] Z [E]) is
0. 8≤[D]/[E]≤1. 0  0. 8≤ [D] / [E] ≤1.0
( [D]はジカルボン酸無水物のモル数であり、 [E]はエポキシドのモル数である） であることが好ましい。 0. 8未満であるとエポキシドが残り好ましくなぐ 1. 0を超える と、「片末端に水酸基を有する所望のポリエーテル及び Z又はポリエステル力 なる 重合体 (PeOH)」が得られず、「片末端にカルボキシル基を有する重合体」ができる ので好ましくない。  ([D] is the number of moles of dicarboxylic anhydride, and [E] is the number of moles of epoxide). If the ratio is less than 8, the epoxide remains unpreferable. If the ratio exceeds 1.0, “a desired polyether having a hydroxyl group at one end and a polymer having Z or polyester strength (PeOH)” cannot be obtained. This is not preferable because a polymer having a carboxyl group can be formed on.
[0071] ジカルボン酸無水物とエポキシドとの交互重合は、好ましくは 50°Cから 180°C、より 好ましくは、 60°C〜150°Cの範囲で行う。反応温度が 50°C以下や 180°C以上では 反応速度がきわめて遅い。  [0071] The alternating polymerization of the dicarboxylic acid anhydride and the epoxide is preferably performed in the range of 50 ° C to 180 ° C, more preferably in the range of 60 ° C to 150 ° C. The reaction rate is very slow when the reaction temperature is below 50 ° C or above 180 ° C.
[0072] ここで、ジカルボン酸無水物のジカルボン酸無水物基以外の部分が前記一般式（5 )における繰り返し単位 G3中の R13を構成し、エポキシドの環状エーテルを形成する 酸素原子以外の部分が前記一般式 (5)における繰り返し単位 G3中の R14を構成する Here, the portion other than the dicarboxylic acid anhydride group of the dicarboxylic acid anhydride constitutes R 13 in the repeating unit G 3 in the general formula (5), and forms a cyclic ether of epoxide. The portion constitutes R 14 in the repeating unit G 3 in the general formula (5)
[0073] 本発明の製造方法において、「ポリエーテル及び Z又はポリエステル力 なる重合 体 (PeOH)」を製造するときにエチレン性不飽和二重結合を有するモノアルコール、 ジカルボン酸無水物、又はエポキシドを使用する場合は、重合禁止剤を使用すること が好ましい。重合禁止剤としては、例えば、ハイドロキノン、メチルノヽイドロキノン、ハイ ドロキノンモノメチルエーテル、 p べンゾキノン、 2, 4 ジメチルー 6—t—ブチルフ ェノール、フエノチアジン等が好ましぐこれらを単独若しくは併用で 0. 01%〜6%、 好ましくは、 0. 05%〜1. 0%の範囲で用いる。 [0073] In the production method of the present invention, a monoalcohol having an ethylenically unsaturated double bond when producing a "polyether and polymer having Z or polyester strength (PeOH)", When using a dicarboxylic acid anhydride or epoxide, it is preferable to use a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, methylneuroquinone, hydroquinone monomethyl ether, p-benzozoquinone, 2,4 dimethyl-6-t-butylphenol, phenothiazine, etc., which are preferred alone or in combination, are used. % To 6%, preferably in the range of 0.05% to 1.0%.
[0074] 次に、「片末端に水酸基を有するビニル共重合体 (PvOH)」の製造方法にっ 、て 説明する。ビニル共重合体 (PvOH)は、分子内に水酸基とチオール基とを有する化 合物を連鎖移動剤として使用し、エチレン性不飽和単量体を重合することで得ること ができる。 Next, a method for producing “a vinyl copolymer having a hydroxyl group at one end (PvOH)” will be described. The vinyl copolymer (PvOH) can be obtained by polymerizing an ethylenically unsaturated monomer using a compound having a hydroxyl group and a thiol group in the molecule as a chain transfer agent.
[0075] 分子内に水酸基とチオール基とを有する化合物としては、例えば、メルカプトメタノ ール、 2 メルカプトエタノール、 3 メルカプト 1 プロパノール、 1 メルカプト 2 ブタノール、 2 メルカプト 3 ブタノールなどが挙げられる。  [0075] Examples of the compound having a hydroxyl group and a thiol group in the molecule include mercapto methanol, 2 mercaptoethanol, 3 mercapto 1 propanol, 1 mercapto 2 butanol, 2 mercapto 3 butanol and the like.
[0076] 水酸基とチオール基とを有する化合物とエチレン性不飽和単量体とを混合してカロ 熱することでビニル共重合体 (PvOH)を得ることができる。好ましくは、エチレン性不 飽和単量体 100重量部に対して、 1〜30重量部の水酸基とチオール基とを有する化 合物を用い、塊状重合又は溶液重合を行う。反応温度は好ましくは 40〜150°C、より 好ましくは 50〜110°C、反応時間は好ましくは 3〜30時間、より好ましくは 5〜20時 間である。  [0076] A vinyl copolymer (PvOH) can be obtained by mixing a compound having a hydroxyl group and a thiol group and an ethylenically unsaturated monomer and heating the mixture. Preferably, bulk polymerization or solution polymerization is performed using a compound having 1 to 30 parts by weight of a hydroxyl group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer. The reaction temperature is preferably 40 to 150 ° C, more preferably 50 to 110 ° C, and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.
[0077] チオール基はエチレン性不飽和単量体を重合するためのラジカル発生基となるた め、該重合には必ずしも別の重合開始剤は必要ではないが、使用することもできる。 該重合開始剤を使用する場合は、エチレン性不飽和単量体 100重量部に対して、 0 . 001〜5重量部が好ましい。重合開始剤としては、例えば、ァゾ系化合物及び有機 過酸化物を用いることができる。ァゾ系化合物の例としては、 2, 2'—ァゾビスイソブ チロ-トリル、 2, 2， 一ァゾビス（2—メチルブチ口-トリル）、 1, 1， 一ァゾビス（シクロへ キサン 1—カルボ-トリル）、 2, 2，—ァゾビス（2, 4 ジメチルバレ口-トリル）、 2, 2， —ァゾビス（2, 4 ジメチル一 4—メトキシバレロ-トリル）、ジメチル 2, 2'—ァゾビス（ 2 メチルプロピオネート）、 4, 4，ーァゾビス（4 シァノバレリック酸）、 2, 2， 一ァゾビ ス（2—ヒドロキシメチルプロピオ-トリル）、 2, 2，—ァゾビス [2— (2—イミダゾリン— 2 ィル)プロパン]等が挙げられる。有機過酸ィ匕物の例としては、過酸化べンゾィル、 t ブチルパーべンゾエイト、タメンヒドロパーォキシド、ジイソプロピルパーォキシジカ ーボネート、ジー n プロピルパーォキシジカーボネート、ジ（2—エトキシェチル）パ ーォキシジカーボネート、 t ブチルパーォキシネオデカノエート、 t ブチルバーオ キシビバレート、 (3, 5, 5—トリメチルへキサノィル）パーォキシド、ジプロピオ-ルバ ーォキシド、ジァセチルバ一才キシド等が挙げられる。これらの重合開始剤は、単独 で、若しくは 2種類以上組み合わせて用いることができる。 [0077] Since the thiol group becomes a radical generating group for polymerizing the ethylenically unsaturated monomer, another polymerization initiator is not necessarily required for the polymerization, but it can also be used. When the polymerization initiator is used, 0.005 to 5 parts by weight is preferable with respect to 100 parts by weight of the ethylenically unsaturated monomer. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of azo compounds include 2, 2'-azobisisobutyro-tolyl, 2, 2, 1-azobis (2-methylbutyoxy-tolyl), 1, 1, 1-azobis (cyclohexane 1-carbo-tolyl) 2,2, -azobis (2,4 dimethylvale-tolyl), 2,2, -azobis (2,4 dimethyl-4-methoxyvalero-tolyl), dimethyl 2,2'-azobis (2 methylpropionate) ), 4, 4, azobis (4 cyanovaleric acid), 2, 2, 1 azobis (2-hydroxymethylpropio-tolyl), 2, 2, azobis [2- (2-imidazoline-2] Yl) propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, tamen hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) Examples thereof include peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl baroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropio-rubberoxide, dicetylba one-year-old oxide. These polymerization initiators can be used alone or in combination of two or more.
[0078] エチレン性不飽和単量体としては、アクリル単量体とアクリル単量体以外の単量体 とが挙げられる。アクリル単量体としては、例えば、メチル (メタ)アタリレート、ェチル（ メタ）アタリレート、 n—プロピル (メタ）アタリレート、イソプロピル (メタ）アタリレート、 n— ブチル (メタ）アタリレート、イソブチル (メタ）アタリレート、 t—ブチル (メタ）アタリレート 、 2—ェチルへキシル（メタ）アタリレート、シクロへキシル (メタ）アタリレート、ステアリル (メタ）アタリレート、ラウリル (メタ）アタリレート、テトラヒドロフルフリル (メタ）アタリレート 、イソボル-ル (メタ）アタリレート、フエ-ル (メタ）アタリレート、ベンジル (メタ）アタリレ レート、メトキシポリプロピレングリコール (メタ）アタリレート、エトキシポリエチレングリコ ール (メタ）アタリレート等の (メタ)アタリレート類、（メタ)アクリルアミド (なお、「(メタ)ァ クリルアミド」と表記した場合には、アクリルアミド及び Z又はメタクリルアミドを示すも のとする。以下同じ。）、 N, N ジメチル (メタ）アクリルアミド、 N, N ジェチル (メタ） [0078] Examples of the ethylenically unsaturated monomer include acrylic monomers and monomers other than acrylic monomers. Examples of acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) Atarylate, t-Butyl (Meth) Atalylate, 2-Ethylhexyl (Meth) Atalylate, Cyclohexyl (Meth) Atalylate, Stearyl (Meth) Atalylate, Lauryl (Meth) Atalylate, Tetrahydroful Furyl (meth) acrylate, isobornyl (meth) acrylate, phenol (meth) acrylate, benzyl (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) ate (Meth) acrylates such as rate, (Meth) acrylic (Note that “(meth) acrylamide” represents acrylamide and Z or methacrylamide. The same shall apply hereinafter.), N, N dimethyl (meth) acrylamide, N, N jetyl (meta )
、及びアタリロイルモルホリン等の（メタ）アクリルアミド類、 N, N ジメチルアミノエチ ル (メタ）アタリレート、 N, N ジェチルアミノエチル (メタ）アタリレート等のアミノ基含 有 (メタ)アタリレート類が挙げられる。 And (meth) acrylamides such as atalyloylmorpholine, N, N dimethylaminoethyl (meth) acrylate, N, N (meth) acrylates containing amino group such as dimethylaminoethyl (meth) acrylate Is mentioned.
[0079] また、前記アクリル単量体以外の単量体としては、例えば、スチレン、 α—メチルス チレン等のスチレン類、ェチルビニルエーテル、 η—プロピルビニルエーテル、イソプ 口ピルビニルエーテル、 η—ブチルビニルエーテル、イソブチルビニルエーテル等の ビュルエーテル類、酢酸ビニル、プロピオン酸ビュル等の脂肪酸ビュル類が挙げら れる。アクリル単量体以外の前記単量体を、前記アクリル単量体と併用することもでき る。 [0079] Examples of monomers other than the acrylic monomer include styrenes such as styrene and α-methylstyrene, ethyl vinyl ether, η -propyl vinyl ether, isopropyl vinyl ether, η -butyl vinyl ether, Examples include butyl ethers such as isobutyl vinyl ether, and fatty acid butyls such as vinyl acetate and propionate. The monomer other than the acrylic monomer can be used in combination with the acrylic monomer. The
[0080] また、カルボキシル基含有エチレン性不飽和単量体を単独で用いる力、もしくは前 記単量体と併用することもできる。カルボキシル基含有エチレン性不飽和単量体とし ては、例えば、アクリル酸、メタクリル酸、 ε—カプラロラタトン付加アクリル酸、 ε—力 プラロラタトン付加メタクリル酸、ィタコン酸、マレイン酸、フマル酸、クロトン酸などから 1種又は 2種以上を選択することができる。  [0080] The ability to use a carboxyl group-containing ethylenically unsaturated monomer alone or in combination with the above-described monomer can also be used. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-coupler loratatone-added acrylic acid, ε-force pralatatatone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. One type or two or more types can be selected.
[0081] 続いて、「片末端に 1級アミノ基を有する重合体 (ΡΝΗ )」を製造する第一の工程に  [0081] Subsequently, in the first step of producing a "polymer having a primary amino group at one end (ΡΝΗ)"
2  2
ついて説明する。本発明の製造方法において、重合体 (ΡΝΗ )は、モノアルコール  explain about. In the production method of the present invention, the polymer (ΡΝΗ) is a monoalcohol.
2  2
を開始剤としてアルキレンオキサイドを開環重合して、「片末端に水酸基を有するポリ エーテル」を生成し、その水酸基を還元アミノ化することによって得られる、「片末端に アミノ基を有するポリエーテル (PeNH；)」であるか、又は、分子内に 1級ァミノ基とチ  Is obtained by ring-opening polymerization of alkylene oxide using as an initiator to produce a “polyether having a hydroxyl group at one end”, and reductive amination of the hydroxyl group, “polyether having an amino group at one end ( PeNH;) "or a primary amino group and
2  2
オール基とを有する化合物若しくは分子内に 1級ァミノ基と水酸基とを有する化合物 を連鎖移動剤として使用し、エチレン性不飽和単量体を重合してなる、「片末端に 1 級アミノ基を有するビニル共重合体 (PvNH )」であることが好ま 、。  A compound having an all group or a compound having a primary amino group and a hydroxyl group in the molecule is used as a chain transfer agent, and an ethylenically unsaturated monomer is polymerized. It is preferable to have a vinyl copolymer (PvNH 2) ”.
2  2
[0082] 「片末端にアミノ基を有するポリエーテル (PeNH )」の製造にっ 、て説明する。  [0082] The production of "polyether having an amino group at one end (PeNH 3)" will be described.
2  2
「片末端にアミノ基を有するポリエーテル (PeNH )」の前駆体としての、「片末端に  As a precursor of "polyether with amino group at one end (PeNH)",
2  2
水酸基を有するポリエーテル (PeOH)」は、既に、前記重合体 (PeOH)の製造方法 に関して説明したとおりであり、この条件や原料についても前記の説明のとおりである 。この「片末端に水酸基を有するポリエーテル (PeOH)」を用い、例えば、アンモニア 、水素及び触媒の存在下に、圧力 5〜30MPa、 170〜250°Cの高温条件で、 0. 15 〜2時間反応することで得られる。このように、水酸基を還元アミノ化することで、「片 末端にアミノ基を有するポリエーテル (PeNH )」が得られる。還元アミノ化する触媒と  The “polyether having a hydroxyl group (PeOH)” has already been described with respect to the production method of the polymer (PeOH), and the conditions and raw materials are also as described above. Using this `` polyether having a hydroxyl group at one end (PeOH) '', for example, in the presence of ammonia, hydrogen and a catalyst, at a pressure of 5 to 30 MPa, at a high temperature of 170 to 250 ° C., 0.15 to 2 hours Obtained by reaction. Thus, by reductive amination of the hydroxyl group, “polyether having an amino group at one end (PeNH 2)” can be obtained. With reductive amination catalyst
2  2
しては、ラネーニッケル Zアルミニウム触媒が好まし 、。  Raney nickel Z aluminum catalyst is preferred.
[0083] 「片末端にアミノ基を有するポリエーテル (PeNH )」は、市販されており、例えば、 [0083] "Polyether having an amino group at one end (PeNH 3)" is commercially available, for example,
2  2
三井化学ファイン社又はハンツマンコーポレーションより、ジェファーミン、又はサーフ ォナミンの商品名で市販されている。本発明の製造方法においては、「片末端にアミ ノ基を有するポリエーテル (PeNH )」として、前記市販品を使用し、第一の工程を省  Commercially available from Mitsui Chemicals Fine or Huntsman Corporation under the trade name Jeffamine or Surfamine. In the production method of the present invention, the above-mentioned commercially available product is used as “polyether having an amino group at one end (PeNH)”, and the first step is omitted.
2  2
略することができる。市販品を具体的に例示すると、ジェファーミン XTJ— 475、 XTJ —436、 XTJ— 505、 XTJ— 506、 XTJ— 507、 M— 2070、サーフォナミン B— 60、 L— 100、 B— 200、 L— 207、 L— 300、 B— 30、 B— 100など力ある。 Can be omitted. Specific examples of commercial products include Jeffermin XTJ—475, XTJ —436, XTJ—505, XTJ—506, XTJ—507, M—2070, Surfonamin B—60, L—100, B—200, L—207, L—300, B—30, B—100, etc. .
[0084] 「片末端に 1級アミノ基を有するビュル共重合体 (PvNH )」の製造にっ 、て説明す [0084] The production of "bule copolymer having a primary amino group at one end (PvNH)" will be described.
2  2
る。「片末端に 1級アミノ基を有するビニル共重合体 (PvNH )」は、 1級ァミノ基とチォ  The “Vinyl copolymer having a primary amino group at one end (PvNH)” has a primary amino group and a thio group.
2  2
ール基とを有する化合物を連鎖移動剤として、 目的とする分子量にあわせてェチレ ン性不飽和単量体と重合開始剤とを混合して加熱することで得ることができる。好ま しくは、エチレン性不飽和単量体 100重量部に対して、 1〜30重量部の 1級ァミノ基 とチオール基とを有する化合物を用い、塊状重合又は溶液重合を行う。使用可能な エチレン性不飽和単量体、重合開始剤及び溶剤の種類、使用量、また重合条件は 前記片末端に水酸基を有する前記ビニル共重合体 (PvOH)で説明したものと同じ である。  It can be obtained by using a compound having an alkyl group as a chain transfer agent and mixing and heating an ethylenically unsaturated monomer and a polymerization initiator in accordance with the target molecular weight. Preferably, bulk polymerization or solution polymerization is performed using 1 to 30 parts by weight of a compound having a primary amino group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer. The types of ethylenically unsaturated monomers, polymerization initiators and solvents that can be used, the amounts used, and the polymerization conditions are the same as those described for the vinyl copolymer (PvOH) having a hydroxyl group at one end.
[0085] 分子内に 1級ァミノ基とチオール基とを有する化合物としては、例えば、 2 アミノエ タンチオール、 6 アミノー 2 メルカプトべンゾチアゾール、 3 アミノー 5 メルカプ ト— 1, 2, 4 トリァゾール、 4 ァミノ 3—メルカプト— 4H—1, 2, 4 トリアゾール 、 4 アミノー 3—メノレカプト 5—メチノレー 4H— 1, 2, 4 トリァゾーノレ、 4 アミノー 2 メルカプトピリミジン、 2 アミノー 5 メルカプト 1, 3, 4ーチアジアゾール、 3— アミノー 5 メルカプト 1, 2, 4 チアゾール、 5 アミノー 2 メルカプトべンゾイミダ ゾールなどが挙げられる。このうち、好ましくは 2—アミノエタンチオールを使用する場 合である。  [0085] Examples of the compound having a primary amino group and a thiol group in the molecule include 2 aminoethanethiol, 6 amino-2 mercaptobenzothiazole, 3 amino-5 mercapto-1, 2, 4 triazole, 4 amino 3— Mercapto—4H—1, 2, 4 Triazole, 4 Amino 3—Menolecapto 5—Methinole 4H— 1, 2, 4 Triazolene, 4 Amino-2 Mercaptopyrimidine, 2 Amino-5 Mercapto 1,3,4 Thiadiazole, 3—Amino-5 Mercapto 1, 2, 4 thiazole, 5 amino-2 mercaptobenzoimidazole and the like. Of these, 2-aminoethanethiol is preferably used.
[0086] 分子内に 1級ァミノ基と水酸基とを有する化合物としては、例えば、 2 アミノエタノ ール、 3—ァミノプロパノール、又は 4 アミノブタノールなどが挙げられる。  [0086] Examples of the compound having a primary amino group and a hydroxyl group in the molecule include 2-aminoethanol, 3-aminopropanol, and 4-aminobutanol.
前記のうち、分子内に 1級ァミノ基とチオール基とを有する化合物は、分子内に 1級 ァミノ基と水酸基とを有する化合物よりも好ま Uヽ。連鎖移動定数が高く重合体製造 後に未反応物として残りにく 、からである。  Of these, compounds having a primary amino group and a thiol group in the molecule are preferred over compounds having a primary amino group and a hydroxyl group in the molecule. This is because the chain transfer constant is so high that it remains as an unreacted product after the production of the polymer.
[0087] 本発明の製造方法では、場合によって、一般式（1)における A〜A4中の 1つ以内 の範囲で、 3つのカルボキシル基〔一 C ( = 0) OH又は— CHじ（=0) 011〕の内の1 [0087] In the production method of the present invention, in some cases, three carboxyl groups [one C (= 0) OH or —CH (= CH) within the range of one of A to A 4 in the general formula (1) (= 0) 011]
2  2
つに、重合体（POH)又は重合体（PNH )以外のモノアルコール由来の残基をエス  In addition, residues derived from monoalcohol other than polymer (POH) or polymer (PNH)
2  2
テル基の形で、あるいは、 1級モノアミン若しくは 2級モノアミン由来の残基をアミド基 の形で導入することができる。重合体 (POH)以外のモノアルコールとしては、前記し たモノアルコールのうち、水酸基とアルキル基とからなり、かつ、アルキル基部分の炭 素原子数が 1〜18であるモノアルコールが好ましい。重合体（PNH )以外の 1級モノ In the form of a tellurium group or a residue derived from a primary monoamine or a secondary monoamine as an amide group Can be introduced. As the monoalcohol other than the polymer (POH), among the above monoalcohols, monoalcohols having a hydroxyl group and an alkyl group and having 1 to 18 carbon atoms in the alkyl group portion are preferable. First-class products other than polymer (PNH)
2  2
ァミン、 2級モノアミンとしては、前記した 1級モノアミン、 2級モノアミンのうち、 1級又 は 2級のアミノ基とアルキル基とからなり、かつ、アルキル基部分の炭素原子数が 1〜 18であるモノアミンが好まし!/、。  As the amine and secondary monoamine, the primary monoamine and secondary monoamine are composed of a primary or secondary amino group and an alkyl group, and the alkyl group portion has 1 to 18 carbon atoms. A certain monoamine is preferred!
[0088] 本発明の製造方法において、重合体 (POH)又は重合体 (PNH )を製造する第一 [0088] In the production method of the present invention, a first method for producing a polymer (POH) or a polymer (PNH)
2  2
の工程では、無溶剤又は場合によって溶剤を使用することができる。溶剤としては、 例えば、酢酸ェチル、酢酸 n—ブチル、酢酸イソブチル、トルエン、キシレン、アセトン 、へキサン、メチルェチルケトン、シクロへキサノン等が用いられる力 特にこれらに限 定されるものではない。これらの重合溶媒は、 2種類以上混合して用いてもよい。使 用した溶媒は、反応終了後、蒸留等の操作により取り除くか、あるいはそのまま、分 散剤の製品の一部として使用することもできる。  In this step, no solvent or a solvent can be used in some cases. As the solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, and the like can be used. Two or more kinds of these polymerization solvents may be mixed and used. The used solvent can be removed by an operation such as distillation after the completion of the reaction, or can be used as it is as a part of the product of the dispersant.
[0089] 次に、「片末端に水酸基を有する重合体 (POH)」又は重合体 (PNH )とテトラカル [0089] Next, "polymer having a hydroxyl group at one end (POH)" or polymer (PNH) and tetracarbonyl
2  2
ボン酸二無水物とを反応させる第二の工程について説明する。  The second step of reacting with boronic acid dianhydride will be described.
本発明の製造方法においては、第一の工程で得られた「片末端に水酸基を有する 重合体 (POH)」の水酸基、又は「片末端に 1級アミノ基を有する重合体 (PNH )」の  In the production method of the present invention, the hydroxyl group of the “polymer having a hydroxyl group at one end (POH)” obtained in the first step, or the “polymer having a primary amino group at one end (PNH)”.
2 2
1級ァミノ基と、テトラカルボン酸二無水物の無水物基とを反応させる。この第二のェ 程によって、例えば、本発明による前記一般式（1)で表される分散剤を得ることがで きる。 A primary amino group is reacted with an anhydride group of tetracarboxylic dianhydride. By this second process, for example, the dispersant represented by the general formula (1) according to the present invention can be obtained.
[0090] テトラカルボン酸二無水物としては、例えば、脂肪族テトラカルボン酸二無水物、芳 香族テトラカルボン酸二無水物、又は多環式テトラカルボン酸二無水物が挙げられる  [0090] Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and polycyclic tetracarboxylic dianhydrides.
[0091] 脂肪族テトラカルボン酸二無水物としては、例えば、 1, 2, 3, 4 ブタンテトラカル ボン酸二無水物、 1, 2, 3, 4ーシクロブタンテトラカルボン酸二無水物、 1, 3 ジメチ ルー 1, 2, 3, 4 シクロブタンテトラカルボン酸二無水物、 1, 2, 3, 4 シクロペンタ ンテトラカルボン酸二無水物、 2, 3, 5 トリカルボキシシクロペンチル酢酸二無水物 、 2, 3, 5, 6—テトラカルボキシシクロへキサン二無水物、 2, 3, 5, 6—テトラカルボ キシノルボルナンニ無水物、 3, 5, 6 トリカルボキシノルボルナン 2 酢酸二無水 物、 2, 3, 4, 5—テトラヒドロフランテトラカルボン酸二無水物、 5—（2, 5 ジォキソ テトラヒドロフラル） 3—メチル 3 シクロへキセン一 1, 2 ジカルボン酸二無水物 、ビシクロ [2, 2, 2]—オタトー 7 ェン 2, 3, 5, 6—テトラカルボン酸二無水物など を挙げることができる。 [0091] Examples of the aliphatic tetracarboxylic dianhydride include 1, 2, 3, 4 butanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 3 Dimethyl 1, 2, 3, 4 Cyclobutane tetracarboxylic dianhydride, 1, 2, 3, 4 Cyclopentane tetracarboxylic dianhydride, 2, 3, 5 Tricarboxycyclopentyl acetic dianhydride, 2, 3 , 5, 6-Tetracarboxycyclohexane dianhydride, 2, 3, 5, 6-tetracarbo Xynorbornanani anhydride, 3, 5, 6 Tricarboxynorbornane 2 acetic acid dianhydride, 2, 3, 4, 5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5 dioxotetrahydrofural) 3-methyl 3 Examples include cyclohexene mono 1,2 dicarboxylic dianhydride and bicyclo [2,2,2] -otato 7-ene 2,3,5,6-tetracarboxylic dianhydride.
[0092] 芳香族テトラカルボン酸無水物としては、例えば、ピロメリット酸二無水物、エチレン グリコールジ無水トリメリット酸エステル、プロピレングリコールジ無水トリメリット酸エス テル、ブチレングリコールジ無水トリメリット酸エステル、 3, 3' , 4, 4，一べンゾフエノン テトラカルボン酸二無水物、 2, 2' , 3, 3，一べンゾフエノンテトラカルボン酸二無水物 、 3, 3，， 4, 4，—ビフエ-ルスルホンテ卜ラカルボン酸二無水物、 2, 2' , 3, 3，—ビフ ェ-ルスルホンテトラカルボン酸二無水物、 1, 4, 5, 8 ナフタレンテトラカルボン酸 二無水物、 2, 3, 6, 7 ナフタレンテトラカルボン酸二無水物、 3, 3' , 4, 4，ービフ ェ-ルエーテルテトラカルボン酸二無水物、 3, 3' , 4, 4'ージメチルジフエ-ルシラ ンテトラカルボン酸二無水物、 3, 3' , 4, 4'ーテトラフエ-ルシランテトラカルボン酸 二無水物、 1, 2, 3, 4 フランテトラカルボン酸二無水物、 4, 4' ビス（3, 4 ジカ ルボキシフエノキシ）ジフエ-ルスルフイド二無水物、 4, 4'—ビス（3, 4—ジカルボキ シフエノキシ）ジフエ-ルスルホン二無水物、 4, 4'—ビス（3, 4—ジカルボキシフエノ キシ）ジフエ-ルプロパン二無水物、 3, 3' , 4, 4，—パーフルォロイソプロピリデンジ フタル酸ニ無水物、 3, 3' , 4, 4'ービフエ-ルテトラカルボン酸二無水物、ビス（フタ ル酸）フエ-ルホスフィンオキサイド二無水物、 p フエ-レン一ビス（トリフエ-ルフタ ル酸）二無水物、 M フエ-レン ビス（トリフエ-ルフタル酸）二無水物、ビス（トリフ ェ-ルフタル酸）—4, 4，ージフエ-ルエーテル二無水物、ビス（トリフエ-ルフタル酸 )—4, 4，—ジフエ-ルメタン二無水物、 9, 9—ビス（3, 4—ジカルボキシフエ-ル）フ ルオレン二無水物、 9, 9一ビス [4一（3, 4—ジカルボキシフエノキシ）フエ-ル]フル オレン無水物などを挙げることができる。  [0092] Examples of the aromatic tetracarboxylic anhydride include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3, 3 ', 4, 4, monobenzophenone tetracarboxylic dianhydride, 2, 2', 3, 3, monobenzophenone tetracarboxylic dianhydride, 3, 3, 4, 4, 4, Biphenylsulfonetetracarboxylic dianhydride, 2, 2 ', 3, 3,-Biphenylsulfonetetracarboxylic dianhydride, 1, 4, 5, 8 Naphthalenetetracarboxylic dianhydride, 2, 3 , 6, 7 Naphthalene tetracarboxylic dianhydride, 3, 3 ', 4, 4, -biphenyl ether tetracarboxylic dianhydride, 3, 3', 4, 4'-dimethyldiphenylsilan tetracarboxylic dianhydride Object, 3, 3 ', 4, 4'-Tetraph Ethylsilanetetracarboxylic dianhydride, 1, 2, 3, 4 furantetracarboxylic dianhydride, 4, 4 'bis (3,4 dicarboxyphenoxy) diphenylsulfide dianhydride, 4 , 4'-bis (3,4-dicarboxiphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3, 3 ' , 4, -perfluoroisopropylidenediphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenolphosphine oxide dianhydride , P-phenolene bis (tri-phthalphthalic acid) dianhydride, M-phenylene bis (tri-phthalphthalic acid) dianhydride, bis (tri-phthalphthalic acid) -4,4, -diphenyl ether Anhydride, Bis (Triphenylphthalic acid) —4, 4, Diphenylmethane dianhydride, 9, 9— Bis (3,4-dicarboxyphenol) fluorene dianhydride, 9,9-bis [4 (3,4-dicarboxyphenoxy) phenol] fluorene anhydride, etc. it can.
[0093] 多環式テトラカルボン酸無水物としては、例えば、 3, 4ージカルボキシ 1, 2, 3, 4—テトラヒドロー 1—ナフタレンコハク酸二無水物、 3, 4 ジカルボキシ一 1, 2, 3, 4ーテトラヒドロ 6—メチルー 1 ナフタレンコハク酸二無水物などを挙げることがで きる。 [0093] Examples of polycyclic tetracarboxylic acid anhydrides include 3,4-dicarboxy 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4 dicarboxy 1,2,3, 4-tetrahydro 6-methyl-1 naphthalene succinic dianhydride wear.
[0094] 本発明の製造方法で使用されるテトラカルボン酸二無水物は、前記に例示したィ匕 合物に限らず、カルボン酸無水物基を二つ持てば、どのような構造をしていてもかま わない。これらは単独で用いても、併用してもカゝまわない。本発明に好ましく使用され るものは、顔料分散体又は各種インクの低粘度化の観点力 芳香族テトラカルボン 酸二無水物である。更には、ピロメリット酸二無水物、 3, 3' , 4, 4'一べンゾフエノン テトラカルボン酸二無水物、エチレングリコールジ無水トリメリット酸エステル、 3, 3' , 4, 4'一べンゾフエノンテトラカルボン酸二無水物、 9, 9 ビス（3, 4—ジカルボキシ フエ-ル）フルオレン二酸無水物、 3, 3' , 4, 4，ービフエ-ルスルホンテトラカルボン 酸二無水物、 2, 3, 6, 7 ナフタレンテトラカルボン酸二無水物、及び 3, 3' , 4, 4， ービフエ-ルテトラカルボン酸二無水物が好ましい。  [0094] The tetracarboxylic dianhydride used in the production method of the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. It doesn't matter. These can be used alone or in combination. What is preferably used in the present invention is an aromatic tetracarboxylic dianhydride, which has a viewpoint of reducing the viscosity of a pigment dispersion or various inks. Furthermore, pyromellitic dianhydride, 3, 3 ', 4, 4' monobenzophenone tetracarboxylic dianhydride, ethylene glycol ditrimellitic anhydride ester, 3, 3 ', 4, 4' monoben Zophenone tetracarboxylic dianhydride, 9, 9 bis (3,4-dicarboxyphenyl) fluorene dianhydride, 3, 3 ', 4, 4, biphenylsulfone tetracarboxylic dianhydride, 2,3,6,7 naphthalenetetracarboxylic dianhydride and 3,3 ', 4,4, -biphenyltetracarboxylic dianhydride are preferred.
[0095] 第二の工程での反応比率は、重合体 (POH)の水酸基又は重合体 (PNH )の 1級  [0095] The reaction ratio in the second step is the hydroxyl group of the polymer (POH) or the first grade of the polymer (PNH).
2 ァミノ基のモル数をく H〉、テトラカルボン酸二無水物のカルボン酸無水物基のモル数 を〈N〉としたとき、 0. 5< <H>/<NX 1. 2が好ましぐ更に好ましくは 0. 7< <H>/ <NX 1. 1、最も好ましくはく H〉Z〈N〉 = 1の場合である。〈H〉Z〈N〉< 1で反応させ る場合は、残存する酸無水物を必要量の水で加水分解して使用してもよい。  2 When <H> is the number of moles of the amino group and <N> is the number of moles of the carboxylic acid anhydride group of the tetracarboxylic dianhydride, 0.5 <<H> / <NX 1.2 is preferred. More preferably, 0.7 << H> / <NX1.1, and most preferably H> Z <N> = 1. When the reaction is performed with <H> Z <N> <1, the remaining acid anhydride may be hydrolyzed with a necessary amount of water and used.
[0096] 第二の工程には触媒を用いても力まわない。触媒としては、例えば、 3級アミン系化 合物が使用でき、例えばトリェチルァミン、トリエチレンジァミン、 N, N ジメチルベン ジルァミン、 N—メチルモルホリン、 1, 8 ジァザビシクロ— [5. 4. 0]— 7 ゥンデセ ン、 1, 5 ジァザビシクロー [4. 3. 0]—5 ノネン等が挙げられる。  [0096] In the second step, even if a catalyst is used, it does not work. As the catalyst, for example, a tertiary amine compound can be used, for example, triethylamine, triethylenediamine, N, N dimethylbenzilamine, N-methylmorpholine, 1,8 diazabicyclo- [5.4.0] — 7undesen, 1, 5 diazabicyclo [4. 3. 0] —5 Nonene.
[0097] 第二の工程は無溶剤で行ってもよいし、適当な脱水有機溶媒を使用してもよい。反 応に使用した溶媒は、反応終了後、蒸留等の操作により取り除くか、あるいはそのま ま分散剤の製品の一部として使用することもできる。  [0097] The second step may be performed without a solvent, or an appropriate dehydrated organic solvent may be used. The solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as part of the product of the dispersant as it is.
[0098] 第二の工程の反応温度は、「片末端に水酸基を有する重合体 (POH)」を使用する 場合は好ましくは 80°C〜180°C、より好ましくは 90°C〜160°Cの範囲で行う。反応温 度が 80°C未満では反応速度が遅ぐ 180°Cを超えると反応して開環した酸無水物が 、再度環状無水物を生成し、反応が終了しに《なる場合がある。また、「片末端に 1 級アミノ基を有する重合体 (PNH )」を使用する場合は、好ましくは 0〜150°C、より 好ましくは 10°C〜100°Cの範囲で行う。 0°C未満では反応が進まない場合があり、 1[0098] The reaction temperature in the second step is preferably 80 ° C to 180 ° C, more preferably 90 ° C to 160 ° C when a "polymer having a hydroxyl group at one end (POH)" is used. Perform in the range. When the reaction temperature is less than 80 ° C, the reaction rate is slow. When the reaction temperature exceeds 180 ° C, the acid anhydride that has reacted and opened the ring forms a cyclic anhydride again, and the reaction may be terminated. In addition, when using a “polymer having a primary amino group at one end (PNH)”, it is preferably 0 to 150 ° C. Preferably, it is performed in the range of 10 ° C to 100 ° C. The reaction may not proceed below 0 ° C. 1
50°Cを超えるとイミド化する場合があり好ましくない。 If it exceeds 50 ° C, imidization may occur, which is not preferable.
[0099] ここで、テトラカルボン酸二無水物の 2つのジカルボン酸無水物基を除いた部分が[0099] Here, the portion of tetracarboxylic dianhydride excluding two dicarboxylic anhydride groups is
、一般式（1)の X1を構成する。 And X 1 of the general formula (1).
[0100] 本発明の分散剤によって、例えば、顔料を良好に分散することができる。本発明の 分散剤によって分散できる顔料は、インク等に使用される種々のものが挙げられる。 有機顔料としては、溶性ァゾ顔料、不溶性ァゾ顔料、フタロシアニン顔料、キナタリド ン顔料、イソインドリノン顔料、イソインドリン顔料、ペリレン顔料、ペリノン顔料、ジォキ サジン顔料、アントラキノン顔料、ジアンスラキノ-ル顔料、アンスラピリミジン顔料、ァ ンサンスロン顔料、インダンスロン顔料、フラノくンスロン顔料、ピランスロン顔料、ジケト ピロロピロール顔料等があり、更に具体的な例をカラーインデックスのジェネリックネ ームで示すと、ビグメントブラック 7、ピグメントブノレ一 15, 15 : 1, 15 : 3, 15 :4, 15 : 6 , 60、ビグメントグリーン 7, 36、ビグメントレッド 9, 48, 49, 52, 53, 57, 97, 122, 144, 146, 149, 166, 168, 177, 178, 179, 185, 206, 207, 209, 220, 221 , 238, 242, 254, 255、ピグメントノ ィォレット 19, 23, 29, 30, 37, 40, 50、ビグ メントイエロー 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 11 7, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 1 68, 180, 185、ビグメントオレンジ 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71 , 74等が挙げられる。 [0100] With the dispersant of the present invention, for example, a pigment can be favorably dispersed. Examples of the pigment that can be dispersed by the dispersant of the present invention include various pigments used in inks and the like. Organic pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinatalidone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinol pigments, anthraquinone pigments. There are pyrimidine pigments, ancestoron pigments, indanthrone pigments, furanosanthrone pigments, pylanthrone pigments, diketopyrrolopyrrole pigments, and more specific examples are shown in Pigment Black 7, Pigment Benore 15, 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 144, 146, 149, 166, 168, 177, 178, 179, 185, 206, 207, 209, 220, 221, 238, 242, 254, 255, Pigment noorette 19, 23, 29, 30, 37, 40 , 50, pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 11 7, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 1 68, 180, 185, pigment orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71, 74 and the like.
[0101] また、本発明の分散剤は、二酸化チタン、酸化鉄、五酸ィ匕アンチモン、酸化亜鉛、 シリカなどの金属酸ィ匕物、硫ィ匕カドミウム、炭酸カルシウム、炭酸バリウム、硫酸バリゥ ム、クレー、タルク、黄鉛、カーボンブラックなどの無機顔料の分散にも使用すること ができる。  [0101] Further, the dispersant of the present invention is composed of metal oxides such as titanium dioxide, iron oxide, pentamonium antimony, zinc oxide, silica, cadmium sulfate, calcium carbonate, barium carbonate, and barium sulfate. It can also be used to disperse inorganic pigments such as clay, talc, yellow lead and carbon black.
[0102] 更に、本発明の分散剤は、顔料以外の微粒子、例えば、金、銀、銅、白金、鉄、コ バルト、ニッケル、チタン及び Z又はこれらの合金などの金属微粒子を含む固体微粒 子の分散に使用することができる。  [0102] Further, the dispersant of the present invention is a solid fine particle containing fine particles other than pigment, for example, fine metal particles such as gold, silver, copper, platinum, iron, cobalt, nickel, titanium and Z or alloys thereof. Can be used for dispersion.
[0103] 本発明の分散剤は、前記例示した顔料に限らず、微粉末状のものであればどのよ うなものに適応しても構わない。但し、本発明の分散剤はカルボキシル基を有してお り、表面が中性〜塩基性を示す固体微粒子 (特に顔料)との相互作用が強 、ため、 そのような固体微粒子 (特に顔料)の分散に用いるのが好ましい。特に有機顔料の場 合は、表面が塩基性に偏った顔料が好ましい。ここで、表面が塩基性に偏った顔料と は、計算式： [0103] The dispersant of the present invention is not limited to the pigments exemplified above, and may be applied to any fine powders. However, the dispersant of the present invention has a carboxyl group. Therefore, since the interaction with solid fine particles (particularly pigments) whose surface is neutral to basic is strong, it is preferable to use such solid fine particles (particularly pigments) for dispersion. In particular, in the case of an organic pigment, a pigment whose surface is biased to basicity is preferable. Here, the pigment whose surface is biased to basic is a calculation formula:
〔P〕 = [As] [Bs]  [P] = [As] [Bs]
(〔As〕は、「顔料の表面塩基量」であり、〔Bs〕は「顔料の表面酸量」である） によって計算される〔P〕値が molZg以上である顔料を意味する。顔料の表面 塩基量と表面酸量は例えば文献 (色材、 61 [12]、 692- 698, 1988)に記載の方 法で求めることができる。  ([As] is “pigment surface base amount” and [Bs] is “pigment surface acid amount”) [P] means a pigment having a [P] value of molZg or more. The surface base amount and the surface acid amount of the pigment can be determined, for example, by the method described in the literature (Coloring Materials, 61 [12], 692-698, 1988).
[0104] [顔料分散体] [0104] [Pigment dispersion]
本発明による顔料分散体 (pigment  Pigment dispersions according to the invention
dispersion)は、少なくとも顔料と前記一般式（1)で表される分散剤とを含む。本発明 による前記顔料分散体は、例えば、ペースト状 (pigment  dispersion) includes at least a pigment and a dispersant represented by the general formula (1). The pigment dispersion according to the present invention is, for example, a paste (pigment).
paste)である力、あるいは固体のチップ状（pigment chip)であることができる。こうした 顔料分散体に、例えば、インク調製に必要な各種成分を配合することによって、最終 的な用途である各種インクを調製することができる。  It can be a force that is a paste) or a solid pigment chip. For example, by blending various components necessary for ink preparation into such a pigment dispersion, various inks for final use can be prepared.
[0105] 本発明の顔料分散体は、その最終的な用途であるインクへの調製過程で、種々の 添加剤が配合される。配合される添加剤の種類は、顔料分散体に求める粘度や分散 安定性、及び最終用途であるインクの種類に応じて変化する。従って、本明細書に ぉ 、て「顔料分散体」とは、顔料及び前記一般式 (1)で表される分散剤のみから実質 的になる状態の分散体から、顔料及び前記一般式 (1)で表される分散剤に加えて種 々の配合成分を更に含有する状態の分散体までを意味し、インクの形態になる直前 までの任意の状態の分散体を包含する概念である。  [0105] The pigment dispersion of the present invention is blended with various additives in the process of preparing the ink, which is its final application. The type of additive to be blended varies depending on the viscosity and dispersion stability required for the pigment dispersion and the type of ink used as the final application. Therefore, for the purposes of this specification, “pigment dispersion” refers to a pigment and a dispersion of the general formula (1) that are substantially composed only of the pigment and the dispersant represented by the general formula (1). In addition to the dispersant represented by the formula (1), it means a dispersion in a state further containing various compounding components, and includes a dispersion in an arbitrary state until just before the ink is formed.
[0106] 本発明による顔料分散体は、シナジスト、特に塩基性シナジスト (basic synergist)を 含むことが好ましい。塩基性シナジストを用いると、本発明の分散剤のみでは分散さ せることが困難な顔料、特に、表面が中性〜塩基性ではない顔料を良好に分散させ ることがでさる。  [0106] The pigment dispersion according to the present invention preferably contains a synergist, particularly a basic synergist. When a basic synergist is used, it is possible to satisfactorily disperse pigments that are difficult to disperse with only the dispersant of the present invention, particularly pigments whose surface is not neutral to basic.
[0107] 本発明の顔料分散体において、前記一般式（1)で表される分散剤の配合量は、顔 料 100重量部に対し、好ましくは 0. 1〜： LOO重量部、更に好ましくは 0. 5〜75重量 部、最も好ましくは 1. 0〜50重量部である。顔料 100重量部に対し分散剤の配合量 が 0. 1重量部未満であると分散性が悪くなる場合があり、分散剤の配合量が 100重 量部を超えると、この場合も分散性が悪くなることがある。 [0107] In the pigment dispersion of the present invention, the amount of the dispersant represented by the general formula (1) is as follows. The amount is preferably 0.1 to: LOO parts by weight, more preferably 0.5 to 75 parts by weight, and most preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the material. If the blending amount of the dispersant is less than 0.1 part by weight with respect to 100 parts by weight of the pigment, the dispersibility may be deteriorated. May be worse.
[0108] 本発明の顔料分散体に含有させることのできる塩基性シナジストは、「塩基性基を 有する顔料誘導体」、「塩基性基を有するアントラキノン誘導体」、「塩基性基を有す るアタリドン誘導体」、及び「塩基性基を有するトリァジン誘導体」からなる群から選ぶ ことができる。 [0108] The basic synergists that can be contained in the pigment dispersion of the present invention include "pigment derivatives having basic groups", "anthraquinone derivatives having basic groups", "ataridon derivatives having basic groups" And “a triazine derivative having a basic group”.
[0109] 塩基性基としては、下記一般式 (8)、下記一般式 (9)、下記一般式（10)、及び下 記一般式（11)で示される基力 なる群力 選ばれる少なくとも 1つの基を挙げること ができる。  [0109] As the basic group, at least one selected from the group forces represented by the following general formula (8), the following general formula (9), the following general formula (10), and the following general formula (11). There are two groups.
[0110] 式（8) :  [0110] Equation (8):
[化 24]
Figure imgf000039_0001
[Chemical 24]
Figure imgf000039_0001
[0111] 式（9) :  [0111] Equation (9):
[化 25]
Figure imgf000039_0002
[Chemical 25]
Figure imgf000039_0002
[0112] 式（10) [0112] Formula (10)
[化 26]  [Chemical 26]
R 38 R 39 R 38 R 39
-N N 37 -N N 37
一 R (10)  One R (10)
R 41 R 40 [0113] 式（11) : R 41 R 40 [0113] Equation (11):
[化 27]  [Chemical 27]
(11)(11)
Figure imgf000040_0001
Figure imgf000040_0001
[0114] 前記一般式 (8)〜前記一般式（11)にお!/、て、 [0114] In the general formula (8) to the general formula (11),! /,
Jは、前記一般式 (8)及び前記一般式（11)においてそれぞれ独立に、 SO  J is independently SO 2 in the general formula (8) and the general formula (11).
2 2
CO—、— CH NHCOCH CH—、又は直接結合を表し、 CO—, —CH NHCOCH CH—, or a direct bond,
2 2 2  2 2 2
fは、 1〜10の整数を表し、  f represents an integer of 1 to 10,
R35及び R36は、前記一般式 (8)〜前記一般式（11)においてそれぞれ独立に、置換 されていてもよいアルキル基、置換されていてもよいァルケ-ル基、置換されていても よいフエニル基である力、又は R35と R36と式中の窒素原子とが一緒になつて、更なる 窒素原子、酸素原子、又は硫黄原子を含み、置換されていてもよい複素環残基を表 し、 R 35 and R 36 are each independently an alkyl group which may be substituted, an alkyl group which may be substituted, or a group which may be substituted, in the general formula (8) to the general formula (11). A good phenyl group, or R 35 and R 36 together with a nitrogen atom in the formula, together with an additional nitrogen, oxygen or sulfur atom, optionally substituted heterocyclic residue Represents
R37は、置換されていてもよいアルキル基、置換されていてもよいァルケ-ル基、又は 置換されて 、てもよ 、フエ-ル基を表し、 R 37 represents an alkyl group which may be substituted, an alkyl group which may be substituted, or a phenyl group which may be substituted;
R38、 R39、 R4°、及び R41は、それぞれ独立に、水素原子、置換されていてもよいアル キル基、置換されていてもよいァルケ-ル基、又は置換されていてもよいフヱ-ル基 を表し、 R 38 , R 39 , R 4 °, and R 41 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted group. Represents a group of radicals,
Kは、 NR42— Z— NR43 又は直接結合を表し、 K represents NR 42 — Z— NR 43 or a direct bond,
R42、及び R43は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置 換されて!/、てもよ!/、ァルケ-ル基、又は置換されて!、てもよ!/、フエ-ル基を表し、 Zは、置換されていてもよいアルキレン基、置換されていてもよいァルケ-レン基、又 は置換されて 、てもよ 、フエ-レン基を表し、 R 42 and R 43 are each independently a hydrogen atom, an optionally substituted alkyl group, a substituted! /, May! /, A alkenyl group, or a substituted! Y! / Represents a phenyl group, Z represents an optionally substituted alkylene group, an optionally substituted alkylene group, or a substituted, optionally substituted phenyl group. ,
Wは、前記一般式 (8)で示される置換基、又は前記一般式（10)で示される置換基を 表し、そして W represents a substituent represented by the general formula (8) or a substituent represented by the general formula (10). Represent, and
Qは、水酸基、アルコキシル基、前記一般式 (8)で示される置換基、又は前記一般式 (10)で示される置換基を表す。  Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (8), or a substituent represented by the general formula (10).
前記一般式 (8)〜前記一般式（11)で示される置換基を形成するために使用され るアミンィ匕合物としては、例えば、 2級もしくは 3級モノアミン、ジァミン、環状ァミン、力 ルポキシル基含有環状ァミン、水酸基含有環状ァミン、あるいは環状ジァミンを挙げ ることができる。具体的には、ジメチルァミン、ジェチルァミン、メチルェチルァミン、 N , N ェチルイソプロピルアミン、 N, N ェチルプロピルアミン、 N, N—メチルブチ ルァミン、 N, N—メチルイソブチルァミン、 N, N ブチルェチルァミン、 N, N-tert ーブチルェチルァミン、ジイソプロピルァミン、ジプロピルァミン、 N, N— sec ブチ ルプロピルァミン、ジブチルァミン、ジ sec ブチルァミン、ジイソブチルァミン、 N, N—イソブチルー sec ブチルァミン、ジアミルァミン、ジイソアミルァミン、ジへキシル ァミン、ジシクロへキシルァミン、ジ（2—ェチルへキシル）ァミン、ジォクチルァミン、 N , N—メチルォクタデシルァミン、ジデシルァミン、ジァリルァミン、 N, N ェチル 1 , 2—ジメチルプロピルァミン、 N, N—メチルへキシルァミン、ジォレイルァミン、ジス テアリルァミン、 N, N ジメチルアミノメチルァミン、 N, N ジメチルアミノエチルアミ ン、 N, N ジメチルアミノアミルァミン、 N, N ジメチルアミノブチルァミン、 N, N— ジェチルアミノエチルァミン、 N, N ジェチルァミノプロピルアミン、 N, N ジェチル ァミノへキシルァミン、 N, N ジェチルアミノブチルァミン、 N, N ジェチルアミノぺ ンチルァミン、 N, N ジプロピルアミノブチルァミン、 N, N ジブチルァミノプロピル ァミン、 N, N ジブチルアミノエチルァミン、 N, N ジブチルアミノブチルァミン、 N , N ジイソブチルァミノペンチルァミン、 N, N—メチルーラウリルアミノプロピルアミ ン、 N, N ェチルーへキシルアミノエチルァミン、 N, N ジステアリルアミノエチル ァミン、 N, N ジォレイルアミノエチルァミン、 N, N ジステアリルアミノブチルァミン 、ピぺリジン、 2 ピペコリン、 3 ピペコリン、 4 ピペコリン、 2, 4—ルペチジン、 2, 6 ールペチジン、 3, 5—ルペチジン、 3—ピペリジンメタノール、ピペコリン酸、イソニぺ コチン酸、イソ二ペコチン酸メチル、イソ二ペコチン酸ェチル、 2—ピペリジンエタノー ル、ピロリジン、 3—ヒドロキシピロリジン、 N—アミノエチルピペリジン、 N—アミノエチ ルー 4ーピペコリン、 N—アミノエチルモルホリン、 N ァミノプロピルピぺリジン、 N— ァミノプロピル 2 ピペコリン、 N ァミノプロピノレー 4ーピペコリン、 N ァミノプロピ ルモルホリン、 N—メチルピペラジン、 N ブチルピペラジン、 N メチルホモピぺラジ ン、 1ーシクロペンチルピペラジン、 1 アミノー 4ーメチルピペラジン、 1ーシクロペン チルピペラジン等が挙げられる。 Examples of the amine compound used to form the substituents represented by the general formula (8) to the general formula (11) include secondary or tertiary monoamines, diamines, cyclic amines, strong loxyl groups. Examples thereof include a cyclic amine, a hydroxyl group-containing cyclic amine, and a cyclic diamine. Specific examples include dimethylamine, jetylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutyramine, N, N-methylisobutylamine, N, N. Butylethylamine, N, N-tert-Butylethylamine, Diisopropylamine, Dipropylamine, N, N—sec Butylpropylamine, Dibutylamine, Disec Butylamine, Diisobutylamine, N, N—Isobutylamine sec Butylamine, Diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N 2, N-methyloctadecylamine, didecylamine, diarylamine, N, N ethyl 1, 2 —Dimethylpropylamine, N, N—Methylhexylamine, dioleylamine Distearylamine, N, N dimethylaminomethylamine, N, N dimethylaminoethylamine, N, N dimethylaminoamylamine, N, N dimethylaminobutylamine, N, N- jetylaminoethylamine, N, N Jetylaminopropylamine, N, N Jetylaminohexylamine, N, N Jetylaminobutyramine, N, N Jetylaminopentylamine, N, N Dipropylaminobutyramine, N, N Dibutyla Minopropylamine, N, N dibutylaminoethylamine, N, N dibutylaminobutylamine, N, N diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N ethylhexyl Aminoethylamine, N, N distearylaminoethylamine, N, N dioleylaminoethylamine, N, N distearylamine Butyramine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Rupetidine, 3,5-Lupetidine, 3-Piperidinemethanol, Pipecolic acid, Isonipecotate, Methyl isopipecotate , Ethyl isopipecotate, 2-piperidine ethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl Lu 4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl 2-pipecoline, N-aminopropinole 4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1 -Cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.
[0116] 「塩基性基を有する顔料誘導体」を構成する顔料部分 (pigment moiety)は、例えば 、ジケトピロロピロール系色素、ァゾ、ジスァゾ、ポリアゾ等のァゾ系色素、フタロシア ニン系色素、ジアミノジアントラキノン、アントラピリミジン、フラバントロン、アントアント ロン、インダントロン、ピラントロン、ビオラントロン等のアントラキノン系色素、キナタリド ン系色素、ジォキサジン系色素、ペリノン系色素、ペリレン系色素、チォインジゴ系色 素、イソインドリン系色素、イソインドリノン系色素、キノフタロン系色素、スレン系色素 、金属錯体系色素等の有機色素から誘導される。また、「塩基性基を有するアントラ キノン誘導体」又は「塩基性基を有するアタリドン誘導体」は、アントラキノン環又はァ クリドン環上に、前記塩基性基の他に、メチル基、ェチル基等のアルキル基、アミノ基[0116] The pigment moiety constituting the "pigment derivative having a basic group" includes, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo and polyazo, phthalocyanine dyes, Anthraquinone dyes such as diaminodianthraquinone, anthrapyrimidine, flavantron, anthrone, indanthrone, pyranthrone, violanthrone, quinatalidine dye, dioxazine dye, perinone dye, perylene dye, thioindigo dye, isoindoline dye It is derived from organic dyes such as dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, and metal complex dyes. In addition, the “anthraquinone derivative having a basic group” or the “ataridon derivative having a basic group” includes an alkyl group such as a methyl group or an ethyl group on the anthraquinone ring or the acridone ring in addition to the basic group. , Amino group
、ニトロ基、水酸基、又はメトキシ基、エトキシ基等のアルコキシ基又は塩素等のハロ ゲン等の置換基を有して 、てもよ 、。 It may have a substituent such as a nitro group, a hydroxyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a halogen such as chlorine.
[0117] また、「塩基性基を有するトリァジン誘導体」を構成するトリァジン部分は、前記塩基 性基の他に、アルキル基 (例えば、メチル基、ェチル基、ブチル基等）、アミノ基、ァ ルキルアミノ基 (例えば、ジメチルァミノ基、ジェチルァミノ基、ジブチルァミノ基等）、 ニトロ基、水酸基、アルコキシ基 (例えば、メトキシ基、エトキシ基、ブトキシ基等）、ハ ロゲン原子 (例えば、塩素原子、臭素原子等）、フ ニル基 (例えば、アルキル基、ァ ミノ基、アルキルアミノ基、ニトロ基、水酸基、アルコキシ基、ハロゲン原子等で置換さ れていてもよい）、及びフエ-ルァミノ基（例えば、アルキル基、アミノ基、アルキルアミ ノ基、ニトロ基、水酸基、アルコキシ基、ハロゲン原子等で置換されていてもよい）等 の置換基を有していてもよい。好ましいトリァジン部分は、 1, 3, 5 トリァジン力 誘 導される。  [0117] Further, the triazine moiety constituting the "triazine derivative having a basic group" includes, in addition to the basic group, an alkyl group (for example, a methyl group, an ethyl group, a butyl group), an amino group, and an alkylamino group. A group (eg, dimethylamino group, jetylamino group, dibutylamino group, etc.), nitro group, hydroxyl group, alkoxy group (eg, methoxy group, ethoxy group, butoxy group, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), A phenyl group (for example, an alkyl group, an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen atom, etc.) and a phenylamino group (for example, an alkyl group, an amino group) Group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen atom, etc.). . The preferred triazine moiety is induced by 1, 3, 5 triazine forces.
[0118] 本発明で用いる「塩基性基を有する顔料誘導体」、「塩基性基を有するアントラキノ ン誘導体」、及び「塩基性基を有するアタリドン誘導体」は、種々の合成経路で、公知 の方法で合成することができる。例えば、有機色素、アントラキノン若しくはアタリドン に、下記式（14)〜下記式（17)で示される置換基を導入した後、これらの置換基と反 応して前記一般式 (8)〜前記一般式（11)で示される置換基を形成することのできる ァミン化合物、例えば、 N, N ジメチルァミノプロピルァミン、 N—メチルビペラジン、 ジェチルァミン又は 4— [4—ヒドロキシ— 6— [3— (ジブチルァミノ）プロピルァミノ] - 1, 3, 5 トリァジン一 2—ィルァミノ]ァ-リン等を反応させることによって得ることがで きる。 [0118] The "pigment derivative having a basic group", "anthraquinone derivative having a basic group", and "ataridon derivative having a basic group" used in the present invention are known by various synthetic routes. It can be synthesized by the method of For example, after introducing a substituent represented by the following formula (14) to the following formula (17) into an organic dye, anthraquinone or attaridone, the above general formula (8) to the above general formula reacts with these substituents. Amine compounds capable of forming the substituent represented by (11), for example, N, N dimethylaminopropylamine, N-methylbiperazine, jetylamine or 4- [4-hydroxy-6- [3- (dibutylamino) Propylamino] -1,3,5 triazin-2-ylamino] aline and the like can be obtained.
[0119] 式（14) : SO C1  [0119] Equation (14): SO C1
2  2
式（15) :— COC1  Formula (15):-COC1
式（16)：— CH NHCOCH C1  Formula (16): — CH NHCOCH C1
2 2  twenty two
式（17)：— CH C1  Formula (17): — CH C1
2  2
[0120] また、有機色素がァゾ系色素である場合は、前記一般式 (8)〜前記一般式（11)で 示される置換基をあらカゝじめジァゾ成分 (例えば、ジァゾ基を有する化合物）又はカツ プリング成分 (例えば、ァセトアミド基を有する化合物）に導入し、その後カップリング 反応を行うことによってァゾ系顔料誘導体を製造することもできる。  [0120] In addition, when the organic dye is a azo dye, the substituents represented by the general formula (8) to the general formula (11) are arranged in advance to obtain a diazo component (for example, having a diazo group). The azo pigment derivative can also be produced by introducing it into a compound) or a coupling component (for example, a compound having a acetoamide group) and then performing a coupling reaction.
[0121] 本発明で用いる「塩基性基を有するトリァジン誘導体」は、種々の合成経路で、公 知の方法で合成することができる。例えば、塩化シァヌルを出発原料とし、塩化シァ ヌルの少なくとも 1つの塩素原子に、前記一般式 (8)〜前記一般式（11)で示される 置換基を形成するァミン化合物、例えば、 N, N ジメチルァミノプロピルアミン又は N—メチルビペラジン等を反応させ、次いで塩ィ匕シァヌルの残りの塩素原子と種々の ァミン化合物又はアルコールィ匕合物等を反応させることによって得られる。  [0121] The "triazine derivative having a basic group" used in the present invention can be synthesized by a known method through various synthetic routes. For example, an amine compound starting from cyanuric chloride and forming a substituent represented by the general formula (8) to the general formula (11) on at least one chlorine atom of the cyanuric chloride, for example, N, N dimethyl It is obtained by reacting aminoaminoamine or N-methylbiperazine and the like, and then reacting the remaining chlorine atom of the salt cyanuric with various amine compounds or alcohol compounds.
[0122] 本発明の顔料分散体において、塩基性シナジストの配合量は、顔料 100重量部に 対し好ましくは 1〜50重量部、更に好ましくは 3〜30重量部、最も好ましくは 5〜25 重量部である。顔料 100重量部に対し塩基性シナジストが 1重量部未満であると分散 性が悪くなる場合があり、 50重量部を超えると耐熱性、及び Z又は耐光性が悪くなる 場合がある。  [0122] In the pigment dispersion of the present invention, the amount of the basic synergist is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 25 parts by weight with respect to 100 parts by weight of the pigment. It is. If the basic synergist is less than 1 part by weight with respect to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and if it exceeds 50 parts by weight, the heat resistance and Z or light resistance may be deteriorated.
[0123] 本発明による顔料分散体は、前記分散剤や前記シナジスト以外にも、種々の顔料 担体 (pigment carrier)を含むことができる。顔料担体の代表例は、溶剤（特に、有機 溶剤)である。溶剤 (特に、有機溶剤）としては、顔料分散体の溶剤として通常用いら れて 、る公知の溶剤を、本発明による顔料分散体にも用いることができる。 [0123] The pigment dispersion according to the present invention may contain various pigment carriers in addition to the dispersant and the synergist. Typical examples of pigment carriers are solvents (especially organic Solvent). As the solvent (particularly, organic solvent), a known solvent which is usually used as a solvent for the pigment dispersion can be used for the pigment dispersion according to the present invention.
[0124] 溶剤としては、例えば、メタノール、エタノール、イソプロピルアルコール、ブタノール 、へキサノール、ヘプタノール、ォクタノール、ノナノール、デカノール、ゥンデカノー ル、シクロへキサノール、ベンジルアルコール、又はアミルアルコールなどのアルコー ノレ類、エチレングリコーノレモノメチノレエーテノレ、エチレングリコーノレモノェチノレエーテ ル、エチレングリコールモノイソプロピルエーテル、エチレングリコーノレモノブチノレエ 一テル、エチレングリコールモノへキシルエーテル、メトキシメトキシエタノール、ジェ チレングリコーノレモノメチノレエーテノレ、ジエチレングリコーノレモノェチノレエーテノレ、ジ エチレングリコーノレモノブチノレエーテノレ、ジエチレングリコールモノメチルエーテルァ セテート、ジエチレングリコーノレモノェチノレエーテノレアセテート、ジエチレングリコール モノブチノレエーテノレアセテート、トリエチレングリコールモノメチルエーテル、トリェチ レングリコーノレモノェチノレエーテノレ、プロピレングリコーノレモノメチノレエーテノレ、プロピ レングリコーノレモノェチノレエーテノレ、プロピレングリコーノレイソプロピノレエーテノレ、プロ ピレングリコーノレモノブチノレエーテル、プロピレングリコーノレモノメチノレエーテノレァセ テート、プロピレングリコールモノェチルエーテルアセテート、 1 ブトキシエトキシプ ロパノール、又は 1ーメトキシ 2—プロピルアセテート等のダリコール誘導体類、ァセ トン、メチルェチルケトン、メチルイソブチルケトン、シクロへキサノン、イソホロン、メチ ルシクロへキサノン、又はァセトフエノンなどのケトン類、酢酸ェチル、酢酸ブチル、酢 酸ァミル、酢酸イソァミル、乳酸ェチル、乳酸プロパン、又は乳酸ブチルなどのエステ ル類、ベンゼン、トルエン、キシレンなどの芳香族炭化水素類、石油系溶剤等が挙げ られ、これらを単独で若しくは組み合わせて用いることができる。  [0124] Examples of the solvent include methanol, ethanol, isopropyl alcohol, butanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, cyclohexanol, benzyl alcohol, alcohol alcohols such as amyl alcohol, ethylene glycol Noremonomethylenoateolene, Ethylene glycol monoethyl etherolate, Ethylene glycol monoisopropyl ether, Ethylene glycol monobutenoyl ether, Ethylene glycol monohexyl ether, Methoxymethoxyethanol, Diethylene glycol nole monomethyl Noleyatenore, Diethyleneglycolenomonochinenoatenore, Diethyleneglycolenobutinolenoatenore, Diethylene glycol monomethyl ether Tercetate, diethyleneglycolenomethinoreethenoreacetate, diethyleneglycol monobutinoleethenoreacetate, triethyleneglycolmonomethylether, triethylenglycolenomonoetinoreatenore, propyleneglycolenomonomethinoreatenore, propylene Ricohone Monoethylenoateolene, Propylene Glycolanol Isopropinoleetenole, Propylene Glyconole Monobutinoleether, Propylene Glycolenomonomethinoleate Monoacetate, Propylene Glycol Monoethyl Acetylate Acetate, 1 Butoxyethoxy Daranol derivatives such as ropanol or 1-methoxy 2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Ketones such as xanone, isophorone, methylcyclohexanone, or acetophenone, esters such as ethyl acetate, butyl acetate, amyl acetate, isoamyl acetate, lactyl ethyl, lactic acid propane, or butyl lactate, benzene, toluene, xylene, etc. Aromatic hydrocarbons, petroleum solvents, and the like, and these can be used alone or in combination.
[0125] 本発明の顔料分散体には、顔料担体として、熱硬化性化合物 (thermosetting comp ound)を含有させることができる。熱硬化性化合物としては、例えば、メラミン榭脂、ベ ンゾグアナミン榭脂、フエノール榭脂、ブロック化イソシァネート、シランカップリングイ匕 合物、エポキシ榭脂、脂環式エポキシ榭脂、ォキセタン榭脂、エチレン性不飽和単量 体、ロジン変性マレイン酸榭脂、ロジン変性フマル酸榭脂、又は尿素樹脂を挙げるこ とができる。これらの熱硬化性化合物は、加熱により容易に反応して架橋構造 (cross linkage structure)を形成するため、熱硬化型インクを調製するための顔料分散体に 、前記熱硬化性化合物を含有させることが好ましい。 [0125] The pigment dispersion of the present invention may contain a thermosetting compound as a pigment carrier. Examples of thermosetting compounds include melamine resin, benzoguanamine resin, phenol resin, blocked isocyanate, silane coupling compound, epoxy resin, alicyclic epoxy resin, oxetane resin, ethylene An unsaturated monomer, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, or urea resin. These thermosetting compounds react easily by heating to form a cross-linked structure (cross In order to form a linkage structure), it is preferable to include the thermosetting compound in a pigment dispersion for preparing a thermosetting ink.
[0126] メラミン榭脂としては、例えば、イミノ基、メチロール基、及び Z又はアルコキシメチ ル基を有するものが挙げられ、特にアルコキシメチル基のみを含有するメラミン榭脂 が好ましい。アルコキシメチル基含有メラミン榭脂の具体例としては、へキサメトキシメ チロールメラミン、又はへキサブトキシメチロールメラミン等を挙げることができるが必 ずしもこれらに限定されるものではない。 [0126] Examples of the melamine resin include those having an imino group, a methylol group, and Z or an alkoxymethyl group, and a melamine resin containing only an alkoxymethyl group is particularly preferable. Specific examples of the alkoxymethyl group-containing melamine resin include hexamethoxymethylol melamine, hexasuboxymethylol melamine and the like, but are not necessarily limited thereto.
[0127] メラミン榭脂としては市販されている榭脂を使用することができ、その市販品の具体 例としては、以下のものを挙げることができる。但し、必ずしもこれらに限定されるもの ではない。その巿販品の具体例としては、三和ケミカル社製-力ラック MW—30M、 MW— 30、 MW— 22、 MS— 21、 MX— 45、 MX— 500、 MX— 520、 MX— 43、 MX— 302、 日本サイテックスインダストリ一社製サイメル 300、 301、 303、 350、 28 5、 232、 235、 236、 238、マイコート 506、 508などを挙げ、ること力 Sできる。  [0127] As melamine rosin, commercially available rosin can be used, and specific examples of the commercially available products include the following. However, it is not necessarily limited to these. Specific examples of the commercial products are Sanwa Chemical Co., Ltd.-Power rack MW-30M, MW-30, MW-22, MS-21, MX-45, MX-500, MX-520, MX-43, MX-302, Nippon Cytex Industries' Cymel 300, 301, 303, 350, 285, 232, 235, 236, 238, My Coat 506, 508, etc.
[0128] ベンゾグアナミン榭脂としては、例えば、イミノ基、メチロール基、及び Z又はアルコ キシメチル基を有するものが挙げられ、特にアルコキシメチル基含有ベンゾグァナミ ン榭脂が好まし ヽ。ベンゾグアナミン榭脂としては市販されて ヽる榭脂を使用すること ができ、その市販品の具体例としては、三和ケミカル社製-力ラック BX— 4000、 SB —401、 日本サイテックスインダストリ一社製サイメル 1123などを挙げることができる。  [0128] Examples of the benzoguanamine resin include those having an imino group, a methylol group, and Z or an alkoxymethyl group, and an alkoxymethyl group-containing benzoguanamine resin is particularly preferable. Commercially available resin can be used as benzoguanamine resin. Specific examples of commercially available products include Sanwa Chemical Co., Ltd.-Power Rack BX-4000, SB-401, Nippon Cytex Industries, Ltd. For example, Cymel 1123 made by the company.
[0129] フエノール榭脂としては、例えば、フエノール類とアルデヒド類を酸性触媒下で反応 させたノボラック型フエノール榭脂、塩基性触媒下で反応させたレゾール型フエノー ル榭脂のどちらも用いることができる。フエノール類としては、例えば、オルトクレゾー ル、パラクレゾール、パラフエ-ルフエノール、パラノ-ルフエノール、 2, 3—キシレノ 一ノレ、フエノーノレ、メタクレゾ一ノレ、 3, 5—キシレノーノレ、レゾノレシノーノレ、力テコーノレ 、ノヽイドロキノン、ビスフエノーノレ A、ビスフエノーノレ F、ビスフエノーノレ B、ビスフエノー ルE、ビスフエノール H、又はビスフエノール S等を挙げることができる。アルデヒド類と しては、例えば、ホルムアルデヒド、又はァセトアルデヒドを挙げることができる。フエノ ール類とアルデヒド類は、それぞれ 1種を単独で、又は 2種以上を組み合わせて用い られる。 [0130] ブロック化イソシァネートイ匕合物の原料となるイソシァネートイ匕合物としては、例えば 、へキサメチレジイソシァネート、イソホロンジイソシァネート、トノレイジンイソシァネート 、ジフエ-ルメタン 4, 4'ージイソシァネート、ジフエ-ルメタン 2, 4'ージイソシァ ネート、ビス（4 イソシァネートシクロへキシル)メタン、テトラメチルキシリレンジイソシ ァネート等のジイソシァネート、これらジイソシァネートのイソシァヌレート体、トリメチロ ールプロパンァダクト型、ビウレット型、イソシァネート残基を有するプレポリマー（ジィ ソシァネートとポリオール力 得られる低重合体)及びイソシァネート残基を有するゥ レトジオン等を挙げることができる力 必ずしもこれに限定されるものではない。 [0129] As the phenolic resin, for example, either a novolac-type phenolic resin obtained by reacting phenols and aldehydes in the presence of an acidic catalyst or a resol-type phenolic resin prepared by reacting in the presence of a basic catalyst may be used. it can. Examples of phenols include ortho-cresol, paracresol, para-phenol, para-phenol, 2,3-xylenol, phenol, metacresanol, 3,5-xylenol, resorino, and tecnore. Examples thereof include neutroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol E, bisphenol H, and bisphenol S. Examples of aldehydes include formaldehyde and acetoaldehyde. The phenols and aldehydes may be used alone or in combination of two or more. [0130] Examples of the isocyanate compound used as a raw material for the blocked isocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, tonoridine resin isocyanate, diphenol methane 4, 4'- Diisocyanates, diphenylmethane 2,4'-diisocyanate, bis (4-isocyanate cyclohexyl) methane, tetramethylxylylene diisocyanate, etc., isocyanurates of these diisocyanates, trimethylolpropane adduct Forces that can include molds, biuret types, prepolymers having isocyanate groups (dipolymers and low polymers obtained with polyol strength), urethane diones having isocyanate residues, and the like are not necessarily limited thereto.
[0131] 前記イソシァネートイ匕合物のブロック剤としては、例えば、フエノール (解離温度 180 °C以上）、 ε一力プロラタタム (解離温度 160〜180°C)、ォキシム (解離温度 130〜1 60°C)、又は活性メチレン（100〜120°C)等を挙げることができる力 必ずしもこれに 限定されるものではない。また、 1種を単独で、あるいは 2種以上を併用して用いられ る。  [0131] Examples of the blocking agent for the isocyanate compound include phenol (dissociation temperature of 180 ° C or higher), ε-prolactam (dissociation temperature of 160 to 180 ° C), oxime (dissociation temperature of 130 to 160 ° C). ), Or an active methylene (100 to 120 ° C.), and the like. One type can be used alone, or two or more types can be used in combination.
[0132] シランカップリング剤としては、例えば、ビュルトリス（ /3—メトキシエトキシ)シラン、ビ -ルエトキシシラン、ビュルトリメトキシシラン等のビュルシラン類、 Ί—メタクリロキシ プロピルトリメトキシシラン等の（メタ）アクリルシラン類、 β - (3, 4—エポキシシクロへ キシル）ェチルトリメトキシシラン、 一（3, 4—エポキシシクロへキシル)メチルトリメト キシシラン、 13 - (3, 4—エポキシシクロへキシル）ェチルトリエトキシシラン、 j8 (3 , 4—エポキシシクロへキシル)メチルトリエトキシシラン、 γ—グリシドキシプロピルトリ メトキシシラン、 γ—グリシドキシプロピノレトリエトキシシラン等のエポキシシラン類、 Ν - β (アミノエチル） - γ—ァミノプロピルトリメトキシシラン、 Ν - β (アミノエチル） - γ—ァミノプロピルトリエトキシシラン、 N— j8 (アミノエチル） γ—ァミノプロピルメチル ジェトキシシシラン、 Ί—ァミノプロピルトリエトキシシラン、 γ—ァミノプロピルトリメトキ シシラン、 Ν フエ二ノレ一 γ—ァミノプロピルトリメトキシシラン、 Ν フエ-ノレ一 γ ァ ミノプロピルトリエトキシシラン等のアミノシラン類、 y—メルカプトプロピルトリメトキシ シラン、 γ—メルカプトプロピルトリエトキシシラン等のチオシラン類等を挙げることが できる。 [0132] Examples of the silane coupling agent include bursilanes such as butyrris (/ 3-methoxyethoxy) silane, butylethoxysilane, butyltrimethoxysilane , and (meth) acrylic such as Ί -methacryloxypropyltrimethoxysilane. Silanes, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mono (3,4-epoxycyclohexyl) methyltrimethoxysilane, 13- (3,4-epoxycyclohexyl) ethylyltri Epoxy silanes such as ethoxysilane, j8 (3, 4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropinoletriethoxysilane, Ν-β (amino Ethyl) -γ-aminopropyltrimethoxysilane, Ν-β (aminoethyl) -γ-aminop Pills triethoxysilane, N-j8 (aminoethyl) .gamma. § amino propyl methyl jet Kishishi silane, Ί - § amino propyl triethoxy silane, .gamma. § amino propyl trimetoquinol Shishiran, New phenylene Honoré one .gamma. Aminopuropiru Examples thereof include aminosilanes such as trimethoxysilane and Ν-phenol γ aminopropyltriethoxysilane, and thiosilanes such as y-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.
[0133] エポキシ榭脂としては、例えば、ビスフエノールフルオレンジグリシジルエーテル、ビ スクレゾールフルオレンジグリシジルエーテル、ビスフエノキシエタノールフルオレンジ グリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、 1, 6—へキサ ンジオールジグリシジルエーテル、グリセロールポリグリシジルエーテル、トリメチロー ルプロパンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ジ グリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ジグリシ ジルテレフタレート、ジグリシジル o—フタレート、エチレングリコールジグリシジルエー テル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジ ルエーテル、及びポリプロピレングリコールジグリシジルエーテル等のポリオールのグ リシジルエーテル、ポリグリシジルイソシァヌレート等を挙げることができる力 必ずしも これらに限定されるものではない。 [0133] Examples of the epoxy resin include bisphenol full orange glycidyl ether and vinyl. Cresol fluoric acid glycidyl ether, bisphenoxyethanol fluoric acid glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol Polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, diglycidyl terephthalate, diglycidyl o-phthalate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. Polyglycolyl ether, polyglycol Force can be given Jill iso Xia isocyanurate, etc. are not necessarily limited thereto.
エチレン性不飽和単量体（ethylenically  Ethylenically unsaturated monomer
unsaturated monomer)としては、具体的にはメチル（メタ）アタリレート、ェチル（メタ） アタリレート、 n—プロピル (メタ）アタリレート、イソプロピル (メタ）アタリレート、 n—ブチ ル (メタ）アタリレート、イソブチル (メタ）アタリレート、 t—ブチル (メタ）アタリレート、 2- ェチルへキシル (メタ）アタリレート、シクロへキシル (メタ）アタリレート、ステアリル (メタ )アタリレート、ラウリル (メタ）アタリレート、テトラヒドロフルフリル (メタ）アタリレート、イソ ボル-ル (メタ）アタリレート、フエ-ル (メタ）アタリレート、ベンジル (メタ）アタリレート、 Specific examples of unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenol (meth) acrylate, benzyl (meth) acrylate,
等のアルキル (メタ）アタリレート類； Alkyl (meth) acrylates such as;
メトキシポリプロピレングリコール (メタ）アタリレート、エトキシポリエチレングリコール (メ タ）アタリレート等のアルコキシポリアルキレングリコール (メタ）アタリレート類； アクリル酸、メタクリル酸、 2—カルボキシェチル (メタ）アタリレート、 ω—カルボキシ— ポリ力プロラタトンモノ (メタ）アタリレート、フタル酸モノヒドロキシェチル (メタ）アタリレ ート及びテトラヒドロフタル酸モノヒドロキシェチル (メタ）アタリレートなどのカルボキシ ル基含有の (メタ)アタリレート類； Alkoxypolyalkylene glycol (meth) acrylates such as methoxy polypropylene glycol (meth) acrylate and ethoxy polyethylene glycol (meth) acrylate; acrylic acid, methacrylic acid, 2-carboxyethyl (meth) acrylate, ω— Carboxy— (meth) acrylates containing carboxyl groups such as poly force prolatatone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, and tetrahydroxyphthalate monohydroxyethyl (meth) acrylate. Kind;
クロトン酸、マレイン酸、フマル酸、ィタコン酸、シトラコン酸などの前記カルボキシル 基含有の (メタ)アタリレート類以外のカルボキシル基含有エチレン性不飽和単量体； 2—ヒドロキシェチル (メタ）アタリレート、 2—ヒドロキシプロピル (メタ）アタリレート、 2- ヒドロキシブチル (メタ）アタリレート、グリセロール (メタ）アタリレート、ポリエチレンダリ コール (メタ）アタリレート、ポリプロピレングリコール (メタ）アタリレート等の水酸基含有 の (メタ)アタリレート類； Carboxyl group-containing ethylenically unsaturated monomers other than the above-mentioned carboxyl group-containing (meth) atalylates such as crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc .; 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 2- Hydroxyl-containing (meth) acrylates such as hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, poly (ethylene) acrylate (meth) acrylate, polypropylene glycol (meth) acrylate.
(メタ）アクリルアミド、及び N, N ジメチル (メタ）アクリルアミド、 N, N ジェチル (メ ミド、アタリロイルモルホリン等の N置換型 (メタ）アクリルアミド類；  (Meth) acrylamide, and N, N dimethyl (meth) acrylamide, N, N Jetyl (N-substituted (meth) acrylamides such as memido and attalyloylmorpholine;
N, N ジメチルアミノエチル (メタ）アタリレート、 N, N ジェチルアミノエチル (メタ） アタリレート等のアミノ基含有 (メタ)アタリレート類；  Amino group-containing (meth) acrylates such as N, N dimethylaminoethyl (meth) acrylate, N, N jetylaminoethyl (meth) acrylate;
(メタ)アクリロニトリル類；  (Meth) acrylonitriles;
スチレン、 α メチルスチレン等のスチレン類； Styrenes such as styrene and α-methylstyrene;
ェチノレビニノレエーテノレ、 η プロピノレビニノレエーテノレ、イソプロピノレビニノレエーテノレ、 η ブチルビ-ルエーテル、イソブチルビ-ルエーテル等のビュルエーテル類； 酢酸ビニル、プロピオン酸ビニル等の脂肪酸ビニル類； Butyl ethers such as ethino levinino le etherenole, η propino levinino le etherenole, isopropino levinino le etherenole, η butyl vinyl ether, isobutyl vinyl ether; fatty acid vinyls such as vinyl acetate and vinyl propionate;
また、 1, 6 へキサンジオールジ (メタ）アタリレート、ネオペンチルグリコールジ（メタ） アタリレート、ポリエチレングリコールジ (メタ）アタリレート等のアルキレングリコールジ（ メタ）アタリレート、グリセリンプロピレンォキシド変性トリ（メタ）アタリレート、トリメチロー ルプロパントリ（メタ）アタリレート、トリメチロールプロパンエチレンォキシド変性トリ（メタ )アタリレート、トリメチロールプロパンプロピレンォキシド変性トリ（メタ）アタリレート、ィ ソシァヌル酸エチレンォキシド変性トリ（メタ）アタリレート、イソシァヌル酸エチレンォキ シド変性 ε—力プロラタトン変性トリ（メタ）アタリレート、 1, 3, 5 トリアタリロイルへキ サヒドロ一 s トリァジン、ペンタエリスリトールトリ（メタ）アタリレート、ジペンタエリスリト ールトリ (メタ)アタリレートトリプロピオネートなどの三官能 (メタ)アタリレート類； また、ペンタエリスリトールテトラ (メタ）アタリレート、ジペンタエリスリトールペンタ (メタ） アタリレートモノプロピオネート、ジペンタエリスリトールへキサ（メタ）アタリレート、テト ラメチロールメタンテトラ (メタ)アタリレート、オリゴエステルテトラ (メタ）アタリレート、トリ ス（ (メタ）アタリロイルォキシ)ホスフェート等の多官能 (メタ)アタリレート類が挙げられ る。 In addition, 1, 6 hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, etc. alkylene glycol di (meth) acrylate, glycerol propylene oxide modified tri (Meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane ethylene oxide modified tri (meth) acrylate, trimethylol propane propylene oxide modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (Meth) atalylate, ethylene cyanide modified with isocyanuric acid ε—force prolatatatone modified tri (meth) acrylate, 1, 3, 5 Triatalyloyl hexahydro-1 s triazine, pentaerythritol tri (meth) ateryl , Trifunctional (meth) atalylates such as dipentaerythritol tri (meth) acrylate tripropionate; pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate monopropionate , Dipentaerythritol hexa (meth) acrylate, tetramethylol methane tetra (meth) acrylate, oligoester tetra (meth) acrylate, tris ((meth) attaroyloxy) phosphate ) Atallate.
更に、前記したような化合物の他、ポリエステル (メタ)アタリレート、ポリウレタン (メタ )アタリレート、エポキシ (メタ）アタリレート、（メタ）アクリルィ匕マレイン酸変性ポリブタジ ェン等を挙げることができる。 In addition to the compounds described above, polyester (meth) acrylate, polyurethane (meta ) Acrylate, epoxy (meth) acrylate, (meth) acrylic maleic acid-modified polybutadiene and the like.
ここで (メタ)アタリレートとはメタタリレート又はアタリレートのことを、 （メタ)アクリルアミ ドとはメタクリルアミド又はアクリルアミドのことを、 （メタ)アクリロニトリルとはメタクリロ- トリル又はアクリロニトリルのことを示す。  Here, (meth) acrylate refers to methacrylate or acrylate, (meth) acrylamide refers to methacrylamide or acrylamide, and (meth) acrylonitrile refers to methacrylo-tolyl or acrylonitrile.
[0136] 本発明の顔料分散体には、顔料担体として、ビニル系榭脂 (アクリル系榭脂、ポリス チレン榭脂、スチレン一マレイン酸榭脂等）、ポリウレタン榭脂、ポリエステル榭脂、ポ リイミド榭脂、プチラール榭脂、塩素化ポリエチレン、塩素化ポリプロピレン、ポリ塩ィ匕 ビュル、塩ィヒビュル 酢酸ビュル共重合体、ポリ酢酸ビュル、アルキッド榭脂、ポリア ミド榭脂、ゴム系榭脂、環化ゴム系榭脂、セルロース類、ポリエチレン、及びポリブタジ ェン力 なる群力 選択される榭脂を含有させることができる。これらの榭脂を含有さ せることにより、顔料の分散性が向上し、経時での安定性も向上させることができる。 また、被塗工物への密着性、着色膜の強度なども向上させることができる。このうち、 特にビュル系榭脂が、榭脂自体の透明性、耐光性、及び耐熱性の点で優れており 好ましい。ここで、ビニル系榭脂とは、前記に例示したエチレン性不飽和単量体を少 なくとも共重合した榭脂をいう。  [0136] In the pigment dispersion of the present invention, as a pigment carrier, vinyl resin (acrylic resin, polystyrene resin, styrene monomaleic acid resin, etc.), polyurethane resin, polyester resin, polyimide Resin, Petitral Resin, Chlorinated Polyethylene, Chlorinated Polypropylene, Polysalt Bull, Salt Butyl Acetate Bull Copolymer, Polyacetate Bull, Alkyd Resin, Polyamide Resin, Rubber Resin, Cyclized Rubber A systemic resin, celluloses, polyethylene, and a polybutadiene force can be selected. By containing these rosins, the dispersibility of the pigment is improved and the stability over time can be improved. Moreover, the adhesiveness to a to-be-coated object, the intensity | strength of a colored film, etc. can be improved. Of these, the bull resin is particularly preferable because of its excellent transparency, light resistance, and heat resistance. Here, the vinyl-based resin means a resin obtained by copolymerizing at least the ethylenically unsaturated monomer exemplified above.
[0137] 本発明で用いるビニル系榭脂は、前記例示したエチレン性不飽和単量体以外に、 リン酸基又はスルホン酸基を有するエチレン性不飽和単量体を重合成分として含有 することができる。  [0137] The vinyl-based resin used in the present invention may contain an ethylenically unsaturated monomer having a phosphoric acid group or a sulfonic acid group as a polymerization component in addition to the ethylenically unsaturated monomer exemplified above. it can.
リン酸基を有するエチレン性不飽和単量体としては、エチレングリコール (メタ)ァク リレートフォスフェート、プロピレングリコール（メタ）アタリレートフォスフェートに代表さ れるような下記一般式（18)で示されるエチレン性不飽和単量体が挙げられる。  The ethylenically unsaturated monomer having a phosphoric acid group is represented by the following general formula (18) as typified by ethylene glycol (meth) acrylate phosphate and propylene glycol (meth) acrylate phosphate. An ethylenically unsaturated monomer is mentioned.
[0138] 一般式（18) : [0138] General formula (18):
[化 28]  [Chemical 28]
R44 O 0 R 44 O 0
H2C= C—— C—— (0—— R45)u ■O P- OH (18) H 2 C = C—— C—— (0—— R 45 ) u ■ O P- OH (18)
OH 一般式（18)において、 R44は、水素原子又はメチル基であり、 R45は、アルキレン基 であり、 uは、 1〜20の整数を表す。 OH In the general formula (18), R 44 is a hydrogen atom or a methyl group, R 45 is an alkylene group, and u represents an integer of 1 to 20.
リン酸基を有するエチレン性不飽和単量体の具体例を以下に示す力 これに限る ものではない。  Specific examples of the ethylenically unsaturated monomer having a phosphoric acid group are as follows.
[化 29]  [Chemical 29]
Figure imgf000050_0001
Figure imgf000050_0001
これらのリン酸基を有するエチレン性不飽和単量体は、例えば、特公昭 50— 2253 6号公報、又は特開昭 58— 128393号公報に記載の方法で製造することができる。 市販品としては、例えば、ホスマー M、ホスマー CL、ホスマー PE、ホスマー MH (以 上ュ-ケミカル社製）、ライトエステル P— 1M (以上共栄社化学社製）、 JAMP- 514 (以上城北化学工業社製）、 KAYAMER PM- 2, KAYAMER PM— 21 (以上 日本化薬社製)等がある。 These ethylenically unsaturated monomers having a phosphoric acid group can be produced, for example, by the method described in JP-B-50-22536 or JP-A-58-128393. Commercial products include, for example, Phosmer M, Phosmer CL, Phosmer PE, Phosmer MH (manufactured by Yu-Chemical), Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.), JAMP-514 (Johoku Chemical Co., Ltd. KAYAMER PM-2, KAYAMER PM—21 (or above) Nippon Kayaku Co., Ltd.).
[0141] スルホン酸基を有するエチレン性不飽和単量体としては、例えば、 2—アクリルアミ ドー 2—メチルプロパンスルホン酸、ビニルスルホン酸、 3 ァリロキシ— 2 ヒドロキシ プロパンスルホン酸、 p—スチレンスルホン酸、メタリルスルホン酸、ァリルスルホン酸 、メタリルォキシベンゼンスルホン酸、ァリルォキシベンゼンスルホン酸、 2—スルホェ チルメタタリレート、 4—スルホブチルメタタリレート等を挙げることができる。  [0141] Examples of the ethylenically unsaturated monomer having a sulfonic acid group include 2-acrylamido 2-methylpropane sulfonic acid, vinyl sulfonic acid, 3 aryloxy-2-hydroxy propane sulfonic acid, and p-styrene sulfonic acid. , Methallyl sulfonic acid, allyl sulfonic acid, methallyl benzene sulfonic acid, allyloxy benzene sulfonic acid, 2-sulfo butyl metatalylate, 4-sulfo butyl metatalylate and the like.
[0142] また、ビニル系榭脂としては、下記一般式（19)又は一般式（20)で示されるェチレ ン性不飽和単量体も用いることが好まし 、。これらのエチレン性不飽和単量体を共重 合したビュル系榭脂を顔料担体として用いることにより、顔料の分散性及び経時での 安定性が向上し、更に顔料ペーストを低粘度とすることができる。  [0142] As the vinyl-based resin, it is preferable to use an ethylenically unsaturated monomer represented by the following general formula (19) or general formula (20). By using a bull-based resin co-polymerized with these ethylenically unsaturated monomers as a pigment carrier, the dispersibility of the pigment and the stability over time can be improved, and the pigment paste can be made to have a low viscosity. it can.
[0143] 一般式（19) : [0143] General formula (19):
[化 30]  [Chemical 30]
Figure imgf000051_0001
Figure imgf000051_0001
[0144] 一般式（20)  [0144] General formula (20)
[化 31]
Figure imgf000051_0002
[Chemical 31]
Figure imgf000051_0002
前記一般式（19)及び一般式 (20)において、 R4b及び R48は、水素原子又はメチル 基を表し、 '及び R は炭素原子数 1〜4のアルキレン基を表し、 V及び wは 1〜： L00 の整数を表す。 In the general formula (19) and the general formula (20), R 4b and R 48 represent a hydrogen atom or a methyl group, 'and R represent an alkylene group having 1 to 4 carbon atoms, and V and w are 1 ~: Represents an integer of L00.
[0145] 前記一般式（ 19)及び一般式（20)で示されるエチレン性不飽和単量体としては、 例えば、パラクミルフエノールエチレンオキサイド変性アタリレート、エチレンォキサイ ド変性ビスフエノール Aジメタクリレート、エチレンオキサイド変性ビスフエノール Aジァ タリレート、プロピレンオキサイド変性ビスフエノール Aジメタクリレート、プロピレンォキ サイド変性ビスフエノール Aジアタリレート、エチレンオキサイド プロピレンオキサイド 変性ビスフエノール Aジメタクリレート、エチレンオキサイド プロピレンオキサイド変 性ビスフエノール Aジアタリレート、プロピレンオキサイドエチレンオキサイド（ブロックタ ィプ）変性ビスフエノール Aジメタクリレート、プロピレンオキサイドテトラメチレンォキサ イド変性ビスフエノール Aジメタクリレート、プロピレンオキサイドテトラメチレンォキサイ ド変性ビスフエノール Aジアタリレート等を挙げることができる。これらは、例えば日本 油脂株式会社よりブレンマーシリーズや東亜合成株式会社よりァロニックスシリーズと して市販されている。 [0145] Examples of the ethylenically unsaturated monomer represented by the general formula (19) and the general formula (20) include, for example, paracumylphenol ethylene oxide-modified acrylate, ethylene oxide-modified bisphenol A dimethacrylate, Ethylene oxide modified bisphenol A ditalylate, propylene oxide modified bisphenol A dimethacrylate, propylene oxide modified bisphenol A ditalylate, ethylene oxide propylene oxide Modified bisphenol A dimethacrylate, ethylene oxide Propylene oxide modified bisphenol A diatalylate, propylene oxide ethylene oxide (block type) modified bisphenol A dimethacrylate, propylene oxide tetramethylene oxide modified bisphenol A dimethacrylate, propylene And oxide tetramethylene oxide-modified bisphenol A diatalylate. These are commercially available as, for example, the Blemmer series from Nippon Oil & Fats Co., Ltd. and the Aronix series from Toa Gosei Co., Ltd.
[0146] ビュル系榭脂の合成は、例えば、開始剤の存在下、不活性ガス気流下、 50-150 °Cで 2〜： LO時間かけて行うことができる。必要に応じて前記溶剤の存在下で行っても 差し支えない。開始剤としては、ベンゾィルパーオキサイド、タメンヒドロパーォキサイ ド、 tーブチルヒドロパーオキサイド、ジイソプロピルパーォキシカーボネート、ジ tーブ チルパーオキサイド、 t ブチルパーォキシベンゾエート等の有機過酸化物、 2, 2， —ァゾビスイソブチ口-トリル等のァゾィ匕合物等を挙げることができる。開始剤は、ェ チレン性不飽和単量体 100重量部に対して好ましくは 1〜20重量部の量で使用され る。  [0146] The synthesis of bur-based rosin can be carried out, for example, in the presence of an initiator, under an inert gas stream at 50-150 ° C for 2 to LO time. If necessary, the reaction may be performed in the presence of the solvent. Initiators include organic peroxides such as benzoyl peroxide, tamen hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-tert-butyl peroxide, and t-butyl peroxybenzoate. And 2, 2, and azo compounds such as azobisisobuty-mouth-tolyl. The initiator is preferably used in an amount of 1 to 20 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer.
[0147] 本発明の顔料分散体に加えることが可能なその他添加剤としては、例えば、光重 合開始剤、連鎖移動剤、可塑剤、表面調整剤、紫外線防止剤、光安定化剤、酸ィ匕 防止剤、帯電防止剤、アンチブロッキング剤、消泡剤、粘度調整剤、ワックス、界面活 性剤、又はレべリング剤等が挙げられる。  [0147] Other additives that can be added to the pigment dispersion of the present invention include, for example, photopolymerization initiators, chain transfer agents, plasticizers, surface conditioners, ultraviolet inhibitors, light stabilizers, acids. Examples thereof include antistatic agents, antistatic agents, antiblocking agents, antifoaming agents, viscosity modifiers, waxes, surfactants, and leveling agents.
[0148] 光重合開始剤について説明する。分散剤以外の前記顔料担体のうち、エポキシ榭 脂、脂環式エポキシ榭脂、ォキセタン榭脂、及びエチレン性不飽和単量体は、活性 エネルギー線硬化性化合物であり、該化合物を含む着色組成物の塗膜は、活性ェ ネルギ一線を照射することで硬化可能である。該活性エネルギー線硬化性ィ匕合物の うち、エチレン性不飽和単量体はラジカル重合で硬化し、エポキシ榭脂、脂環式ェポ キシ榭脂、ォキセタン榭脂、及びエチレン性不飽和単量体に含まれるビニルエーテ ル類はカチオン重合で硬化する。ここで、活性エネルギー線とは電子線や紫外線な どの電離放射線のことを示す。  [0148] The photopolymerization initiator will be described. Among the pigment carriers other than the dispersant, the epoxy resin, the alicyclic epoxy resin, the oxetane resin, and the ethylenically unsaturated monomer are active energy ray-curable compounds, and a coloring composition containing the compound The coated film can be cured by irradiating with active energy lines. Among the active energy ray-curable compounds, the ethylenically unsaturated monomer is cured by radical polymerization, and epoxy resin, cycloaliphatic epoxy resin, oxetane resin, and ethylenically unsaturated monomer. Vinyl ethers contained in the polymer are cured by cationic polymerization. Here, active energy rays indicate ionizing radiation such as electron beams and ultraviolet rays.
[0149] ラジカル重合系で使用できる光重合開始剤としては、例えば、ァセトフエノン系光重 合開始剤、ベンゾイン系光重合開始剤、ベンゾフエノン系光重合開始剤、チォキサン ソン系光重合開始剤、トリアジン系光重合開始剤、ホスフィン系光重合開始剤、ォキ シム系光重合開始剤、イミダゾール系光重合開始剤、ボレート系光重合開始剤、力 ルバゾール系光重合開始剤、キノン系光重合開始剤、チタノセン系光重合開始剤等 が挙げられる。 [0149] Examples of the photopolymerization initiator that can be used in the radical polymerization system include, Initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thixoxane photopolymerization initiator, triazine photopolymerization initiator, phosphine photopolymerization initiator, oxime photopolymerization initiator, imidazole Photopolymerization initiator, borate photopolymerization initiator, rubazole photopolymerization initiator, quinone photopolymerization initiator, titanocene photopolymerization initiator, and the like.
[0150] ァセトフエノン系光重合開始剤としては、例えば、 4—フエノキシジクロロアセトフエノ ン、 4—tーブチルージクロロアセトフエノン、ジエトキシァセトフエノン、 1一（4 イソプ 口ピルフエ-ル） 2—ヒドロキシ一 2—メチルプロパン一 1オン、 1—ヒドロキシシクロ へキシルフエ-ルケトン、 2 ベンジル一 2 ジメチルァミノ一 1— (4 モルフオリノフ ェニル） ブタン 1 オン等が挙げられる。  [0150] As the acetophenone photopolymerization initiator, for example, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1 (4 isopropylpyrethane- 2) 2-hydroxy-1,2-methylpropane 1-one, 1-hydroxycyclohexyl phenyl ketone, 2 benzyl 1-2 dimethylamino 1- (4 morpholinophenyl) butane 1-on, and the like.
[0151] ベンゾイン系光重合開始剤としては、例えば、ベンゾイン、ベンゾインメチルエーテ ル、ベンゾインェチルエーテル、ベンゾインイソプロピルエーテル、ベンジルジメチル ケタール等が挙げられる。  [0151] Examples of the benzoin photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal.
[0152] ベンゾフエノン系光重合開始剤としては、例えば、ベンゾフエノン、ベンゾィル安息 香酸、ベンゾィル安息香酸メチル、 4 フエ-ルペンゾフエノン、ヒドロキシベンゾフエ ノン、アクリル化べンゾフエノン、 4一べンゾィルー 4'ーメチルジフエ-ルサルファイド 等が挙げられる。  [0152] Benzophenone-based photopolymerization initiators include, for example, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenolpenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl 4'-methyldiphenol. Such as sulfide.
[0153] チォキサンソン系光重合開始剤としては、例えば、チォキサンソン、 2 クロルチオ キサンソン、 2—メチルチオキサンソン、イソプロピルチォキサンソン、 2, 4 ジイソプ ロピルチオキサンソン等が挙げられる。  [0153] Examples of the thixanthone photopolymerization initiator include thixanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthixanthone, 2,4 diisopropylthioxanthone, and the like.
[0154] トリアジン系光重合開始剤としては、例えば、 2, 4, 6 トリクロ口一 s トリアジン、 2 —フエ-ル一 4, 6 ビス（トリクロロメチル） s トリァジン、 2— (p—メトキシフエ-ル )—4, 6 ビス（トリクロロメチル）—s トリアジン、 2— (p トリル）— 4, 6 ビス（トリク 口ロメチル） s トリァジン、 2 ピぺ口-ルー 4, 6 ビス（トリクロロメチル） s トリ ァジン、 2, 4 ビス（トリクロロメチル） 6—スチリル一 s トリァジン、 2— (ナフト一 1 —ィル） 4, 6 ビス（トリクロロメチル） s トリァジン、 2— (4—メトキシ一ナフト一 1 ィル） 4, 6 ビス（トリクロロメチル） s トリァジン、 2, 4 トリクロロメチル一（ピ ぺロニル） 6 トリァジン、 2, 4 トリクロロメチル（4'—メトキシスチリル） 6 トリア ジン等が挙げられる。 [0154] Examples of the triazine-based photopolymerization initiator include 2, 4, 6 trichlorine s triazine, 2—phenol 1, 6 bis (trichloromethyl) s triazine, 2— (p-methoxyphenol). ) —4, 6 Bis (trichloromethyl) —s triazine, 2— (p-tolyl) — 4, 6 Bis (trimethyl) s Triazine, 2 Pipet-Lu 4, 6 Bis (trichloromethyl) s Triazine 2, 4 Bis (trichloromethyl) 6-styryl 1 s triazine, 2— (Naphtho 1-yl) 4, 6 Bis (trichloromethyl) s triazine, 2— (4-Methoxy 1-naphthyl) 4, 6 Bis (trichloromethyl) s triazine, 2, 4 Trichloromethyl mono (piperonyl) 6 Triazine, 2, 4 Trichloromethyl (4'-methoxystyryl) 6 Tria Examples include gin.
[0155] ホスフィン系光重合開始剤としては、例えば、ビス（2, 4, 6 トリメチルベンゾィル） フエ-ルホスフィンオキサイド、 2, 4, 6 トリメチルベンゾィルジフエ-ルホスフィンォ キサイド等が挙げられる。  [0155] Examples of the phosphine photopolymerization initiator include bis (2,4,6 trimethylbenzoyl) phenol phosphine oxide, 2,4,6 trimethylbenzoyl diphenylphosphine oxide, and the like.
[0156] キノン系光重合開始剤としては、例えば、 9, 10 フエナンスレンキノン、カンファー キノン、ェチルアントラキノン等が挙げられる。  [0156] Examples of the quinone-based photopolymerization initiator include 9, 10 phenanthrenequinone, camphor quinone, and ethyl anthraquinone.
[0157] ォキシム系光重合開始剤としては、例えば、下記式（21)で示される化合物、 1 [9 —ェチルー 6— (2—メチルベンゾィル）—9H—力ルバゾール—3—ィル]一、 1— (O —ァセチルォキシム）や、 1, 2—オクタンジオン、 1—〔4— (フエ-ルチオ）一、 2 (O —ベンゾィルォキシム）〕、 O (ァセチル） N— (1—フエ-ル一 2—ォキソ 2— (4  [0157] Examples of the oxime-based photopolymerization initiator include compounds represented by the following formula (21): 1 [9-ethyl 6- (2-methylbenzoyl) -9H-power rubazole-3-yl] — (O —acetyloxime), 1, 2-octanedione, 1— [4— (phenylthio) one, 2 (O —benzoyloxime)], O (acetyl) N— (1—phenol 1 2-Oxo 2— (4
Figure imgf000054_0001
Figure imgf000054_0001
[0158] イミダゾール系光重合開始剤としては、例えば、 2, 2'ビス（o クロ口フエ-ル）ー4 , 5, 4' , 5，ーテトラフエ-ルー 1, 2，ービイミダゾールが挙げられる。  [0158] Examples of the imidazole-based photopolymerization initiator include 2,2'bis (o black-mouthed phenol) -4,5,4 ', 5, -tetraphenyl-1,2, -biimidazole.
[0159] ボレート系光重合開始剤としては、例えば、下記式（22)〜（25)で示される化合物 が挙げられる。  [0159] Examples of the borate photopolymerization initiator include compounds represented by the following formulas (22) to (25).
式（22)：  Formula (22):
[化 33] [Chemical 33]
Figure imgf000055_0001
式（23) [化 34]
Figure imgf000055_0002
式（24) [化 35]
Figure imgf000055_0003
式（25) [化 36] N+十 CH2CH2CH2CH3 (25)
Figure imgf000056_0001
Figure imgf000055_0001
Formula (23) [Chemical Formula 34]
Figure imgf000055_0002
Formula (24) [Chemical 35]
Figure imgf000055_0003
Formula (25) [Chemical 36] N + 10 CH 2 CH 2 CH 2 CH 3 (25)
Figure imgf000056_0001
[0160] ラジカル重合で硬化させる場合で、活性エネルギー線に電子線を使用する場合は 、光重合開始剤は必ずしも必要ではない。  [0160] In the case of curing by radical polymerization and an electron beam is used as the active energy ray, the photopolymerization initiator is not necessarily required.
[0161] カチオン重合で硬化させる場合は、活性エネルギー線種によらず、カチオン光重 合開始剤は必須成分である。カチオン光重合開始剤として、具体的には、ァリールス ルホ-ゥム塩誘導体（例えばユニオン 'カーバイド社製のサイラキュア UVI— 6990、 サイラキュア UVI— 6974、旭電化工業社製のアデカオプトマー SP— 150、アデカオ プトマー SP— 152、アデカオプトマー SP— 170、アデカオプトマー SP— 172)、ァリ ルョードニゥム塩誘導体（例えばローディア社製の RP— 2074)、アレン イオン錯体 誘導体 (例えばチバガイギ一社製のィルガキュア 261)、ジァゾ -ゥム塩誘導体、トリ アジン系開始剤及びその他のハロゲンィ匕物等の酸発生剤が挙げられる。カチオン光 重合開始剤と併用して使用する光重合促進剤としては、アントラセン、アントラセン誘 導体 (例えば旭電ィ匕工業社製のアデカオブトマー SP— 100、川崎化成の 9, 10 ジ ブトキシアントラセン、 9, 10 ェトキシアントラセン、 9, 10 ジプロポキシアントラセ ン）が挙げられる。これらのカチオン光重合開始剤、又はカチオン光重合促進剤は、 それぞれ、 1種又は複数を組み合わせて使用することができる。  [0161] In the case of curing by cationic polymerization, the cationic photopolymerization initiator is an essential component regardless of the active energy ray type. Specific examples of cationic photopolymerization initiators include arylsulphum salt derivatives (for example, Cyracure UVI-6990 manufactured by Union Carbide, Silacure UVI-6974, Adekaoptomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd., Adeka optomer SP-152, Adeka optomer SP-170, Adeka optomer SP-172), Allyodonium salt derivatives (eg RP-2074 made by Rhodia), Allen ion complex derivatives (eg Irgacure 261 made by Ciba-Gigi Co., Ltd.) ), Diazo-um salt derivatives, triazine-based initiators and other halogenated compounds. Examples of the photopolymerization accelerator used in combination with the cationic photopolymerization initiator include anthracene and anthracene derivatives (for example, Adekaobomer SP-100, manufactured by Asahi Denki Kogyo Co., Ltd., 9, 10 dibutoxyanthracene, 9, 10 ethoxyanthracene, 9, 10 dipropoxyanthracene). These cationic photopolymerization initiators or cationic photopolymerization accelerators can be used alone or in combination.
[0162] 連鎖移動剤について説明する。本発明の顔料分散体に使用できる連鎖移動剤とし ては、チオールィ匕合物が挙げられ、特にチオール基を 2個以上有する多官能チォー ルが好ましい。例えば、へキサンジチオール、デカンジチオール、 1, 4 ブタンジォ 一ノレビスチォプロピオネート、 1, 4 ブタンジオールビスチォグリコレート、エチレン グリコールビスチォグリコレート、エチレングリコールビスチォプロピオネート、トリメチロ  [0162] The chain transfer agent will be described. Examples of the chain transfer agent that can be used in the pigment dispersion of the present invention include thiol compounds, and polyfunctional thiols having two or more thiol groups are particularly preferable. For example, hexanedithiol, decanedithiol, 1,4 butanedio monorebisthiopropionate, 1,4 butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylo
'一ト、トリメチロールプロパントリスチォプロピオネート、 トリメチロールプロパントリス（3—メルカプトブチレート）、ペンタエリスリトールテトラキ スチオダリコレート、ペンタエリスリトールテトラキスチォプロピオネート、トリメルカプト プロピオン酸トリス（2 ヒドロキシェチル)イソシァヌレート、 1, 4 ジメチルメルカプト ベンゼン、 2、 4、 6 トリメルカプト一 s トリァジン、 2— (N, N ジブチルァミノ） 4 , 6—ジメルカプト— s トリァジン， トリメチロールプロパントリス（3—メルカプトイソブ チレート）等が挙げられる。これらの多官能チオールは、 1種を単独で又は 2種以上を 組み合わせて用いることができる。 'Ito, trimethylolpropane tristipropionate, Trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetraxthiodaricolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionate tris (2 hydroxyethyl) isocyanurate, 1,4 dimethylmercaptobenzene, 2 4, 6-trimercapto-s-triazine, 2- (N, N-dibutylamino) 4,6-dimercapto-s-triazine, trimethylolpropane tris (3-mercaptoisobutyrate), and the like. These polyfunctional thiols can be used singly or in combination of two or more.
[0163] これらの多官能チオールのうち、トリメチロールプロパントリスチォプロピオネート、ト リメチロールプロパントリス（3—メルカプトブチレート）、トリメチロールプロパントリス（3 メルカプトイソプチレート）を好ましく用いることができる。また、これらの多官能チォ ールは、前記光重合開始剤のうち、特にイミダゾール系光重合開始剤と組み合わせ ると、感度が増加し活性エネルギー線硬化性が向上するため好ましい。  [0163] Of these polyfunctional thiols, trimethylolpropane tristipropionate, trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3 mercaptoisoptylate) can be preferably used. . In addition, among these photopolymerization initiators, these polyfunctional wheels are particularly preferable when combined with an imidazole photopolymerization initiator because the sensitivity is increased and the active energy ray curability is improved.
[0164] [分散方法]  [0164] [Distribution method]
本発明の顔料分散体は、顔料と前記一般式 (1)で表される分散剤とを必須として、 前記の塩基性シナジスト、溶剤、前記分散剤以外の顔料担体、及びその他添加剤を 必要に応じて混合した混合物を、シエイカー、横型サンドミル、縦型サンドミル、了二 ユラ一型ビーズミル、又はアトライター等で分散することにより、顔料を顔料担体に分 散せしめて調製することができる。顔料、塩基性シナジスト、前記一般式（1)で表され る分散剤、分散剤以外の顔料担体、及びその他添加剤は、すべての成分を混合して 力も分散してもよいが、初めに顔料と塩基性シナジストとのみ、あるいは、塩基性シナ ジストと前記分散剤とのみ、あるいは、顔料と塩基性シナジストと前記分散剤とのみを 分散し、次いで、他の成分を添加して再度分散を行ってもよい。  The pigment dispersion of the present invention essentially includes the pigment and the dispersant represented by the general formula (1), and the basic synergist, the solvent, the pigment carrier other than the dispersant, and other additives. The mixture thus mixed can be prepared by dispersing the pigment in a pigment carrier by dispersing it with a shaker, horizontal sand mill, vertical sand mill, Ryura Yura type bead mill, or attritor. The pigment, the basic synergist, the dispersant represented by the general formula (1), the pigment carrier other than the dispersant, and other additives may mix all the components to disperse the force. And only the basic synergist, or only the basic synergist and the dispersing agent, or only the pigment, the basic synergist and the dispersing agent, and then add another component and perform dispersion again. May be.
[0165] また、シエイカー、横型サンドミル、縦型サンドミル、ァ-ユラ一型ビーズミル、又はァ トライター等で分散を行う前に、ニーダー、又は 3本ロールミル等の練肉混合機を使 用した前分散、 2本ロールミル等による固形分散、又は顔料への塩基性シナジスト及 び Z又は前記分散剤の処理を行ってもよい。また、ハイスピードミキサー、ホモミキサ 一、ボールミル、ロールミル、石臼式ミル、又は超音波分散機等のあらゆる分散機や 混合機が、本発明の顔料分散体を製造するために利用できる。それぞれの分散機に おいて、分散に適切な粘度領域がある場合には、各種配合成分と顔料との比率を変 えて粘度を調整することができる。 [0165] Before dispersing with a shaker, horizontal sand mill, vertical sand mill, airer type bead mill, or lighter, etc., before using a kneader or a kneader mixer such as a three-roll mill Dispersion, solid dispersion by a two-roll mill or the like, or basic synergist and Z or treatment of the dispersant may be performed on the pigment. Also, any disperser or mixer such as a high speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic disperser can be used to produce the pigment dispersion of the present invention. For each disperser In the meantime, when there is a viscosity region suitable for dispersion, the viscosity can be adjusted by changing the ratio of various blending components and pigments.
[0166] このうち 2本ロールミルを用いて顔料を予め被覆処理する工程により、チップ状顔料 分散体 (pigment dispersion chip)を得ることが好ましい。顔料を被覆処理する際の原 料の配合量は、顔料 100重量部に対して、塩基性シナジスト 1〜30重量部、前記一 般式（1)で表される分散剤及び前記分散剤以外の顔料担体 20〜200重量部、及び 溶剤 4〜200重量部の範囲であることが好ましい。塩基性シナジストの配合量が 1重 量部未満の場合は、こうして得られたチップ状顔料分散体からペースト状顔料分散 体 (pigment  [0166] Of these, it is preferable to obtain a pigment dispersion chip by performing a coating treatment of the pigment in advance using a two-roll mill. The compounding amount of the raw material when coating the pigment is 1 to 30 parts by weight of a basic synergist with respect to 100 parts by weight of the pigment, the dispersant represented by the general formula (1) and other than the dispersant. The range is preferably 20 to 200 parts by weight of the pigment carrier and 4 to 200 parts by weight of the solvent. If the amount of basic synergist is less than 1 part by weight, the paste-like pigment dispersion (pigment)
dispersion paste)を調製する場合に、ペースト状顔料分散体を低粘度化させる効果 力 、さぐ 30重量部を超える場合は、塩基性シナジストが過剰となり、未吸着の塩基 性シナジスト同士が凝集するため、チップ状顔料分散体力も調製されるペースト状顔 料分散体が増粘する。また、前記分散剤及び分散剤以外の顔料担体の合計配合量 が 20重量部未満の場合は、充分に顔料表面を被覆できず、顔料の分散安定性が低 くなり、 200重量部を超える場合は、顔料に吸着しない遊離の前記分散剤及び分散 剤以外の顔料担体により、チップ状顔料分散体から調製されるペースト状顔料分散 体の粘度が上昇する。また、溶剤の配合量が 4重量部未満の場合は、塩基性シナジ スト及び前記分散剤及び分散剤以外の顔料担体の顔料に対する初期の塗れが不充 分で、充分に顔料を被覆しないため、チップ状顔料分散体から調製されるペースト状 顔料分散体の粘度が安定しないことがあり、 200重量部を超える場合は、顔料の被 覆処理が困難となる。  When preparing dispersion paste), the effect of reducing the viscosity of the paste-like pigment dispersion is over 30 parts by weight.If the amount exceeds 30 parts by weight, the basic synergists become excessive and the unadsorbed basic synergists aggregate. The paste-like pigment dispersion, which also has a chip-like pigment dispersion strength, thickens. Further, when the total amount of the dispersant and the pigment carrier other than the dispersant is less than 20 parts by weight, the pigment surface cannot be sufficiently covered, and the dispersion stability of the pigment is lowered, and the amount exceeds 200 parts by weight. The viscosity of the paste-like pigment dispersion prepared from the chip-like pigment dispersion is increased by the free dispersant that is not adsorbed on the pigment and the pigment carrier other than the dispersant. In addition, when the amount of the solvent is less than 4 parts by weight, the initial coating on the pigment of the basic carrier and the pigment carrier other than the dispersant and the dispersant is insufficient, and the pigment is not sufficiently covered. The viscosity of the paste-like pigment dispersion prepared from the chip-like pigment dispersion may not be stable, and when it exceeds 200 parts by weight, it is difficult to cover the pigment.
[0167] 顔料の被覆処理は、具体的には、下記の 2段階の工程により行うことができる。  [0167] Specifically, the coating treatment of the pigment can be performed by the following two-stage process.
第 1工程は、顔料、前記一般式 (1)で表される分散剤及び前記分散剤以外の顔料 担体、及び溶剤等を含む組成物を、 20回程度 2本ロールに通すことにより顔料への 榭脂成分の濡れと吸着を進行させるチップ化工程である。このチップ化工程で、配合 した溶剤のうち約 80重量％程度が揮発する。また、前記分散剤及び前記分散剤以 外の顔料担体が顔料に吸着した混練物が得られる。  In the first step, the composition containing the pigment, the dispersant represented by the general formula (1), the pigment carrier other than the dispersant, and the solvent is passed through the two rolls about 20 times to obtain the pigment. This is a chip forming process in which wetting and adsorption of the rosin component proceed. In this chipping process, about 80% by weight of the blended solvent is volatilized. Further, a kneaded product is obtained in which the dispersant and a pigment carrier other than the dispersant are adsorbed on the pigment.
第 2工程は、チップ化工程（1)により前記分散剤及び前記分散剤以外の顔料担体 が顔料に吸着した混練物の加熱、混練を続けて、顔料粒子表面に被覆層を形成す る被覆処理工程である。混練物の粘度が高ぐ機械上、混練できない場合は、適量 の溶剤を追加し、混練を助けることができる。 In the second step, the dispersant and the pigment carrier other than the dispersant are converted into the chip forming step (1). Is a coating treatment step in which the kneaded material adsorbed on the pigment is continuously heated and kneaded to form a coating layer on the surface of the pigment particles. If the kneaded product cannot be kneaded on a machine with high viscosity, an appropriate amount of solvent can be added to aid kneading.
[0168] 前記一般式 (1)で表される分散剤及び前記分散剤以外の顔料担体が、架橋可能 な官能基を有する場合には、前記被覆処理工程 (2)で榭脂成分の架橋が生じ、一 部に榭脂切断も見られる。この反応は、過度な機械的な加圧と磨砕、更には加熱の 結果によるもので、メカノケミカルな反応（mechanochemical reaction)であり、顔料と前 記分散剤及び前記分散剤以外の顔料担体のみでは榭脂成分の架橋反応は生じに くい。顔料と榭脂成分とを混練する際に、塩基性シナジストを用いることにより、塩基 性シナジストと前記分散剤及び前記分散剤以外の顔料担体とが顔料表面に強固に 吸着し、更に加熱と加圧混練を行うことにより前記分散剤及び前記分散剤以外の顔 料担体の架橋が生じると推定される。  [0168] When the dispersant represented by the general formula (1) and the pigment carrier other than the dispersant have a crosslinkable functional group, the resin component is crosslinked in the coating treatment step (2). It occurs, and part of the oil is cut. This reaction is the result of excessive mechanical pressure and grinding, and further heating, and is a mechanochemical reaction. Only the pigment, the dispersant and the pigment carrier other than the dispersant are used. Then, it is difficult for the cross-linking reaction of the resin component to occur. By using a basic synergist when kneading the pigment and the resin component, the basic synergist, the dispersant and the pigment carrier other than the dispersant are firmly adsorbed on the pigment surface, and further heated and pressurized By kneading, it is presumed that crosslinking of the dispersant and a pigment carrier other than the dispersant occurs.
[0169] 前記被覆処理工程（2)での加熱温度は、 80°C〜120°Cの範囲であることが好まし い。 80°C未満の温度では、前記一般式（1)で表される分散剤及び前記分散剤以外 の顔料担体が十分に架橋しない場合があり、 120°Cを超える温度では、前記分散剤 及び前記分散剤以外の顔料担体の劣化が生じる場合がある。  [0169] The heating temperature in the coating treatment step (2) is preferably in the range of 80 ° C to 120 ° C. When the temperature is less than 80 ° C, the dispersant represented by the general formula (1) and the pigment carrier other than the dispersant may not be sufficiently crosslinked, and when the temperature exceeds 120 ° C, the dispersant and the Deterioration of the pigment carrier other than the dispersant may occur.
[0170] 顔料表面に吸着しなかった余剰の前記分散剤及び前記分散剤以外の顔料担体は 、チップ状顔料分散体から調製されるペースト状顔料分散体の粘度等の物性に影響 を及ぼすことがあるので、洗浄やろ過等により除去してもよい。また、被覆処理顔料は 、乾燥しても凝集しない場合には、洗浄後に乾燥してもよいが、被覆処理時に用いた 溶剤が、目的の用途に問題のないものであれば乾燥する必要がない。  [0170] The surplus dispersant that has not been adsorbed on the pigment surface and the pigment carrier other than the dispersant may affect physical properties such as the viscosity of the paste-like pigment dispersion prepared from the chip-like pigment dispersion. Therefore, it may be removed by washing or filtration. The coated pigment may be dried after washing if it does not agglomerate after drying, but it is not necessary to dry it if the solvent used in the coating treatment is satisfactory for the intended use. .
[0171] [インク]  [0171] [Ink]
本発明の顔料分散体から、種々のインク (ink  From the pigment dispersion of the present invention, various inks (ink
compositions)を調製することができ、インクの種類は限定されない。代表的なインクと しては、例えば、非水系インク、水系インク、又は無溶剤系の塗料、グラビアインク、ォ フセットインク、カラーフィルタ用インク（ink  compositions) can be prepared and the type of ink is not limited. Typical inks include, for example, non-aqueous inks, water-based inks, or solvent-free paints, gravure inks, offset inks, and color filter inks (inks).
composition for color filter)、フ Jフ' ~~フイノレタ用黒色インク (black ink composition for color filter)、インクジェットインク (ink composition for inkjet printing)、アンタルぺ' ~~ノ ~~ 用インク、プラスチック着色剤等に利用できる。 composition for color filter), black ink composition for color filter), ink composition for inkjet printing, ink for anthalpe, and colorants for plastics.
[0172] 特に、微細な顔料を用いる必要があるカラーフィルタ用インク、感光性黒色インク (p hotosensitive black ink composition)、インクジェットインク、及びカラーフイノレタ用イン クジエツトインク (inkjet [0172] In particular, color filter inks that require the use of fine pigments, photosensitive black ink compositions, ink-jet inks, and ink jet inks for color finalizers (inkjet
ink for color filter)には好適である。これら用途においては、分散機で分散後に、粗 大粒子や異物除去を目的にフィルタや遠心法により濾過することが好ましい。  ink for color filter). In these applications, it is preferable to filter by a filter or centrifugal method for the purpose of removing coarse particles and foreign matters after being dispersed by a disperser.
[0173] [カラーフィルタ用インク] [0173] [Color filter ink]
カラーフィルタ用インクに適用する場合について説明する。本発明のカラーフィルタ 用インクは、例えば、薄型テレビジョンなどに利用されている液晶ディスプレイパネル のカラーフィルタ基板の製造に好適に用いることができる。本発明のカラーフィルタ用 インクは、顔料、前記一般式（1)で表される分散剤、及び前記エチレン性不飽和単 量体を必須とし、必要に応じてその他の顔料担体、及びその他添加剤を配合して構 成される。  The case of applying to color filter ink will be described. The color filter ink of the present invention can be suitably used for the production of a color filter substrate of a liquid crystal display panel used for, for example, a thin television. The color filter ink of the present invention essentially comprises a pigment, the dispersant represented by the general formula (1), and the ethylenically unsaturated monomer, and other pigment carriers and other additives as necessary. It is composed of
[0174] 更に、感光性榭脂を配合することができる。感光性榭脂としては、例えば、水酸基、 カルボキシル基、及び Z又はアミノ基等の反応性の置換基を有する榭脂に、イソシァ ネート基、アルデヒド基、又はエポキシ基等の反応性置換基を有する (メタ)アクリル 化合物やケィヒ酸を反応させて、（メタ)アタリロイル基、又はスチリル基等の光架橋性 基を該高分子に導入した榭脂が用いられる。また、スチレン 無水マレイン酸共重合 物や α—ォレフィン 無水マレイン酸共重合物等の酸無水物を含む高分子を、ヒド ロキシアルキル (メタ)アタリレート等の水酸基を有する (メタ)アクリルィ匕合物によりノヽ 一フェステルィ匕して得られたものも用いられる。  [0174] Furthermore, a photosensitive resin can be blended. As the photosensitive resin, for example, a resin having a reactive substituent such as a hydroxyl group, a carboxyl group, and a Z or amino group has a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group. A resin obtained by reacting a (meth) acrylic compound or keihynoic acid to introduce a photocrosslinkable group such as a (meth) atallyloyl group or a styryl group into the polymer is used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are used as (meth) acrylic compounds having a hydroxyl group such as hydroxyalkyl (meth) acrylate. The one obtained by using the no-festeri method is also used.
[0175] また、本発明のカラーフィルタ用インクを用いてアルカリ現像によりフィルタセグメン トを形成させる場合には、顔料担体に、アルカリ可溶型非感光性榭脂を含有させるこ とが好ましい。アルカリ可溶型非感光性榭脂とは、アルカリ水溶液に溶解し、ラジカル により架橋しない榭脂であり、例えば、カルボキシル基、又はスルホン基などの酸性 官能基を有する重量平均分子量 1000〜500000、好ましくは 5000〜 100000の榭 脂が挙げられる。アルカリ可溶型非感光性榭脂として、具体的には、酸性官能基を 有するビニル系榭脂、 a一才レフイン Z (無水）マレイン酸共重合体、スチレン Z (無 水）マレイン酸共重合体、スチレン Zスチレンスルホン酸共重合体、エチレン Z (メタ） アクリル酸共重合体、又はイソブチレン Z (無水）マレイン酸共重合体などが挙げられ る。中でも、酸性官能基を有するビュル系榭脂、《—才レフイン Z (無水)マレイン酸 共重合体、スチレン ζ (無水）マレイン酸共重合体、及びスチレン Ζスチレンスルホン 酸共重合体力 選ばれる少なくとも 1種の榭脂、特に酸性官能基を有するビニル系 榭脂は、耐熱性、透明性が高いため、好適に用いられる。酸性官能基を有するビ- ル系榭脂は、前記エチレン性不飽和単量体のうち、カルボキシル基、リン酸基、又は スルホン酸基を有するエチレン性不飽和単量体を前記方法で共重合することにより 容易に得ることができる。 [0175] Further, when the filter segment is formed by alkali development using the color filter ink of the present invention, the pigment carrier preferably contains an alkali-soluble non-photosensitive resin. Alkali-soluble non-photosensitive resin is a resin that dissolves in an alkaline aqueous solution and does not crosslink with radicals, and has a weight average molecular weight of 1,000 to 500,000 having an acidic functional group such as a carboxyl group or a sulfone group, preferably Examples include 5000 to 100000 resins. As an alkali-soluble non-photosensitive resin, specifically, an acidic functional group Vinyl having榭脂, one year old Refuin Z (anhydride) maleic acid copolymers a, styrene Z (anhydrous) maleic acid copolymers, styrene Z styrene sulfonic acid copolymer, ethylene Z (meth) acrylic acid copolymerization And an isobutylene Z (anhydrous) maleic acid copolymer. Among them, bur resin having an acidic functional group, <<-year-old refin Z (anhydrous) maleic acid copolymer, styrene ζ (anhydrous) maleic acid copolymer, and styrene-styrene sulfonic acid copolymer power at least 1 selected A seed resin, especially a vinyl resin having an acidic functional group, is preferably used because of its high heat resistance and transparency. The beer-based resin having an acidic functional group is a copolymer of ethylenically unsaturated monomers having a carboxyl group, a phosphoric acid group, or a sulfonic acid group among the ethylenically unsaturated monomers by the above method. This can be easily obtained.
[0176] 本発明のカラーフィルタ用インクは、「塩基性基を有する化合物」を含有することが 好ましい。顔料の分散に優れた「塩基性基を有する化合物」は、分散後の顔料の再 凝集を抑制する効果が大きい。従って、前記一般式 (1)で表される本発明の分散剤 を用い、その優れた分散性を利用して、顔料担体中に良好に分散された顔料を含む インクを調製する場合には、顔料の再凝集を抑制して、透明性に優れたカラーフィル タを得るために、「塩基性基を有する化合物」を用いるのが好ましい。本発明による力 ラーフィルタ用インクに、「塩基性基を有する化合物」を含有させることは、分散剤が 顔料に対し、より良好な吸着 Ζ配向面を形成することができるため好ましい。「塩基性 基を有する化合物」の配合量は、顔料 100重量部に対し、好ましくは 1〜40重量部、 更に好ましくは 5〜 15重量部である。「塩基性基を有する化合物」の配合量が 1重量 部より少ないと、分散効果が不十分となり、 40重量部より多いと、これも分散に影響を 及ぼすことがある。  [0176] The color filter ink of the present invention preferably contains "a compound having a basic group". A “compound having a basic group” excellent in pigment dispersion has a great effect of suppressing reaggregation of the pigment after dispersion. Therefore, when using the dispersant of the present invention represented by the general formula (1) and utilizing its excellent dispersibility to prepare an ink containing a pigment well dispersed in a pigment carrier, In order to suppress reaggregation of the pigment and obtain a color filter having excellent transparency, it is preferable to use a “compound having a basic group”. It is preferable to add “a compound having a basic group” to the ink for a power filter according to the present invention, because the dispersant can form a better adsorption / alignment surface with respect to the pigment. The amount of the “compound having a basic group” is preferably 1 to 40 parts by weight, and more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the pigment. If the amount of the “compound having a basic group” is less than 1 part by weight, the dispersion effect is insufficient, and if it is more than 40 parts by weight, this may also affect the dispersion.
[0177] 「塩基性基を有する化合物」としては、塩基性榭脂ゃ塩基性界面活性剤、上述した 塩基性シナジストなどが挙げられる。中でも、顔料に対し、より良好な吸着 Ζ配向を 形成する塩基性シナジストが好まし ヽ。  [0177] Examples of the “compound having a basic group” include a basic linseed basic surfactant and the above-mentioned basic synergist. Of these, basic synergists that form better adsorption and orientation of pigments are preferred.
[0178] 塩基性榭脂としては、例えば、脂肪族ポリアミン Ζポリエステルグラフト重合体など が挙げられる。  [0178] Examples of the basic rosin include aliphatic polyamines and polyester graft polymers.
塩基性界面活性剤としては、例えば、ラウリル硫酸モノエタノールァミン、ラウリル硫 酸トリエタノールァミン、ラウリル硫酸アンモ-ゥム、ステアリン酸モノエタノールァミン、 又はスチレン アクリル酸共重合体のモノエタノールァミンなどのァ-オン性界面活 性剤、アルキルジメチルァミノ酢酸べタインなどのアルキルべタイン、アルキルイミダゾ リンなどの両性界面活性剤等が挙げられる。これらは、単独で又は 2種以上を組み合 わせて用いることができる。 Examples of basic surfactants include lauryl sulfate monoethanolamine, lauryl sulfate. Key-on surfactants such as triethanolamine acid, ammonium lauryl sulfate, monoethanolamine stearate, or monoethanolamine of styrene acrylic acid copolymer, alkyldimethylaminoacetic acid betaine And amphoteric surfactants such as alkylbetaines and alkylimidazolines. These can be used alone or in combination of two or more.
[0179] 本発明のカラーフィルタ用インクには、顔料を充分に顔料担体中に分散させ、ガラ ス等の透明基板上に乾燥膜厚が 0. 2〜5 mとなるように塗布してフィルタセグメント を形成することを容易にするために、前記溶剤を含有させることができる。  [0179] In the color filter ink of the present invention, the pigment is sufficiently dispersed in a pigment carrier and applied to a transparent substrate such as glass so that the dry film thickness is 0.2 to 5 m. In order to facilitate the formation of segments, the solvent can be included.
[0180] 本発明のカラーフィルタ用インクを紫外線照射により硬化する場合には、該インクに 、前記光重合開始剤が添加される。  [0180] When the color filter ink of the present invention is cured by ultraviolet irradiation, the photopolymerization initiator is added to the ink.
また、本発明のカラーフィルタ用インクには、インクの経時粘度を安定ィ匕させるため に、貯蔵安定剤を含有させることができる。貯蔵安定剤としては、例えば、ベンジルト リメチルクロライド、又はジェチルヒドロキシァミンなどの 4級アンモ-ゥムクロライド、乳 酸、又はシユウ酸などの有機酸及びそのメチルエーテル、 t ブチルピロカテコール、 テトラエチルホスフィン、又はテトラフエ-ルフォスフィンなどの有機ホスフィン、あるい は亜リン酸塩等が挙げられる。  Further, the color filter ink of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the ink over time. Examples of storage stabilizers include benzyltrimethyl chloride or quaternary ammonium chloride such as jetylhydroxyamine, organic acids such as lactic acid or oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, Alternatively, organic phosphines such as tetraphenylphosphine, phosphites, and the like can be given.
[0181] フィルタセグメントをフォトリソグラフィ一法により形成するために、本発明のカラーフ ィルタ用インクを用いる場合には、そのカラーフィルタ用インク中に、顔料が 1. 5〜15 重量％の割合で含有されることが好ましい。また、フィルタセグメントを印刷法により形 成するために、本発明のカラーフィルタ用インクを用いる場合には、そのカラーフィル タ用インク中に、顔料が 1. 5〜45重量％の割合で含有されることが好ましい。また、 顔料は、最終フィルタセグメント中に、好ましくは 10〜50重量％、より好ましくは 20〜 45重量％の割合で含有され、その残部は、分散剤を含む顔料担体により提供されて 、ることが好まし!/、。  [0181] When the color filter ink of the present invention is used to form the filter segment by a photolithography method, the pigment is contained in the color filter ink in a proportion of 1.5 to 15% by weight. It is preferred that In addition, when the color filter ink of the present invention is used to form a filter segment by a printing method, a pigment is contained in the color filter ink in a proportion of 1.5 to 45% by weight. It is preferable. Further, the pigment is preferably contained in the final filter segment in a proportion of 10 to 50% by weight, more preferably 20 to 45% by weight, and the remainder is provided by a pigment carrier containing a dispersant. Is preferred!
[0182] 本発明のカラーフィルタ用インクは、グラビアオフセット用印刷インク、水無しオフセ ット印刷インク、シルクスクリーン印刷用インク、溶剤現像型あるいはアルカリ現像型 着色レジスト材として調製することができる。特に、アルカリ現像型着色レジスト材であ ることが好ましい。 [0183] [感光性黒色インク] [0182] The color filter ink of the present invention can be prepared as a gravure offset printing ink, a waterless offset printing ink, a silk screen printing ink, a solvent developing type or an alkali developing type colored resist material. In particular, an alkali development type colored resist material is preferable. [0183] [Photosensitive black ink]
感光性黒色インク（photosensitive  Photosensitive black ink (photosensitive
black ink composition)に適用する場合を説明する。本発明の感光性黒色インクは、 カーボンブラック、光重合開始剤、塩基性シナジスト、エチレン性不飽和単量体、及 び分散剤を含有してなる。本発明の感光性黒色インクは、特にカラーフィルタのブラ ックマトリックス用途 (application  A case of applying to black ink composition) will be described. The photosensitive black ink of the present invention comprises carbon black, a photopolymerization initiator, a basic synergist, an ethylenically unsaturated monomer, and a dispersant. The photosensitive black ink of the present invention is particularly used in black matrix applications for color filters.
for black matrix on color filter)とすること力 S好まし ヽ。  for black matrix on color filter).
[0184] 本発明の感光性黒色インクにおいて、前記一般式（1)で表される分散剤の含有量 は、感光性黒色インクの全固形分重量を基準（100重量％)として、好ましくは 0. 01 〜30重量部、より好ましくは 0. 1〜30重量部、更に好ましくは 0. 5〜20重量部であ る。前記分散剤の含有量が 0. 01重量部より少ないとガラスへの密着性や感光性黒 色インクの安定効果が不十分となり、 30重量部を超えるとガラスへの密着性や感光 性黒色インクの安定効果が悪くなる場合がある。  In the photosensitive black ink of the present invention, the content of the dispersant represented by the general formula (1) is preferably 0 on the basis of the total solid weight of the photosensitive black ink (100% by weight). .01 to 30 parts by weight, more preferably 0.1 to 30 parts by weight, still more preferably 0.5 to 20 parts by weight. When the content of the dispersant is less than 0.01 parts by weight, the adhesion to glass and the photosensitive black ink are insufficient, and when it exceeds 30 parts by weight, the adhesion to glass and the photosensitive black ink are insufficient. The stability effect may be worse.
[0185] 更に、本発明の感光性黒色インクには、前記一般式（1)で表される分散剤以外の 顔料担体を配合することができる。  [0185] Further, the photosensitive black ink of the present invention may contain a pigment carrier other than the dispersant represented by the general formula (1).
本発明の感光性黒色インクにおいて、榭脂の重量 [P1]とエチレン性不飽和単量 体の重量 [Ml]との比率 [M1ZP1]は、 0. 10〜0. 70であること力 子ましく、 0. 15 〜0. 65であることがより好ましぐ 0. 20-0. 60であることが特に好ましい。 [M1/P 1]が 0. 10未満であると低感度となり、 [M1ZP1]が 0. 70を超えるとブラックマトリツ タスのパターン形状の直線性不良、断面形状不良あるいはタック等が生じる。  In the photosensitive black ink of the present invention, the ratio [M1ZP1] of the weight [P1] of the resin and the weight [Ml] of the ethylenically unsaturated monomer is from 0.10 to 0.70. In particular, 0.15 to 0.65 is more preferable, and 0.20 to 60.60 is particularly preferable. When [M1 / P 1] is less than 0.10, the sensitivity is low, and when [M1ZP1] is more than 0.70, the black matrix pattern shape is poor in linearity, cross-sectional shape, or tack.
エチレン性不飽和単量体の重量 [Ml]と光重合開始剤の重量 [II]との比率 [II Z Ml]は、 0. 15-0. 62であることが好ましい。 [I1ZM1]力 0. 15未満では、低感 度となり、光重合の進行が困難となるからである。また、 [I1ZM1]が 0. 62を超えると ブラックマトリックスのパターン形状の直線性不良、断面形状不良あるいはタック等が 生じるカゝらである。  The ratio [II Z Ml] between the weight [Ml] of the ethylenically unsaturated monomer and the weight [II] of the photopolymerization initiator is preferably 0.15-0.62. This is because if the [I1ZM1] force is less than 0.15, the sensitivity becomes low and the progress of photopolymerization becomes difficult. In addition, when [I1ZM1] exceeds 0.62, the black matrix pattern shape may have poor linearity, cross-sectional shape failure, or tack.
[0186] 本発明の感光性黒色インクでは、遮光成分として、カーボンブラックを使用する。力 一ボンブラックは、前記顔料として説明したものを使用できるが、特に平均一次粒子 径 20〜40nm、比表面積 70〜180m2Zg、吸油量 100cm3Zl00g以下のカーボン ブラックを好ましく使用することができる。なお、本発明の吸油量とはフタル酸ジブチ ルの吸油量をいう。 In the photosensitive black ink of the present invention, carbon black is used as a light shielding component. As the one-bon black, those described above as the pigment can be used, but in particular, carbon having an average primary particle diameter of 20 to 40 nm, a specific surface area of 70 to 180 m 2 Zg, and an oil absorption of 100 cm 3 Zl00 g or less Black can be preferably used. The oil absorption amount of the present invention refers to the oil absorption amount of dibutyl phthalate.
[0187] 平均一次粒子径が 20nm未満であるカーボンブラックを単独で使用した感光性黒 色インクでは、単位体積当たりのカーボンブラック粒子数が多数となり、遮光性の観 点で有利であるが、高遮光性のため光硬化性が劣る。更に、カーボンブラックの安定 分散が困難であり、現像後のガラス基板に黒色組成物の一部が残る現象、又は残渣 (あるいは地汚れとも呼ばれる）という現象を引き起こす問題がある。  [0187] A photosensitive black ink using carbon black having an average primary particle size of less than 20 nm alone is advantageous in terms of light shielding properties because it has a large number of carbon black particles per unit volume. Photocurability is inferior due to light-shielding properties. Further, it is difficult to stably disperse carbon black, and there is a problem that a phenomenon that a part of the black composition remains on a glass substrate after development or a phenomenon of residue (also called background stain) occurs.
[0188] 一方、平均一次粒子径カ 0nmを超えるカーボンブラックを含む感光性黒色インク では、単位体積当たりのカーボンブラック粒子数が少数となり、光硬化性の点では有 利となる力 遮光性及びブラックマトリックスのパターン形状、特に直線性が不十分で ある。  On the other hand, the photosensitive black ink containing carbon black having an average primary particle size exceeding 0 nm has a small number of carbon black particles per unit volume, which is advantageous in terms of photocuring properties. The matrix pattern shape, especially linearity, is insufficient.
[0189] 比表面積が 70m2/g未満のカーボンブラックを用いる場合には、ブラックマトリック スのパターン形状の劣化や密着性の低下を引き起こし易ぐ 180m2Zgより大きい力 一ボンブラックを用いる場合は、カーボンブラックの安定分散が難しくなる。 [0189] When using carbon black with a specific surface area of less than 70 m 2 / g, a force greater than 180 m 2 Zg is likely to cause deterioration of the black matrix pattern shape and adhesion. , It becomes difficult to stably disperse carbon black.
[0190] カーボンブラックの吸油量は、光硬化性の観点から 100cm3Zl00g以下であること が好ましぐ 0〜80cm3Zl00gであることがより好ましぐ 0〜50cm3ZlOOgであるこ とが特に好ましい。 [0190] oil absorption of the carbon black, and it is Dearuko more preferably tool 0~50cm 3 ZlOOg from the viewpoint of photocuring is 100cm 3 Zl00g following are preferred instrument 0~80cm 3 Zl00g particularly preferable.
[0191] 平均一次粒子径 20〜40nm、比表面積 70〜180m2Zg、吸油量 100cm3Zl00g 以下であるカーボンブラックとしては、例えば、 CABOT製の MOGUL L、 BLACK PEARLS (L, 520, 450, 430) , REGAL (660R, 660, 500R, 330R, 330, 3 00R, 250R, 250, 99R, 991)、三菱ィ匕学製の MA (77, 7, 8, 11, 100, 100R, 1 00S, 200RB, 14)、 # (52, 50, 47, 45, 45L, 44, 33, 32, 95, 85, 260)、 CF 9、 DEGUSSA製の Special Black550、 Printex (55, 45, 300, ES23, 35) , 3 50、旭カーボン製の旭 # 70L N— 326、コロンビヤン'カーボン製の RAVEN (125 5, 1250, 1200, 1170, 1040, 1035, 1030, 1020, 1000, 890POWDER, 8 90H POEDER, 850)等を挙げることができ、好ましくは、 CABOT製の REGAL ( 250R, 250)、三菱ィ匕学製の # 47、特に好ましくは三菱ィ匕学製の # 47を用いること ができる。 [0192] 一方、ブラックマトリックスの遮光性を向上させる目的で、 2種類の遮光性材料を併 用して光学濃度 (OD値)を高める手法、すなわち平均粒径の小さいカーボンブラック と平均粒径の大き 、カーボンブラックとを併用して、ブラックマトリックス内で最密充填 構造を形成することにより、 OD値を向上させることが提案されている（例えば、特開 平 9 133806号公報、特開平 9 279082号公報、特開平 11— 80584号公報)。 本発明の感光性黒色インクにおいても、同様に 2種類のカーボンブラックを併用して OD値を高める手法を採用することが可能である。 [0191] Carbon black having an average primary particle size of 20 to 40 nm, a specific surface area of 70 to 180 m 2 Zg, and an oil absorption of 100 cm 3 Zl00 g or less is, for example, MOGUL L, BLACK PEARLS (L, 520, 450, 430 manufactured by CABOT) ), REGAL (660R, 660, 500R, 330R, 330, 300R, 250R, 250, 99R, 991), MA (77, 7, 8, 11, 100, 100R, 100S, 200RB, manufactured by Mitsubishi Chemical) , 14), # (52, 50, 47, 45, 45L, 44, 33, 32, 95, 85, 260), CF 9, Special Black550 from DEGUSSA, Printex (55, 45, 300, ES23, 35) , 3 50, Asahi Carbon's Asahi # 70L N- 326, Colombian 'Carbon RAVEN (125 5, 1250, 1200, 1170, 1040, 1035, 1030, 1020, 1000, 890POWDER, 8 90H POEDER, 850) etc. Preferably, REGAL (250R, 250) manufactured by CABOT, # 47 manufactured by Mitsubishi Kagaku, and particularly preferably # 47 manufactured by Mitsubishi Kagaku can be used. [0192] On the other hand, for the purpose of improving the light-shielding property of the black matrix, a method of increasing the optical density (OD value) by combining two kinds of light-shielding materials, that is, carbon black having a small average particle size and an average particle size It has been proposed to improve the OD value by forming a close-packed structure in a black matrix in combination with carbon black (for example, JP-A-9 133806 and JP-A-9 279082). No., JP-A-11-80584). Similarly, in the photosensitive black ink of the present invention, it is possible to employ a technique for increasing the OD value by using two types of carbon black in combination.
[0193] 本発明の感光性黒色インクにおいて、 OD値を高めるために 2種類以上のカーボン ブラックを併用する場合は、遮光成分として、  [0193] In the photosensitive black ink of the present invention, when two or more types of carbon black are used in combination to increase the OD value,
平均一次粒子径の差が 5nm以上であり、  The average primary particle size difference is 5nm or more,
(al)平均一次粒子径が 8〜20nmである第 1のカーボンブラックと、  (al) a first carbon black having an average primary particle size of 8 to 20 nm;
(a2)平均一次粒子径が 21〜40nmである第 2のカーボンブラックとを含有し、かつ (a2) containing a second carbon black having an average primary particle diameter of 21 to 40 nm, and
40nmを超えるカーボンブラックを含まな!/、インクを用いることが好まし!/、。 Does not contain carbon black exceeding 40nm! /, Preferably using ink! /.
[0194] 平均一次粒子径が 8〜20nmである第 1のカーボンブラック（al)を単独で使用した 感光性黒色インクでは、単位体積当たりのカーボンブラック粒子数が多数となり、遮 光性の観点で有利であるが、高遮光性のため光硬化性が劣る。更に、カーボンブラ ックの安定分散が困難であり、現像後のガラス基板に黒色組成物の一部が残る現象 、又は残渣 (あるいは地汚れとも呼ばれる） t 、う現象を引き起こすと 、う問題がある。  [0194] In the photosensitive black ink using the first carbon black (al) having an average primary particle diameter of 8 to 20 nm alone, the number of carbon black particles per unit volume is large, and from the viewpoint of light shielding properties. Although advantageous, it is inferior in photocurability because of its high light shielding properties. In addition, it is difficult to stably disperse carbon black, and if a phenomenon occurs in which a part of the black composition remains on the glass substrate after development, or a residue (also called background stain), or a phenomenon that occurs, is there.
[0195] 一方、平均一次粒子径が 21〜40nmである第 2のカーボンブラック（a2)を単独で 使用した感光性黒色インクでは、単位体積当たりのカーボンブラック粒子数が少数と なり、光硬化性は有利となるが遮光性が不十分である。  [0195] On the other hand, the photosensitive black ink using the second carbon black (a2) having an average primary particle diameter of 21 to 40 nm alone has a small number of carbon black particles per unit volume, and is photocurable. Is advantageous, but the light shielding property is insufficient.
[0196] また、平均一次粒子径カ 0nmを超えるカーボンブラックを含む感光性黒色インク では、単位体積当たりのカーボンブラック粒子数が少数となり、光硬化性は有利とな る力 遮光性及びブラックマトリックスのパターン形状、特に直線性が不十分である。  [0196] In addition, in the photosensitive black ink containing carbon black having an average primary particle size of more than 0 nm, the number of carbon black particles per unit volume is small, and photocurability is advantageous. The pattern shape, particularly the linearity, is insufficient.
[0197] 前記のように 2種類以上のカーボンブラックを併用する場合、第 1のカーボンブラッ ク（al)としては、平均一次粒子径が 10〜18nmのものが好ましぐ更に比表面積が 2 00〜600m2Zgであるカーボンブラックを好適に使用することができる。比表面積が 200m2Zg未満のカーボンブラックを用いる場合には、ブラックマトリックスのパターン 形状の劣化や密着性の低下を引き起こし易ぐ 600m2Zgより大きいカーボンブラッ クを用いる場合は、カーボンブラックの安定分散が難しくなる。なお、平均一次粒子 径が 8nm未満のカーボンブラックは製造が困難であるため、第 1のカーボンブラック（ al)として適当ではない。 [0197] When two or more types of carbon black are used in combination as described above, the first carbon black (al) is preferably one having an average primary particle size of 10 to 18 nm. Carbon black which is ˜600 m 2 Zg can be preferably used. When using carbon black with a specific surface area of less than 200 m 2 Zg, the black matrix pattern When carbon black larger than 600m 2 Zg, which tends to cause shape deterioration and adhesion deterioration, is used, it becomes difficult to stably disperse carbon black. Carbon black having an average primary particle size of less than 8 nm is difficult to produce and is not suitable as the first carbon black (al).
[0198] また、第 2のカーボンブラック（a2)としては、平均一次粒子径が 22〜37nmのもの が好ましく、更に比表面積力 0〜600m2/gであるカーボンブラックを好適に使用す ることができる。比表面積力 0m2/g未満のカーボンブラックを用いる場合には、ブ ラックマトリックスのパターン形状の劣化や密着性の低下を引き起こし易く、 600m2Z gより大きいカーボンブラックを用いる場合は、カーボンブラックの安定分散が難しくな る。 [0198] The second carbon black (a2) preferably has an average primary particle diameter of 22 to 37 nm, and carbon black having a specific surface area force of 0 to 600 m 2 / g is preferably used. Can do. When using carbon black with a specific surface area of less than 0 m 2 / g, it tends to cause deterioration of the pattern shape and adhesion of the black matrix. When using carbon black larger than 600 m 2 Z g, Stable dispersion becomes difficult.
[0199] 更に、第 1のカーボンブラック（al)と第 2のカーボンブラック（a2)の平均一次粒子径 の差が 5nm未満の場合は、第 1のカーボンブラック（al)と第 2のカーボンブラック（a2 )を併用する場合に発現する高 、遮光性の効果が期待できな 、。  [0199] Furthermore, when the difference in average primary particle size between the first carbon black (al) and the second carbon black (a2) is less than 5 nm, the first carbon black (al) and the second carbon black The high and light shielding effect that can be expected when (a2) is used in combination.
[0200] 平均一次粒子径が 8〜20nmである第 1のカーボンブラック（al)としては、例えば、 CABOT製の MONARCH、あるいは、 BLACK PERLS (1400, 1300, 1100, 1000, 900, 880, 800, 700)、 VULCAN (P, 9A32)、三菱ィ匕学製の # (2700B , 2650, 2600, 2450B, 2400B, 2350, 2300, 1000, 990, 980, 970, 960, 9 50, 900, 850)、 MCF88、 MA600、 DEGUSSA製の Color Black (FW2000, FW2, FW2V, FWl, FW18, S170, S 160) , Special Black (6, 5)、 Printex ( 95, 90, 85, 80, 75, 40, 60)、東海カーボン製のシース卜（9H SAF-HS, 9 S AF)、旭カーボン製の旭 # 80、コロンビヤン'カーボン製の ROYAL SPECTRA, NEO SPECTRA MARK (I及び II)、 NEO SPECTRA AG、 SUPERB A (N EO MK III) , NEO SPECTRA MARK IV, RAVEN (5000, 7000, 5750 , 5250, 3500, 3200, 2000, 1500)、 CONDUCTEX(40— 220, SC) , RAVE N C BEADSなどを挙げることができる。好ましくは CABOT製の MONARCH (1 100, 800)、 BLACK PERLS (1100, 800)、三菱ィ匕学製の # 850、 DEGUSS A製の Printex95、特に好ましくは CABOT製の MONARCH1100、 DEGUSSA 製の Printex95を用いることができる。 ¾士 ^— ί¾
Figure imgf000067_0001
、： KOSO][0200] As the first carbon black (al) having an average primary particle diameter of 8 to 20 nm, for example, MONARCH made by CABOT or BLACK PERLS (1400, 1300, 1100, 1000, 900, 880, 800, 700), VULCAN (P, 9A32), # (2700B, 2650, 2600, 2450B, 2400B, 2350, 2300, 1000, 990, 980, 970, 960, 9 50, 900, 850), Color Black (FW2000, FW2, FW2V, FWl, FW18, S170, S 160), Special Black (6, 5), Printex (95, 90, 85, 80, 75, 40, 60) from MCF88, MA600, DEGUSSA , Tokai Carbon sheath 卜 (9H SAF-HS, 9 S AF), Asahi Carbon's Asahi # 80, Colombian 'Carbon ROYAL SPECTRA, NEO SPECTRA MARK (I and II), NEO SPECTRA AG, SUPERB A ( NEO MK III), NEO SPECTRA MARK IV, RAVEN (5000, 7000, 5750, 5250, 3500, 3200, 2000, 1500), CONDUCTEX (40-220, SC), RAVE NC BEADS, and the like. Preferably, CABOT MONARCH (1 100, 800), BLACK PERLS (1100, 800), Mitsubishi Igaku # 850, DEGUSS A Printex95, CABOT MONARCH1100, DEGUSSA Printex95 are used. be able to. ¾ 士 ^ — ί¾
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S09CTC/900Zdf/X3d ャ9 S89.00/.00Z OAV の異なるカーボンブラックを併用する場合も含めて、感光性黒色インクの全固形分重 量を基準（100重量％)として、好ましくは合計して 40〜65重量％、より好ましくは合 計して 45〜60重量％の量で用いることができる。 S09CTC / 900Zdf / X3d9 S89.00 / .00Z OAV The total solid weight of the photosensitive black ink, including the case where carbon blacks of different types are used together, is preferably 40 to 65% by weight in total, more preferably 45% in total. It can be used in an amount of ˜60% by weight.
[0204] また、本発明の感光性黒色インクでは、前記多官能チオールを使用することができ る。多官能チオールは、感光性黒色インクの全固形分重量を基準（100重量％)とし て、好ましくは 0. 1〜30重量％、より好ましくは 1〜20重量％の量で用いることができ る。 0. 1重量％未満では多官能チオールの添加効果が不充分であり、 30重量％を 超えると感度が高すぎて解像度が低下したり、感光性黒色インクの安定性が低下し たりする。 [0204] In the photosensitive black ink of the present invention, the polyfunctional thiol can be used. The polyfunctional thiol can be used in an amount of preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the total solid weight of the photosensitive black ink (100% by weight). . If the amount is less than 1% by weight, the effect of adding a polyfunctional thiol is insufficient. If the amount exceeds 30% by weight, the sensitivity is too high and the resolution is lowered, or the stability of the photosensitive black ink is lowered.
[0205] また、本発明の感光性黒色インクに用いられる溶剤は、感光性黒色インクの全固形 分 100重量部に対して、好ましくは 150〜3500重量部、より好ましくは 250〜2000 重量部の量で用いることができる。  [0205] The solvent used in the photosensitive black ink of the present invention is preferably 150 to 3500 parts by weight, more preferably 250 to 2000 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive black ink. Can be used in quantities.
[0206] また、本発明の感光性黒色インクに用いられる顔料担体は、前記カラーフィルタ用 インクと同様のものを使用することができる。  [0206] The pigment carrier used in the photosensitive black ink of the present invention may be the same as the color filter ink.
[0207] [インクジェットインク]  [0207] [Inkjet ink]
インクジェットインク（ink  Inkjet ink
composition for inkjet printing) ,特にカラーフイノレタ用インクジェットインクに適用す る場合について説明する。本発明のインクジェットインクは、顔料、前記一般式（1)で 表される分散剤、及び前記分散剤以外の前記顔料担体を含む。  Composition for inkjet printing), especially when applied to color inkjet ink-jet ink. The inkjet ink of the present invention includes a pigment, a dispersant represented by the general formula (1), and the pigment carrier other than the dispersant.
[0208] 本発明のインクジェットインクは、分散剤以外の前記顔料担体として、エチレン性不 飽和単量体を含有させ、紫外線や電子線で硬化させる活性エネルギー線硬化型ィ ングンエツトインク、 activated energy-ray Hardening ink composition for inkjet printing )としても使用することができる。重合方法は、ラジカル重合、又はカチオン重合のど ちらでもよい。  [0208] The inkjet ink of the present invention contains an ethylenically unsaturated monomer as the pigment carrier other than the dispersant, and is an active energy ray curable ink jet ink that is cured with ultraviolet rays or an electron beam. -ray Hardening ink composition for inkjet printing). The polymerization method may be either radical polymerization or cationic polymerization.
[0209] また、本発明のインクジ ットインクは、分散剤以外の前記顔料担体として、前記熱 硬化性化合物を含有させ、熱硬化型インクジェットインク（thermosetting ink composit ion for inkjet printing)としても使用することができる。  [0209] In addition, the ink jet ink of the present invention may contain the thermosetting compound as the pigment carrier other than the dispersant, and may be used as a thermosetting ink composition for inkjet printing. it can.
[0210] この活性エネルギー線硬化型インクジェットインク及び熱硬化型インクジェットインク は、カラーフィルタ用インクジェットインクとして好適であり、特に熱硬化型インクジエツ トインクは、活性エネルギー線照射設備が不要であるため好適である。本発明のカラ 一フィルタ用インクジェットインクに用いることのできる前記熱硬化性ィ匕合物の数平均 分子量は、特に限定されるものではないが、好ましくは 50〜2000、より好ましくは 10 0〜： L 000である。 [0210] This active energy ray-curable inkjet ink and thermosetting inkjet ink Is suitable as an ink-jet ink for a color filter, and in particular, a thermosetting ink jet ink is suitable because it does not require an active energy ray irradiation facility. The number average molecular weight of the thermosetting compound that can be used in the inkjet ink for a color filter of the present invention is not particularly limited, but is preferably 50 to 2000, more preferably 100 to L000. It is.
[0211] これらの熱硬化性化合物のうち、メラミン榭脂又はべンゾグアナミン樹脂が、本発明 のカラーフィルタ用インクジェットインクに 1重量％〜40重量％の量で含有されている ことが好ましい。また、エポキシ榭脂、フエノール榭脂、ブロック化イソシァネートイ匕合 物、又はエチレン性不飽和単量体などについては、本発明のカラーフィルタ用インク ジェットインク中に 1重量％〜40重量％の量で含有されていることが好ましい。また、 シランカップリング剤は、本発明のインク組成物中に 0. 1重量％〜40重量％の量で 含有されていることが好ましい。熱硬化性化合物の含有量が不足すると、耐熱性、又 は耐薬品性に劣る場合がある。また、含有量が 40%より多くなると、カラーフィルタ用 インクジェットインクの粘度の増カロ、又は保存安定性の低下が生じる場合がある。  [0211] Among these thermosetting compounds, it is preferable that the melamine resin or benzoguanamine resin is contained in the ink for a color filter of the present invention in an amount of 1 wt% to 40 wt%. In addition, epoxy resin, phenol resin, blocked isocyanate compound, or ethylenically unsaturated monomer is contained in an amount of 1% to 40% by weight in the ink jet ink for color filter of the present invention. It is preferably contained. The silane coupling agent is preferably contained in the ink composition of the present invention in an amount of 0.1 wt% to 40 wt%. If the content of the thermosetting compound is insufficient, the heat resistance or chemical resistance may be poor. On the other hand, when the content exceeds 40%, the viscosity of the inkjet ink for color filter may increase, or the storage stability may decrease.
[0212] 本発明のカラーフィルタ用インクジェットインクは、溶剤を含有することが好ましい。  [0212] The inkjet ink for a color filter of the present invention preferably contains a solvent.
溶剤としては、顔料担体に対して高い溶解性を有するとともに、プリンタのノズルにお けるインクの非乾燥性がよぐインクと接するプリンタ部材に対して膨潤作用が少なぐ 溶剤の粘度がなるべく低いものが好ましい。これらの観点から、溶剤は、前記したもの のうち、アルコール類、グリコール誘導体類、エステル類、及び Z又はケトン類の 1種 類を単独で、又は 2種類以上を組み合わせて使用することが好ま 、。  The solvent is highly soluble in the pigment carrier, and the non-drying property of the ink at the printer nozzles is low. The solvent is less swelled with the printer member in contact with the ink. The solvent viscosity is as low as possible. Is preferred. From these viewpoints, among the solvents described above, it is preferable to use one of alcohols, glycol derivatives, esters, and Z or ketones alone or in combination of two or more. .
[0213] カラーフィルタ用インクジェットインクには、分散剤以外の前記顔料担体を用いるこ とができる。これら顔料担体のうち、架橋可能な官能基を有するものを用いることもで きる。架橋可能な官能基としては、水酸基、カルボキシル基、スルホン酸基、リン酸基 、又はアルコキシル基等を挙げることができる。  [0213] The pigment carrier other than the dispersant can be used in the inkjet ink for a color filter. Among these pigment carriers, those having a crosslinkable functional group can also be used. Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and an alkoxyl group.
[0214] 架橋可能な官能基を有する榭脂としては、エステル化反応により榭脂が緩やかに 架橋するため、水酸基又はカルボキシル基を有するビュル系榭脂が好ま 、。 水酸基又はカルボキシル基を有するビュル系榭脂は、水酸基を有するエチレン性 不飽和単量体又はカルボキシル基を有するエチレン性不飽和単量体と、水酸基及 びカルボキシル基を有さないエチレン性不飽和単量体とを共重合することにより得ら れる榭脂である。 [0214] The resin having a crosslinkable functional group is preferably a bull resin having a hydroxyl group or a carboxyl group because the resin is slowly crosslinked by an esterification reaction. The bull resin having a hydroxyl group or a carboxyl group is composed of an ethylenically unsaturated monomer having a hydroxyl group or an ethylenically unsaturated monomer having a carboxyl group, a hydroxyl group and And a resin obtained by copolymerizing an ethylenically unsaturated monomer having no carboxyl group.
[0215] 水酸基を有するエチレン性不飽和単量体としては、前記水酸基含有の (メタ)アタリ レート類が挙げられ、カルボキシル基を有するエチレン性不飽和単量体は前記した ものが挙げられる。  [0215] Examples of the ethylenically unsaturated monomer having a hydroxyl group include the above-mentioned hydroxyl group-containing (meth) acrylates, and examples of the ethylenically unsaturated monomer having a carboxyl group include those described above.
[0216] 水酸基及びカルボキシル基を有さないエチレン性不飽和単量体としては、前記し たエチレン性不飽和単量体のうち、水酸基及びカルボキシル基を有さな 、ものが挙 げられる。  [0216] Examples of the ethylenically unsaturated monomer having no hydroxyl group and carboxyl group include those having no hydroxyl group and carboxyl group among the above ethylenically unsaturated monomers.
また、架橋可能な官能基を有する顔料担体としては、顔料の分散性及び経時での 安定性が向上し、更にインクが低粘度となるため、リン酸基又はスルホン酸基を有す る顔料担体が好ましい。  In addition, as a pigment carrier having a crosslinkable functional group, the pigment carrier having a phosphate group or a sulfonic acid group is improved because the dispersibility of the pigment and the stability over time are improved and the ink has a low viscosity. Is preferred.
[0217] リン酸基及びスルホン酸基は、ナトリウム、カリウム、リチウム等のアルカリ金属、カル シゥム、マグネシウム、アルミニウム、亜鉛等の多価金属、アンモニア、又はェチルァ ミン、ジブチルァミン、トリエタノールァミン、ェチルァミン、プロピルァミン、ブチルアミ ン、ペンチルァミン、へキシルァミン、ォクチルァミン、ドデシルァミン、ステアリルアミ ン、ォレイルァミン、ジステアリルアミン等の有機ァミンと塩を形成していてもよい。  [0217] The phosphate group and the sulfonate group are alkali metals such as sodium, potassium and lithium, polyvalent metals such as calcium, magnesium, aluminum and zinc, ammonia, or ethylamine, dibutylamine, triethanolamine and ethylamine. A salt may be formed with an organic amine such as propylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, stearylamine, oleylamine, distearylamine and the like.
[0218] リン酸基を有する榭脂に含まれるリン酸基は、下記式（26)で示される 1価のリン酸 基であっても下記式（27)で示される 2価のリン酸基であってもよ 、。  [0218] Even if the phosphoric acid group contained in the resin having a phosphoric acid group is a monovalent phosphoric acid group represented by the following formula (26), a divalent phosphoric acid group represented by the following formula (27): Even so.
式（26)：  Formula (26):
[化 37]  [Chemical 37]
0 0
II  II
— P— OH (26)  — P— OH (26)
OH  OH
式（27) :  Formula (27):
[化 38] O [Chemical 38] O
II  II
—— P― OH (27)  —— P— OH (27)
[0219] リン酸基又はスルホン酸基を有する顔料担体としては、前記リン酸基を有するェチ レン性不飽和単量体又は前記スルホン酸基を有するエチレン性不飽和単量体を共 重合したビニル系重合体が好ま ヽ。 [0219] As the pigment carrier having a phosphoric acid group or a sulfonic acid group, the ethylenic unsaturated monomer having a phosphoric acid group or the ethylenic unsaturated monomer having a sulfonic acid group was copolymerized. A vinyl polymer is preferred.
[0220] これらのリン酸基を有するエチレン性不飽和単量体又は前記スルホン酸基を有す るエチレン性不飽和単量体は、単独あるいは 2種以上の組み合わせで用いることが できる。また、ビュル系重合体において、リン酸基を有するエチレン性不飽和単量体 又は前記スルホン酸基を有するエチレン性不飽和単量体の共重合比は、全エチレン 性不飽和単量体 100重量部に対して 0. 1〜30重量部以下であることが好ましぐ 0. 1〜5重量部以下であることが更に好ましい。  [0220] These ethylenically unsaturated monomers having a phosphoric acid group or the ethylenically unsaturated monomers having a sulfonic acid group can be used alone or in combination of two or more. In the bull polymer, the copolymerization ratio of the ethylenically unsaturated monomer having a phosphoric acid group or the ethylenically unsaturated monomer having a sulfonic acid group is 100% by weight of the total ethylenically unsaturated monomer. The amount is preferably 0.1 to 30 parts by weight or less, more preferably 0.1 to 5 parts by weight or less.
[0221] リン酸基又はスルホン酸基を有するビニル系榭脂の重量平均分子量 (Mw)は、好 まし <は 1000〜50000であり、更に好まし <は 2000〜30000である。  [0221] The weight-average molecular weight (Mw) of the vinyl-based resin having a phosphoric acid group or a sulfonic acid group is preferably <1000 to 50000, and more preferably <2000 to 30000.
[0222] 前記一般式（19)又は一般式（20)で示されるエチレン性不飽和単量体を重合成 分として含有するビニル系榭脂を用いることが好ま 、。前記一般式（19)又は一般 式（20)で示されるエチレン性不飽和単量体は、単独ある!/、は 2種以上の組み合わ せで用いることができる。また、共重合体において、前記一般式（19)又は一般式（2 0)で示されるエチレン性不飽和単量体の共重合比は、全エチレン性不飽和単量体 100重量部に対して 0. 1〜50重量部であることが好ましい。  [0222] It is preferable to use a vinyl resin containing the ethylenically unsaturated monomer represented by the general formula (19) or the general formula (20) as a polysynthetic component. The ethylenically unsaturated monomer represented by the general formula (19) or the general formula (20) may be used alone or in combination of two or more. In the copolymer, the copolymerization ratio of the ethylenically unsaturated monomer represented by the general formula (19) or the general formula (20) is 100 parts by weight of the total ethylenically unsaturated monomer. 0.1 to 50 parts by weight is preferred.
[0223] 前記一般式（19)又は一般式（20)で示されるエチレン性不飽和単量体を重合成 分として含有するビニル系榭脂の重量平均分子量 (Mw)は、好ましくは 5000〜100 000であり、更に好まし <は 10000〜50000である。  [0223] The weight average molecular weight (Mw) of the vinyl-based resin containing the ethylenically unsaturated monomer represented by the general formula (19) or the general formula (20) as a polysynthesis component is preferably 5000 to 100. 000, more preferably <is 10000-50000.
[0224] 本発明によるカラーフィルタ用インクジェットインクに用いる顔料は、前記方法で被 覆処理されて 、ることが好ま 、。  [0224] The pigment used in the inkjet ink for a color filter according to the present invention is preferably coated with the above method.
[0225] カラーフィルタ用インクジェットインクにおいて、固形分含有量は、インク組成物全重 量に対して、好ましくは 3〜60重量％、より好ましくは 4〜40重量％である。固形分含 有量が、 3重量％未満になるとインク皮膜の濃度や耐性が不足し、 60重量％を超え るとインクの粘度が上昇し、経時安定性が低下することがある。 [0225] In the inkjet ink for color filter, the solid content is preferably 3 to 60 wt%, more preferably 4 to 40 wt%, based on the total weight of the ink composition. If the solid content is less than 3% by weight, the concentration and resistance of the ink film will be insufficient, exceeding 60% by weight. As a result, the viscosity of the ink increases and the stability over time may decrease.
[0226] 本発明のインクジェットインクの粘度としては、 2mPa' s以上 40mPa' s以下が好まし く、 3mPa' s以上 30mPa' s以下がより好ましぐ更には 4mPa' s以上 20mPa' s以下 がー層好ましい。粘度が大きすぎると、連続して吐出する場合に、安定した吐出がで きない。  [0226] The viscosity of the inkjet ink of the present invention is preferably 2 mPa's or more and 40 mPa's or less, more preferably 3 mPa's or more and 30 mPa's or less, and further preferably 4 mPa's or more and 20 mPa's or less. -Layer is preferred. If the viscosity is too large, stable discharge cannot be achieved when discharging continuously.
[0227] 本発明のインクジェットインクの平均分散粒子径としては、 5nm以上 200nm以下が 好ましぐ lOnm以上 150nm以下がより好ましい。平均分散粒子径が大きすぎるとノ ズルが目詰まりを起こしやすぐ安定した吐出ができない。また平均分散粒子径が小 さすぎると、再凝集を引き起こし易くなり、経時安定性が悪ィ匕する。  [0227] The average dispersed particle size of the inkjet ink of the present invention is preferably 5 nm or more and 200 nm or less, more preferably lOnm or more and 150 nm or less. If the average dispersed particle size is too large, the nozzles may become clogged and stable ejection cannot be performed immediately. On the other hand, if the average dispersed particle size is too small, reaggregation is likely to occur, and the stability over time deteriorates.
[0228] 本発明のインクジェットインクの表面張力としては、 20mNZm以上 40mNZm以 下が好ましぐ 24mNZm以上 35mNZm以下がより好ましい。表面張力が高すぎる とノズルからインクが安定して吐出することができず、逆に表面張力が低すぎるとノズ ルから吐出後インクが液滴を形成することができなくなる。  [0228] The surface tension of the inkjet ink of the present invention is preferably 20 mNZm or more and 40 mNZm or less, more preferably 24 mNZm or more and 35 mNZm or less. If the surface tension is too high, the ink cannot be stably ejected from the nozzle. Conversely, if the surface tension is too low, the ink cannot form droplets after ejection from the nozzle.
[0229] インクジェットインクには、インクの粘度が 25°Cで 3〜50mPa' sとなる範囲で、前記 その他添加剤を含有させることができる。  [0229] The ink jet ink may contain the above-mentioned other additives in the range where the viscosity of the ink becomes 3 to 50 mPa's at 25 ° C.
本発明のインクジェットインクは、顔料濃度を高くしても、低粘度であるため、吐出安 定性に優れ、顔料含有量を通常のインクジェットインクに比べて多くすることができる ので、吐出量を少なくすることができる。従って、カラーフィルタ基板用をはじめ、高い 印字濃度が望まれている印刷物の生産性及び品位を向上させることができる。特に、 本発明のインクジェットインクは、高い生産性及び品位が求められるカラーフィルタ基 板の製造に好適である。  Since the inkjet ink of the present invention has a low viscosity even when the pigment concentration is high, it is excellent in ejection stability, and the pigment content can be increased as compared with a normal inkjet ink, so that the ejection amount is reduced. be able to. Therefore, it is possible to improve the productivity and quality of printed matter for which a high print density is desired, including for color filter substrates. In particular, the ink-jet ink of the present invention is suitable for production of a color filter substrate that requires high productivity and quality.
[0230] また、本発明のインクジェットインクは、顔料濃度が高いので、インクが深さ方向に浸 透する紙や横方向への濡れ広がるプラスチック、ガラス及び金属であっても、印字濃 度を高くできる。更に、吐出量を抑えることができるので、受容層のインク受容量を超 えた場合にインクが流出して混色したり、ドット形状が真円とならない現象も回避する ことができるので、従来のインクジェット印刷では制限された用途にも用いることがで きる。  [0230] Further, since the ink-jet ink of the present invention has a high pigment concentration, the printing density can be increased even with paper in which the ink permeates in the depth direction or plastic, glass, and metal that spreads in the lateral direction. it can. Further, since the discharge amount can be suppressed, it is possible to avoid the phenomenon that ink flows out and mixes when the ink receiving amount of the receiving layer is exceeded, and the phenomenon that the dot shape does not become a perfect circle can be avoided. It can also be used for limited applications in printing.
[0231] [カラーフィルタ] ここで、本発明によるインクの適用対象の 1つであるカラーフィルタ（color filter)に ついて説明する。カラーフィルタは、ガラス板等の透明基板上に、ブラックマトリックス と、黒以外の少なくとも 2色のフィルタセグメントとを備えるものである。フィルタセグメ ントの色は、青色、緑色、赤色、シアン、エロー、マゼンタ、橙色、又は紫色などから 2 〜6色程度選択される。同色系の色で、濃度の違うフィルタセグメントが形成されてい てもよい。カラーフィルタ基板は、例えば、薄型テレビジョンなどに利用されている液 晶ディスプレイパネルに利用することができる。 [0231] [Color filter] Here, a color filter which is one of the objects to which the ink according to the present invention is applied will be described. The color filter includes a black matrix and at least two color filter segments other than black on a transparent substrate such as a glass plate. The color of the filter segment is selected from about 2 to 6 colors from blue, green, red, cyan, yellow, magenta, orange or purple. Filter segments with the same color and different densities may be formed. The color filter substrate can be used for, for example, a liquid crystal display panel used for a thin television.
[0232] ブラックマトリックスは、例えば、ラジカル重合型の感光性黒色インクを塗布し、露光 し、そして現像してパターユングするフォトリソグラフィ一法、黒色インクを印刷する印 刷法、又は金属を蒸着した後にエッチングする蒸着法等により透明基板上に形成す ることがでさる。 [0232] The black matrix is, for example, a photolithographic method in which a photosensitive black ink of radical polymerization type is applied, exposed, developed, and patterned, a printing method for printing a black ink, or a metal is deposited. It can be formed on a transparent substrate by an evaporation method or the like to be etched later.
[0233] フォトリソグラフィ一法は、透明基板上に、スピンコート、スリットコート、又はロールコ ート等の塗布方法により、本発明の感光性黒色インクを塗布したのち、フォトマスクを 介して、組成物塗布面側カゝら活性エネルギー線を照射し、溶剤又はアルカリ現像液 に漬浸する力、スプレーなどにより現像液を噴霧して、未照射部（すなわち未硬化部 )を除去して現像を行うことにより、 目的とする画像 (すなわち、ブラックマトリックス)を 形成する方法である。  [0233] One photolithography method is to apply the photosensitive black ink of the present invention on a transparent substrate by a coating method such as spin coating, slit coating, or roll coating, and then through a photomask. The active surface is irradiated with active energy rays from the coating surface side, and the developer is sprayed with a force immersed in a solvent or alkaline developer, spraying, etc., and the unirradiated part (that is, the uncured part) is removed for development. This is a method for forming a target image (that is, a black matrix).
[0234] また、透明基板あるいは反射基板上に各色フィルタセグメントを形成する前に、あら 力じめブラックマトリックスを形成しておくと、液晶表示パネルのコントラストを一層高め ることができるので好ましい。この場合は、ブラックマトリックスの形成に、本発明の感 光性黒色インクを用いることもできるが、通常の感光性黒色インクやその他にも黒色 クロムやクロム Z酸化クロムの多層膜、窒化チタニウムなどの無機膜や、遮光剤を分 散した榭脂膜を用いてよい。好ましい態様は、本発明の感光性黒色インクを用いる場 合である。  [0234] In addition, it is preferable to preliminarily form a black matrix before forming each color filter segment on a transparent substrate or a reflective substrate, since the contrast of the liquid crystal display panel can be further increased. In this case, the photosensitive black ink of the present invention can be used for forming the black matrix, but other than the usual photosensitive black ink and other multilayer films of black chromium and chromium Z chromium oxide, titanium nitride, etc. An inorganic film or a resin film in which a light shielding agent is dispersed may be used. A preferred embodiment is when the photosensitive black ink of the present invention is used.
[0235] 感光性黒色インクの塗布膜厚は、 0. 2〜5 μ m (乾燥時)の範囲であることが好まし ぐ塗工性と遮光性のバランス取りが容易な 0. 5〜2 mの範囲であることがより好ま しい。  [0235] The coating thickness of the photosensitive black ink is preferably in the range of 0.2 to 5 μm (when dry), and it is easy to balance coating properties and light shielding properties. 0.5 to 2 A range of m is more preferable.
[0236] また、ブラックマトリックスの乾燥膜厚 1 μ mあたりの光学濃度 (OD値）は、高遮光性 の観点から、 3. 0以上であることが好ましぐ特に好ましくは 3. 5以上、更に好ましく は 3. 8以上である。光学濃度は、高いほど好ましいが、活性エネルギー線力 紫外 線や可視光である場合に、硬化塗膜が得られに《なることから、概ね、 3. 0以上 4. 7以下が望ましい。 [0236] In addition, the optical density (OD value) per 1 μm dry film thickness of the black matrix is highly light-shielding. In view of the above, it is particularly preferably 3.0 or more, more preferably 3.5 or more, and still more preferably 3.8 or more. The higher the optical density, the better. However, in the case of ultraviolet rays or visible light, it is generally desirable that the optical density is 3.0 or more and 4.7 or less because a cured coating film can be obtained.
[0237] アルカリ現像液としては、炭酸ナトリウム、又は水酸ィ匕ナトリウム等の水溶液が使用 され、ジメチルベンジルァミン、又はトリエタノールァミン等の有機アルカリを用いるこ ともできる。また、現像液には、消泡剤や界面活性剤を添加することもできる。  [0237] As the alkali developer, an aqueous solution such as sodium carbonate or sodium hydroxide is used, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
[0238] なお、活性エネルギー線による露光感度を上げるために、感光性黒色インクを塗布 乾燥後、水溶性あるいはアルカリ可溶性榭脂、例えばポリビニルアルコールや水溶 性アクリル榭脂等を塗布乾燥し、酸素による重合阻害を防止する膜を形成した後、ィ ンク塗布面側カゝら活性エネルギー線を照射することもできる。  [0238] In order to increase the exposure sensitivity by active energy rays, after applying and drying a photosensitive black ink, water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried, and oxygen is used. After forming a film for preventing polymerization inhibition, active energy rays can be irradiated from the ink coating surface side.
[0239] 活性エネルギー線としては、電子線、紫外線、又は 400〜500nmの可視光を使用 することができる。インク塗布面側から照射する電子線の線源には、熱電子放射銃、 又は電界放射銃等を使用することができる。また、紫外線及び 400〜500nmの可視 光の線源 (光源）には、例えば、高圧水銀灯、超高圧水銀灯、メタルハライド灯、ガリ ゥム灯、キセノン灯、又はカーボンアーク灯等を使用することができる。具体的には、 点光源であること、輝度が安定であることから、超高圧水銀ランプ、又はキセノン水銀 ランプが用いられることが多 、。組成物塗布面側力 照射する活性エネルギー線量 は、 5〜： LOOOmJの範囲で適時設定できる力 工程上管理しやすい 20〜300mJの 範囲であることが好ましい。  [0239] As the active energy ray, an electron beam, ultraviolet rays, or visible light of 400 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source irradiated from the ink application surface side. For example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, or a carbon arc lamp can be used as a source (light source) of ultraviolet light and visible light of 400 to 500 nm. . Specifically, an ultra-high pressure mercury lamp or a xenon mercury lamp is often used because it is a point light source and the brightness is stable. Force applied to the composition surface side The active energy dose to be irradiated is preferably in the range of 5 to: LOOOmJ, which can be set in a timely manner.
[0240] カラーフィルタのフィルタセグメントの組み合わせとしては、赤色フィルタセグメント、 緑色フィルタセグメント、及び青色フィルタセグメントを具備するもの、又はマゼンタ色 フィルタセグメント、シアン色フィルタセグメント、及びイェロー色フィルタセグメントを 具備するものが挙げられる。  [0240] The combination of filter segments of the color filter includes a red filter segment, a green filter segment, and a blue filter segment, or includes a magenta filter segment, a cyan filter segment, and a yellow filter segment. Is mentioned.
[0241] これらのフィルタセグメントは、本発明のカラーフィルタ用インクやカラーフィルタ用ィ ンクジェットインクを用いて形成することができる。本発明のカラーフィルタ用インクジ エツトインクを用いる場合、活性エネルギー線照射装置は必ずしも必要でな 、。  [0241] These filter segments can be formed using the color filter ink or the color filter ink jet ink of the present invention. When the ink jet ink for color filter of the present invention is used, an active energy ray irradiation device is not necessarily required.
[0242] 透明基板としては、ソーダ石灰ガラス、低アルカリ硼珪酸ガラス、又は無アルカリア ルミノ硼珪酸ガラスなどのガラス板や、ポリカーボネート、ポリメタクリル酸メチル、又は ポリエチレンテレフタレートなどの榭脂板が用いられる。また、ガラス板ゃ榭脂板の表 面には、パネルイ匕後の液晶駆動のために、酸化インジウム、又は酸ィ匕錫など力もなる 透明電極が形成されて！、てもよ!/、。 [0242] As the transparent substrate, soda-lime glass, low alkali borosilicate glass, or non-alkali alloy is used. Glass plates such as luminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate are used. In addition, a transparent electrode with intensities such as indium oxide or oxide tin is formed on the surface of the glass plate and the resin plate to drive the liquid crystal after the panel is turned on! Well! /
[0243] また、前記の透明基板ある!/、は反射基板上に薄膜トランジスター (TFT)をあらかじ め形成しておき、その後にフィルタセグメントを形成することもできる。 TFT基板上に フィルタセグメントを形成することにより、液晶表示パネルの開口率を高め、輝度を向 上させることができる。 [0243] In addition, a thin film transistor (TFT) may be formed in advance on the reflective substrate, and a filter segment may be formed thereafter. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.
[0244] 基板としては、ガラス板や、ポリカーボネート、ポリメタクリル酸メチル、又はポリェチ レンテレフタレート等の榭脂板を用いることができる。各色フィルタセグメントの形成方 法としては、フォトリソグラフィ一法、インクジェット法、印刷法、電着法、及び転写法な どがある。  [0244] As the substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate can be used. Methods for forming each color filter segment include a photolithography method, an ink jet method, a printing method, an electrodeposition method, and a transfer method.
[0245] フォトリソグラフィ一法による各色フィルタセグメントの形成は、例えば、下記の方法 で行うことができる。すなわち、溶剤現像型あるいはアルカリ現像型着色レジスト材と して調製した本発明のカラーフィルタ用インクを、ガラス等の透明基板上に、スプレー コートやスピンコート、スリットコート、ロールコート等の塗布方法により、乾燥膜厚が 0 . 2〜： LO /z mとなるように、より好ましくは 0. 2〜5 /ζ πιとなるように塗布する。塗布膜を 乾燥させる際には、減圧乾燥機、コンペクシヨンオーブン、 IRオーブン、又はホットプ レート等を使用してもよい。必要により乾燥された膜には、この膜と接触あるいは非接 触状態で設けられた所定のパターンを有するマスクを通して紫外線露光を行う。その 後、溶剤又はアルカリ現像液に浸漬するカゝ、若しくはスプレーなどにより現像液を噴 霧して未硬化部を除去し、所望のパターンを形成してカラーフィルタを製造すること ができる。アルカリ現像には、前記ブラックマトリックスの形成と同様のアルカリ現像液 を用いることができる。また、ブラックマトリックスと同様に、紫外線露光感度を上げる ために、前記着色レジスト材を塗布乾燥後、酸素による重合阻害を防止する膜を形 成した後、紫外線露光を行うこともできる。  [0245] The formation of each color filter segment by a photolithography method can be performed, for example, by the following method. That is, the color filter ink of the present invention prepared as a solvent development type or alkali development type colored resist material is applied to a transparent substrate such as glass by a coating method such as spray coating, spin coating, slit coating or roll coating. The coating is applied so that the dry film thickness is 0.2 to: LO / zm, more preferably 0.2 to 5 / ζ πι. When drying the coating film, a vacuum dryer, a competition oven, an IR oven, a hot plate, or the like may be used. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or not in contact with the film. Thereafter, the color filter can be manufactured by forming the desired pattern by spraying the developer with a spray immersed in a solvent or an alkaline developer, or spraying to remove the uncured portion. For alkali development, an alkali developer similar to the formation of the black matrix can be used. Similarly to the black matrix, in order to increase the ultraviolet exposure sensitivity, after applying and drying the colored resist material, a film for preventing polymerization inhibition by oxygen can be formed, and then the ultraviolet exposure can be performed.
[0246] 更に、着色レジスト材の重合を促進するため、必要に応じて加熱を施すこともできる インクジェット印刷法は、インクジェットインク吐出装置を用いて、ブラックマトリックス が形成された基板のブラックマトリックスで区分けされた領域内に、本発明のカラーフ ィルタ用インクジェットインクを吐出して、カラーフィルタを形成するものである。本発 明のカラーフィルタ用インクジェットインクを使用する場合、加熱を施すことが好ま ヽ [0246] Furthermore, in order to accelerate the polymerization of the colored resist material, heating may be performed as necessary. In the inkjet printing method, a color filter is formed by ejecting the inkjet ink for the color filter of the present invention into an area divided by the black matrix of the substrate on which the black matrix is formed using an inkjet ink ejection device. It is. When using the color filter inkjet ink of the present invention, it is preferable to heat it.
[0247] 電着法は、透明基板上に形成した透明導電膜を利用して、コロイド粒子の電気泳 動により、各色フィルタセグメントを透明導電膜の上に電着形成することで、カラーフ ィルタを製造する方法である。 [0247] The electrodeposition method uses a transparent conductive film formed on a transparent substrate to form a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoretic colloidal particles. It is a manufacturing method.
転写法は、剥離性の転写ベースシートあるいは転写胴の表面に、あら力じめフィル タセグメントを形成しておき、このフィルタセグメントを所望の透明基板に転写させる方 法である。  The transfer method is a method in which a filter segment is preliminarily formed on the surface of a peelable transfer base sheet or transfer cylinder, and the filter segment is transferred to a desired transparent substrate.
[0248] カラーフィルタ上には、必要に応じてオーバーコート膜や柱状スぺーサ一、透明導 電膜、又は液晶配向膜などが形成される。  [0248] On the color filter, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, or the like is formed as necessary.
液晶表示パネルは、例えば、前記のとおり製造されたカラーフィルタを、シール剤を 用いて対向基板と張り合わせ、シール部に設けられた注入口から液晶を注入したの ちに、注入口を封止し、必要に応じて偏光膜や位相差膜を基板の外側に張り合わせ ること〖こより製造することができる。  The liquid crystal display panel, for example, bonds the color filter manufactured as described above to a counter substrate using a sealing agent, injects liquid crystal from the injection port provided in the seal portion, and then seals the injection port. If necessary, it can be manufactured by laminating a polarizing film or a retardation film on the outside of the substrate.
[0249] こうして製造された液晶表示パネルは、ッイステッド'ネマティック（TN : Twisted Nem atic)、スーパー ·ッイステッド ·ネマティック（STN： Super Twisted Nematic)、イン ·プ レイス'スイッチング（IPS : In- Place- Switching)、ヴアーティカリ^ ~ ·ァライメン HVA:V ertical [0249] The liquid crystal display panels thus manufactured are Twisted Nematic (TN), Super Twisted Nematic (STN), In-Placed Switching (IPS). ), Vaticari ^ ~ Alaimen HVA: Vertical
Alignment)、又はォプティカリー'コンペンセィテッド'ベンド（OCB : Optically Compe nsated Bend)などの液晶表示モードに使用することができる。  Alignment), or an optically-compensated bend (OCB) or other liquid crystal display mode.
実施例  Example
[0250] 以下、実施例を挙げて本発明を具体的に説明するが、本発明は実施例に特に限 定されるものではない。なお、実施例中、「部」は「重量部」を表し、「％」は「重量％」 を表す。また、以下の実施例において、数平均分子量、及び重量平均分子量は東ソ 一株式会社製ゲルパーミエイシヨンクロマトグラフィー HLC - 8120GPCにお!/、て、 分離カラムを 4本直列に繋ぎ、充填剤には順に東ソー株式会社製 TSK— GEL SU PER H5000, H4000, H3000,及び H2000を用!ヽ、移動ネ目【こテ卜ラヒドロフラン を用いて測定したポリスチレン換算分子量である。また、酸価、水酸基価及びアミン 価は以下の方法により測定した値である。 [0250] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not particularly limited to the examples. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”. Further, in the following examples, the number average molecular weight and the weight average molecular weight are obtained from Tosoichi Co., Ltd. Gel Permeation Chromatography HLC-8120GPC! / Four separation columns are connected in series, and TSK-GEL SUPER H5000, H4000, H3000, and H2000 manufactured by Tosoh Corporation are used as packing materials in order. Polystyrene measured using mobile hydrolyzer It is a converted molecular weight. The acid value, hydroxyl value, and amine value are values measured by the following methods.
[0251] [酸価] [0251] [Acid value]
酸価を測定する対象物（Sample)の約 lgを秤量し、ピリジン 30g、及び水 lgをカロえ、 10分間攪拌した後、 0. 1N水酸ィ匕カリウムエタノール溶液にて電位差滴定を行った 。また、同様の方法で空試験をおこなった。得られた滴定値から、分散剤 lgに含まれ るカルボキシル基と当量の水酸化カリウムの mg数を求めた。  About 1 lg of the sample (Sample) whose acid value is to be measured, weighed 30 g of pyridine and lg of water, stirred for 10 minutes, and then potentiometric titration was performed with 0.1N aqueous solution of potassium hydroxide and potassium ethanol. . A blank test was conducted in the same manner. From the obtained titration value, the number of mg of potassium hydroxide equivalent to the carboxyl group contained in the dispersant lg was determined.
[0252] [水酸基価] [Hydroxyl value]
水酸基価を測定する対象物の約 5gを秤量し、ァセチル化試薬 (無水酢酸 Zピリジ ン = 2Z7) 5mLを加えた後、 100°Cで 30分間攪拌し、その後冷却し、蒸留水 50mL を加え、 0. 5Nの水酸ィ匕カリウム水溶液を用いて電位差滴定により逆滴定を行った。 また、同様の方法で空試験をおこなった。得られた滴定値から分散剤 lgに含まれる 水酸基と当量の水酸化カリウムの mg数を求めた。  Weigh about 5 g of the target for hydroxyl value measurement, add 5 mL of acetylating reagent (acetic anhydride Z-pyridine = 2Z7), stir at 100 ° C for 30 minutes, then cool, and add 50 mL of distilled water. Back titration was performed by potentiometric titration using 0.5N potassium hydroxide aqueous solution. A blank test was conducted in the same manner. From the obtained titration value, the number of mg of potassium hydroxide equivalent to the hydroxyl group contained in the dispersant lg was determined.
[0253] [ァミン価] [0253] [Amin number]
アミン価を測定する対象物の約 lgを秤量し、トルエン Zイソプロピルアルコール（= 8Z2)の混合溶媒 50gを加え、 10分間攪拌した後、 0. 1N塩酸エタノール溶液にて 電位差滴定を行った。また同様の方法で空試験をおこなった。得られた滴定値から、 分散剤 lgに含まれるァミノ基と当量の水酸ィ匕カリウムの mg数を求めた。  About 1 lg of the object to be measured for amine value was weighed, 50 g of a mixed solvent of toluene Z isopropyl alcohol (= 8Z2) was added, and the mixture was stirred for 10 minutes, and potentiometric titration was performed with 0.1N hydrochloric acid ethanol solution. A blank test was conducted in the same manner. From the obtained titration value, the number of mg of potassium hydroxide and potassium equivalent to the amino group contained in the dispersant lg was determined.
[0254] 《実施例 1》 [0254] Example 1
ガス導入管、温度計、コンデンサー、及び攪拌機を備えた反応容器に、 1 ドデカ ノール 62. 6部、 ε一力プロラタトン 287. 4部、及び触媒としてモノブチルスズ (IV)ォ キシド 0. 1部を仕込み、窒素ガスで置換した後、 120°Cで 4時間加熱下に撹拌した。 固形分測定により 98%が反応したことを確認し、第一の工程 (以下の各表に記載の「 製造工程 1」）を終了した。この反応生成物の数平均分子量は 1350、重量平均分子 量は 1890であった。  In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 12.6 parts of dodecanol, 287.4 parts of epsilon prolatathone, and 0.1 part of monobutyltin (IV) oxide as a catalyst After charging and replacing with nitrogen gas, the mixture was stirred with heating at 120 ° C for 4 hours. It was confirmed that 98% had reacted by solid content measurement, and the first step (“Manufacturing step 1” described in each table below) was completed. The number average molecular weight of this reaction product was 1350, and the weight average molecular weight was 1890.
前記反応生成物にピロメリット酸二無水物 36. 6部を追加し、 100°Cで 5時間反応さ せた。酸価の測定で 97%以上の酸無水物がハーフエステルイ匕していることを確認し 、第二の工程 (以下の各表に記載の「製造工程 2」）を終了した。得られた分散剤は 2 5°Cでロウ状固体であり、数平均分子量 2430、重量平均分子量 3590、酸価 49mg KOHZgであった。ここで、ロウ状固体とは、常温では不透明の固体であるが加熱に より透明な液体に変化するものを意味し、この実施例 1で得られた分散剤は約 50°C で透明な液状になるものであった。 Add 36. 6 parts of pyromellitic dianhydride to the reaction product and react at 100 ° C for 5 hours. Let When the acid value was measured, it was confirmed that 97% or more of the acid anhydride was half-esterified, and the second step (“Production Step 2” described in the following tables) was completed. The obtained dispersant was a waxy solid at 25 ° C., and had a number average molecular weight of 2430, a weight average molecular weight of 3590, and an acid value of 49 mg KOHZg. Here, the waxy solid means a solid that is opaque at room temperature but changes to a transparent liquid upon heating. The dispersant obtained in Example 1 is a transparent liquid at about 50 ° C. It was to become.
実施例 1で得られた分散剤の赤外線吸収スペクトルを図 1に示し、 13C— NMR^ぺ タトル (重クロ口ホルム溶媒中）を図 2に示す。 The infrared absorption spectrum of the dispersant obtained in Example 1 is shown in FIG. 1, and the 13 C-NMR ^ petatre (in a heavy chloroform solvent) is shown in FIG.
[0255] 《実施例 2〜15》  [0255] Examples 2 to 15
実施例 1と同様の装置、触媒、及び反応操作を用いるが、出発材料として表 1及び 表 2に記載の化合物を表 1及び表 2に記載の使用量で用いて各分散剤を得た。但し 、実施例 4、 5、 9、 12、 13及び 15においては、反応容器内を窒素ガスで置換する代 わりに、乾燥空気で置換した。また、実施例 7及び実施例 13に記載の「水」とは、テト ラカルボン酸二無水物と片末端に水酸基を有するポリエステルの水酸基との反応終 了を酸価で確認した後に添加して、残存する酸無水物を加水分解するために用いた 水である。  The same apparatus, catalyst, and reaction procedure as in Example 1 were used, but each dispersant was obtained using the compounds shown in Tables 1 and 2 as starting materials in the amounts used in Tables 1 and 2. However, in Examples 4, 5, 9, 12, 13, and 15, the inside of the reaction vessel was replaced with dry air instead of nitrogen gas. In addition, “water” described in Example 7 and Example 13 is added after confirming the completion of the reaction between tetracarboxylic dianhydride and the hydroxyl group of the polyester having a hydroxyl group at one end by an acid value, Water used to hydrolyze the remaining acid anhydride.
[0256] [表 1] [0256] [Table 1]
Figure imgf000079_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000080_0001
〔〕0257 [0258] ※：水酸基価 65.8mgKOH/g (ペンタエリスリトールトリアタリレートとペンタエリスリ トールテトラアタリレートの混合物） [] 0257 [0258] *: Hydroxyl value 65.8mgKOH / g (mixture of pentaerythritol triatrate and pentaerythritol tetraatrate)
表 1及び表 2中の略称：  Abbreviations in Table 1 and Table 2:
メトキシ PEG400' · '片末端メトキシィ匕ポリエチレングリコール (数平均分子量 395、 水酸基価： 142mgKOHZg)  Methoxy PEG400 '·' One-end methoxy polyethylene glycol (Number average molecular weight 395, Hydroxyl value: 142mgKOHZg)
ブレンマー PP— 500· · 'ポリプロピレングリコールモノメタタリレート（日本油脂株式会 社製：商品名ブレンマー PP— 500、数平均分子量 590、水酸基価： 95. lmgKOH  BLEMMER PP-500 ·· 'Polypropylene glycol monometatalylate (manufactured by NOF Corporation: Brand name: BLEMMER PP-500, number average molecular weight 590, hydroxyl value: 95. lmgKOH
PMA.. 'ピロメリット酸二無水物 PMA .. 'Pyromellitic dianhydride
BTDA- · ·3, 3，， 4, 4，一べンゾフエノンテトラカルボン酸二無水物  BTDA- · 3, 3, 4, 4, monobenzophenone tetracarboxylic dianhydride
DSDA---3, 3', 4, 4，ービフエ-ルスルホンテトラカルボン酸二無水物  DSDA --- 3, 3 ', 4, 4, Biphenylsulfone tetracarboxylic dianhydride
TMEG- · 'エチレングリコールジ無水トリメリット酸エステル (新日本理化株式会社製： 商品名リカシッド TMEG— 100)  TMEG- · 'Ethylene glycol ditrimellitic anhydride ester (manufactured by Shin Nippon Chemical Co., Ltd .: trade name Ricacid TMEG-100)
BPAF---9, 9 ビス（3, 4—ジカルボキシフエ-ル）フルオレン二酸無水物  BPAF --- 9, 9 Bis (3,4-dicarboxyphenol) fluorenedioic anhydride
ΒΤΑ···1, 2, 3, 4 ブタンテトラカルボン酸二無水物  2, ... 1, 2, 3, 4 Butanetetracarboxylic dianhydride
BPDA---3, 3', 4, 4，ービフエ-ルテトラカルボン酸二無水物  BPDA --- 3, 3 ', 4, 4, Biphenyl tetracarboxylic dianhydride
NPDA---1, 4, 5, 8 ナフタレンテトラカルボン酸二無水物  NPDA --- 1, 4, 5, 8 Naphthalenetetracarboxylic dianhydride
DBU---1, 8 ジァザビシクロ一 [5.4.0]— 7 ゥンデセン  DBU --- 1, 8 Gazabicyclo 1 [5.4.0] — 7 Undecene
DMBA- · ·Ν, Ν ジメチルベンジルァミン  DMBA- · · Ν, Ν Dimethylbenzylamine
[0259] 《実施例 16》  [0259] <Example 16>
実施例 1と同様の反応容器に、片末端メトキシィ匕ポリエチレングリコール (数平均分 子量 960、水酸基価： 58.4mgKOH/g) 350.0部、及びピロメリット酸二無水物 39 .7部を加えて 100°Cで 5時間反応させた。酸価の測定で 97%以上の酸無水物がハ 一フェステルィ匕していることを確認し、反応を終了した。得られた分散剤は 25°Cで口 ゥ状固体であり、数平均分子量 2040、重量平均分子量 3060、酸価 54mgKOHZg であった。  In a reaction vessel similar to that in Example 1, 350.0 parts of one terminal methoxypolyethylene glycol (number average molecular weight 960, hydroxyl value: 58.4 mg KOH / g) and 39.7 parts of pyromellitic dianhydride were added. The reaction was carried out at ° C for 5 hours. The acid value was measured and it was confirmed that 97% or more of the acid anhydride had been condensed, and the reaction was completed. The obtained dispersant was a mouth-like solid at 25 ° C, and had a number average molecular weight of 2040, a weight average molecular weight of 3060, and an acid value of 54 mgKOHZg.
[0260] 《実施例 17〜19》  [0260] Examples 17 to 19
実施例 16と同様の反応容器を用いるが、出発材料として表 3に記載の化合物を表 3に示す使用量で用いて各分散剤を得た。但し、反応温度と反応時間について、 施例 17は 100°Cで 5時間、実施例 18及び 19につ!/、ては 50°C3時間で行った。 The same reaction vessel as in Example 16 was used, but the compounds listed in Table 3 were used as starting materials. Each dispersant was obtained using the amount shown in 3. However, with respect to the reaction temperature and reaction time, Example 17 was carried out at 100 ° C for 5 hours, and Examples 18 and 19 were carried out at 50 ° C for 3 hours.
[表 3] [Table 3]
Figure imgf000082_0001
[0262] 表 3中の略称
Figure imgf000082_0001
[0262] Abbreviations in Table 3
メトキシ PEGIOOO ' · '片末端メトキシィ匕ポリエチレングリコール (数平均分子量 960、 水酸基価： 58mgKOHZg)  Methoxy PEGIOOO '·' One-end methoxy polyethylene glycol (number average molecular weight 960, hydroxyl value: 58mgKOHZg)
ブレンマー 10ΡΡΒ— 500Β · · ·プロピレングリコールポリブチレングリコールモノメタク リレート（日本油脂株式会社製:商品名ブレンマー 10PPB— 500B、数平均分子量 5 50、水酸基価： 102mgKOHZg)  Blemer 10ΡΡΒ- 500Β ··· Propylene glycol polybutylene glycol monomethacrylate (manufactured by NOF Corporation: Brand name Blemmer 10PPB-500B, number average molecular weight 550, hydroxyl value: 102mgKOHZg)
ジェファーミン XTJ— 506 ' · '片末端メトキシ化ポリオキシエチレンポリオキシプレピレ ンァミン (三井ィ匕学ファイン株式会社製:商品名ジェファーミン XTJ— 506、数平均分 子量 1000、アミン価 56mgKOHZg)  Jeffamine XTJ— 506 '·' One-end methoxylated polyoxyethylene polyoxyprepyramine (Mitsui Chemicals Co., Ltd .: trade name Jeffamine XTJ-506, number average molecular weight 1000, amine number 56 mg KOHZg)
サーフォナミン L 207 · · '片末端メトキシィ匕ポリオキシエチレンポリオキシプレビレン ァミン (三井化学ファイン株式会社製：商品名サーフォナミン L 207、数平均分子量 2000、ァ 価 28mgKOHZg)  Surfonamin L 207 ··· 'One-end methoxy-polyoxyethylene polyoxypreylene rubber (Mitsui Chemical Fine Co., Ltd .: trade name Surfonamin L 207, number average molecular weight 2000, alpha 28 mg KOHZg)
PMA. . 'ピロメリット酸二無水物  PMA.. 'Pyromellitic dianhydride
TMEG - · 'エチレングリコールジ無水トリメリット酸エステル (新日本理化株式会社製： 商品名リカシッド TMEG— 100)  TMEG-· 'Ethylene glycol ditrimellitic anhydride (manufactured by Nippon Nippon Chemical Co., Ltd .: trade name Ricacid TMEG-100)
[0263] 《実施例 20》  [0263] << Example 20 >>
ガス導入管、温度計、コンデンサー、及び攪拌機を備えた反応容器に、 1 ドデカ ノール 62. 6部、 ε一力プロラタトン 287. 4部、及び触媒としてモノブチルスズ (IV)ォ キシド 0. 1部を仕込み、窒素ガスで置換した後、 120°Cで 4時間加熱、撹拌した。固 形分測定により 98%が反応したことを確認した。この後、無水コハク酸 33. 6部、 2— ェチルへキシルグリシジルエーテル 62. 5部、及び N, N ジメチルベンジルァミン 2 . 0部を加え 80°Cで 8時間反応させた。この反応生成物の数平均分子量は 1700、重 量平均分子量は 2260であった。  In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 12.6 parts of dodecanol, 287.4 parts of epsilon prolatathone, and 0.1 part of monobutyltin (IV) oxide as a catalyst After charging and replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C for 4 hours. It was confirmed that 98% had reacted by solid content measurement. Thereafter, 33.6 parts of succinic anhydride, 62.5 parts of 2-ethylhexyl glycidyl ether, and 2.0 parts of N, N dimethylbenzylamine were added and reacted at 80 ° C. for 8 hours. The number average molecular weight of this reaction product was 1700, and the weight average molecular weight was 2260.
前記反応生成物にピロメリット酸二無水物 28. 8部を追加し 100°Cで 5時間反応さ せた。酸価の測定で 97%以上の酸無水物がハーフエステルイ匕していることを確認し 反応を終了した。得られた分散剤は 25°Cでロウ状固体であり、数平均分子量 3640、 重量平均分子量 5460、酸価 40mgKOHZgであった。  28.8 parts of pyromellitic dianhydride was added to the reaction product and reacted at 100 ° C for 5 hours. The acid value was measured to confirm that 97% or more of the acid anhydride was half-esterified, and the reaction was completed. The obtained dispersant was a waxy solid at 25 ° C., and had a number average molecular weight of 3640, a weight average molecular weight of 5460, and an acid value of 40 mgKOHZg.
[0264] 前記のうち実施例 2、 9、 12、 14、 15、 17、 18及び 19で得られた分散剤は 25°Cで 溶剤を含まなくても液状であるため取扱いに優れて 、た。 [0264] Among the above, the dispersants obtained in Examples 2, 9, 12, 14, 15, 17, 18, and 19 were 25 ° C. Even if it does not contain a solvent, it is liquid and is excellent in handling.
[0265] 《実施例 21》  [Example 21]
ガス導入管、温度計、コンデンサー、及び攪拌機を備えた反応容器に、 n—ブチル メタタリレート 200部及び 2—メルカプトエタノール 10部を仕込み、窒素ガスで置換し た。反応容器内を 80°Cに加熱して 12時間反応した。固形分測定により 95%が反応 したことを確認した。得られた反応生成物（重合体)の数平均分子量は 2460、重量 平均分子量 4530であった。  A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 200 parts of n-butyl metatalylate and 10 parts of 2-mercaptoethanol and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C and reacted for 12 hours. A solid content measurement confirmed that 95% had reacted. The number average molecular weight of the obtained reaction product (polymer) was 2460, and the weight average molecular weight was 4530.
前記反応生成物にピロメリット酸二無水物 14. 0部、シクロへキサノン 95. 9部、及 び触媒として 1, 8—ジァザビシクロー [5. 4. 0]—7—ゥンデセン（DBU) O. 4部を追 加し、 130°Cで 7時間反応させた。酸価の測定で 98%以上の酸無水物がハーフエス テルイ匕していることを確認し、シクロへキサノン 127. 6部を加え反応を終了した。反 応生成物は数平均分子量 3620、重量平均分子量 6190、酸価 29mgKOHZgであ つた o  Pyromellitic dianhydride (14.0 parts), cyclohexanone (95.9 parts), and 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) O. 4 Part was added and reacted at 130 ° C for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and 127.6 parts of cyclohexanone was added to complete the reaction. The reaction product had a number average molecular weight of 3620, a weight average molecular weight of 6190, and an acid value of 29 mg KOHZg.
[0266] 《実施例 22〜26》  [Examples 22 to 26]
実施例 16と同様の装置及び反応操作を用い、表 4に記載のエチレン性不飽和単 量体、連鎖移動剤、重合開始剤、及びテトラカルボン酸二無水物を、表 4に記載の使 用量で反応させて各分散剤を得た。  Using the same apparatus and reaction procedure as in Example 16, the ethylenically unsaturated monomer, chain transfer agent, polymerization initiator, and tetracarboxylic dianhydride listed in Table 4 were used in the dosages listed in Table 4. To obtain each dispersant.
[0267] [表 4] [0267] [Table 4]
櫥tKt ,s¾5#j9¾¾A^MviYY;^/u〜〜〜... 櫥 tKt, s¾5 # j9¾¾A ^ MviYY; ^ / u ~~~ ...
《 ^室》 〔¾·0261
Figure imgf000085_0001
《^ Room》 〔¾ · 0261
Figure imgf000085_0001
備えた反応容器に、 2—ェチルへキシルアルコール 39. 0部、ピロメリット酸無水物 2 1. 8部、及びメトキシプロピルアセテート 50部の混合物を窒素気流中 5時間、沸点で 反応させた。発生した水分はジーンスタークトラップで分離した。反応終了後、メトキ シプロピルアセテートで不揮発分を 50%に調整して比較分散剤を得た。反応生成物 の不揮発分あたりの酸価は 96mgKOHZgであった。 In a reaction vessel provided, a mixture of 39.0 parts of 2-ethylhexyl alcohol, 21.8 parts of pyromellitic anhydride and 50 parts of methoxypropyl acetate was reacted at the boiling point in a nitrogen stream for 5 hours. The generated water was separated with a gene stark trap. After completion of the reaction, the non-volatile content was adjusted to 50% with methoxypropyl acetate to obtain a comparative dispersant. The acid value per nonvolatile content of the reaction product was 96 mgKOHZg.
[0269] 《参考例 2》 [0269] <Reference Example 2>
ガス導入管、温度計、攪拌機、及びコンデンサーを備えた反応容器に、ネオペンチ ルグリコール 17. 8部、ピロメリット酸無水物 31. 9部、及びメトキシプロピルアセテート 75. 0部を仕込み、 150〜160°Cに昇温し、窒素気流中 5時間反応させた。酸価が 3 34mgKOHZg以下になった時点で 50°Cまで冷却し、 ε一力プロラタトン 249. 7部 、及びテトラブチルチタネート 0. 6部をカ卩え、 150°Cで 5時間反応させた。不揮発分 が 76%以上になった時点で冷却し、メトキシプロピルアセテートを追カ卩して不揮発分 を 50%に調整して比較分散剤を得た。反応生成物の不揮発分あたりの酸価は 55m gKOHZgであった。  A reaction vessel equipped with a gas inlet tube, a thermometer, a stirrer, and a condenser is charged with 17.8 parts neopentyl glycol, 31.9 parts pyromellitic anhydride, and 75.0 parts methoxypropyl acetate, and 150-160 The temperature was raised to ° C and the reaction was carried out in a nitrogen stream for 5 hours. When the acid value became 3 34 mgKOHZg or less, the mixture was cooled to 50 ° C, and ε 1-strength prolatatone (249.7 parts) and tetrabutyl titanate (0.6 parts) were added and reacted at 150 ° C for 5 hours. When the non-volatile content reached 76% or more, the mixture was cooled and methoxypropyl acetate was added to adjust the non-volatile content to 50% to obtain a comparative dispersant. The acid value per nonvolatile content of the reaction product was 55 mg KOHZg.
[0270] 《参考例 3》 [0270] << Reference Example 3 >>
ガス導入管、温度計、コンデンサー、及び攪拌機を備えた反応容器に、ブレンマー 55PET— 800〔日本油脂株式会社製:ポリ（エチレングリコール—テトラメチレンダリ コール）モノメタタリレート；数平均分子量： 840、水酸基価： 67mgKOHZg〕49. 5部 、 ε一力プロラタトン 50. 5部、触媒としてモノブチルスズ (IV)ォキシド 0. 04部及び 重合禁止剤としてメチルハイドロキノンを仕込み、 120°Cで 5時間乾燥空気を導入し ながら反応させた。固形分測定により 98%が反応したことを確認したのち、 70°Cに温 度を下げ無水コハク酸 5. 9部を添加した。そのまま 70°Cで 4時間反応させ比較分散 剤を得た。反応生成物の不揮発分あたりの酸価は 63mgKOHZgであった。 In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, BLEMMER 55PET-800 [manufactured by NOF Corporation: poly (ethylene glycol-tetramethylene glycol) monometatalylate; number average molecular weight: 840, Hydroxyl value: 67mgKOHZg] 49. 5 parts, epsilon prolatathone 50.5 parts, monobutyltin (IV) oxide 0.04 parts as catalyst and methylhydroquinone as polymerization inhibitor were charged and dried air at 120 ° C for 5 hours. The reaction was carried out while introducing. After confirming that 98% had reacted by solid content measurement, the temperature was lowered to 70 ° C. and 5.9 parts of succinic anhydride was added. The reaction was carried out at 70 ° C for 4 hours to obtain a comparative dispersant. The acid value per non-volatile content of the reaction product was 63 mgKOHZg.
[0271] 《参考例 4》 [0271] <Reference Example 4>
ガス導入管、温度計、コンデンサー、及び攪拌機を備えた反応容器に、ブレンマー 55PET— 800〔日本油脂株式会社製:ポリ（エチレングリコール—テトラメチレンダリ コール）モノメタタリレート；数平均分子量： 840、水酸基価： 67mgKOHZg〕49. 5部 、 ε一力プロラタトン 50. 5部、触媒としてモノブチルスズ (IV)ォキシド 0. 04部及び 重合禁止剤としてメチルハイドロキノンを仕込み、 120°Cで 5時間乾燥空気を導入し ながら反応させた。固形分測定により 98%が反応したことを確認したのち、 70°Cに温 度を下げ無水フタル酸 8. 7部を添加した。そのまま 70°Cで 4時間反応させ比較分散 剤を得た。反応生成物の不揮発分あたりの酸価は 61mgKOHZgであった。 In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, BLEMMER 55PET-800 [manufactured by NOF Corporation: poly (ethylene glycol-tetramethylene glycol) monometatalylate; number average molecular weight: 840, Hydroxyl value: 67 mg KOHZg] 49.5 parts, epsilon prolatathone 50.5 parts, monobutyltin (IV) oxide 0.04 parts as catalyst Methylhydroquinone was charged as a polymerization inhibitor and reacted while introducing dry air at 120 ° C for 5 hours. After confirming that 98% had reacted by solid content measurement, the temperature was lowered to 70 ° C and 8.7 parts of phthalic anhydride was added. The reaction was carried out at 70 ° C for 4 hours to obtain a comparative dispersant. The acid value per nonvolatile content of the reaction product was 61 mgKOHZg.
[0272] 《参考例 5》 [0272] <Reference Example 5>
ガス導入管、温度計、コンデンサー、及び攪拌機を備えた反応容器に、ジエチレン グリコールモノメチルエーテル 100. 0部、ピロメリット酸二無水物 64. 9部、メチルェ チルケトン 144. 5部、及び 1, 8—ジァザビシクロ— [5. 4. 0]— 7—ゥンデセン 0. 20 部をカ卩えて 80°Cで 20時間反応させた。酸価の測定で 97%以上の酸無水物がハー フェステルィ匕して ヽることを確認し反応を終了した。得られた分散剤は 25°Cで半透 明の液体であり、数平均分子量 550、重量平均分子量 700、酸価 205mgKOHZg であった。  In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, diethylene glycol monomethyl ether 100.0 parts, pyromellitic dianhydride 64.9 parts, methyl ethyl ketone 144.5 parts, and 1, 8— Diazabicyclo- [5. 4. 0]-7-Undecene 0.20 parts were added and reacted at 80 ° C for 20 hours. The reaction was completed when it was confirmed by acid value measurement that 97% or more of the acid anhydride had been formed into a haloester. The obtained dispersant was a semi-transparent liquid at 25 ° C. and had a number average molecular weight of 550, a weight average molecular weight of 700, and an acid value of 205 mgKOHZg.
[0273] 《参考例 6》 [0273] 《Reference Example 6》
ガス導入管、温度計、コンデンサー、及び攪拌機を備えた反応容器に、 2—ェチル へキシルアルコール 8. 7部、 ε一力プロラタトン 341. 3部、及び触媒としてモノブチ ルスズ (IV)ォキシド 0. 1部を仕込み、 130°Cで 5時間反応させた。固形分測定により 98%が反応したことを確認し第一の工程を終了した。この反応生成物の数平均分子 量は 5570、重量平均分子量は 8520であった。  In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 8.7 parts of 2-ethylhexyl alcohol, 341.3 parts of epsilon prolatathone, and monobutyltin (IV) oxide as catalyst 0.1 The parts were charged and reacted at 130 ° C for 5 hours. The first step was completed after confirming that 98% had reacted by solid content measurement. The number average molecular weight of this reaction product was 5570, and the weight average molecular weight was 8520.
前記反応生成物にピロメリット酸二無水物 7. 2部を追加し 100°Cで 5時間反応させ た。酸価の測定で 97%以上の酸無水物がハーフエステルイ匕していることを確認し第 二の工程を終了した。得られた分散剤は 25°Cでロウ状固体であり、数平均分子量 10 860、重量平均分子量 17700、酸価 l lmgKOHZgであった。  An additional 7.2 parts of pyromellitic dianhydride was added to the reaction product and reacted at 100 ° C for 5 hours. The acid value was measured to confirm that 97% or more of the acid anhydride was half-esterified, and the second step was completed. The obtained dispersant was a waxy solid at 25 ° C., and had a number average molecular weight of 10 860, a weight average molecular weight of 17700, and an acid value of 1 mgKOHZg.
[0274] 《実施例 27》 [Example 27]
顔料として二酸ィ匕チタン 24g、実施例 1で得られた分散剤 4g、メトキシプロピルァセ テート 32g、及びガラスビーズ（直径 0. 8mm) 60gを 140mLのマヨネーズ瓶に仕込 み、シエイカー（F&FM社製スキャンデッタス SO400) (以下スキャンデッタスと呼ぶ） に設置して 3時間分散した。得られた分散液力 ガラスビーズを取り除き分散体を得 た。この分散体を 24時間 25°Cで放置した後、直径 60mm、角度 0度 59分のコーン プレートを用いたコーンプレート型粘度計で、 lOradZ秒の回転速度で 25°Cでの粘 度〔これを初期粘度 (Vi)と呼ぶ〕を測定したところ 50mPa' sであった。また、この分散 体を 40°Cのオーブンで 1週間保存したものを前記と同様の方法で粘度〔これを経時 粘度 (Vs)と呼ぶ〕を測定したところ 53mPa · sであり、粘度の変化率 (R)を以下の計 算式（1) : As a pigment, 24 g of titanium dioxide and 4 g of the dispersant obtained in Example 1, 32 g of methoxypropyl phosphate, and 60 g of glass beads (0.8 mm in diameter) were charged into a 140 mL mayonnaise bottle, and shaker (F & FM) It was installed on a Scandetta SO400) (hereinafter referred to as Scandettas) and dispersed for 3 hours. The obtained dispersion power glass beads were removed to obtain a dispersion. This dispersion is left for 24 hours at 25 ° C and then cones with a diameter of 60 mm and an angle of 0 degrees 59 minutes. The viscosity at 25 ° C. (called the initial viscosity (Vi)) was measured with a cone-plate viscometer using a plate at a rotation speed of lOradZ seconds, and it was 50 mPa's. In addition, when this dispersion was stored in an oven at 40 ° C for 1 week, the viscosity (this is called the viscosity with time (Vs)) was measured in the same manner as described above, and it was 53 mPa · s, and the rate of change in viscosity. (R) is calculated using the following formula (1):
R= (Vs/Vi) X 100 (1)  R = (Vs / Vi) X 100 (1)
(式中、 Rは粘度変化率であり、 Vsは経時粘度であり、そして Viは初期粘度である） 力も計算したところ、 106%であった。  (Where R is the rate of viscosity change, Vs is the viscosity over time, and Vi is the initial viscosity) The force was also calculated to be 106%.
[0275] 《実施例 28〜41》 [0275] Examples 28 to 41
実施例 27と同様の方法で、前記実施例で得られた分散剤を用いて得た分散体の 初期粘度、経時粘度及び粘度の変化率を測定した。但し、実施例 37〜41について は使用する溶剤を実施例 27におけるメトキシプロピルアセテートから n—ォクタノール に変更して分散体を作製した。結果を表 5〜7に示す。  In the same manner as in Example 27, the initial viscosity, the viscosity with time, and the rate of change in viscosity of the dispersion obtained using the dispersant obtained in the above Example were measured. However, in Examples 37 to 41, dispersions were prepared by changing the solvent to be used from n-octanol to methoxypropyl acetate in Example 27. The results are shown in Tables 5-7.
[0276] [表 5] [0276] [Table 5]
Figure imgf000088_0001
Figure imgf000088_0001
[0277] [表 6]  [0277] [Table 6]
Figure imgf000088_0002
Figure imgf000088_0002
[0278] [表 7] 実施例 37 実施例 38 実施例 39 実施例 40 実施例 41 [0278] [Table 7] Example 37 Example 38 Example 39 Example 40 Example 41
実施例 16で 実施例 17で 実施例 18で 実施例 19で 実施例 20で 得られたもの得られたもの得られたもの得られたもの得られたもの 初期粘度 35 45 38 48 55 経時粘度 35 42 39 50 55 変化率 100% 93% 103% 104% 100%  Example 16 Example 17 Example 18 Example 18 Example 19 Example 20 What was obtained What was obtained What was obtained What was obtained Initial viscosity 35 45 38 48 55 Viscosity over time 35 42 39 50 55 Rate of change 100% 93% 103% 104% 100%
[0279] 《実施例 42〜47》 [Examples 42 to 47]
実施例 27 (分散体の製造実施例）に記載の操作において、実施例 1で得られた分 散剤 4gの代わりに、それぞれ実施例 21〜26で得られた分散剤 (不揮発分 50重量 %) 8gを用い、メトキシプロピルアセテート 32gの代わりにシクロへキサノン 28gを用い ること以外は、全て実施例 27に記載の操作及び評価方法によって、分散体を製造し 、分散体の初期粘度、経時粘度及び粘度の変化率を測定し、評価した。結果を表 8 に示す。  In the operation described in Example 27 (Dispersion Production Example), instead of 4 g of the dispersant obtained in Example 1, each of the dispersants obtained in Examples 21 to 26 (nonvolatile content: 50% by weight) Except for using 8 g and using 28 g of cyclohexanone instead of 32 g of methoxypropyl acetate, a dispersion was produced by the operation and evaluation method described in Example 27. The rate of change in viscosity was measured and evaluated. The results are shown in Table 8.
[0280] [表 8]  [0280] [Table 8]
Figure imgf000089_0001
Figure imgf000089_0001
[0281] 《比較例 1〜4》  [0281] Comparative Examples 1 to 4
実施例 27 (分散体の製造実施例）に記載の操作において、参考例 1、 2、 5及び 6 で得られた分散剤を用いて製造した分散体の初期粘度、経時粘度及び粘度の変化 率を測定した。但し、比較例 3については、使用する溶剤を実施例 27で用いたメトキ シプロピルアセテートの代わりに n—ォクタノールに変更して分散体を作成した。結果 を表 9に示す。  In the operation described in Example 27 (Dispersion Production Example), the initial viscosity, the time-dependent viscosity and the rate of change of the viscosity of the dispersion produced using the dispersants obtained in Reference Examples 1, 2, 5 and 6 Was measured. However, for Comparative Example 3, a dispersion was prepared by changing the solvent used to n-octanol instead of the methoxypropyl acetate used in Example 27. The results are shown in Table 9.
[0282] [表 9] 比較例 1 比較例 2 比較例 3 比較例 4 参考例 1で 参考例 2で 参考例 5で 参考例 6で 得られたもの得られたもの得られたもの得られたもの 初期粘度 700 410 500 200 経時粘度 ゲル化 720 550 220 変化率 ― 176% 110% 110% [0283] 《実施例 48》 [0282] [Table 9] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Reference Example 1 Reference Example 2 Reference Example 5 Reference Example 6 What was obtained What was obtained Things Initial viscosity 700 410 500 200 Viscosity with time Gelation 720 550 220 Rate of change ― 176% 110% 110% [0283] <Example 48>
以下の計算式：  The following formula:
F = B— A  F = B— A
(式中、 Fは、顔料の表面余剰官能性量 molZg)であり、 Bは顔料の表面塩基量 molZg)であり、 Aは、顔料の表面酸量 molZg)である）  (In the formula, F is the surface excess functionality of the pigment molZg), B is the surface base amount of the pigment molZg), and A is the surface acid amount of the pigment molZg)
から計算される F値 (顔料の表面余剰官能性量)力 + 140 μ molZgである塩基性 表面を有する銅フタロシアニン顔料 9g、実施例 1で得られた分散剤 3g、メトキシプロ ピルアセテート 48g、及びガラスビーズ（直径 0. 8mm) 60gを 140mLのマヨネーズ 瓶に仕込み、スキャンデッタスに設置して 3時間分散した。得られた分散液力 ガラス ビーズを取り除き分散体を得た。この分散体を 24時間 25°Cで放置した後、直径 60m m、角度 0度 59分のコーンプレートを用いたコーンプレート型粘度計で、 lOradZ秒 の回転速度で 25°Cでの粘度〔=初期粘度 (Vi)〕を測定したところ 3. 5mPa' sであつ た。また、この分散体を 40°Cのオーブンで 1週間保存したものを前記と同様の方法で 粘度〔=経時粘度 ( 〕を測定したところ 3. 5mPa' sであり、前記計算式（1)によつ て計算した粘度変化率 (R)は 100%であった。  F value (excess surface functionality of pigment) calculated from: 9 g of copper phthalocyanine pigment having a basic surface of 140 μmolZg, 3 g of the dispersant obtained in Example 1, 48 g of methoxypropyl acetate, and 60 g of glass beads (0.8 mm in diameter) were placed in a 140 mL mayonnaise bottle, placed in a scandetta and dispersed for 3 hours. The obtained dispersion liquid glass beads were removed to obtain a dispersion. This dispersion was allowed to stand at 25 ° C for 24 hours, and then the viscosity at 25 ° C at a rotation speed of lOradZ seconds (= The initial viscosity (Vi)] was measured and found to be 3.5 mPa's. In addition, when this dispersion was stored in an oven at 40 ° C. for 1 week, the viscosity (= viscosity with time ()) was measured by the same method as described above, which was 3.5 mPa's. The viscosity change rate (R) thus calculated was 100%.
[0284] 《実施例 49〜52》  [Examples 49-52]
実施例 48と同じ方法で、実施例 3、 9、 18及び 22で得られた分散剤を用いて得た 分散体の初期粘度、経時粘度及び粘度の変化率を測定した。なお、実施例 52にお いては、実施例 48に記載の操作を繰り返す際に、「実施例 1で得られた分散剤 3g」 に代えて「実施例 22で得られた分散剤 (不揮発分 50%) 6g」を用い、「メトキシプロピ ルアセテート 48g」に代えて「メトキシプロピルアセテート 45g」を用いて分散体を得た 。結果を表 10に示す。  In the same manner as in Example 48, the initial viscosity, the time-dependent viscosity, and the rate of change in viscosity of the dispersions obtained using the dispersants obtained in Examples 3, 9, 18 and 22 were measured. In Example 52, when the operation described in Example 48 was repeated, instead of “3 g of the dispersant obtained in Example 1”, the “dispersant obtained in Example 22 (nonvolatile content) was replaced. 50%) 6 g ”was used, and“ Methoxypropyl acetate 45 g ”was used instead of“ Methoxypropyl acetate 48 g ”to obtain a dispersion. The results are shown in Table 10.
[0285] [表 10]  [0285] [Table 10]
Figure imgf000090_0001
Figure imgf000090_0001
[0286] 《比較例 5〜8》 参考例 1〜4で得られた分散剤を用いること以外は、実施例 27と同様の方法で得た 分散体について、それらの初期粘度、経時粘度及び粘度の変化率を測定した。結果 を表 11に示す。 [0286] Comparative Examples 5 to 8 With respect to the dispersions obtained by the same method as in Example 27 except that the dispersants obtained in Reference Examples 1 to 4 were used, their initial viscosity, time-dependent viscosity, and rate of change in viscosity were measured. The results are shown in Table 11.
[表 11]  [Table 11]
Figure imgf000091_0001
Figure imgf000091_0001
[0288] 本発明の分散剤を用いることにより、顔料を低粘度で分散することが可能になり、保 存安定性も良好な分散体が得られた。  [0288] By using the dispersant of the present invention, it was possible to disperse the pigment with a low viscosity, and a dispersion having good storage stability was obtained.
一方、特許文献 1の実施例 5に記載の方法により得られる比較分散剤を用いた比 較例 1及び 5では、分散剤に重合体部 (P)が存在しないため分散能が著しく低ぐ分 散操作中又は 40°C保存中にゲルィ匕した。  On the other hand, in Comparative Examples 1 and 5 using the comparative dispersant obtained by the method described in Example 5 of Patent Document 1, since the polymer part (P) does not exist in the dispersant, the dispersibility is extremely low. Gelling occurred during spraying or storage at 40 ° C.
特許文献 2の実施例 1に記載の方法により得られる比較用分散剤を用いたに比較 例 2及び 6では、テトラカルボン酸二無水物部分が一分子中に二個以上含まれてい る化合物ができていることから、初期粘度が高くなり、経時保存安定性が悪力つた。 また、重合体部 (P)の分子量力 168であり、本発明の範囲 200よりも低い分散剤を 用いた比較例 3、又は重合体部（P)の分子量が 5570であり、本発明の範囲 5000よ りも高 、分散剤を用いた比較例 4では、 V、ずれも分散体の粘度が高力つた。  In Comparative Examples 2 and 6 in which the comparative dispersant obtained by the method described in Example 1 of Patent Document 2 was used, a compound containing two or more tetracarboxylic dianhydride moieties in one molecule was obtained. As a result, the initial viscosity was high, and the storage stability with time was bad. Further, the molecular weight of the polymer part (P) is 168, and the molecular weight of Comparative Example 3 using a dispersant lower than the range 200 of the present invention, or the polymer part (P) is 5570, which is within the scope of the present invention. In Comparative Example 4 where the dispersant was used, the viscosity of the dispersion was higher than 5000 and V was higher than 5000.
更に、基 X1の置換基としてカルボキシル基を 2つ以上含まな 、分散体を用いた比 較例 7及び 8では粘度が高ぐまた保存安定性が悪力つた。以上のように、比較用分 散剤では欠点が存在した。 Further, Comparative Examples 7 and 8 using a dispersion that did not contain two or more carboxyl groups as a substituent of the group X 1 had high viscosity and poor storage stability. As described above, the comparative dispersants have drawbacks.
[0289] [分散剤の用途に関する実施例及び比較例] [Examples and comparative examples concerning use of dispersant]
《塩基性シナジストの製造例》  《Examples of basic synergist production》
分散剤の用途に関する以下の実施例及び比較例で用いた塩基性誘導体 α 1〜ひ 14を、以下の表 12〜14に示した。塩基性誘導体 a 1〜 a 14は、公知の製造方法に より、原料となる色素にアミンィ匕合物を反応させることにより製造した。 [0290] [表 12] The basic derivatives α 1 to 14 used in the following Examples and Comparative Examples relating to the use of the dispersant are shown in Tables 12 to 14 below. The basic derivatives a 1 to a 14 were produced by reacting an amine compound with a dye as a raw material by a known production method. [0290] [Table 12]
Figure imgf000092_0001
Figure imgf000092_0001
[0291] [表 13]
Figure imgf000093_0001
14]
Figure imgf000094_0001
[0291] [Table 13]
Figure imgf000093_0001
14]
Figure imgf000094_0001
《実施例 53〜70》 << Examples 53 to 70 >>
ペースト状顔料分散体の製造を実施例 53〜70に示す。表 15に示す配合比 (重量 比）により、顔料、塩基性シナジスト、分散剤、アルキッド榭脂（日立化成社製「フタル キッド 133— 60」）、メラミン榭脂（日立化成社製「メラン 20」）、及び溶剤〔シクロへキ サノン Zキシレン Zn—ブタノール =6Z2Z2 (重量比）からなる混合シンナー〕を、 マヨネーズ瓶に仕込み、デイスパーで予備分散した後、直径 0. 5mmのジルコ-アビ ーズ 250部を分散メディアとして仕込み、スキャンデッタスにて本分散を行い、ペース ト状顔料分散体を得た。 The preparation of paste pigment dispersions is shown in Examples 53-70. Depending on the blending ratio (weight ratio) shown in Table 15, pigment, basic synergist, dispersant, alkyd resin (Hitachi Chemical Co., Ltd. “Phtalkid 133-60”), melamine resin (Hitachi Chemical Co., Ltd. “Melan 20”) ) And a solvent (mixed thinner consisting of cyclohexanone Z-xylene Zn-butanol = 6Z2Z2 (weight ratio)) is pre-dispersed in a mayonnaise bottle, predispersed with a disperser, and then Zirco-Abye's with a diameter of 0.5 mm 250 The department is prepared as a distributed medium, and the main distribution is performed at scan depth. A pigment dispersion was obtained.
[0294] 得られたペースト状顔料分散体の粘度を B型粘度計で測定し、粘度及び TI値でぺ 一スト状顔料分散体の性能を評価した。結果を表 16に示す。なお、 TI値は、以下の 計算式（2) :  [0294] The viscosity of the obtained paste-like pigment dispersion was measured with a B-type viscometer, and the performance of the paste-like pigment dispersion was evaluated based on the viscosity and the TI value. The results are shown in Table 16. The TI value is calculated using the following formula (2):
TI=V6/V60 (2)  TI = V6 / V60 (2)
(式中、 V6は、 6rpmでの粘度であり、 V60は、 60rpmでの粘度である）  (Where V6 is the viscosity at 6 rpm and V60 is the viscosity at 60 rpm)
力 得られる値である。  Force Value obtained.
また、得られた顔料ペーストペースト状顔料分散体を 50°Cの恒温機に 1週間保存し て、経時変化を促進させた後、経時変化発生前後での粘度変化 (％)を測定し、粘度 安定性を以下の 2段階で評価した。結果を表 16に示す。  The obtained pigment paste paste-like pigment dispersion was stored in a thermostat at 50 ° C for 1 week to accelerate the change over time, and the change in viscosity (%) before and after the change over time was measured. Stability was evaluated in the following two steps. The results are shown in Table 16.
〇： 50°C1週間保存前後の粘度の変化率が ± 10%以内。  ○: Viscosity change rate before and after storage at 50 ° C for 1 week is within ± 10%.
X： 50°C1週間保存前後の粘度の変化率が ± 10%を超える。  X: Viscosity change rate before and after storage at 50 ° C for 1 week exceeds ± 10%.
[0295] 更に、実施例 53、実施例 59、実施例 60、実施例 62、及び実施例 63で得られたぺ 一スト状顔料分散体を、それぞれアルミ板にバーコ一ター # 5で塗工して、 180°Cで 1時間焼き付けた後、濃度 5%の食塩水に 24時間漬けたところ、塗膜のプリスターは 生じなかった。 [0295] Further, the pasty pigment dispersions obtained in Example 53, Example 59, Example 60, Example 62, and Example 63 were applied to an aluminum plate with bar coater # 5, respectively. Then, after baking at 180 ° C for 1 hour and then immersing in a 5% strength saline solution for 24 hours, no paint film prestar was formed.
[0296] [表 15] [0296] [Table 15]
〔3029 [3029
Figure imgf000096_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000097_0001
[0298] 《比較例 9〜25》  [0298] <Comparative Examples 9 to 25>
表 17に示す配合比 (重量比）に従って、実施例 53〜70と同様の方法で、比較用 ペースト状顔料分散体を製造した。また、得られた比較用ペースト状顔料分散体の 粘度、 TI値、及び粘度安定性を同様に測定し、その結果を表 18に示す。  According to the blending ratio (weight ratio) shown in Table 17, comparative paste-like pigment dispersions were produced in the same manner as in Examples 53 to 70. In addition, the viscosity, TI value, and viscosity stability of the obtained comparative paste pigment dispersion were measured in the same manner, and the results are shown in Table 18.
[0299] 更に、比較例 12、比較例 16、比較例 20、比較例 22、及び比較例 23で得られた比 較用ペースト状顔料分散体をそれぞれアルミ板にバーコ一ター # 5で塗工して、 180 °Cで 1時間焼き付けた後、濃度 5%の食塩水に 24時間漬けたところ、全ての塗膜に ブリスターを生じた。  [0299] Further, the comparative paste-like pigment dispersions obtained in Comparative Example 12, Comparative Example 16, Comparative Example 20, Comparative Example 22, and Comparative Example 23 were each coated on an aluminum plate with bar coater # 5. Then, after baking at 180 ° C for 1 hour, when immersed in a 5% strength saline solution for 24 hours, blisters were formed on all coating films.
[0300] [表 17] [0300] [Table 17]
s §§¾l s §§¾l
Figure imgf000098_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000099_0001
[0302] 《実施例 71〜75及び比較例 26〜28》  [0302] Examples 71 to 75 and Comparative Examples 26 to 28
非水性インクジェットインク用のペースト状顔料分散体の製造を実施例 71〜75に 示す。表 19に示す配合比 (重量比）により、有機溶剤中に顔料、顔料誘導体及び分 散剤を投入し、ハイスピードミキサー等で均一になるまで撹拌した後、得られたミルべ 一スを横型サンドミルで約 1時間分散して作製した。同様の方法で、比較用ペースト 状顔料分散体を製造した。  Examples 71-75 show the preparation of paste pigment dispersions for non-aqueous inkjet inks. In accordance with the blending ratio (weight ratio) shown in Table 19, the pigment, pigment derivative, and dispersing agent were added to the organic solvent and stirred with a high-speed mixer, etc. until uniform, and then the resulting mill base was mixed with a horizontal sand mill. And dispersed for about 1 hour. A comparative paste-like pigment dispersion was produced in the same manner.
[0303] [表 19] [0303] [Table 19]
Figure imgf000100_0001
Figure imgf000100_0001
表 19中の略称は以下の通りである。  Abbreviations in Table 19 are as follows.
Ε5Β02· · ·クラリアント社製；キナクリドン顔料； Hostaperm Red E5B 02 FG7351 - - '東洋インキ製造社製；フタロシアニン顔料； Lionol Blue FG- 7351 R960 · · ·ディポン社製：酸化チタン顔料；タイピュア R960 BGAc - - 'エチレングリコールモノブチルエーテルアセテート Ε5Β02 · · · Clariant; Quinacridone pigment; Hostaperm Red E5B 02 FG7351--'Toyo Ink Co., Ltd .; Phthalocyanine pigment; Lionol Blue FG-7351 R960 · · · Dipon: Titanium oxide pigment; Taipure R960 BGAc--'Ethylene glycol monobutyl ether acetate
BYK111 · · · BYK Chemie社製；酸性高分子分散剤； Disperbyk- 111  BYK111 · · · BYK Chemie; acidic polymer dispersant; Disperbyk-111
[0305] 《実施例 76〜80及び比較例 29〜 31》 << Examples 76 to 80 and Comparative Examples 29 to 31 >>
前記実施例 71〜75及び比較例 26〜28によって調製したペースト状顔料分散体 をインク化し、表 20に示す配合比（重量比）により、非水性インクジェットインクを製造 した。なお、表 20において「ビュル榭脂 VYHD」は、ダウケミカルズ社製の塩ィ匕酢酸 ビニル榭脂である。  The pasty pigment dispersions prepared in Examples 71 to 75 and Comparative Examples 26 to 28 were converted into inks, and non-aqueous inkjet inks were produced at the blending ratios (weight ratios) shown in Table 20. In Table 20, “Bull resin VYHD” is a salted vinyl acetate resin manufactured by Dow Chemicals.
[0306] 実施例 76〜80及び比較例 29〜31で調製されたインクジェットインクについて、分 散性の尺度として「分散粒径」、流動性の尺度として「粘度」、印字安定性の尺度とし て「吐出状態」をそれぞれ下記の条件で評価した。  [0306] For the inkjet inks prepared in Examples 76 to 80 and Comparative Examples 29 to 31, "dispersion particle size" as a measure of dispersibility, "viscosity" as a measure of fluidity, and a measure of print stability Each “discharge state” was evaluated under the following conditions.
[0307] (1)分散粒径：  [0307] (1) Dispersed particle size:
インクジェットインクを酢酸ェチルで 200〜 1000倍に希釈し、粒度分布計〔マイクロ トラック UPA150 (日機装社製)〕で測定した。  The inkjet ink was diluted 200-1000 times with ethyl acetate and measured with a particle size distribution meter [Microtrac UPA150 (Nikkiso Co., Ltd.)].
[0308] (2)粘度：  [0308] (2) Viscosity:
インクジェットインクを 25°Cに調整し、 E型粘度計〔RE80 (東機産業社製)〕にて測 し 7こ。  Adjust the inkjet ink to 25 ° C and measure with an E-type viscometer [RE80 (manufactured by Toki Sangyo)].
[0309] (3)印字安定性： [0309] (3) Printing stability:
インクジェットインクを大判インクジェットプリンタ〔IP— 6500 (セイコーアイ'インフォ テック社製)〕で印字して、ノズルチヱックパターンの印刷状態を観察し、以下の 3段階 で評価した：  Ink-jet ink was printed with a large-format ink-jet printer [IP-6500 (manufactured by Seiko I Infotech)], and the printing state of the nozzle check pattern was observed and evaluated in the following three stages:
〇· · ·ノズル抜けや曲がりといった印字欠陥が 1%以下；  ○ · · · Print defects such as missing nozzles and bending are less than 1%;
△ · · 'ノズル抜けや曲がりといった印字欠陥が 1〜10%；  △ · · '1-10% print defects such as missing nozzles or bending;
X · · 'ノズル抜けや曲がりといった印字欠陥が 10%を超える。  X · · 'Print defects such as missing nozzles and bending exceed 10%.
[0310] これらの評価結果も表 20に示す。実施例 76〜80のインクジェットインクでは、粘度 及び分散粒径がともにインクジェットインクに適した値を示し、結果として優れた印字 安定性を示した。一方、比較例 29及び 30のインクは粘度が高ぐまた分散粒径が大 きいこともあり、プリンタヘッドからインクを吐出させることが殆どできな力つた。比較例 31のインクは、吐出させることはできた力 粘度が高いために印字欠陥が 25%に達 した。 [0310] These evaluation results are also shown in Table 20. In the inkjet inks of Examples 76 to 80, the viscosity and the dispersed particle diameter both showed values suitable for the inkjet ink, and as a result, excellent printing stability was exhibited. On the other hand, the inks of Comparative Examples 29 and 30 had a high viscosity and a large dispersed particle size, and thus the ink could hardly be ejected from the printer head. The ink of Comparative Example 31 was able to be ejected. The viscosity was high and the printing defect reached 25%. did.
[表 20][Table 20]
Figure imgf000102_0001
Figure imgf000102_0001
《実施例 81 100及び比較例 32 37》  << Example 81 100 and Comparative Example 32 37 >>
(1)アクリル榭脂溶液 Iの調製 (1) Preparation of acrylic resin solution I
反応容器にシクロへキサノン 370部を入れ、容器に窒素ガスを注入しながら 80°Cに 加熱して、同温度でメタクリル酸 20. 0部、メチルメタタリレート 10. 0部、 n—ブチルメ タクリレート 55. 0部、 2—ヒドロキシェチルメタタリレート 15. 0部、及び 2, 2，—ァゾビ スイソプチ口-トリル 4. 0部の混合物を 1時間かけて滴下して重合反応を行った。滴 下終了後、更に 80°Cで 3時間反応させた後、ァゾビスイソブチ口-トリル 1. 0部をシク 口へキサノン 50部に溶解させた溶液を添カ卩し、更に 80°Cで 1時間反応を続けて、ァ クリル樹脂の溶液を得た。アクリル榭脂の重量平均分子量は、約 40000であった。室 温まで冷却した後、アクリル榭脂溶液約 2gをサンプリングし、 180°Cで 20分間加熱し て乾燥して不揮発分を測定し、アクリル榭脂溶液の不揮発分が 20重量％になるよう に、先に合成したアクリル榭脂溶液にシクロへキサノンを添加してアクリル榭脂溶液 I を調製した。 Place 370 parts of cyclohexanone in a reaction vessel, heat to 80 ° C while injecting nitrogen gas into the vessel, and at the same temperature, 20.0 parts of methacrylic acid, 10.0 parts of methyl metatalylate, n-butyl methacrylate. A mixture of 55.0 parts of tacrylate, 15.0 parts of 2-hydroxyethyl methacrylate, and 4.0 parts of 2,2, -azobisisobutyl-tolyl was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 3 hours, and then a solution prepared by dissolving 1.0 part of azobisisobutyor-tolyl in 50 parts of hexanone was added, and further at 80 ° C for 1 hour. The reaction was continued to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 40000. After cooling to room temperature, sample approximately 2 g of the acrylic resin solution, heat at 180 ° C for 20 minutes and dry to measure the nonvolatile content, so that the nonvolatile content of the acrylic resin solution is 20% by weight. Then, cyclohexanone was added to the previously synthesized acrylic resin solution to prepare an acrylic resin solution I.
[0313] (2)アクリル榭脂溶液 IIの調製 [0313] (2) Preparation of acrylic resin solution II
反応容器にシクロへキサノン 370部を入れ、容器に窒素ガスを注入しながら 80°Cに 加熱して、同温度でメタクリル酸 20. 0部、メチルメタタリレート 10. 0部、 n—ブチルメ タクリレート 35. 0部、 2—ヒドロキシェチルメタタリレート 15. 0部、 2, 2，—ァゾビスィ ソブチ口-トリル 4. 0部、及びパラクミルフエノールエチレンオキサイド変性アタリレー ト (東亞合成社製「ァロニックス M— 110」） 20. 0部の混合物を 1時間かけて滴下して 重合反応を行った。滴下終了後、更に 80°Cで 3時間反応させた後、ァゾビスイソプチ 口-トリル 1. 0部をシクロへキサノン 50部に溶解させた溶液を添カ卩し、更に 80°Cで 1 時間反応を続けて、アクリル榭脂の溶液を得た。アクリル榭脂の重量平均分子量は、 約 40000であった。室温まで冷却した後、アクリル榭脂溶液約 2gをサンプリングし、 1 80°Cで 20分間加熱して乾燥して不揮発分を測定し、アクリル榭脂溶液の不揮発分 が 20重量％になるように、先に合成したアクリル榭脂溶液にシクロへキサノンを添カロ してアクリル榭脂溶液 IIを調製した。  Place 370 parts of cyclohexanone in a reaction vessel and heat to 80 ° C while injecting nitrogen gas into the vessel. At the same temperature, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, n-butyl methacrylate 35.0 parts, 2-hydroxyethyl methacrylate 15.0 parts, 2, 2, azobisi sotochi-tolyl 4.0 parts, and paracumylphenol ethylene oxide modified atrelate (“Aronix M” manufactured by Toagosei Co., Ltd.) —110 ”) 20. The polymerization reaction was carried out by adding 0 part of the mixture dropwise over 1 hour. After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 3 hours, and then a solution in which 1.0 part of azobisisobutyl-tolyl was dissolved in 50 parts of cyclohexanone was added, and the reaction was further conducted at 80 ° C for 1 hour. Subsequently, a solution of acrylic resin was obtained. The weight average molecular weight of the acrylic resin was about 40000. After cooling to room temperature, sample about 2 g of acrylic resin solution, heat at 180 ° C for 20 minutes and dry to measure the non-volatile content, so that the non-volatile content of the acrylic resin solution is 20% by weight. Acrylic resin solution II was prepared by adding cyclohexanone to the previously synthesized acrylic resin solution.
[0314] (3)コントラスト比の測定法 [0314] (3) Contrast ratio measurement method
カラーフィルタ用インクの調製手順を説明する前に、レジスト材塗布基板のコントラ スト比の測定法にっ 、て説明する。  Before describing the procedure for preparing the color filter ink, a method for measuring the contrast ratio of the resist-coated substrate will be described.
レジスト材塗布基板を 2枚の偏光板の間に挟み、一方の偏光板側カゝら液晶ディスプ レー用バックライト 'ユニットを用いて光を照射する。ノ ックライト 'ユニットから出た光は 、 1枚目の偏光板を通過して偏光され、次いでレジスト材塗布基板を通過し、 2枚目 の偏光板に到達する。 1枚目の偏光板と 2枚目の偏光板の偏光面が平行であれば、 光は 2枚目の偏光板を透過するが、偏光面が直行して!/、る場合には光は 2枚目の偏 光板により遮断される。しかし、 1枚目の偏光板によって偏光された光が、レジスト材 塗布基板を通過するときに、顔料粒子による散乱等が起こり偏光面の一部にずれを 生じると、偏光板が平行のときは 2枚目の偏光板を透過する光量が減り、偏向板が直 行のときは 2枚目の偏光板を光の一部が透過する。この透過光を偏光板上の輝度と して測定し、 2枚の偏光板が相互に平行である場合の輝度と、 2枚の偏光板が相互 に直行する場合の輝度との比をコントラスト比とし、以下の計算式（3)： A resist-coated substrate is sandwiched between two polarizing plates, and light is irradiated using a backlight unit for a liquid crystal display from the side of one polarizing plate. The light emitted from the knock light 'unit passes through the first polarizing plate and is then polarized, and then passes through the resist-coated substrate. To reach the polarizing plate. If the planes of polarization of the first and second polarizers are parallel, light will pass through the second polarizer, but if the plane of polarization is perpendicular! It is blocked by the second polarizing plate. However, when the light polarized by the first polarizing plate passes through the resist material-coated substrate, scattering by pigment particles or the like causes a deviation in a part of the polarization plane. When the amount of light transmitted through the second polarizing plate is reduced and the deflecting plate is perpendicular, a part of the light is transmitted through the second polarizing plate. This transmitted light is measured as the luminance on the polarizing plate, and the ratio of the luminance when the two polarizing plates are parallel to each other and the luminance when the two polarizing plates are orthogonal to each other is shown as the contrast ratio. And the following formula (3):
Cr= (Bp) / (Bs) (3)  Cr = (Bp) / (Bs) (3)
(式中、 Crはコントラスト比であり、 Bpは 2枚の偏光板が相互に平行である場合の輝 度であり、 Bsは 2枚の偏光板が相互に直行する場合の輝度である）  (In the formula, Cr is the contrast ratio, Bp is the brightness when the two polarizing plates are parallel to each other, and Bs is the brightness when the two polarizing plates are orthogonal to each other.)
によって計算することができる。  Can be calculated by:
従って、レジスト材塗布膜中の顔料により散乱が起こると、平行のときの輝度が低下 し、かつ直行のときの輝度が増加するため、コントラスト比が低くなる。なお、輝度計は 株式会社トプコン社製の色彩輝度計 BM— 5Aを用い、偏光板はサンリツ社製の偏光 フィルム LLC2— 92— 18を用いた。なお、測定に際しては、不要光を遮断するため に、測定部分に lcm角の孔を開けた黒色のマスクを当てて測定を行った。  Therefore, when scattering occurs due to the pigment in the resist material coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, and the contrast ratio is lowered. The luminance meter used was a color luminance meter BM-5A manufactured by Topcon Corporation, and the polarizing film used was a polarizing film LLC2-92-18 manufactured by Sanritsu. In the measurement, in order to block unnecessary light, the measurement was carried out by applying a black mask with lcm square holes in the measurement area.
[0315] (4)カラーフィルタ用インクの調製 [0315] (4) Preparation of color filter ink
実施例 81〜： LOO及び比較例 32〜37のカラーフィルタ用インクの製造は、表 20に 示す配合比 (重量比）に従った。まず、顔料、分散剤、アクリル榭脂溶液の一部、及 びシクロへキサンノンの一部を均一に撹拌混合した後、直径 lmmのジルコ-アビー ズを用いて、アイガーミル（アイガージャパン社製「ミニモデル M— 250 ΜΚΠ」）で 2 時間分散し、 5 mのフィルタで濾過し、顔料分散体を作製した。なお、分散剤は事 前にシクロへキサノンに溶解して添加した。  Example 81-: The color filter inks of LOO and Comparative Examples 32-37 were produced according to the blending ratio (weight ratio) shown in Table 20. First, a pigment, a dispersant, a part of an acrylic resin solution, and a part of cyclohexanone are stirred and mixed uniformly, and then a Eiger mill ("Eger Japan" Dispersion was carried out for 2 hours using model M-250 mm and filtered through a 5 m filter to prepare a pigment dispersion. The dispersant was added in advance dissolved in cyclohexanone.
[0316] 次いで、前記顔料分散体、アクリル榭脂溶液の残り、モノマー、光重合開始剤、増 感剤、及びシクロへキサンノンの残りの混合物を均一になるように攪拌混合した後、 1 mのフィルタで濾過して、カラーフィルタ用インクを製造した。なお、最終的に表 20 に示す配合比 (重量比)を保ち、かつ分散を行える限りは、前記顔料分散体の製造 段階及びカラーフィルタ用インクの製造段階におけるアクリル榭脂溶液及びシクロ キサノンの添加量は自由に決定してょ 、。 [0316] Next, the pigment dispersion, the remainder of the acrylic resin solution, the monomer, the photopolymerization initiator, the sensitizer, and the remaining mixture of cyclohexanone were stirred and mixed uniformly, and then 1 m of Filtration through a filter produced a color filter ink. As long as the blending ratio (weight ratio) shown in Table 20 is finally maintained and dispersion can be performed, the pigment dispersion can be produced. The amount of the acrylic resin solution and cycloxanone added in the stage and the color filter ink manufacturing stage can be freely determined.
[表 21] [Table 21]
Figure imgf000106_0001
Figure imgf000106_0001
[0318] 表 21中の略称は以下の通りである。 [0318] Abbreviations in Table 21 are as follows.
青: ：青用顔料 · · · •C. I. Pigment Blue 15 : 6  Blue:: Blue pigment · · · • C. I. Pigment Blue 15: 6
緑: ：緑用顔料 · · · '下記顔料の混合による。  Green:: Green pigment · · · 'By mixing the following pigments.
C. I. Pigment Green 36 58wt%  C. I. Pigment Green 36 58wt%
C. I. Pigment Yellow 139 42wt%  C. I. Pigment Yellow 139 42wt%
赤: ：赤用顔料 · · · '下記顔料の混合による。  Red:: Red pigment · · · 'By mixing the following pigments.
C. I. Pigment Red 254 83. 3wt%  C. I. Pigment Red 254 83. 3wt%
C. I. Pigment Red 177 13. 4wt%  C. I. Pigment Red 177 13. 4wt%
C. I. Pigment Yellow 199 3. 3wt%  C. I. Pigment Yellow 199 3. 3wt%
黄' ：黄用顔料 · · · ■C. I. Pigment Yellow 139  Yellow ': Yellow pigment · · · ■ C. I. Pigment Yellow 139
モノマー：トリメチロールプロパントリアタリレート（新中村化学社製「NKエステル ATM PTJ )  Monomer: Trimethylolpropane tritalylate (“NK ester ATM PTJ” manufactured by Shin-Nakamura Chemical Co., Ltd.)
開始剤：チバガイギ一社製光重合開始剤「ィルガキュア 907」  Initiator: Photopolymerization initiator "Irgacure 907" manufactured by Ciba-Gaigi
増感剤：保土ケ谷ィ匕学社製 ΓΕΑΒ FJ  Sensitizer: ΓΕΑΒ FJ manufactured by Hodogaya Co., Ltd.
溶剤：シクロへキサノン  Solvent: cyclohexanone
Disperbyk- 111 :ビックケミ一社製のリン酸基含有顔料分散剤  Disperbyk- 111: Phosphoric acid group-containing pigment dispersant manufactured by Big Chemi
ソルスパーズ 41000：日本ルーブリゾール社製のリン酸基含有顔料分散剤  Solspers 41000: Phosphate group-containing pigment dispersant manufactured by Nippon Lubrizol
PB-821：味の素ファインテクノ社製の塩基性基を有する榭脂型分散剤  PB-821: Axillary dispersant with basic group manufactured by Ajinomoto Fine Techno Co., Ltd.
[0319] (5)物性の評価 [0319] (5) Physical property evaluation
(a)粘度安定性  (a) Viscosity stability
カラーフィルタ用インクを調製した日の翌日に測定した初期粘度値 (VI)と、 40°C で 1週間放置して経時促進させた経時粘度値 (V2)を、 E型粘度計 (東機産業社製「 ELD型粘度計」）を用いて、 25°Cにおいて回転数 20rpmという条件で測定した。こ の初期粘度値及び経時粘度値から、経時粘度変化率 (Vr)を以下の計算式 (4)： The initial viscosity value (VI) measured the day after the color filter ink was prepared, and the time-dependent viscosity value (V2) that was allowed to stand for one week at 40 ° C and accelerated over time. Using an ELD viscometer manufactured by the company, measurement was performed at 25 ° C under the condition of a rotation speed of 20 rpm. From this initial viscosity value and the viscosity value with time, the rate of change in viscosity (Vr) with time is calculated using the following formula (4):
[Vr] = [ (VI - V2) /VI] X 100 (4) [Vr] = [(VI-V2) / VI] X 100 (4)
(式中、 Vrは、経時粘度変化率であり、 VIは、初期粘度値であり、 V2は経時粘度値 である）  (Where Vr is the rate of change in viscosity over time, VI is the initial viscosity value, and V2 is the viscosity value over time)
で算出した。 [0320] (b)コントラスト比 Calculated with [0320] (b) Contrast ratio
カラーフィルタ用インクをガラス基板（100mm X 100mm; 1. 1mm厚）上に、スピン コーターを用いて 500rpm、 1000rpm、又は 1500rpmの回転数で塗布し、膜厚が 異なる 3種の塗布基板を得た。レジスト材塗布基板を、 70°Cで 20分間乾燥した後、 超高圧水銀ランプを用いて積算光量 150mjZcm2で紫外線露光を行い、 230°Cで 1時間加熱し、放冷した後、コントラスト比を測定した。次いで、塗膜の C光源での色 度 (Υ, X, y)を顕微分光光度計 (ォリンパス光学社製「OSP— SP100」）を用いて測 定した。 3組のコントラスト比及び色度測定結果から、レジスト材塗布基板について青 色塗膜については y=0. 14、緑色塗膜については y = 0. 60、赤色塗膜については x=0. 64、黄色塗膜については x=0. 48におけるコントラスト比を、それぞれ近似 法を用いて求めた。 Color filter ink was applied onto a glass substrate (100mm X 100mm; 1.1mm thickness) using a spin coater at 500rpm, 1000rpm, or 1500rpm, and three types of coated substrates with different film thicknesses were obtained. . After the resist material coating the substrate, and dried at 70 ° C 20 minutes, subjected to ultraviolet exposure in integrated light intensity 150MjZcm 2 using an ultra-high pressure mercury lamp, heated at 230 ° C, After cooling, the contrast ratios It was measured. Next, the chromaticity (Υ, X, y) of the coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the three sets of contrast ratio and chromaticity measurement results, the resist-coated substrate is y = 0.14 for the blue coating, y = 0.60 for the green coating, and x = 0.64 for the red coating. For the yellow paint film, the contrast ratio at x = 0.48 was obtained using an approximate method.
[0321] (c)密着性  [0321] (c) Adhesion
カラーフィルタ用インクをガラス基板（100mm X 100mm; 1. 1mm厚）上に乾燥後 の膜厚が 2. 0 mになる回転数にてスピンコーターを用いて塗布し、得られた基板を 、 70°Cで 20分間乾燥した後、幅 100 mのストライプ状の開口部を有するフォトマス クを介して超高圧水銀ランプを用いて積算光量 150mjZcm2で紫外線露光を行い、 5%の炭酸ナトリウム水溶液で未露光部を洗い流し、 230°Cで 30分間、熱風オーブ ンでベータして、基板上に幅 100 mのストライプ状のパターンを形成した。ガラスへ の密着性に関する試験として、得られた塗膜の耐薬品性にっ 、ての評価を行った。 試験方法としては、 5%水酸化ナトリウム水溶液 25°Cで 30分浸漬し、浸漬前後での ガラスへの密着性を目視で観察し、 3段階で評価した。 The color filter ink was applied on a glass substrate (100 mm X 100 mm; 1.1 mm thickness) using a spin coater at a rotational speed of 2.0 m after drying. after drying for 20 minutes at ° C, subjected to ultraviolet exposure in integrated light intensity 150MjZcm 2 using an ultra-high pressure mercury lamp through a photo mask having a stripe-shaped opening having a width 100 m, with 5% aqueous sodium carbonate The unexposed area was washed away and beta-patterned with a hot air oven at 230 ° C for 30 minutes to form a 100 m wide stripe pattern on the substrate. As a test for adhesion to glass, the chemical resistance of the obtained coating film was evaluated. As a test method, the sample was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C for 30 minutes, and the adhesion to the glass before and after immersion was visually observed and evaluated in three stages.
〇：全く剥離が認められない  ○: No peeling at all
△：わずかに剥離が認められる  Δ: Slight peeling is observed
X：剥離が認められる  X: Peeling is observed
[0322] (d)縦スジムラ及びレジスト材固化物の有無 [0322] (d) Presence / absence of vertical stripes and solidified resist material
乾燥塗膜の縦スジムラ、及びヘッド先端部力 脱離したレジスト材固化物の有無を 評価した。具体的には、ダイコート方式の塗布装置を用いて、カラーフィルタ用インク をガラス基板（lOOmmX 100mm; 1. 1mm厚）上に塗布し、得られた塗工基板を 70 °Cで 20分間乾燥した後、乾燥塗膜を形成し、下記の方法で得られた乾燥塗膜の縦 スジムラ (塗布方向の縦状の塗布スジ)を目視観察により 3段階で評価した。また、乾 燥塗膜上における、ヘッド先端部力 脱離したレジスト材固化物の有無を目視観察 により 3段階で評価した。 The presence or absence of the vertical streaks of the dried coating and the resist material solidified from the head tip force was evaluated. Specifically, the color filter ink was applied onto a glass substrate (lOOmmX 100mm; 1.1mm thickness) using a die coat type coating device, and the resulting coated substrate was 70%. After drying at 20 ° C. for 20 minutes, a dry coating film was formed, and vertical stripes (vertical coating stripes in the coating direction) of the dried coating film obtained by the following method were evaluated in three stages by visual observation. In addition, the presence or absence of the resist material solidified from the head tip force separation on the dry coating film was evaluated in three stages by visual observation.
縦スジムラ  Vertical stripes
〇：全く縦スジムラが認められな 、。  〇: Vertical stripes are not recognized at all.
△：わずかに縦スジムラが認められる。  Δ: Slight vertical stripes are observed.
X：顕著に縦スジムラが認められる。  X: Remarkably vertical stripes are observed.
固化物  Solidified material
〇：全く固化物が認められな 、。  〇: No solidified material is recognized.
△:固化物 1個以上 10個未満。  Δ: 1 to less than 10 solidified products.
X：固化物 10個以上。  X: 10 or more solidified products.
[表 22] [Table 22]
Figure imgf000110_0001
Figure imgf000110_0001
[0324] 《実施例 101〜109及び比較例 38〜43》  [0324] Examples 101 to 109 and Comparative Examples 38 to 43
以下、熱硬化性インクジェットインクの製造にっ 、て説明する。  Hereinafter, the production of the thermosetting inkjet ink will be described.
[0325] (1)バインダー榭脂〔R1〕の製造 [0325] (1) Manufacture of binder resin [R1]
セパラブル 4口フラスコに、温度制御用レギュレーター、冷却管、及び撹拌装置を 取り付けて、溶剤（CBAc :ジエチレングリコールモノェチルエーテルアセテート） 100 部を仕込み、 100°Cに昇温し、反応容器内を窒素置換した後、滴下管より下記の原 料：  Attach a temperature control regulator, condenser, and stirrer to a separable four-necked flask, charge 100 parts of solvent (CBAc: diethylene glycol monoethyl ether acetate), raise the temperature to 100 ° C, and add nitrogen to the reaction vessel. After replacement, the following raw material is added from the dropping tube:
メタクリル酸 20部  Methacrylic acid 20 parts
2—ヒドロキシェチルメタタリレート 20部  2-hydroxyethyl methacrylate 20 parts
n—ブチノレメタタリレート 57咅  n—Bucinole Metatalylate 57 咅
ホスマー M 3部 及び 2, 2，一ァゾビスイソブチ口-トリル 4部 Hosmer M 3 parts and 2, 2, 1azobisisobuti mouth-tolyl 4 parts
を添カ卩し、 5時間反応を継続し、重量平均分子量 (Mw) 20, 000のアクリル榭脂の溶 液（固形分 50%)を得た。なお、アクリル榭脂の重量平均分子量は、 GPC (ゲルパー ミエイシヨンクロマトグラフィー）を用いて測定し、ポリスチレン換算で求めた。こうして 得られた榭脂溶液を、バインダー榭脂〔R1〕として用いた。  The reaction was continued for 5 hours to obtain a solution of acrylic resin having a weight average molecular weight (Mw) of 20,000 (solid content: 50%). The weight average molecular weight of acrylic resin was measured using GPC (gel permeation chromatography) and determined in terms of polystyrene. The resin solution thus obtained was used as binder resin [R1].
[0326] (2)実施例 101〜102、及び比較例 38 (2) Examples 101 to 102 and Comparative Example 38
表 23及び表 24に示す配合比 (重量比）により、レッド顔料、塩基性シナジスト、顔料 担体、及び溶剤（CBAc)、更に実施例 101〜102については分散剤をサンドミルに 入れて 4時間分散を行い、更にメラミン化合物 MX— 43 (アルコキシアルキル基含有 メラミンィ匕合物；三和ケミカル社製）、実施例 102につ 、てはエポキシィ匕合物 EPPN - 201 ( 0本化薬社製）、及び溶剤 (CBAc)をミキサーに入れて混合し、メンブランフ ィルタで加圧濾過し、顔料濃度 (PC) 13%のインクジェットインクを製造した。  Depending on the blending ratio (weight ratio) shown in Table 23 and Table 24, red pigment, basic synergist, pigment carrier, and solvent (CBAc), and for Examples 101-102, the dispersant was placed in a sand mill and dispersed for 4 hours. Melamine compound MX-43 (alkoxyalkyl group-containing melamine compound; manufactured by Sanwa Chemical Co., Ltd.), Example 102, epoxy compound EPPN-201 (manufactured by Honka Pharmaceutical Co., Ltd.), and Solvent (CBAc) was mixed in a mixer, and pressure filtered with a membrane filter to produce an inkjet ink with a pigment concentration (PC) of 13%.
[0327] (3)実施例 103〜104、及び比較例 39 (3) Examples 103 to 104 and Comparative Example 39
表 23及び表 24に示す配合比（重量比）により、グリーン顔料、塩基性シナジスト、 顔料担体、更に実施例 103〜104については分散剤を均一に撹拌し、混合物を得 た。 60°Cに加温した 2本ロールに、混合物を入れて 10分間練肉したところ、溶剤が 揮発してシート状となった。更に、溶剤（PGMAc :プロピレングリコールモノメチルェ 一テルアセテート）を加え、 2本ロールを 80°Cに加熱して混練を行った。分散操作の 途中で溶剤が揮発し、加熱混練物は弾性をもつ固形物となった。得られた固形物（ 顔料チップ)を冷却後、粉砕し、被覆処理顔料を得た。  According to the blending ratio (weight ratio) shown in Table 23 and Table 24, the green pigment, the basic synergist, the pigment carrier, and the dispersants of Examples 103 to 104 were uniformly stirred to obtain a mixture. When the mixture was put into a two-roll roll heated to 60 ° C and kneaded for 10 minutes, the solvent volatilized to form a sheet. Further, a solvent (PGMAc: propylene glycol monomethyl ether acetate) was added, and the two rolls were heated to 80 ° C and kneaded. During the dispersion operation, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid (pigment chip) was cooled and pulverized to obtain a coated pigment.
被覆処理顔料、及び溶剤（CBAc)をミキサーに入れて混合し、更にサンドミルに入 れて分散を行い、更にメラミン化合物 MX— 43、実施例 103〜104についてはベン ゾグアナミン化合物-力ラック SB— 401 (アルコキシアルキル基含有ベンゾグァナミ ン化合物 三和ケミカル社製)、及び溶剤 (CBAc)を加え混合した。ゴミゃ粗大物を フィルタ濾過し、顔料濃度 18%のインクジェットインクを得た。  Coated pigment and solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, for melamine compound MX-43 and Examples 103 to 104, benzoguanamine compound-power rack SB-401 (Alkoxyalkyl group-containing benzoguanamine compound manufactured by Sanwa Chemical Co., Ltd.) and a solvent (CBAc) were added and mixed. The coarse particles were filtered and an ink jet ink having a pigment concentration of 18% was obtained.
[0328] (4)実施例 105及び比較例 40 (4) Example 105 and Comparative Example 40
表 23及び表 24に示す配合比（重量比）により、イェロー顔料、塩基性シナジスト、 顔料担体、更に実施例 105については分散剤を均一に撹拌し、混合物を得た。 60 °Cに加温した 2本ロールに、前記混合物を入れて 10分間練肉したところ、溶剤が揮 発してシート状となった。 According to the blending ratio (weight ratio) shown in Table 23 and Table 24, the yellow pigment, the basic synergist, the pigment carrier, and the dispersant for Example 105 were uniformly stirred to obtain a mixture. 60 When the mixture was put into a two-roll roll heated to ° C and kneaded for 10 minutes, the solvent was volatilized to form a sheet.
更に、溶剤（PGMAc)をカ卩え、 2本ロールを 80°Cに加熱して混練を行った。分散操 作の途中で溶剤が揮発し、加熱混練物は弾性をもつ固形物となった。得られた固形 物を冷却後、粉砕し、顔料チップを得た。  Further, the solvent (PGMAc) was added and the two rolls were heated to 80 ° C. and kneaded. During the dispersion operation, the solvent was volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a pigment chip.
被覆処理顔料、及び溶剤（CBAc)をミキサーに入れて混合し、更にサンドミルに入 れて分散を行い、更にメラミン化合物 MX— 43、及び溶剤（CBAc)を加え混合した。 ゴミゃ粗大物をフィルタ濾過し、顔料濃度 19%の熱硬化性インクジェットインクを得た  The coated pigment and solvent (CBAc) were mixed in a mixer, and further dispersed in a sand mill, and melamine compound MX-43 and solvent (CBAc) were further added and mixed. The dust was coarse filtered and a thermosetting inkjet ink with a pigment concentration of 19% was obtained.
[0329] (5)実施例 106及び比較例 41 (5) Example 106 and Comparative Example 41
表 23及び表 24に示す配合比（重量比）により、ブルー顔料、塩基性シナジスト、顔 料担体、更に実施例 106については分散剤を均一に撹拌し、混合物を得た。 60°C に加温した 2本ロールに、前記混合物を入れて 10分間練肉したところ、溶剤が揮発 してシート状となった。更に、溶剤をカ卩え、 2本ロールを 80°Cに加熱して混練を行った 。分散操作の途中で溶剤が揮発し、加熱混練物は弾性をもつ固形物となった。得ら れた固形物を冷却後、粉砕し、顔料チップを得た。  According to the blending ratio (weight ratio) shown in Table 23 and Table 24, the blue pigment, the basic synergist, the pigment carrier, and the dispersant for Example 106 were uniformly stirred to obtain a mixture. When the mixture was put into a two-roll roll heated to 60 ° C and kneaded for 10 minutes, the solvent volatilized to form a sheet. Further, the solvent was added and the two rolls were heated to 80 ° C. and kneaded. During the dispersion operation, the solvent volatilized, and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a pigment chip.
被覆処理顔料、及び溶剤（CBAc)をミキサーに入れて混合し、更にサンドミルに入 れて分散を行い、更にメラミン化合物 MX— 43、溶剤（CBAc)を加え混合した。ゴミ や粗大物をフィルタ濾過し、顔料濃度 12%の熱硬化性インクジェットインクを得た。  The coated pigment and solvent (CBAc) were mixed in a mixer, and further dispersed in a sand mill, and melamine compound MX-43 and solvent (CBAc) were further added and mixed. Waste and coarse substances were filtered and a thermosetting inkjet ink with a pigment concentration of 12% was obtained.
[0330] (6)実施例 107 [0330] (6) Example 107
表 23に示す配合比（重量比）により、ブルー顔料、塩基性シナジスト、顔料担体、 及び分散剤を均一に撹拌し、混合物を得た。 60°Cに加温した 2本ロールに、前記混 合物を入れて 10分間練肉したところ、溶剤が揮発してシート状となった。更に、溶剤（ PGMAc)を加え、 2本ロールを 80°Cに加熱して混練を行った。分散操作の途中で 溶剤が揮発し、加熱混練物は弾性をもつ固形物となった。得られた固形物を冷却後 、粉砕し、顔料チップを得た。  The blue pigment, basic synergist, pigment carrier, and dispersant were uniformly stirred at the blending ratio (weight ratio) shown in Table 23 to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C and kneaded. During the dispersion operation, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a pigment chip.
被覆処理顔料及び溶剤 (CBAc)をミキサーに入れて混合し、更にサンドミルに入 れて分散を行い、更にメラミン化合物 MX— 43、アクリルモノマー（カラャッド TPA— 330 ;日本ィ匕薬製）、及び溶剤（CBAc)を加え混合した。ゴミゃ粗大物をフィルタ濾 過し、顔料濃度 12%の熱硬化性インクジェットインクを得た。 Coated pigment and solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, melamine compound MX-43, acrylic monomer (Karaad TPA) 330; Nippon Gyaku Co., Ltd.) and solvent (CBAc) were added and mixed. The coarse particles were filtered and a thermosetting inkjet ink having a pigment concentration of 12% was obtained.
[0331] (7)実施例 108及び比較例 42  (7) Example 108 and Comparative Example 42
表 23及び表 24に示す配合比（重量比）により、シアン顔料、塩基性シナジスト、顔 料担体、及び溶剤 (BuCBAc：ジエチレングリコールモノブチルエーテルアセテート） 、更に実施例 108については分散剤をサンドミルに入れて 4時間分散を行い、更にメ ラミンィ匕合物 MX— 43、及び溶剤（BuCBAc)をミキサーに入れて混合し、メンブラン フィルタで加圧濾過し、顔料濃度 (PC) 15%の熱硬化性インクジェットインクを得た。  According to the mixing ratio (weight ratio) shown in Table 23 and Table 24, cyan pigment, basic synergist, pigment carrier, and solvent (BuCBAc: diethylene glycol monobutyl ether acetate), and for Example 108, a dispersant was put in a sand mill. Disperse for 4 hours, mix melamine compound MX-43 and solvent (BuCBAc) in a mixer, mix with pressure, filter with membrane filter, and thermosetting inkjet ink with 15% pigment concentration (PC). Got.
[0332] (8)実施例 109及び比較例 43  [0332] (8) Example 109 and Comparative Example 43
マゼンタ顔料、塩基性シナジスト、顔料担体、及び溶剤（BuCBAc)、更に実施例 1 09については分散剤をサンドミルに入れて 4時間分散を行い、更にメラミンィ匕合物 M X— 43、及び溶剤（BuCBAc)をミキサーに入れて混合し、メンブランフィルタで加圧 濾過し、顔料濃度 (PC) 15%の熱硬化性インクジェットインクを得た。  Magenta pigment, basic synergist, pigment carrier, and solvent (BuCBAc). In Example 109, the dispersant was placed in a sand mill and dispersed for 4 hours. Further, Melamine compound MX-43 and solvent (BuCBAc) Were mixed in a mixer and pressure filtered through a membrane filter to obtain a thermosetting inkjet ink having a pigment concentration (PC) of 15%.
[0333] (9)熱硬化性インクジェットインクの物性評価  [0333] (9) Physical property evaluation of thermosetting inkjet ink
熱硬化性インクジェットインクの粘度、流動性、及び保存安定性を下記の方法で評 価した。また、熱硬化性インクジェットインクを、 4〜10KHzの周波数変化が可能なピ ェゾヘッドを有するインクジェットプリンタで吐出し、下記の方法で吐出安定性を評価 した。結果を表 23及び表 24に示す。  The viscosity, fluidity, and storage stability of the thermosetting inkjet ink were evaluated by the following methods. Moreover, the thermosetting inkjet ink was ejected by an inkjet printer having a piezo head capable of changing the frequency of 4 to 10 KHz, and the ejection stability was evaluated by the following method. The results are shown in Table 23 and Table 24.
[0334] (a)粘度  [0334] (a) Viscosity
動的粘弾性測定装置により、ずり速度 lOO (lZs)の粘度（r? : mPa ' s)を測定した [0335] (b)流動性  The viscosity (r ?: mPa's) at the shear rate lOO (lZs) was measured with a dynamic viscoelasticity measuring device. [0335] (b) Fluidity
動的粘弾性測定装置により、ずり速度 10 (lZs)の粘度（r? a : mPa ' S)を測定し、 先に測定したずり速度 100 (lZs)の粘度（r?： mPa ' s)との比 rj aZ r?を求め、下記 の基準で流動性を評価した。The dynamic viscoelasticity measuring apparatus, the viscosity of the shear rate 10 (lZs) (r a: ? MPa and 'S) was measured, the viscosity of the shear rate 100 measured earlier (lZs) (r ?: mPa' s) The ratio rj aZ r? Was calculated and the fluidity was evaluated according to the following criteria.
Figure imgf000113_0001
Figure imgf000113_0001
X： 1. ύ≥ 77 a/ η  X: 1. ύ≥ 77 a / η
[0336] (c)保存安定性 45°Cのオーブンで、 7日間加熱後、前項 (a)と同様に粘度を測定した。[0336] (c) Storage stability After heating in a 45 ° C oven for 7 days, the viscosity was measured as in (a) above.
〇：加熱前の粘度と比して増粘率 5%以内 ○: Thickening rate within 5% compared to the viscosity before heating
X：加熱前の粘度と比して増粘率 5%以上  X: Thickening rate 5% or more compared to the viscosity before heating
[0337] (d)吐出安定性 [0337] (d) Discharge stability
印字状態を目視で観察し、下記の基準で吐出安定性を評価した。 The printing state was visually observed, and the ejection stability was evaluated according to the following criteria.
〇：間欠 15分後ノズル抜けが 5%以下である。 ○: Nozzle missing after intermittent 15 minutes is 5% or less.
△：間欠 15分後ノズル抜けが 5%を超え、 10%以下である。  Δ: Nozzle drop after 5 minutes intermittently exceeds 5% and 10% or less.
X：間欠 15分後ノズル抜けが 10%以上である。  X: Nozzle missing after 15 minutes intermittent is 10% or more.
[0338] [表 23] [0338] [Table 23]
Figure imgf000115_0001
Figure imgf000115_0001
[0339] 前記表 23において、略号は以下の意味である。  [0339] In Table 23, the abbreviations have the following meanings.
※ェ 数値は固形分を示す。  * D Numerical values indicate solid content.
※ 2 数値は生成されたインク組成物中での含有量を示す。  * 2 The value indicates the content in the ink composition produced.
[0340] [表 24] 比較例 38 39 40 41 42 43 顔料 I. No. ) [0340] [Table 24] Comparative Example 38 39 40 41 42 43 Pigment I. No.)
Pigment Red 254 90  Pigment Red 254 90
Pigment ween 36 90  Pigment ween 36 90
Pigment Yel low 138 90  Pigment Yel low 138 90
Pigment Blue 15 : 6 90  Pigment Blue 15: 6 90
Pigment Blue 15 : 3 90  Pigment Blue 15: 3 90
Pigment Red 122 90 組 塩基性シナジス卜 a 13 10  Pigment Red 122 90 pairs Basic Synagis A 13 10
成 α 2 10 10 10 α 8 10  Adult α 2 10 10 10 α 8 10
α 3 10 バインダー樹脂 R l※l 67 50 67 67 67 67 顔料被覆工程の有無 ― 有 有 一有 ― ― メラミン樹脂 MX- 43 40 40 40 40 40 40 溶剤※ 2 CBAc 562 366 612  α 3 10 Binder resin R l * l 67 50 67 67 67 67 Presence or absence of pigment coating process-Yes Yes One Yes--Melamine resin MX- 43 40 40 40 40 40 40 Solvent * 2 CBAc 562 366 612
BuCBAc 320 460 460 評 粘度（mPa - s) 26 27 27 22 23 25 価 流動性 1. 3 1. 3 1. 3 1. 2 1. 2 1. 3 結 保存安定性 (%) 6 4 8 -4 -4 4 果 吐出安定性 Δ 〇 ο △ Δ X  BuCBAc 320 460 460 Rating Viscosity (mPa-s) 26 27 27 22 23 25 Value Flowability 1. 3 1. 3 1. 3 1. 2 1. 2 1. 3 Result Storage stability (%) 6 4 8 -4 -4 4 Results Discharge stability Δ ○ ο △ Δ X
[0341] 前記表 24において、略号は以下の意味である。 [0341] In Table 24, the abbreviations have the following meanings.
※ェ 数値は固形分を示す。  * D Numerical values indicate solid content.
※ 2 数値は生成されたインク組成物中での含有量を示す。  * 2 The value indicates the content in the ink composition produced.
[0342] 《実施例 110〜 117、及び比較例 44》 << Examples 110 to 117 and Comparative Example 44 >>
感光性黒色インクの製造を実施例 110〜117、及び比較例 44に示す。 (1)榭脂溶液 B1の調製  Production of photosensitive black ink is shown in Examples 110-117 and Comparative Example 44. (1) Preparation of rosin solution B1
実施例 1の分散剤を不揮発分が 30%になるようにシクロへキサノンを添加して榭脂 溶液 Β2を調製した。  Cyclohexanone was added to the dispersant of Example 1 so that the non-volatile content was 30% to prepare a resin solution Β2.
[0343] (2)榭脂溶液 Β2の調製 [0343] (2) Preparation of rosin solution Β2
反応容器にプロピレングリコールモノメチルエーテルアセテート 370部を入れ、容器 に窒素ガスを注入しながら 80°Cに加熱して、同温度で下記モノマー及び熱重合開 始剤の混合物を 1時間かけて滴下して重合反応を行った。  370 parts of propylene glycol monomethyl ether acetate is put into a reaction vessel, heated to 80 ° C while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator is dropped at the same temperature over 1 hour. A polymerization reaction was performed.
メタクジノレ酸 20. 0  Metacudinoleic acid 20.0
メチルメタクジレー卜 10. 0部  Methyl meta whale bowl 10.0 parts
n—ブチルメタタリレート 35. 0部  n-Butylmetatalylate 35.0 parts
2—ヒドロキシェチノレメタタリレート 15. 0咅 2、 2，ーァゾビスイソブチロニトリル 4. 0部 2-Hydroxyethinoremetatalylate 15. 0 咅 2, 2, azobisisobutyronitrile 4.0 parts
パラクミルフエノールエチレンオキサイド変性アタリレート 20. 0部  Paracumylphenol ethylene oxide modified attalylate 20.0 parts
(東亞合成社製「ァロニックス M—110」）  ("Aronix M-110" manufactured by Toagosei Co., Ltd.)
[0344] 滴下終了後、更に 80°Cで 3時間反応させた後、ァゾビスイソブチ口-トリル 1. 0部を シクロへキサノン 50部に溶解させたものを添カ卩し、更に 80°Cで 1時間反応を続けて、 アクリル榭脂の溶液を得た。アクリル榭脂の重量平均分子量 (GPC測定）は、約 400 00であった。室温まで冷却した後、アクリル榭脂溶液約 2gをサンプリングし、 180°C、 20分間加熱乾燥して不揮発分を測定し、アクリル榭脂溶液の不揮発分が 30%にな るように、先に合成したアクリル榭脂溶液にプロピレングリコールモノメチルエーテル アセテートを添加して榭脂溶液 B2を調製した。  [0344] After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 3 hours, and then 1.0 part of azobisisobutyoxy-tolyl was dissolved in 50 parts of cyclohexanone, and further added at 80 ° C. The reaction was continued for a time to obtain a solution of acrylic resin. The weight average molecular weight (GPC measurement) of the acrylic resin was about 400000. After cooling to room temperature, sample approximately 2 g of the acrylic resin solution, heat and dry at 180 ° C for 20 minutes, and measure the non-volatile content, so that the non-volatile content of the acrylic resin solution is 30% first. Propylene glycol monomethyl ether acetate was added to the synthesized acrylic resin solution to prepare resin solution B2.
[0345] (3)カーボンブラック分散体 Aの調製  [0345] (3) Preparation of carbon black dispersion A
カーボンブラック（三菱ィ匕学製 # 47,平均一次粒子径 23nm,比表面積 132m2Z g,吸油量 cm3/100g) 100部、塩基性シナジスト ( a 14) 4部、榭脂溶液 B1を 14部 、及び榭脂溶液 B2を 56部混合し、シクロへキサノンで希釈して最終固形分を 20%と した。これを、直径 0. 8mmのガラスビーズを用い、ペイントシェーカーにて 2時間分 散することによりカーボンブラック分散体 Aを調製した。分散体 Aの粘度は 25°Cのとき 8. 70mPa' sであった。 Carbon black (Mitsubishi Chemical # 47, average primary particle size 23nm, specific surface area 132m 2 Z g, oil absorption cm 3 / 100g) 100 parts, basic synergist (a 14) 4 parts, oil solution B1 14 And 56 parts of rosin solution B2 were mixed and diluted with cyclohexanone to a final solid content of 20%. This was dispersed in a paint shaker for 2 hours using glass beads having a diameter of 0.8 mm to prepare a carbon black dispersion A. Dispersion A had a viscosity of 8.70 mPa's at 25 ° C.
[0346] (4)カーボンブラック分散体 Bの調製  [0346] (4) Preparation of carbon black dispersion B
カーボンブラック分散体 Aの調製において、カーボンブラックを、 CABOT製 REG AL250R (平均一次粒子径 35nm,比表面積 50m2Zg,吸油量 46cm3Zl00g) 80 gと、 DEGUSSA製の Printex95 (平均一次粒子径 15nm,比表面積 250m2Zg, 吸油量 52g/100g) 20gに変更したこと以外は、カーボンブラック分散体 Aの調製と 同様の操作を行ってカーボンブラック分散体 Bを調製した。得られたカーボンブラック 分散体 Bの粘度は 25°Cのとき 6. 27mPa' sであった。 In the preparation of carbon black dispersion A, carbon black was mixed with CABOT REG AL250R (average primary particle size 35 nm, specific surface area 50 m 2 Zg, oil absorption 46 cm 3 Zl00 g) 80 g and DEGUSSA Printex95 (average primary particle size 15 nm Carbon black dispersion B was prepared in the same manner as in the preparation of carbon black dispersion A, except that the specific surface area was 250 m 2 Zg and the oil absorption was 52 g / 100 g. The obtained carbon black dispersion B had a viscosity of 6.27 mPa's at 25 ° C.
[0347] (5)カーボンブラック分散体 Cの調製  [0347] (5) Preparation of carbon black dispersion C
カーボンブラック分散体 Aの調製において、カーボンブラックを、 CABOT製 MON 八1¾ 11120 (平均ー次粒子径7511111,比表面積 25m2Zg,吸油量 72cm3Zl00g) 100gに変更したこと以外は、カーボンブラック分散体 Aの調製と同様の操作を行つ てカーボンブラック分散体 cを調製した。得られたカーボンブラック分散体 cの粘度はCarbon black dispersion except that carbon black was changed to 100 g in the preparation of carbon black dispersion A, MON 81¾ 11120 manufactured by CABOT (average primary particle size 7511111, specific surface area 25 m 2 Zg, oil absorption 72 cm 3 Zl00 g) Follow the same procedure as for preparation of body A To prepare a carbon black dispersion c. The viscosity of the obtained carbon black dispersion c is
25°Cのとき 5. 88mPa ' sであった。 It was 5. 88 mPa's at 25 ° C.
[0348] (6)カーボンブラック分散体 Dの調製 [0348] (6) Preparation of carbon black dispersion D
カーボンブラック分散体 Aの調製において、榭脂溶液 B1を 14部、榭脂溶液 B2を 5 In the preparation of carbon black dispersion A, 14 parts of resin solution B1 and 5 parts of resin solution B2
6部混合する代わりに、榭脂溶液 B2のみを 70部使用したこと以外は、カーボンブラッ ク分散体 Aの調製と同様の操作を行ってカーボンブラック分散体 Dを調製した。得ら れた分散体 Dの粘度は 25°Cのとき 10. 82mPa · sであつた。 Carbon black dispersion D was prepared in the same manner as in preparation of carbon black dispersion A, except that 70 parts of rosin solution B2 alone was used instead of mixing 6 parts. The viscosity of Dispersion D obtained was 10.82 mPa · s at 25 ° C.
[0349] (7)感光性黒色インクの調製 [0349] (7) Preparation of photosensitive black ink
表 25に示す配合比 (重量比)で、混合物が均一になるように攪拌混合した後、 2 μ mのフィルタで濾過して、実施例110〜117、及び比較例 44の感光性黒色インクを 得た。  The mixture was stirred and mixed so that the mixture became uniform at the blending ratio (weight ratio) shown in Table 25, and then filtered through a 2 μm filter, and the photosensitive black inks of Examples 110 to 117 and Comparative Example 44 were used. Obtained.
[0350] (8)物性評価  [0350] (8) Physical property evaluation
得られた感光性黒色インクについて、感度、安定性、遮光性 (単位膜厚当たりの O D値）、ブラックマトリックスのパターン形状、ガラスに対する密着性を下記の方法で評 価した。得られた結果も表 25に示す。  The resulting photosensitive black ink was evaluated for sensitivity, stability, light-shielding property (OD value per unit film thickness), black matrix pattern shape, and adhesion to glass by the following methods. The results obtained are also shown in Table 25.
(a)感度  (a) Sensitivity
感光性黒色インクを、スピンコート法によりガラス基板（lOOmm X 100mm ; 1. lm m厚）に塗工した後、 70°Cで 15分間の乾燥により、乾燥膜厚約 1 μ mの塗膜を作成 し、膜厚を測定した。その後、超高圧水銀ランプを用い、フォトマスクを介して各種露 光量 (mjZcm2)の紫外線を露光した。炭酸ナトリウム水溶液を用いて現像した後、ィ オン交換水で洗浄することで未露光部分を取り除いた。現像'水洗後の露光部分の 膜厚を測定し、現像前の膜厚に対し 95%以上の膜厚が得られる最小露光量 (mjZc m2)を感度とした。感度を以下の 2段階で評価した。 A photosensitive black ink is applied to a glass substrate (lOOmm X 100mm; 1. lm m thickness) by spin coating, and then dried at 70 ° C for 15 minutes to form a coating film with a dry film thickness of about 1 μm. Prepared and measured film thickness. Then, using an ultra-high pressure mercury lamp, various exposure amounts (mjZcm 2 ) of ultraviolet rays were exposed through a photomask. After developing with an aqueous sodium carbonate solution, the unexposed portion was removed by washing with ion exchanged water. The film thickness of the exposed portion after development and washing with water was measured, and the minimum exposure amount (mjZcm 2 ) at which a film thickness of 95% or more with respect to the film thickness before development was obtained was taken as the sensitivity. Sensitivity was evaluated in the following two steps.
〇：感度が 10〜50mjZcm2の場合 ◯: When sensitivity is 10-50mjZcm 2
X：感度が、 50mjZcm2を超える場合。 X: If the sensitivity is, more than 50mjZcm 2.
なお、フォトマスクには 10マイクロメーターのマスクパターンを使用し、ストライプ状 のブラックマトリックスパターンを形成した。  A 10-micrometer mask pattern was used for the photomask, and a striped black matrix pattern was formed.
[0351] (b)安定性 感光性黒色インクの作成直後と 40°Cで 7日間保存後の現像速度を比較し、安定性 を評価した。 [0351] (b) Stability The stability was evaluated by comparing the development speed immediately after preparation of photosensitive black ink and after storage for 7 days at 40 ° C.
ここで、現像速度は、以下の方法で測定した。すなわち、感光性黒色インクをスピン コート法によりガラス基板（lOOmm X 100mm; 1. 1mm厚）に塗工した後、 70°Cで 1 5分間の乾燥により乾燥膜厚約 1 μ mの塗膜を作成し、膜厚を測定した。このものを、 炭酸ナトリウム水溶液を用いてスプレー現像し、感光性黒色インクが消失する時間を 測定した。測定時間を測定膜厚で除し、単位膜厚当たりの時間 (秒 Z m)を現像速 度とした。  Here, the developing speed was measured by the following method. That is, photosensitive black ink is applied to a glass substrate (lOOmm X 100mm; 1.1 mm thickness) by spin coating, and then dried at 70 ° C for 15 minutes to form a coating film with a dry film thickness of about 1 μm. Prepared and measured the film thickness. This was spray-developed using an aqueous sodium carbonate solution, and the time for the photosensitive black ink to disappear was measured. The measurement time was divided by the measured film thickness, and the time per unit film thickness (second Zm) was taken as the development speed.
安定性を以下の 2段階で評価した。  Stability was evaluated in the following two steps.
〇：保存後の現像速度が、保存前の現像速度に対して ± 15%以内の変化であった ¾ σ；  ◯: The development speed after storage was within ± 15% of the development speed before storage ¾ σ;
X：保存後の現像速度が、保存前の現像速度に対して ± 15%を超えて高速変化あ るいは低速変化した場合。  X: When the development speed after storage exceeds ± 15% of the development speed before storage and changes at high speed or low speed.
但し、比較例 44に関し、 40°Cで 7日間保存後の感光性黒色インクでは、粘度が 25 °Cで lOOmPa' sを超え、更にゲル状となった。そのため、現像速度評価を行うに際し て必要な塗工工程を行うことができず、本発明の感光性黒色インクとして不適格であ つた。よって、比較例 44では、感光性黒色インクを 40°Cで 7日間保存した後の現像 速度評価は行わずに、評価は「 X Jとした。  However, with respect to Comparative Example 44, the photosensitive black ink after storage for 7 days at 40 ° C. had a viscosity of more than lOOmPa's at 25 ° C. and further became a gel. For this reason, the coating process necessary for developing speed evaluation cannot be performed, and it is not suitable as the photosensitive black ink of the present invention. Therefore, in Comparative Example 44, the evaluation was “X J” without evaluating the developing speed after the photosensitive black ink was stored at 40 ° C. for 7 days.
[0352] (c)遮光性〔光学濃度 (OD値)〕  [0352] (c) Light shielding [optical density (OD value)]
前項 (a)の「感度」測定と同様の方法で、感光性黒色インクをガラス基板に塗工し、 露光工程は行わずに、 230°Cで 1時間加熱した後、膜厚を測定した。このようにして 得られた感光性黒色インク塗工基板の光学濃度 (OD値)を、マクベス濃度計 (GRE TAG D200-II)により測定し、測定光学濃度 (OD値)を測定膜厚で除し、単位膜 厚当たりの光学濃度 (ODZ μ m)を求めた。  In the same manner as the “sensitivity” measurement in the previous section (a), a photosensitive black ink was applied to a glass substrate, and the film thickness was measured after heating at 230 ° C. for 1 hour without performing an exposure step. The optical density (OD value) of the photosensitive black ink coated substrate thus obtained was measured with a Macbeth densitometer (GRE TAG D200-II), and the measured optical density (OD value) was divided by the measured film thickness. Then, the optical density (ODZ μm) per unit film thickness was determined.
[0353] (d)形状  [0353] (d) Shape
ブラックマトリックスのパターン形状の評価は、以下の方法によって実施した。すな わち、前項 (a)の「感度」測定と同様の方法において、露光量 70miZcm2でストライ プ状のブラックマトリックスパターンを形成し、作成されたストライプ状のブラックマトリ ッタスのパターン形状を、光学顕微鏡あるいは電子線走査顕微鏡で観察し、直線性' 断面形状を観察した。但し、実施例 112の感光性黒色インクは感度が低力つたため 3The black matrix pattern shape was evaluated by the following method. In other words, in the same method as the “sensitivity” measurement in the previous section (a), a striped black matrix was formed by forming a striped black matrix pattern with an exposure dose of 70 miZcm 2. The pattern shape of the dust was observed with an optical microscope or an electron beam scanning microscope, and the cross-sectional shape of the linearity was observed. However, since the photosensitive black ink of Example 112 had low sensitivity, 3
OOm] Zcm2で露光した。 OOm] Zcm 2 exposed.
[0354] (e)直線性 [0354] (e) Linearity
直線性の評価は、以下の 3段階で行った。  The linearity was evaluated in the following three stages.
〇：直線部分に欠けやギザギザが見られな 、場合；  〇: When there is no chipping or jaggedness in the straight line part;
△:直線部分の一部にギザギザあるいは欠けが見られる場合；  △: When a jagged or chipped part is seen in a part of the straight line part;
X：直線部分の全体にわたってギザギザあるいは欠けが多数見られる場合。  X: When a lot of jaggedness or chipping is seen over the entire straight line portion.
[0355] (f)断面形状 [0355] (f) Sectional shape
断面形状の評価は、以下の 2段階で行った。  The cross-sectional shape was evaluated in the following two stages.
〇：断面形状が順テーパー (ガラスに接触する面である底辺が上底より幅広)力 垂 直の場合；  ○: When the cross-sectional shape is a forward taper (the bottom which is the surface in contact with the glass is wider than the top), when the force is vertical;
X：断面形状がオーバーハング (上底がガラスに接触する面である底辺より幅広）の ¾ σ ο  X: ¾ σ ο of cross-sectional shape is overhang (wider than the base where the upper base is in contact with the glass)
[0356] (g)初期密着性  [0356] (g) Initial adhesion
前項 (a)の「感度」測定と同様の方法で、感光性黒色インクをガラス基板に塗工し、 露光工程は行わずに、 230°Cで 1時間加熱した。得られた感光性黒色インク塗工基 板上の感光性黒色インク塗工面に、高性能エポキシ急速硬化接着剤（室温 1時間硬 化型)を付け、 JIS K5400に準じた碁盤目付着性試験方法により、塗膜のガラス密 着性を評価した。剥離は、 M6ボルトの頭に高性能エポキシ急速硬化接着剤（室温 1 時間硬化型)を付け、碁盤目上に接着（自重)し、 90°Cで 5分間加熱した後、手でボ ルトを剥がした。 1mm X 1mm X 100個の碁盤目に比べてボルトが小さいので、ボル トの接着面積に対する塗膜の非剥離面積率で初期密着性を表した。  In the same manner as the “sensitivity” measurement in the previous section (a), a photosensitive black ink was applied to a glass substrate and heated at 230 ° C. for 1 hour without performing an exposure step. A high-performance epoxy rapid-curing adhesive (cured at room temperature for 1 hour) is attached to the photosensitive black ink coated surface of the resulting photosensitive black ink coated substrate, and a cross-cut adhesion test method according to JIS K5400 Thus, the glass adhesion of the coating film was evaluated. To peel off, attach a high-performance epoxy quick-curing adhesive (cured at room temperature for 1 hour) to the head of the M6 bolt, bond (self-weight) on the grid, heat at 90 ° C for 5 minutes, and then bolt by hand. I peeled it off. Since the bolts were smaller than the 1 mm x 1 mm x 100 grids, the initial adhesion was expressed by the ratio of the non-peeled area of the coating film to the bolt adhesion area.
[0357] (h) PCT後密着性  [0357] (h) Adhesion after PCT
前項 (a)の「感度」測定と同様の方法で、感光性黒色インクをガラス基板に塗工し、 露光工程は行わずに、 230°Cで 1時間加熱した。得られた感光性黒色インク塗工基 板に関し、プレッシャータッカー試験 (PCT)を行った。すなわち、高度加速寿命試験 装置（エスペック株式会社製 EHS— 411)を用い、 IEC68— 2— 66に規格化されて いる HAST (Highly Accelerated temperature and humidity Test)と呼ばれる不飽和 プレッシャータッカー試験（USPCT; Unsaturated In the same manner as the “sensitivity” measurement in the previous section (a), a photosensitive black ink was applied to a glass substrate and heated at 230 ° C. for 1 hour without performing an exposure step. The resulting photosensitive black ink coated substrate was subjected to a pressure tacker test (PCT). In other words, it was standardized to IEC68-2-66 using an advanced accelerated life test device (EHS-411 manufactured by Espec Corporation). Unsaturated pressure tacker test (USPCT), called HAST (Highly Accelerated temperature and humidity Test)
Press.Test)に準じて、 120°C、 2気圧、 100%RHの条件で 5時間のプレッシャータツ カー試験を行った。この後、前記初期密着性と同様の試験により PCT後密着性を評 価し 7こ。  According to Press.Test), a pressure tucker test was conducted for 5 hours under the conditions of 120 ° C., 2 atm and 100% RH. After this, the post-PCT adhesion was evaluated by the same test as the initial adhesion.
[0358] なお、密着性 (％)は、初期密着性及び PCT後密着性の両者ともに、下記の計算 式 (5) :  [0358] The adhesion (%) is calculated by the following formula (5) for both initial adhesion and post-PCT adhesion:
Ad (%) = [ (Nr-Nt) /Nt] X 100 (5)  Ad (%) = [(Nr-Nt) / Nt] X 100 (5)
〔式中、 Adは密着性であり、 Nrは、接着面碁盤目数であり、 Ntは、ボルト接着面の 碁盤目数である）  (In the formula, Ad is adhesion, Nr is the number of grids on the bonding surface, and Nt is the number of grids on the bolt bonding surface)
より算出した (少数点以下四捨五入)。算出された結果を以下の 4段階で評価した。 ◎： 80 %≤密着性≤ 100%  (Rounded to the nearest whole number). The calculated results were evaluated in the following four stages. A: 80% ≤ Adhesion ≤ 100%
〇： 60%≤密着性く 80%  ○: 60% ≤ 80% adhesion
△： 30%≤密着性< 60%  Δ: 30% ≤ adhesion <60%
X : 20% <密着性 < 30%  X: 20% <Adhesion <30%
[0359] [表 25] [0359] [Table 25]
Figure imgf000122_0001
Figure imgf000122_0001
表 25中の略称は以下の意味である：  Abbreviations in Table 25 have the following meanings:
エチレン性不飽和化合物：ジペンタエリスリトールへキサアタリレート（DPHA) 光重合開始剤 A:エタノン、 1 [9ーェチルー 6—（2 メチルベンゾィル）—9H—力 ルバゾール—3—ィル]一、 1— (O—ァセチルォキシム）、チノく'スペシャルティ'ケミ カルズ社製「ィルガキュア OXE02」 Ethylenically unsaturated compound: Dipentaerythritol hexaatalylate (DPHA) Photoinitiator A: Etanone, 1 [9-ethyl-6- (2 methylbenzoyl) -9H-force [Luvazole-3-yl] 1, 1- (O-acetyloxyme), Chinoku “Specialty” Chemicals “Irgacure OXE02”
光重合開始剤 B : 2, 2，ビス（o—クロ口フエ-ル）一 4, 5, 4，， 5， 一テトラフエ-ルー 1 , 2，ービイミダゾール Photoinitiator B: 2, 2, Bis (o-black mouth) 1, 4, 5, 4, 5, Tetraphenol 1, 2, 2-biimidazole
光重合開始剤 C：前記式（22)で示されるボレート系光重合開始剤 Photopolymerization initiator C: borate-based photopolymerization initiator represented by the formula (22)
光重合開始剤 D： 2 -ベンジル - 2-ジメチルァミノ— 1— (4—モルフォリノフエ-ル）Photopolymerization initiator D: 2-Benzyl-2-dimethylamino-1 (4-morpholinophenol)
—ブタノン一 1 (チノく'スペシャルティ'ケミカルズ社製「ィルガキュア 369」） 多官能チオール：トリメチロールプロパントリス（3—メルカプトブチレート） —Butanone 1 (“Irgacure 369” manufactured by Chinoku 'Specialty' Chemicals) Multifunctional thiol: Trimethylolpropane tris (3-mercaptobutyrate)
溶剤：シクロへキサノン Solvent: cyclohexanone
産業上の利用可能性 Industrial applicability
本発明の分散剤を用いることにより、低使用量で、分散性、流動性、及び保存安定 性に優れる顔料分散体を得ることができる。従って、本発明の分散剤を用いて安定 性及び乾燥再溶解性、場合により印字安定性に優れたカラーフィルタ用インク、感光 性黒色インク、インクジェットインク及びカラーフィルタ用インクジェットインクを提供す ることができる。更に、本発明の顔料分散体又は前記インキを用いて塗膜と基材との 間で強固な密着性を有する、高品質なカラーフィルタ基盤を提供することができる。 以上、本発明を特定の態様に沿って説明したが、当業者に自明の変形や改良は 本発明の範囲に含まれる。  By using the dispersant of the present invention, a pigment dispersion excellent in dispersibility, fluidity and storage stability can be obtained at a low use amount. Therefore, it is possible to provide a color filter ink, a photosensitive black ink, an inkjet ink, and an inkjet ink for a color filter, which are excellent in stability, drying re-dissolution property, and in some cases, printing stability, using the dispersant of the present invention. it can. Furthermore, a high-quality color filter substrate having strong adhesion between the coating film and the substrate can be provided using the pigment dispersion of the present invention or the ink. As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.

Claims

請求の範囲 下記一般式 (1)で示される分散剤： 一般式 (1): [化 1] \ メ Claims Dispersant represented by the following general formula (1): General formula (1):
(1)  (1)
A2 、4 A 2 , 4
一般式（1)中、 A〜A4は、 In the general formula (1), A to A 4 are
2つ力 相互に同じか若しくは異なる分子量 200〜5000の一価の重合体部分 (P)で あり、他の 2つが、相互に同じか若しくは異なる— C( = 0)OH又は—CH C( = 0)0  Two forces are monovalent polymer parts (P) having the same or different molecular weights of 200-5000, and the other two are the same or different from each other — C (= 0) OH or —CH C (= 0) 0
2  2
Hである糸且合せであるか、  Whether the thread is H
1つが分子量 200〜5000の一価の重合体部分（P)であり、他の 3つが、相互に同じ か若しくは異なる— C( = 0)OH又は— CH C( = 0)OHである組合せである力、又  One is a monovalent polymer part (P) having a molecular weight of 200 to 5000, and the other three are combinations that are the same or different from each other — C (= 0) OH or —CHC (= 0) OH. A force, also
2  2
は、 Is
1つが分子量 200〜5000の一価の重合体部分（P)であり、他の 2つが、相互に同じ か若しくは異なる— C( = 0)OH又は— CH C( = 0)OHであり、他のもう 1つが— C(  One is a monovalent polymer part (P) with a molecular weight of 200-5000, and the other two are the same or different from each other — C (= 0) OH or —CH C (= 0) OH, the other Another one is — C (
2  2
=0)— Xa— Ra (但し、 Xaは、— 0-、又は— N(Ra2)—であり、 Raは、炭素原子数 1 〜18のアルキル基、炭素原子数 2〜18のァルケ-ル基、炭素原子数 3〜18のシクロ アルキル基及び炭素原子数 6〜18のァリール基力 なる群力 選択される基であり、 Ra2は、水素原子又は炭素原子数 1〜18のアルキル基、炭素原子数 2〜18のァルケ -ル基、炭素原子数 3〜 18のシクロアルキル基及び炭素原子数 6〜 18のァリール基 力もなる群力も選択される基である）である組合せであって、 = 0) —X a — R a (where X a is —0—or —N (R a2 ) —, R a is an alkyl group having 1 to 18 carbon atoms, 2 to 18 alkenyl groups, cycloalkyl groups having 3 to 18 carbon atoms, and aryl group forces having 6 to 18 carbon atoms are selected groups, and R a2 is a hydrogen atom or 1 to 18 alkyl groups, alkenyl groups having 2 to 18 carbon atoms, cycloalkyl groups having 3 to 18 carbon atoms, and group forces that also include aryl groups having 6 to 18 carbon atoms). A combination of:
X1は、下記一般式（2)、一般式（3)又は一般式 (4)で示される四価の基である： 一般式 (2): X 1 is a tetravalent group represented by the following general formula (2), general formula (3), or general formula (4): General formula (2):
[化 2]
Figure imgf000125_0001
[Chemical 2]
Figure imgf000125_0001
〔一般式（2)中、 kは 1又は 2を示す。〕；  [In general formula (2), k represents 1 or 2. ];
一般式 (3): General formula (3):
[化 3] [Chemical 3]
Figure imgf000125_0002
Figure imgf000125_0002
〔一般式 (3)中、 R2は、直接結合、 -CH―、— O—、— C( = 0)— [In general formula (3), R 2 is a direct bond, —CH—, —O—, —C (= 0) —
2  2
H CH 0C( = 0)—、 -C( = 0)0CH(0C( = 0)CH )CH OC( H CH 0C (= 0) —, -C (= 0) 0CH (0C (= 0) CH) CH OC (
2 2 3 2 一、 C(CF ) 一、式： 2 2 3 2 1, C (CF) 1, Formula:
3 2  3 2
[化 4]  [Chemical 4]
Figure imgf000125_0003
Figure imgf000125_0003
：?表される基である。〕； 一般式 (4) : Is the group represented. ]; General formula (4)
[化 6]  [Chemical 6]
Figure imgf000126_0001
Figure imgf000126_0001
〔一般式 (4)で示される基 X1が有する合計炭素原子数は 4〜20であって [The total number of carbon atoms of the group X 1 represented by the general formula (4) is 4 to 20
一般式 (4)中、 R3は、直接結合、— O—、又は炭素原子数 1〜8の二価又は三価の 炭化水素基であり、 In the general formula (4), R 3 is a direct bond, —O—, or a divalent or trivalent hydrocarbon group having 1 to 8 carbon atoms,
R4、 R5、 R6、及び R9はそれぞれ独立に水素原子、若しくは炭素原子数 1〜8の炭化 水素基であるか、又は、 R4と R6と及び/又は R5と R9とで直接結合して不飽和二重結 合を形成してもよぐ R 4 , R 5 , R 6 and R 9 are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, or R 4 and R 6 and / or R 5 and R 9. May be directly bonded to form an unsaturated double bond.
R7及び R8はそれぞれ独立に水素原子、若しくは炭素原子数 1〜8の炭化水素基で あるか、又は R7と R8とで直接結合又は炭素原子数 1〜8の二価炭化水素基を形成し て環状基 X1を形成してもよぐあるいは R3と R7と又は R3と R8とで炭素原子数 1〜8の 三価炭化水素基を形成して環状基 X1を形成してもよぐあるいは R3と R7と R8とで炭素 原子数 1〜8の四価炭化水素基を形成して多環状基 X1を形成してもよい。〕 R 7 and R 8 are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, or a direct bond between R 7 and R 8 or a divalent hydrocarbon group having 1 to 8 carbon atoms. To form a cyclic group X 1 or R 3 and R 7 or R 3 and R 8 to form a trivalent hydrocarbon group having 1 to 8 carbon atoms to form a cyclic group X 1 Alternatively, R 3 , R 7 and R 8 may form a tetravalent hydrocarbon group having 1 to 8 carbon atoms to form a polycyclic group X 1 . ]
[2] 一価の重合体部分 (P) 、ポリエーテル鎖基、ポリエステル鎖基、及びビニル共重 合体鎖基からなる群から選択されることを特徴とする、請求項 1に記載の分散剤。  [2] The dispersant according to claim 1, wherein the dispersant is selected from the group consisting of a monovalent polymer part (P), a polyether chain group, a polyester chain group, and a vinyl copolymer chain group. .
[3] 一価の重合体部分 (Ρ)力 下記一般式（5)で示される一価のポリエーテル鎖基及 び Ζ又はポリエステル鎖基力もなる重合体部分 (Pe)であることを特徴とする、請求項 1に記載の分散剤：  [3] Monovalent polymer part (Ρ) force A monovalent polyether chain group represented by the following general formula (5) and a polymer part (Pe) also having Ζ or polyester chain group force The dispersant according to claim 1, wherein:
一般式 (5) :  General formula (5):
[化 7]  [Chemical 7]
Y1― X」 (G1), ml ■(G2)m2- (G3), m3 R 17 〔一般式 (5)中、 Y 1 ― X '' (G 1 ), ml ∎ (G 2 ) m2- (G 3 ), m3 R 17 [In general formula (5),
Y1は、炭素原子数 1〜20、酸素原子数 0〜12、及び窒素原子数 0〜3を含む 1価の 末端基、 Y 1 is a monovalent terminal group containing 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms,
X2は、 O—、— S—、又は— N (Rb)—(但し、 Rbは水素原子又は炭素原子数 1〜1 8の直鎖状若しくは分岐状のアルキル基)であり、 X 2 is O—, —S—, or —N (R b ) — (where R b is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms),
X3は、 OC ( = 0) OC ( = 0) CH -N (Rc) C ( = 0) 又は一 N (RC) C X 3 is OC (= 0) OC (= 0) CH -N (R c ) C (= 0) or one N (R C ) C
2  2
( = 0) CH （但し、 は水素原子又は炭素原子数 1〜18の直鎖状若しくは分岐状  (= 0) CH (where is a hydrogen atom or a straight or branched chain having 1 to 18 carbon atoms)
2  2
のアルキル基）であり、 An alkyl group of
G1は、—尺11。—で示される繰り返し単位であり、 G 1— scale 11 . It is a repeating unit indicated by —
G2は、— C ( = O) R120 -で示される繰り返し単位であり、 G 2 is a repeating unit represented by —C (═O) R 12 0 —
G3は、 C ( = 0)R13C ( = 0)— OR140—で示される繰り返し単位であり、 G 3 is a repeating unit represented by C (= 0) R 13 C (= 0) —OR 14 0—
R11は炭素原子数 2〜8の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数 3R 11 is a linear or branched alkylene group having 2 to 8 carbon atoms, or 3 carbon atoms.
〜8のシクロアルキレン基であり、 A cycloalkylene group of ~ 8,
R12は炭素原子数 1〜8の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数 4 〜8のシクロアルキレン基であり、 R 12 is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms,
R13は炭素原子数 2〜6の直鎖状若しくは分岐状のアルキレン基、炭素原子数 2〜6 の直鎖状若しくは分岐状のァルケ-レン基、炭素原子数 3〜20のシクロアルキレン 基、又は炭素原子数 6〜20ァリーレン基であり、 R 13 is a linear or branched alkylene group having 2 to 6 carbon atoms, a linear or branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, Or a C 6-20 arylene group,
R14は、—CH (R15)—CH (R16)—で示され、 R 14 is represented by —CH (R 15 ) —CH (R 16 ) —
R15と R16は、どちらか一方が水素原子であり、もう一方が炭素原子数 1〜20のアルキ ル基、炭素原子数 2〜20のァルケ-ル基、炭素原子数 6〜20のァリール基、アルキ ル部分の炭素原子数 1〜20のアルキルォキシメチレン基、アルケニル部分の炭素原 子数 2〜20のァルケ-ルォキシメチレン基、ァリール部分の炭素原子数 6〜20でァリ ール部分が場合によりハロゲン原子で置換されていることのあるァリールォキシメチレ ン基、 N—メチレン フタルイミド基であって、 One of R 15 and R 16 is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. Group, alkyloxymethylene group having 1 to 20 carbon atoms in the alkyl moiety, alkoxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety, and aryl moiety having 6 to 20 carbon atoms in the aryl moiety. Is an aryloxymethylene group, an N-methylene phthalimide group, optionally substituted with a halogen atom,
R17は、前記尺11、前記一 C ( = 0)R12—、又は一 C ( = 0)R13C ( = 0)—OR14—であ り、 R 17 is the scale 11 , the one C (= 0) R 12 —, or one C (= 0) R 13 C (= 0) — OR 14 —,
mlは 0〜100の整数であり、 m2は 0〜60の整数であり、 m3は 0〜30の整数であり、 但し ml +m2+m3は 1以上 100以下であり、 ml is an integer from 0 to 100, m2 is an integer from 0 to 60, m3 is an integer from 0 to 30, However, ml + m2 + m3 is 1 or more and 100 or less,
一般式（5)における前記繰り返し単位 G1〜G3の配置は、その順序を限定するもので はなぐ一般式 (5)で表される重合体部分 (P)において、基 X2と基 R17との間に繰り返 し単位 G G3が任意の順序で含まれていることを示し、更に、それらの繰り返し単位 G'-G3^,それぞれランダム型又はブロック型のどちらでもよい。〕 The arrangement of the repeating units G 1 to G 3 in the general formula (5) is not limited to the order thereof. In the polymer part (P) represented by the general formula (5), the group X 2 and the group R 17 indicates that repeating units GG 3 are included in an arbitrary order, and these repeating units G′-G 3 ^ may be either random type or block type, respectively. ]
[4] Y1が炭素原子数 1〜18の直鎖状若しくは分岐状のアルキル基であることを特徴と する、請求項 3に記載の分散剤。 [4] Y 1 is characterized in that it is a linear or branched alkyl group having 1 to 18 carbon atoms, dispersing agent according to claim 3.
[5] Y1がエチレン性不飽和二重結合を有することを特徴とする、請求項 3に記載の分 散剤。 [5] Y 1 is characterized by having an ethylenically unsaturated double bond, a dispersant as claimed in claim 3.
[6] m2が 3〜 15の整数であることを特徴とする、請求項 3に記載の分散剤。  [6] The dispersant according to claim 3, wherein m2 is an integer of 3 to 15.
[7] 25°Cでロウ状固体であることを特徴とする、請求項 1に記載の分散剤。  [7] The dispersant according to claim 1, which is a waxy solid at 25 ° C.
[8] 25°Cで液状であることを特徴とする、請求項 1に記載の分散剤。  [8] The dispersant according to claim 1, which is liquid at 25 ° C.
[9] 一価の重合体部分 (P)が、下記一般式 (6)で示される一価のビニル共重合体 (Pv) であることを特徴とする、請求項 1に記載の分散剤：  [9] The dispersant according to claim 1, wherein the monovalent polymer portion (P) is a monovalent vinyl copolymer (Pv) represented by the following general formula (6):
一般式 (6)  General formula (6)
[化 8]  [Chemical 8]
Figure imgf000128_0001
Figure imgf000128_0001
〔一般式 (6)中、 Y2は、ビニル重合体の重合停止基であり、 [In general formula (6), Y 2 is a polymerization termination group of the vinyl polymer,
R21及び R22は、それぞれ独立に水素原子又はメチル基であり、 R 21 and R 22 are each independently a hydrogen atom or a methyl group,
R23及び R24は、いずれか一方が水素原子、他の一方が芳香族基、又は C ( = 0)One of R 23 and R 24 is a hydrogen atom, the other is an aromatic group, or C (= 0)
— X6— R25 (但し、 X6は、 O 若しくは— N (R26)—であり、 R25及び R26は水素原子 又は置換基として芳香族基を有していてもよい炭素原子数 1〜18の直鎖状若しくは 分岐状のアルキル基であり、 — X 6 — R 25 (where X 6 is O or —N (R 26 ) —, and R 25 and R 26 are hydrogen atoms or carbon atoms which may have an aromatic group as a substituent. 1 to 18 linear or branched alkyl groups,
X4は、 O— R27—又は— S— R27—であり、 R27は炭素原子数 1 18の直鎖状若しくは分岐状のアルキレン基であり、 X 4 is O—R 27 —or — S—R 27 —, R 27 is a linear or branched alkylene group having 1 to 18 carbon atoms,
X5は、 OC ( = 0) -OC ( = 0) CH N (Rd) C ( = 0)—、又は N (Rd) C X 5 is OC (= 0) -OC (= 0) CH N (R d ) C (= 0) —, or N (R d ) C
2  2
( = 0) CH （但し、 Rdは水素原子又は炭素原子数 1 18の直鎖状若しくは分岐状 (= 0) CH (where R d is a hydrogen atom or a straight or branched chain having 1 to 18 carbon atoms)
2  2
のアルキル基）であり、  An alkyl group of
nは 2 50である。〕  n is 250. ]
[10] 顔料と請求項 1に記載の分散剤とを含む顔料分散体。 [10] A pigment dispersion comprising a pigment and the dispersant according to claim 1.
[11] ペースト状又はチップ状である、請求項 10に記載の顔料分散体。 [11] The pigment dispersion according to claim 10, which is in the form of a paste or a chip.
[12] 顔料と請求項 1に記載の分散剤とに加えて、塩基性基を有する顔料誘導体、塩基 性基を有するアントラキノン誘導体、塩基性基を有するアタリドン誘導体、及び塩基 性基を有するトリァジン誘導体力 なる群力 選ばれる少なくとも一種の塩基性シナ ジストを更に含む、請求項 10に記載の顔料分散体。 [12] In addition to the pigment and the dispersant according to claim 1, a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an attaridone derivative having a basic group, and a triazine derivative having a basic group The pigment dispersion according to claim 10, further comprising at least one basic synergist selected.
[13] 顔料と、請求項 1に記載の分散剤と、顔料担体とを含むことを特徴とするインクジ ットインク。 [13] An ink jet ink comprising a pigment, the dispersant according to claim 1, and a pigment carrier.
[14] 顔料と、モノマーを含む顔料担体と、請求項 1に記載の分散剤とを含有することを 特徴とするカラーフィルタ用インク。  [14] A color filter ink comprising a pigment, a pigment carrier containing a monomer, and the dispersant according to claim 1.
[15] 顔料、熱硬化性化合物、有機溶剤、及び請求項 1に記載の分散剤を含むことを特 徴とする熱硬化性インクジヱットインク。 [15] A thermosetting ink jet ink comprising a pigment, a thermosetting compound, an organic solvent, and the dispersant according to claim 1.
[16] 顔料、熱硬化性化合物、有機溶剤、及び請求項 1に記載の分散剤を含むことを特 徴とするカラーフィルタ用インクジェットインク。 [16] An inkjet ink for a color filter, comprising a pigment, a thermosetting compound, an organic solvent, and the dispersant according to claim 1.
[17] カーボンブラックと、光重合開始剤と、塩基性基を有する顔料誘導体、塩基性基を 有するアントラキノン誘導体、塩基性基を有するアタリドン誘導体、及び塩基性基を 有するトリァジン誘導体力 なる群力 選ばれる少なくとも一種の塩基性シナジストと[17] Group power of carbon black, photopolymerization initiator, pigment derivative having basic group, anthraquinone derivative having basic group, attaridone derivative having basic group, and triazine derivative having basic group At least one kind of basic synergist
、エチレン性不飽和単量体と、請求項 1に記載の分散剤とを含むことを特徴とする、 感光性黒色インク。 A photosensitive black ink comprising: an ethylenically unsaturated monomer; and the dispersant according to claim 1.
[18] 片末端に水酸基を有する重合体 (POH)を製造するか、若しくは片末端に 1級アミ ノ基を有する重合体 (PNH )を製造する第一の工程と、該重合体 (POH)若しくは重  [18] A first step of producing a polymer having a hydroxyl group at one end (POH) or producing a polymer having a primary amino group at one end (PNH), and the polymer (POH) Or heavy
2  2
合体 (PNH )とテトラカルボン酸二無水物とを反応させる第二の工程とを含む、分散  A dispersion comprising a second step of reacting the union (PNH) with tetracarboxylic dianhydride
2  2
剤の製造方法。 Manufacturing method.
[19] 第一の工程が、モノアルコール、 1級モノアミン、 2級モノアミン、及びモノチオール 力もなる群力も選択される化合物を開始剤として、アルキレンオキサイド、ラタトン、ラ クチド、及びジカルボン酸無水物とエポキシドとの組合せ力 なる群力 選択される 環状ィ匕合物を開環重合して片末端に水酸基を有するポリエーテル及び Z又はポリェ ステルカもなる重合体 (PeOH)を製造することを特徴とする、請求項 18に記載の製 造方法。 [19] In the first step, monoalcohol, primary monoamine, secondary monoamine, and monothiol, a compound that also has a group power selected as an initiator, an alkylene oxide, a rataton, a lactide, and a dicarboxylic acid anhydride are used. Combined force with epoxides Group force selected Ring-opening polymerization of selected cyclic compound to produce polyether having hydroxyl group at one end and polymer (PeOH) also having Z or polyester. The production method according to claim 18.
[20] 第一の工程が、モノアルコール、 1級モノアミン、 2級モノアミン、及びモノチオール 力もなる群力 選択される化合物を開始剤として、アルキレンオキサイドを開環重合し て片末端に水酸基を有する重合体を得た後、該水酸基を還元アミノ化して片末端に アミノ基を有するポリエーテル (PeNH )を製造することを特徴とする、請求項 18に記  [20] The first step is a monoalcohol, primary monoamine, secondary monoamine, and monothiol group power. The compound selected by the ring-opening polymerization of the alkylene oxide and having a hydroxyl group at one end 19. After obtaining a polymer, the hydroxyl group is reductively aminated to produce a polyether (PeNH 2) having an amino group at one end.
2  2
載の製造方法。  The manufacturing method described.
[21] 第一の工程が、分子内に水酸基とチオール基とを有する化合物を連鎖移動剤とし て使用して、エチレン性不飽和単量体を重合して、片末端に水酸基を有するビニル 共重合体 (PvOH)を製造するか、若しくは分子内に 1級ァミノ基とチオール基とを有 する化合物を連鎖移動剤として使用して、エチレン性不飽和単量体を重合して、片 末端に水酸基を有するビュル共重合体 (PvNH )を製造することを特徴とする、請求  [21] In the first step, a compound having a hydroxyl group and a thiol group in the molecule is used as a chain transfer agent to polymerize an ethylenically unsaturated monomer, and a vinyl copolymer having a hydroxyl group at one end is used. Polymer (PvOH) is produced, or an ethylenically unsaturated monomer is polymerized using a compound having a primary amino group and a thiol group in the molecule as a chain transfer agent. A butyl copolymer (PvNH 2) having a hydroxyl group is produced.
2  2
項 18に記載の製造方法。  Item 19. The production method according to Item 18.
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JPWO2017122695A1 (en) * 2016-01-14 2018-11-01 東洋インキＳｃホールディングス株式会社 Thermosetting coloring composition and method for producing color filter for solid-state imaging device
EP3404453A4 (en) * 2016-01-14 2019-06-26 Toyo Ink SC Holdings Co., Ltd. Thermosetting coloring composition and method for producing color filer for solid-state imaging elements
US10915028B2 (en) 2016-01-14 2021-02-09 Toyo Ink Sc Holdings Co., Ltd. Thermosetting coloring composition and method of producing color filter for solid-state imaging element

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CN101218017A (en) 2008-07-09
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TW200709846A (en) 2007-03-16
CN101218017B (en) 2012-10-03

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