Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
  • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
  • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
  • C07D235/26—Oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
  • C07C233/17—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
  • C07C233/18—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/0802—Preparation methods
  • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
  • G03G9/0806—Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G9/08706—Polymers of alkenyl-aromatic compounds
  • G03G9/08708—Copolymers of styrene
  • G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/09—Colouring agents for toner particles
  • G03G9/0902—Inorganic compounds
  • G03G9/0904—Carbon black

Definitions

• the present invention uses a dispersant suitable for dispersing various insoluble colorants (hereinafter also simply referred to as “colorants”) such as pigments and oil-soluble dyes, a compound for constituting the dispersant, and this dispersant.
• colorants such as pigments and oil-soluble dyes
• a color material is dispersed in a medium such as a solvent or a resin (hereinafter also simply referred to as “medium”) and used as an ink, a paint, or a toner.
• a dispersant such as a dispersant or a surfactant is generally used in combination.
• a general dispersant for a color material is composed of an “adsorption site” having an adsorptivity to a color material and a “dispersion site” having an affinity for a medium. Since each site can be designed to be compatible with color materials and media, various dispersants have been developed and reported so far.
• Patent Document 1 proposes a low-molecular compound containing a benzimidazolinone skeleton as a structure in which the same structure as a color material is introduced into an adsorption site to improve the adsorption power to the color material.
• Patent Document 2 proposes a polymer compound obtained by polymerizing a monomer containing a benzimidazolinone skeleton.
• Patent Document 3 proposes a polymer in which a site having both a benzimidazolinone skeleton and an azo group is grafted in the molecule.
• Patent Document 4 discloses an example of a polymer dispersant in which a chromophore having a molecular weight lower than 95% of an azo pigment is bonded to a water-soluble polymer main chain as a dispersant for a color material for ink jet recording.
• Patent Document 5 discloses a polymer pigment dispersant in which an azo or disazo chromophore containing a substituted acetoacetanilide is bonded to a polymer.
• the low molecular weight compound having a benzimidazolinone skeleton described in Patent Document 1 is rigid, it has low solubility in a solvent and hardly exhibits a dispersion effect.
• the compound proposed in Patent Document 2 is a polymer, the solubility in a solvent is relatively good.
• the site exhibiting adsorptivity to the colorant for example, ether structure, ester structure, amide structure, amine structure, urethane structure, urea structure, etc. Since the number of sites where bonds can be formed is small, the adsorptive power to the coloring material is relatively weak.
• an object of the present invention is to provide a dispersant that is excellent in solubility in a solvent, adsorbing power to a color material, and color material dispersibility, and having reduced self-coloring properties.
• Another object of the present invention is to provide a compound for preparing the dispersant.
• Another object of the present invention is to provide a toner having a wide selection range of applicable color materials and high coloring power.
• the present inventors have found that the above problems can be solved by introducing a specific structure into the adsorption site of the dispersant having an adsorption site and a dispersion site, and the present invention It came to be completed.
• the present invention relates to a compound represented by the following formula (1) or a tautomer thereof.
• X, Y, and Z are each independently any of —O—, a methylene group, and —NR 4 —.
• R 4 represents hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms.
• R 1 represents a substituted or unsubstituted phenyl group, a polycyclic aromatic group, or a heterocyclic group.
• R 2 is a hydrogen atom, a substituted or unsubstituted phenyl group, an aralkyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a methylene group of an alkyl group having 1 to 18 carbon atoms, an ether bond, A monovalent group derived by replacing with an ester bond or an amide bond is shown.
• R 3 is a substituted or unsubstituted phenylene group, a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, or a methylene group in the main chain of an alkylene group having 1 to 18 carbon atoms, an ether bond or an ester bond Or a divalent group derived by replacing with an amide bond.
• W represents a reactive group or a polymerizable functional group that can be introduced into the polymer portion.
• the substituent of the substituted phenyl group and the substituent of the substituted phenylene group are methyl group, methoxy group, hydroxy group, nitro group, chloro group, carboxy group, amino group, dimethylamino group, carboxylic acid amide group or ureido group. is there.
• the polycyclic aromatic group is a group derived by removing one hydrogen atom from naphthalene, anthracene, phenanthrene or anthraquinone.
• the heterocyclic group is a group derived by removing one hydrogen atom from imidazole, oxazole, thiazole, pyridine, indole, benzimidazole, benzimidazolinone or phthalimide. )
• the present invention also relates to a dispersant having a structure in which a structure represented by the following formula (3) or a tautomer thereof is bonded to a polymer part.
• X 2 , Y 2 and Z 2 are each independently any of —O—, a methylene group, and —NR 10 —.
• R 10 represents hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms.
• R 7 represents a substituted or unsubstituted phenyl group, a polycyclic aromatic group, or a heterocyclic group.
• R 8 is a hydrogen atom, a substituted or unsubstituted phenyl group, an aralkyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a methylene group of an alkyl group having 1 to 18 carbon atoms.
• a monovalent group derived by replacing with an ester bond or an amide bond is shown.
• R 9 is a substituted or unsubstituted phenylene group, a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, or a methylene group in the main chain of the alkylene group having 1 to 18 carbon atoms, an ether bond or an ester bond Or a divalent group derived by replacing with an amide bond.
• W 3 being showing the connection portion of the polymer portion.
• the substituent of the substituted phenyl group and the substituent of the substituted phenylene group are methyl group, methoxy group, hydroxy group, nitro group, chloro group, carboxy group, amino group, dimethylamino group, carboxylic acid amide group or ureido group. is there.
• the polycyclic aromatic group is a group derived by removing one hydrogen atom from naphthalene, anthracene, phenanthrene or anthraquinone.
• the heterocyclic group is a group derived by removing one hydrogen atom from imidazole, oxazole, thiazole, pyridine, indole, benzimidazole, benzimidazolinone or phthalimide.
• the present invention also relates to a toner having toner particles containing a binder resin, a color material, and a dispersant, wherein the dispersant is the above-described dispersant.
• the present invention it is possible to provide a dispersant that is excellent in solubility in a solvent, adsorbing power to a color material, and dispersibility of a color material, and in which self-coloring properties are reduced. Moreover, according to this invention, the compound which can prepare the dispersing agent which has the said characteristic can be provided. Furthermore, by using the dispersant of the present invention, it is possible to provide a toner having a wide selection range of applicable color materials and high coloring power.
• the mechanism of the effect expression of the dispersant of the present invention is considered as follows.
• the dispersant of the present invention has a feature that it includes a triketone structure at the adsorption site, has a plurality of hydrogen bonding points, and has high structural flexibility. Therefore, it is possible to adsorb at a plurality of points with respect to the color material, and the direction of adsorption can be freely changed in accordance with the functional group of the color material. Furthermore, the planarity of the adsorption site of the compound is improved by causing keto-enol isomerism in the molecule as shown in the following formula, and the adsorption force due to the ⁇ - ⁇ interaction between the double bond site and the coloring material is further increased. I believe.
• examples of the adsorption site with the color material include a compound represented by the formula (1).
• X, Y, and Z are each independently any of —O—, a methylene group, and —NR 4 —.
• R 4 represents hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms.
• R 1 represents a substituted or unsubstituted phenyl group, a polycyclic aromatic group, or a heterocyclic group.
• R 2 is a hydrogen atom, a substituted or unsubstituted phenyl group, an aralkyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a methylene group of an alkyl group having 1 to 18 carbon atoms, an ether bond, A monovalent group derived by replacing with an ester bond or an amide bond is shown.
• R 3 is a substituted or unsubstituted phenylene group, a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, or a methylene group in the main chain of an alkylene group having 1 to 18 carbon atoms, an ether bond or an ester bond Or a divalent group derived by replacing with an amide bond.
• W represents a reactive group or a polymerizable functional group that can be introduced into the polymer portion.
• the substituent of the substituted phenyl group and the substituent of the substituted phenylene group are methyl group, methoxy group, hydroxy group, nitro group, chloro group, carboxy group, amino group, dimethylamino group, carboxylic acid amide group or ureido group. is there.
• the polycyclic aromatic group is a group derived by removing one hydrogen atom from naphthalene, anthracene, phenanthrene or anthraquinone.
• the heterocyclic group is a group derived by removing one hydrogen atom from imidazole, oxazole, thiazole, pyridine, indole, benzimidazole, benzimidazolinone or phthalimide. ) Therefore, the compound represented by the formula (1) and the structure represented by the formula (3) can take a tautomer such as the following formula. These tautomers are also within the scope of the present invention.
• the adsorption action of the adsorption site in the present invention is considered to be caused by the hydrogen bonding action by polar groups such as ketones, amides and esters and the ⁇ - ⁇ interaction derived from double bonds and aromatic moieties.
• the dispersant used in the present invention has a structure in which the structure represented by the formula (3) or a tautomer thereof is bonded to the polymer part.
• X 2 , Y 2 and Z 2 are each independently any of —O—, a methylene group, and —NR 10 —.
• R 10 represents hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms.
• R 7 represents a substituted or unsubstituted phenyl group, a polycyclic aromatic group, or a heterocyclic group.
• R 8 is a hydrogen atom, a substituted or unsubstituted phenyl group, an aralkyl group, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a methylene group of an alkyl group having 1 to 18 carbon atoms.
• a monovalent group derived by replacing with an ester bond or an amide bond is shown.
• R 9 is a substituted or unsubstituted phenylene group, a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, or a methylene group in the main chain of the alkylene group having 1 to 18 carbon atoms, an ether bond or an ester bond Or a divalent group derived by replacing with an amide bond.
• W 3 being showing the connection portion of the polymer portion.
• the substituent of the substituted phenyl group and the substituent of the substituted phenylene group are methyl group, methoxy group, hydroxy group, nitro group, chloro group, carboxy group, amino group, dimethylamino group, carboxylic acid amide group or ureido group. is there.
• the polycyclic aromatic group is a group derived by removing one hydrogen atom from naphthalene, anthracene, phenanthrene or anthraquinone.
• the heterocyclic group is a group derived by removing one hydrogen atom from imidazole, oxazole, thiazole, pyridine, indole, benzimidazole, benzimidazolinone or phthalimide.
• R 7 in the formula (3) is a site mainly responsible for ⁇ - ⁇ interaction with the colorant. Therefore, R 7 may be a compound having ⁇ planarity. Among them, a heterocyclic compound or an aromatic compound substituted with a polar group is preferable because it has both ⁇ planarity and hydrogen bonding properties.
• the optimum R 7 structure is a benzimidazolinone structure, which exhibits high adsorptivity to the color material and improves the coloring power.
• a compound having ⁇ planarity to supplement the adsorptivity to the coloring material may be introduced, or a structure for adjusting the solubility in a dispersion medium such as an alkyl group may be introduced.
• R 8 is an alkyl group having 1 to 12 carbon atoms or a benzyl group, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.
• R 9 may be a divalent functional group, but an alkylene group having 2 to 4 carbon atoms is preferred.
• X 2 , Y 2 , and Z 2 may be any divalent linking group, but if two or more of X 2 , Y 2 , and Z 2 are —NH—, the structural stability of the compound is improved. preferable.
• X 2 and Z 2 are preferably —NH—. The reason is that when X 2 is —NH—, an amide bond is formed, which is advantageous for adsorption to the coloring material.
• Z 2 is preferably —NH— for production.
• Y 2 is most preferably —O—, which has many commercially available reagents, for diversifying the structure of R 8 .
• W 3 is a connecting part to the polymer part, and is preferably an amide bond or an ester bond from the viewpoint of ease of production.
• part of the dispersing agent of this invention has a structure shown by following formula (4).
• R 11 represents an alkyl group having 2 to 12 carbon atoms or a benzyl group.
• R 11 is more preferably an alkyl group having 2 to 8 carbon atoms.
• R 12 represents an alkylene group having 2 to 4 carbon atoms.
• W 4 represents a connecting portion with a polymer portion, and the connecting portion is an ester bond or an amide bond.
• the structure shown by Formula (4) can take a tautomer like the following formula, these tautomers are also within the scope of the present invention.
• the compound shown by the said Formula (1) is a compound shown by Formula (2).
• R 5 represents an alkyl group having 2 to 12 carbon atoms or a benzyl group.
• R 5 is more preferably an alkyl group having 2 to 8 carbon atoms.
• R 6 represents an alkylene group having 2 to 4 carbon atoms.
• W 2 represents an amino group, acryloyloxy group, methacryloyloxy group, acryloylamino group or methacryloylamino group. W 2 is more preferably an acryloyloxy group or a methacryloyloxy group.
• preferred structural examples of the structure represented by the formula (3) are the structures represented by the following formulas (6) to (8), but the adsorption site of the dispersant used in the present invention is limited to these. It is not something.
• * represents a connecting portion with the polymer portion.
• the dispersant used in the present invention can be used alone or in combination of two or more of the aforementioned adsorption sites.
• the polymer part of this invention should just be a polymer which shows affinity to a dispersion medium, and a well-known polymer can be selected. Specific examples include vinyl resins using vinyl monomers, polyesters, polyethers, polyamides, and composite polymers in which these partial structures coexist.
• the polymer part preferably has a vinyl copolymer structure obtained by using a highly versatile monomer or a polyester structure. By freely selecting from various monomer types, the SP value (solubility parameter) of the dispersion site polymer can be brought close to that of the medium, and the dispersion effect is easily exhibited.
• the compound having an adsorption site has a polymerizable functional group because the production of the dispersant is facilitated.
• the dispersion site of the dispersant of the present invention has a vinyl copolymer structure
• it is derived from the unit B derived from the compound B which is an aromatic vinyl monomer and the compound C which is an acrylic acid monomer or a methacrylic acid monomer. It is preferable to have at least one of the units C.
• the compound B constituting the unit B is preferably an aromatic vinyl monomer having an affinity for the medium in which the coloring material is dispersed.
• Specific examples of the compound B include styrene, vinyl toluene, ⁇ -methyl styrene and the like. Can do. These compounds B can be used singly or in combination of two or more. Compound B may be appropriately selected depending on the medium used.
• the compound C constituting the unit C is preferably an acrylic acid monomer or a methacrylic acid monomer having an affinity for the medium in which the color material is dispersed.
• Specific examples of compound C include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, behenyl acrylate, acrylic Acrylic acid monomers such as hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, benzyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Octyl, dodecyl methacrylate, stearyl meth
• the content (molar part) of the structure represented by the formula (3) which is the adsorption site of the present invention is a
• the content (molar part) of the unit B based on the molecular weight of the compound B is b
• the content (molar part) of the unit C based on the molecular weight of the compound C is c
• the balance between the amount of the adsorption site and the amount of the dispersion site becomes good, so the high adsorption power to the color material and the stable dispersibility of the color material in the medium. And can be achieved.
• the values of a, b and c can be calculated by GPC (gel permeation chromatography) measurement and NMR measurement of the dispersant. Specifically, it can be calculated from the weight average molecular weight of the dispersant calculated by GPC and the ratio of each unit calculated by 1 H-NMR.
• the polyester structure has a unit derived from a polyvalent carboxylic acid and a unit derived from a polyol.
• polyvalent carboxylic acids include oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, ⁇ -methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid , Dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, Tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylene
• polyvalent carboxylic acid other than dicarboxylic acid examples include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.
• Polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentane.
• the dispersion site may be a composite polymer having a polyester structure and a vinyl copolymer structure.
• Specific examples include a composite polymer having a structure in which a vinyl polymer structure is grafted to a polyester main chain, or a structure in which a polyester structure and a vinyl polymer structure are bonded by a block.
• the adsorption site (structure represented by the formula (3)) may be bonded to either the polyester structure site or the vinyl polymer site.
• the weight average molecular weight of the dispersant used in the present invention is preferably in the range of 5,000 to 200,000.
• the weight average molecular weight is 5,000 or more, the aggregation between the color materials can be suppressed by the excluded volume effect of the dispersant, so that the coloring power is easily improved.
• the weight average molecular weight is 200,000 or less, the coloring power is likely to be improved because the coloring materials are not easily cross-linked via the dispersant. More preferably, it is the range of 10,000 or more and 50,000 or less.
• the weight average molecular weight of the dispersant can be controlled by changing the temperature and reaction time during polymerization.
• color materials applicable to the dispersant of the present invention include known insoluble color materials.
• specific examples of the color material include black / yellow / magenta / cyan pigments and oil-soluble dyes.
• suitable color materials to which the dispersant of the present invention can be applied include conventionally known insoluble color materials.
• Specific examples of the color material include black / yellow / magenta / cyan pigments and oil-soluble dyes.
• black pigments and oil-soluble dyes include carbon black.
• yellow pigments and oil-soluble dyes examples include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. More specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, 180, and the like; I.
• Solvent Yellow 1 2, 3, 13, 14, 19, 21, 22, 29, 36, 37, 38, 39, 40, 42, 43, 44, 45, 47, 62, 63, 71, 76, 79, Examples thereof include oil-soluble dyes such as 81, 82, 83: 1, 85, 86, 88, and 151.
• magenta pigments and oil-soluble dyes examples include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.
• Condensed azo compounds diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.
• Solvent Red 8 27, 35, 36, 37, 38, 39, 40, 49, 58, 60, 65, 69, 81, 83: 1, 86, 89, 91, 92, 97, 99, 100, 109, Examples thereof include oil-soluble dyes such as 118, 119, 122, 127, and 218.
• cyan pigments and oil-soluble dyes include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. More specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like; I. Examples thereof include oil-soluble dyes such as Solvent Blue 14, 24, 25, 26, 34, 37, 38, 39, 42, 43, 44, 45, 48, 52, 53, 55, 59, 67, and 70. These pigments and oil-soluble dyes can be used singly or in combination of two or more.
• a color material dispersion containing a medium and a color material dispersed in the medium by the dispersant can be produced.
• the type of medium in which the color material is dispersed is not particularly limited, and water, water-soluble organic solvents, water-soluble organic solvents, polymerizable monomers, resins, and the like conventionally used for inks, paints, and toners are used alone. Or it can be mixed and used.
• resins that can be used as the medium include known resins such as vinyl resins, maleic acid copolymer resins, polyester resins, epoxy resins, and composite resins in which partial structures thereof are bonded. .
• additives such as surfactants, pH adjusters, antioxidants, and antifungal agents are added to the colorant dispersion obtained using the dispersant of the present invention. Also good.
• the amount of the dispersant used when dispersing the color material as described above in the medium is 0.05 to 200 parts, further 0.1 to 100 parts, relative to 100 parts of the color material. Is preferable, and the effect of the dispersant of the present invention is easily exhibited.
• the toner of the present invention is a toner having toner particles containing a binder resin, a color material, and the dispersant.
• a binder resin such as a vinyl resin, a maleic acid copolymer resin, a polyester resin, an epoxy resin, and a composite resin in which partial structures thereof are combined may be used. it can.
• the vinyl resin is a resin obtained by polymerizing a vinyl monomer capable of radical polymerization.
• vinyl monomers examples include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p Tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, and p-phenyl Styrene derivatives such as styrene; Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n
• multifunctional polymerizable monomers examples include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tripropylene glycol.
• the binder resin that can be used in the present invention include a composite polymer in which the partial structure of the polymer coexists.
• Specific examples include a composite polymer having a structure in which a vinyl polymer structure is grafted to a polyester main chain, or a structure in which a polyester structure and a vinyl polymer structure are bonded by a block.
• the dispersant used in the present invention is obtained by copolymerizing the compound of the present invention in which a polymerizable group is introduced at the adsorption site and the monomer constituting the dispersion site, or by adding the compound of the present invention to a prepolymerized polymer. be able to.
• it can be obtained by a known synthesis method or polymerization method. For example, it can be synthesized according to the scheme shown below. In the scheme, “-co-” means copolymerization, and m and n represent repeating structural units.
• the adsorption site into which the polymerizable functional group of the scheme is introduced can be polymerized with a dispersion site monomer by a conventionally known method such as radical polymerization, living radical polymerization, anionic polymerization, or cationic polymerization to form a dispersant.
• the adsorption site and the dispersion site may exist in a random state or in a block state. What is necessary is just to select suitably the reaction temperature of each process, reaction time, the kind of a solvent, a catalyst, etc. to be used, the purification method after a synthesis
• the molecular structure of the synthesized adsorption site and the physical properties of the polymerized dispersant are measured using NMR (nuclear magnetic resonance apparatus), IR (infrared spectrophotometer), MS (mass spectrometer), GPC (gel permeation chromatography), etc. Can be identified.
• W in Formula (1) is preferably a reactive group such as an amino group or a hydroxyl group.
• a compound having an amino group or a hydroxyl group can be added by acid chlorination of the carboxy group with thionyl chloride or the like.
• the color material dispersion can be produced, for example, by kneading or pulverizing the dispersant of the present invention and the color material in a medium.
• a dispersing agent and a coloring material are mixed in a medium, and a mechanical shearing force is applied using a dispersing machine to adsorb an adsorption site derived from a compound in the dispersing agent to the coloring material surface. Disperse into uniform fine particles.
• the medium is an organic solvent
• the organic solvent may be removed by a conventional method such as reduced pressure as necessary, and the dispersant may be immobilized on the color material surface.
• the medium is a polymerizable monomer
• the polymerizable monomer may be polymerized as necessary, and the dispersant may be immobilized on the surface of the color material.
• a colorant dispersion can be obtained by performing filtration, centrifugation, and drying as necessary.
• the kind of the disperser used when manufacturing the color material dispersion is not particularly limited, and a commonly used disperser can be used.
• Specific examples of the disperser include a ball mill, a bead mill, an ultrasonic disperser, a paint shaker, a sand mill, a homogenizer, a vibrating ball mill, a roll mill, a homomixer, a trade name “Microfluidizer” (manufactured by Microfluidics), and a trade name “ Nanomizer "(manufactured by Nanomizer), biaxial kneader and the like.
• the toner particles of the present invention can be produced by a known method. For example, polymerization is performed by suspending a polymerizable monomer composition containing a polymerizable monomer, a colorant, a dispersant, and, if necessary, a release agent in order to obtain a binder resin in an aqueous medium.
• a suspension polymerization method in which a binder monomer is produced by polymerizing a polymerizable monomer; a kneading and pulverizing method in which various toner constituent materials are kneaded, pulverized, and classified; a dispersion in which the binder resin is emulsified and dispersed; a coloring material; A dispersion of a dispersant and, if necessary, a dispersion of a release agent or the like are mixed, and then aggregated and heat-fused to obtain toner particles; emulsion polymerization of a binder resin polymerizable monomer An emulsion polymerization aggregation method in which the formed dispersion is mixed with a dispersion of a colorant and a dispersant and, if necessary, a dispersion such as a release agent, and agglomerated and heat-fused to obtain toner particles; A solution suspension method in which a resin, a coloring material, a dispersing agent
• the toner of the present invention may contain a charge control agent.
• the charge control agent include organometallic compounds such as a salicylic acid metal compound, charge control resins having a sulfonic acid group and a carboxy group, and the like.
• an external additive is externally added to the toner particles in order to improve the image quality of the toner.
• inorganic fine powder such as silica fine powder, titanium oxide fine powder, or aluminum oxide fine powder is preferably used.
• These inorganic fine powders are preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil or a mixture thereof.
• the toner of the present invention external additives other than those described above may be mixed with the toner particles as necessary.
• the total amount of the inorganic fine powder added is preferably 1.0 part or more and 5.0 parts or less with respect to 100.0 parts of the toner particles.
• the intermediate (1) was synthesized with reference to the description of Synthesis Example 1 in JP-A-10-316643. Specifically, 20.6 parts (0.129 mol) of diethyl malonate, 19.8 parts (0.128 mol) of 2-methacryloyloxyethyl isocyanate (trade name “Karenz MOI”, Showa Denko), and 0.284 parts (1.29 mmol) of 2,6-di-tert-butyl-p-cresol was dissolved in 100 parts (0.942 mol) of xylene and heated to 60 ° C.
• the obtained dispersant (D1) was purified by solid-liquid separation in methanol, which is a poor solvent, and then the weight average molecular weight was measured using NMR and GPC.
• the UV absorption at 480 nm was measured using a spectrophotometer, and the content a (mole part) of unit A based on the molecular weight of compound A (1) was calculated.
• the values of unit B content b (mole part) and a / (b + c) based on the molecular weight of styrene were calculated.
• Table 2 shows the polymer type and weight average molecular weight (Mw) of the resulting dispersant (D1).
• the reaction was stopped by cooling with ice water to obtain a dispersant (D2).
• the obtained dispersant (D2) was purified by solid-liquid separation in methanol as a poor solvent, and the weight average molecular weight was measured using NMR and GPC.
• UV absorption amount in 480 nm of a dispersing agent (D2) was measured using the spectrophotometer, and content a (mol part) on the basis of the molecular weight of a compound (A1) was computed.
• the values of unit B content b (mole part) and a / (b + c) based on the molecular weight of styrene were calculated. The calculated results are shown in Table 2.
• Table 2 shows the polymer type and the weight average molecular weight (Mw) of the obtained dispersant (D2).
• the acid value of this polyester resin A was 9 mgKOH / g, and the weight average molecular weight was 8200. Subsequently, 30 parts of the prepared polyester resin A was dissolved in 500 parts of dimethylformamide, 0.1 part of 4-N, N-dimethylaminopyridine and 0.7 part of phthalic anhydride were added, and reacted at room temperature for 3 hours. A polyester resin B having carboxylic acid groups at all terminals was obtained. The acid value of this polyester resin B was 19 mgKOH / g.
• polyester resin B (acid value: 19.0 mg KOH / g) (COOH group amount: 6.77 mmol) was charged into a nitrogen-substituted eggplant-shaped flask and dissolved in 300 parts of N, N-dimethylformamide. .
• This solution was cooled to 5 ° C. or lower, 1.61 parts (13.5 mmol) of thionyl chloride was slowly added dropwise, and after the addition, the reaction solution was heated to 60 ° C. After reacting at 60 ° C. for 6 hours, excess thionyl chloride was distilled off under reduced pressure to obtain a polyester resin C solution in which the terminal carboxyl group was acid-chlorinated.
• Compound (A3) solution was prepared by dissolving 2.85 parts (8.11 mmol) of compound (A3) in 20 parts of N, N-dimethylformamide. This compound (A3) solution was slowly added dropwise to the previous polyester resin solution C at 5 ° C. or lower, and then reacted at 60 ° C. for 2 hours. After the reaction, the solvent was distilled off under reduced pressure, washed with methanol, and dried to obtain a dispersant (D34) in which the compound (A3) was added to the end of the polyester resin. This dispersant had an acid value of 0 and a weight average molecular weight of 8,800. Table 3 shows the polymer type and weight average molecular weight (Mw) of the resulting dispersant (D34).
• a styrene-acrylic acid polymer having an acid value of 27.4 mgKOH / g and a weight average molecular weight of 20,500 was obtained.
• the carboxy group of the styrene-acrylic acid polymer was acid chlorinated and reacted with the compound (A12) to obtain a dispersant (D35).
• the acid value of this dispersant (D35) was 0, and the weight average molecular weight was 22,200.
• the a / (b + c) value was 0.053.
• Other polymer types and weight average molecular weights (Mw) are shown in Table 3.
• Dispersant (D36) was synthesized in the same manner as in the synthesis of dispersant (D34) described above, except that compound (A3) was changed to (A13).
• the weight average molecular weight of this dispersing agent D36 was 9000.
• Table 3 shows the polymer type of the obtained dispersant (D36) and the weight average molecular weight (Mw).
• dispersant (D37) was a polyester / styrene graft composite polymer.
• the weight average molecular weight of this dispersant (D37) was 23500.
• Table 3 shows the polymer type and weight average molecular weight (Mw) of the resulting dispersant (D37).
• Dispersant (D42) 0.213 parts (0.509 mmol) of the obtained compound X, 103 parts (5.00 mmol) of a styrene-acrylic acid polymer, and 40 parts of a tetrahydrofuran-methanol mixture (1: 1 by volume) were mixed with a roll mill. . After mixing, the solvent was removed to obtain a dispersant (D42). Further, x / (b + c) calculated from the amount x (mole part) of compound X and the content b (mole part) of unit B and the content c (mole part) of unit C in the styrene-acrylic acid polymer. The value of was 0.102.
• the obtained dispersant (D43) was purified by solid-liquid separation in methanol as a poor solvent, and then the weight average molecular weight was measured using NMR and GPC. Further, the UV absorption at 480 nm was measured using a spectrophotometer, and the content y (mole part) of the unit Y based on the molecular weight of the compound Y was calculated. Furthermore, the value of unit B content b (mole part) and y / (b + c) based on the molecular weight of styrene was calculated. The calculated results are shown in Table 4. In addition, Table 4 shows the polymer type and weight average molecular weight (Mw) of the dispersant (D43) obtained.
• the obtained dispersant (D44) was purified by solid-liquid separation in methanol as a poor solvent, and the weight average molecular weight was measured using NMR and GPC. Further, the UV absorption amount at 380 nm of the dispersant (D44) was measured using a spectrophotometer, and the content z (molar part) of the unit Z based on the molecular weight of the compound Z was calculated. Further, the values of unit B content b (mole part) and z / (b + c) based on the molecular weight of styrene were calculated. The calculated results are shown in Table 4. In addition, Table 4 shows the polymer type of the obtained dispersant (D44) and the weight average molecular weight (Mw).
• the material was introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.), and the mixture was stirred at 200 rpm and 25 ° C. for 180 minutes using zirconia beads (200 parts) having a radius of 2.5 mm to prepare a colorant dispersion 1.
• the above materials are mixed, heated to 65 ° C., and uniformly dissolved and dispersed at 5,000 rpm for 60 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Obtained.
• Hydrochloric acid was added to the toner particle dispersion to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve calcium phosphate. This was subjected to solid-liquid separation with a pressure filter to obtain a toner cake. The washing operation using ion-exchanged water was repeated 5 times and then dried to obtain black toner particles.
• TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.
• the obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a coarsely pulverized product.
• the resulting coarsely pulverized product was finely pulverized using a mechanical pulverizer (manufactured by Turbo Kogyo; turbo mill T250-RS type). Thereafter, the obtained finely pulverized product was classified using a multi-division classifier utilizing the Coanda effect to obtain black toner particles.
• the material was introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.), and stirred for 180 minutes at 200 rpm and 25 ° C. using zirconia beads (200 parts) having a radius of 2.5 mm to prepare a colorant dispersion 3.
• toner composition solution 3 Colorant dispersion 3 53.9 parts Styrene 19.6 parts N-butyl acrylate 24.5 parts Paraffin wax 10.0 parts (HNP-9: Nippon Seiwa Co., Ltd., melting point 75 ° C)
• the material was introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.), and the mixture was stirred at 200 rpm and 25 ° C. for 180 minutes using zirconia beads (200 parts) having a radius of 2.5 mm to prepare a colorant dispersion 4.
• toner composition solution 4 Colorant dispersion 4 53.9 parts Styrene 19.6 parts n-Butyl acrylate 24.5 parts Paraffin wax 10.0 parts (HNP-9: Nippon Seiwa Co., Ltd., melting point 75 ° C)
• toner composition solution 5 Colorant dispersion 5 53.9 parts Styrene 19.6 parts N-butyl acrylate 24.5 parts Paraffin wax 10.0 parts (HNP-9: Nippon Seiwa Co., Ltd., melting point 75 ° C)
• Table 5 shows the formulation and physical properties of the toner particles obtained.
• Toners 1 to 49 were obtained by mixing 1 to 49 and 100.0 parts of the obtained toner particles and 1.5 parts of hydrophobic silica fine powder with a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) for 300 seconds, respectively.
• the used silica fine powder is the hydrophobic silica fine powder surface-treated with hexamethyldisilazane, and the number average particle diameter (D1) of the primary particles is 10 nm.
• a solution (O) was prepared by dissolving 0.2 parts of each compound in 20 parts of N, N-dimethylformamide. One part of carbon black as a coloring material was added to 10 parts of this solution (O), and ultrasonic dispersion was performed for 30 minutes. After leaving still at room temperature for 1 hour, it centrifuged and collect
• Adsorption rate 95% or more B: Adsorption rate 90% or more and less than 95%
• the dispersants of the examples had good solubility in the medium and excellent adsorptivity to the coloring material. Furthermore, the dispersants of the examples exhibited excellent colorant dispersibility in organic solvents.
• the dispersant (D44) of Comparative Example 7 was colored yellow and had a strong absorption near a wavelength of 380 nm.
• the dispersants (D1) to (D37) were colored from pink to red, but were very thin.
• the dispersants (D1) to (D37) have absorption in the vicinity of a wavelength of 480 to 490 nm, but were colored so that they could not be detected unless they were 5000 times darker than the dispersant (D44).
• the toner contained inside was removed from a cartridge for a commercially available color laser printer, Satera LBP7700C (manufactured by Canon Inc.), the inside was cleaned by air blow, and each toner (150 g) was filled.
• Satera LBP7700C manufactured by Canon Inc.
• the cartridge is mounted on a printer, and the amount of applied toner is set to be 0.30 mg / cm 2.
• a rectangular solid image of 6.5 cm ⁇ 14.0 cm is output at the center of the transfer material to obtain an evaluation image. .
• Image density is 1.50 or more
• Image density is 1.35 or more and less than 1.50
• C Image density is 1.20 or more and less than 1.35
• D Image density is less than 1.20
• the dispersant of the present invention is superior in solubility in a solvent, adsorbing power to a color material, and dispersibility of a color material, and can be widely applied to different types of color materials.
• the compound of the present invention is a useful compound for preparing the dispersant.
• the dispersant of the present invention is used in paints, powder paints, toners and the like and exhibits excellent coloring power.

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