WO2015146498A9 - 樹脂粒子の製造方法およびトナー粒子の製造方法 - Google Patents
樹脂粒子の製造方法およびトナー粒子の製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—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
- C08F12/00—Homopolymers and 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
- C08F12/24—Phenols or alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- 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
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- 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
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- 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
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- 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
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- 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
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08755—Polyesters
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- 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
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
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- 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
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
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- 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
Definitions
- the present invention relates to a method for producing resin particles mainly used for producing toner particles for electrophotography, and a method for producing toner particles.
- image forming apparatuses such as copying machines and printers are required to have high image output speed and high output image stability for use in various environments.
- printers that have been mainly used in the office in the past have recently been used even in harsh high-temperature and high-humidity environments.
- printers using a one-component developing method suitable for miniaturization and high speed are increasing due to demands for miniaturization and high speed. Since the one-component development method has fewer opportunities for contact between the toner and the member for charging the toner than the two-component development method using a carrier, the required charge amount is applied to the toner by applying a relatively high stress. Have to give. For these reasons, it is necessary to improve the durability and chargeability of the toner not only in a normal environment but also in a high temperature and high humidity environment.
- Patent Document 1 describes a charge control agent that has reduced hygroscopicity in a high-humidity environment.
- Patent Document 2 describes a toner obtained by aggregating and fusing resin particles obtained by a phase inversion emulsification method on the surface of core particles.
- the resin particles are likely to be selectively present on the outermost surface of the toner particles.
- Patent Document 2 the resin particles described in Patent Document 2 have insufficient charging stability under a high humidity environment, and the density of the output image may be reduced under the high humidity environment.
- Patent Document 3 describes a toner in which resin particles having units having a salicylic acid-based substituent are fixed.
- Patent Document 3 the resin particles described in Patent Document 3 have a broad particle size distribution and may have poor durability.
- An object of the present invention is to provide a method for producing resin particles that are excellent in environmental stability (particularly, charging stability in a high humidity environment) and have a sharp particle size distribution.
- the above object can be achieved by the present invention.
- the present invention A resin having a pKa having an ionic functional group of 6.0 or more and 9.0 or less, An organic solvent having a solubility parameter capable of dissolving the resin of 12.0 or less, Water and A method for producing resin particles, comprising using a liquid prepared using a neutralizing agent in an amount capable of neutralizing 50 mol% or more and 90 mol% or less of the ionic functional group, the particles containing the resin,
- the neutralizing agent contains at least one selected from the group consisting of an acid having a pKa of 3.0 or less and a base having a pKb of 3.0 or less.
- a resin having a functional group such as sulfonic acid or carboxylic acid is generally used as a resin having an ionic functional group.
- a resin having an ionic functional group tends to adsorb moisture, and as a result, the charge amount of the toner may be reduced under a high humidity environment.
- the present inventors focused on the pKa of the ionic functional group.
- pKa of the resin having an ionic functional group is 6.0 or more and 9.0 or less, the hygroscopicity of the functional group is reduced and the decrease in the toner charge amount in a high humidity environment is suppressed. is doing.
- pKa is 7.0 or more and 8.5 or less, and more preferably 7.0 or more and 8.0 or less.
- the resin having an ionic functional group examples include a resin having a hydroxy group bonded to an aromatic ring and a carboxy group bonded to an aromatic ring. These resins can easily have a pKa in the above range. Among such resins, resins obtained by polymerizing vinyl salicylic acid, 1 vinyl phthalate, vinyl benzoic acid, and 1-vinylnaphthalene-2-carboxylic acid are preferable.
- the polymer A which has a monovalent group shown by following formula (1) is more preferable.
- R 11 represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.
- R 12 represents a hydrogen atom, A hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, g is an integer of 1 to 3, and h is an integer of 0 to 3. When h is 2 or 3, h R 11 s may be the same or different.
- Examples of the alkyl group in R 11 and R 12 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a tert-butyl group.
- alkoxy group a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example.
- Examples of the structure of the main chain of the polymer A include various polymers.
- vinyl polymer, polyester, polyamide, polyurethane, polyether and the like can be mentioned.
- the hybrid type polymer which combined these 2 or more types is also mentioned.
- a vinyl polymer is preferable.
- Methacrylic acid Non-esters; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone; N-vinyl compounds such as N-vinyl pyrrole; vinyl naphthalenes; acrylic acid such as acrylonitrile, methacrylonitrile, acrylamide; Examples include methacrylic acid derivatives, acrylic acid, and methacrylic acid. In addition, you may use a vinyl monomer in combination of 2 or more type as needed.
- the content of the monovalent group represented by the above formula (1) contained in the polymer A is the total unit (derived from the monomer) constituting the polymer A. Unit) is 100 mol%, it is preferably 0.1 mol% or more and 10.0 mol% or less. By setting it to 0.1 mol% or more, the chargeability and durability of the toner become better. Further, by setting the amount to 10.0 mol% or less, it is possible to further suppress toner charge-up.
- the organic solvent used in the present invention is an organic solvent having a solubility parameter of 12.0 or less.
- the solubility parameter is a value defined by the regular solution theory introduced by Hildebrand and is a measure of the solubility of the binary solution.
- the organic solvent In order to produce resin particles, it is necessary for the organic solvent to phase separate from water while dissolving the resin having the ionic functional group. Since the solubility parameter of water is 24.3, by using an organic solvent with a solubility parameter of 12.0 or less that is separated from water, water and the organic solvent are phase-separated to produce resin particles with a sharp particle size distribution. can do.
- organic solvents examples include normal pentane (7.0), normal hexane (7.3), diethyl ether (7.4), normal octane (7.6), cyclohexane (8.2), and acetic acid.
- the numbers in parentheses are the solubility parameters of
- the neutralizing agent used in the present invention contains at least one selected from the group consisting of an acid having a pKa in water of 3.0 or less and a base having a pKb in water of 3.0 or less. .
- the values of pKa and pKb are not specified, but it is clear that pKa or pKb is 3.0 or less, and these are also acids and water having a pKa of 3.0 or less.
- PKb is contained in a base of 3.0 or less.
- Examples of the acid having a pKa of 3.0 or less in water include hydrochloric acid, odorous acid, iodic acid, perbromic acid, metaperiodic acid, permanganic acid, thiocyanic acid, sulfuric acid, nitric acid, phosphonic acid, phosphoric acid, Diphosphoric acid, hexafluorophosphoric acid, tetrafluoroboric acid, tripolyphosphoric acid, aspartic acid, o-aminobenzoic acid, p-aminobenzoic acid, isonicotinic acid, oxaloacetic acid, citric acid, 2-glycerin phosphoric acid, glutamic acid, Examples include cyanoacetic acid, oxalic acid, trichloroacetic acid, o-nitrobenzoic acid, nitroacetic acid, picric acid, picolinic acid, pyruvic acid, fumaric acid, fluoroace
- monovalent acids are preferred because of easy washing after the production of the resin particles.
- hydrochloric acid and nitric acid are preferable.
- Examples of the base having a pKb of 3.0 or less in water include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, calcium hydroxide. Strontium hydroxide, barium hydroxide, magnesium hydroxide, europium hydroxide, thallium hydroxide, guanidine and the like.
- monovalent bases that easily dissociate the ionic functional groups are preferable.
- a base having Li a base having Na, and a base having K are preferable.
- lithium hydroxide (LiOH), sodium hydroxide (NaOH), and potassium hydroxide (KOH) are preferable.
- the salt which is not related to neutralization may be added separately, or an acid and a base may be used together.
- an acid and a base may be used together.
- a small amount of hydrochloric acid and a large amount of sodium hydroxide may be added to generate sodium chloride that is not involved in neutralization.
- Examples of the method for producing the resin particles include an emulsion polymerization method, a soap-free emulsion polymerization method, a phase inversion emulsification method, and a mechanical emulsification method.
- the phase inversion emulsification method is preferable because it does not require an emulsifier or a dispersion stabilizer and resin particles having a small particle diameter can be easily obtained.
- a resin having an ionic functional group that exhibits self-emulsifying properties by neutralization is used. Specifically, by using a resin having an ionic functional group and a pKa of 6.0 to 9.0, and further neutralizing 50 mol% to 90 mol% of the ionic functional group, Expresses self-emulsifying properties.
- resin particles are produced by self-emulsifying a resin having an ionic functional group.
- a resin having an ionic functional group In order to self-emulsify, it is necessary to control the balance between the hydrophilic group and the hydrophobic group of the resin.
- the composition of the resin is changed.
- the composition of the produced resin particles changes, when the resin particles are used in the toner, the performance of the toner also changes.
- this is a method of using a resin having an ionic functional group and having a pKa of 6.0 or more and 9.0 or less, and further neutralizing 50 mol% or more and 90 mol% or less of the ionic functional group. .
- a resin having a pKa having an ionic functional group of 6.0 or more and 9.0 or less has high environmental stability because it is close to neutrality. And such resin can dissociate an ionic functional group by neutralizing an ionic functional group with a neutralizing agent.
- the neutralization rate (50 mol% or more and 90 mol% or less)
- the hydrophilic group and the hydrophobic group of the resin can be balanced, and the self-emulsifying property of the resin is expressed.
- the neutralization rate can be controlled by adjusting the amount of neutralizing agent used.
- the neutralization rate is less than 50 mol%, the degree of dissociation of the ionic functional group is small, and the hydrophilicity of the resin is low (because the hydrophobicity is high). The diameter will increase.
- the resin particles produced by the above-described method can give good chargeability to the toner by fixing to the surface of the toner base particles.
- high chargeability is exhibited even in a high temperature and high humidity environment, the change in the density of the output image due to the environment is small.
- the particle size distribution of the resin particles is sharp, the detachment of the resin particles from the toner base particles can be suppressed, and the durability of the toner is improved.
- the following steps (1) to (4) are preferably performed in this order.
- a resin having a pKa having an ionic functional group of 6.0 or more and 9.0 or less and an organic solvent having a solubility parameter capable of dissolving the resin of 12.0 or less are mixed, and the resin becomes the organic
- a step of obtaining a resin solution dissolved in a solvent is obtained.
- Agent mixing step is preferably performed in this order.
- granulation may be performed using phase inversion emulsification, or granulation may be performed by stirring.
- the volume-based median diameter (Dv50) of the resin particles is preferably 5 nm or more and 200 nm or less. More preferably, it is 20 nm or more and 130 nm or less. When the median diameter is 5 nm or more, the durability of the toner is further improved. Further, when the median diameter is 200 nm or less, the resin particles are more uniformly fixed to the toner base particles.
- Dv50 / Dn50 which is the ratio of the volume-based median diameter (Dv50) of the resin particles to the number-based median diameter (Dn50), is preferably 2.5 or less. More preferably, it is 2.2 or less.
- the resin particles having a sharper particle size distribution can be more uniformly fixed to the toner base particles, so that the durability of the toner is improved.
- the fixing amount of the resin particles is preferably 0.1 parts by mass or more and less than 5.0 parts by mass with respect to 100 parts by mass of the toner base particles.
- the content is preferably 0.1 parts by mass or more, it is possible to obtain fixing uniformity between toner particles. As a result, the chargeability of the toner becomes better and the durability of the toner becomes better.
- the amount is possible to suppress adverse effects on the output image due to excessive resin particles while ensuring good durability of the toner.
- the resin particles may be embedded in the mother particles by mechanical impact force in order to adhere sufficiently to the surface of the mother particles after being adhered. Further, it may be fixed by heating to a glass transition temperature (Tg) or higher of the resin particles or toner base particles and smoothing.
- Tg glass transition temperature
- binder resin used for the toner base particles of the toner particles of the present invention examples include styrene resin, acrylic resin, methacrylic resin, styrene-acrylic resin, styrene-methacrylic resin, styrene-acrylic-methacrylic resin, polyethylene, and ethylene.
- styrene resin acrylic resin, methacrylic resin, styrene-acrylic resin, styrene-methacrylic resin, styrene-acrylic-methacrylic resin, polyethylene, and ethylene.
- -Vinyl acetate copolymer polyvinyl acetate, polybutadiene, phenol resin, polyurethane, polybutyral, polyester and the like.
- the hybrid resin which combined these resin is also mentioned.
- styrene resin acrylic resin, methacrylic resin, styrene-acrylic resin, styrene-methacrylic resin, polyester, styrene-acrylic resin, or hybrid resin in which styrene-methacrylic resin and polyester are combined are preferable.
- the polyester is preferably a polyester produced by using an alcohol component such as a polyhydric alcohol and an acid component such as a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid ester as raw material monomers.
- an alcohol component such as a polyhydric alcohol
- an acid component such as a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid ester
- polyesters obtained by polycondensation of diols such as bisphenol derivatives and divalent or higher carboxylic acids or acid anhydrides thereof are preferable.
- divalent or higher carboxylic acid examples include fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid.
- the toner using the resin particles of the present invention may be a magnetic toner.
- the magnetic material used in the magnetic toner include iron oxide such as magnetite, maghemite, and ferrite or iron oxide containing other metal oxides, metals such as Fe, Co, and Ni, or these metals and Al, Co, and the like.
- examples thereof include alloys with metals such as Cu, Pb, Mg, Ni, Sn, Zn, Sb, Ca, Mn, Se, and Ti, and mixtures thereof. More specifically, for example, iron trioxide (Fe 3 O 4 ), iron sesquioxide ( ⁇ -Fe 2 O 3 ), iron oxide zinc (ZnFe 2 O 4 ), copper iron oxide (CuFe 2 O 4 ).
- triiron tetroxide (Fe 3 O 4 ) and iron sesquioxide ( ⁇ -Fe 2 O 3 ) are preferable.
- One of these magnetic materials may be used alone, or two or more thereof may be used in combination.
- These magnetic materials preferably have an average particle size of 0.1 ⁇ m to 2 ⁇ m, and more preferably 0.1 ⁇ m to 0.3 ⁇ m.
- the magnetic characteristics when 795.8 kA / m (10 k Oersted) is applied are such that the coercive force (Hc) is 1.6 kA / m to 12 kA / m (20 Oersted to 150 Oersted).
- the saturation magnetization ([sigma] s) is preferably 5Am at 2 / kg or more 200 Am 2 / kg or less, and more preferably less 50 Am 2 / kg or more 100 Am 2 / kg.
- Residual magnetization (.sigma.r) is preferably not more than 2Am 2 / kg or more 20 Am 2 / kg.
- the amount of the magnetic material contained in the toner particles (toner mother particles) is 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the binder resin contained in the toner particles (toner mother particles). It is preferable that More preferably, it is 20 to 150 mass parts.
- the toner using the resin particles of the present invention may be a non-magnetic toner.
- colorant used for the toner particles various dyes and pigments can be used.
- magenta coloring pigments examples include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 185, 202, 206, 207, 209, 238, 269, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
- color pigment for cyan examples include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like.
- Examples of the colored pigment for yellow include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.
- C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20, etc. are mentioned.
- black colorant examples include carbon black, aniline black, acetylene black, and titanium black. Further, it is also possible to use the above-mentioned yellow colorant / magenta colorant / cyan colorant, which is toned in black.
- the said coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type.
- the toner particles (toner mother particles) of the toner using the resin particles of the present invention may contain a release agent.
- the release agent examples include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; aliphatic hydrocarbons Block copolymers of waxes; waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanic acid ester wax; fatty acid esters such as deoxidized carnauba wax deoxidized partly or entirely; behen Examples include partially esterified products of fatty acids such as acid monoglycerides and polyhydric alcohols; methyl ester compounds having a hydroxy group obtained by hydrogenating vegetable oils and fats, and the like.
- aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax
- oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax
- the main peak is preferably in a region having a molecular weight of 400 or more and 2400 or less, and more preferably in a region of 430 or more and 2000 or less. Thereby, preferable melting characteristics can be imparted to the toner.
- the addition amount of the release agent is preferably 2.50 parts by mass or more and 40.0 parts by mass or less with respect to 100 parts by mass of the binder resin contained in the toner particles (toner base particles). More preferably, it is 15.0 parts by mass or less.
- the toner particles in the present invention are obtained by fixing resin particles on the surface of toner base particles containing a binder resin and, if necessary, a colorant and a release agent.
- the method for producing toner particles (toner mother particles) is preferably a suspension polymerization method.
- volume-based Dv50 and number-based Dn50 of resin particles are measured using a dynamic light scattering method (DLS: Dynamic Light Scattering) using a Zetasizer Nano-ZS (trade name) manufactured by MALVERN. And was calculated by measuring the particle size.
- DLS Dynamic Light Scattering
- Measurement mode Particle diameter Material: Polystyrene latex (RI: 1.59, Absorption: 0.01) Dispersant: Water (Temperature: 25 ° C., Viscosity: 0.8872 cP, RI: 1.330) Temperature: 25.0 ° C Cell: Clear disposable zetacell Measurement duration: Automatic A sample was prepared by diluting with water to 0.50% by mass, filled into a disposable capillary cell (DTS1060), and the cell was loaded into a cell holder of the apparatus.
- DTS1060 disposable capillary cell
- the measurement was started by pressing the Start button on the measurement display screen.
- volume-based Dv50 and the number-based Dn50 of the resin particles were calculated.
- a precision particle size distribution measuring apparatus (trade name: Coulter Counter Multisizer 3) manufactured by Beckman Coulter Inc. equipped with a 100 ⁇ m aperture tube using a pore electrical resistance method was used.
- the attached dedicated software (trade name: Beckman Coulter Multisizer 3, Version 3.51) manufactured by Beckman Coulter, Inc. was used. The measurement was performed with 25,000 effective measurement channels.
- the electrolytic aqueous solution used for the measurement was prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of 1% by mass, specifically, an electrolytic aqueous solution manufactured by Beckman Coulter (trade name: ISOTON II). )It was used.
- the bin interval is set to logarithmic particle size
- the particle size bin is set to 256 particle size bin
- the particle size range is set from 2 ⁇ m to 60 ⁇ m. .
- the specific measurement method is as follows.
- An ultrasonic disperser (trade name: Ultrasonic Dispensing System Tetra 150) manufactured by Nikka Ki Bios Co., Ltd. was prepared. This ultrasonic disperser incorporates two oscillators with an oscillation frequency of 50 kHz with the phase shifted by 180 degrees. 3.3 L of ion-exchanged water was placed in a water tank of an ultrasonic dispersing device having an electric output of 120 W, and 2 mL of the above contamination N was added to this water tank.
- the measurement data was analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) were calculated.
- the “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle diameter (D4).
- the “average diameter” on the “analysis / number statistics (arithmetic average)” screen when the graph / number% is set in the dedicated software is the number average particle diameter (D1).
- the acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample.
- the acid value in the present invention is measured according to JISK0070-1992. Specifically, it measured according to the following procedures.
- Titration was performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.).
- the factor of the potassium hydroxide ethyl alcohol solution was determined using a potentiometric titrator (trade name: AT-510) manufactured by Kyoto Electronics Industry Co., Ltd.
- 100 mL of 0.100 mol / L hydrochloric acid was placed in a 250 mL tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization.
- the 0.100 mol / L hydrochloric acid used was prepared according to JIS K8001-1998.
- Titration device Potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.) -Electrode: Composite glass electrode double junction type (Kyoto Electronics Industry Co., Ltd.) ⁇ Control software for titrator: AT-WIN ⁇ Titration analysis software: Tview The titration parameters and control parameters at the time of titration were as follows.
- A [(CB) ⁇ f ⁇ 5.611] / S
- A represents the acid value (mgKOH / g) of the sample.
- B represents the amount (mL) of the potassium hydroxide ethyl alcohol solution in the blank test.
- C represents the potassium hydroxide in this test.
- F is a factor of potassium hydroxide solution.
- S is a mass (g) of the sample.
- a 0.1 mol / L potassium hydroxide ethyl alcohol solution was added until the pH became 10 or more and there was no change in pH even when 30 ⁇ L was added. From the obtained results, the pH was plotted against the addition amount of 0.1 mol / L potassium hydroxide ethyl alcohol solution to obtain a titration curve.
- the acid value (mgKOH / g) was calculated from the amount of potassium hydroxide added, with the neutralization point being the place where the slope of the pH change was greatest from the obtained titration curve. Since pKa is the same value as the pH in half of the 0.1 mol / L potassium hydroxide ethyl alcohol solution required up to the neutralization point, the pH in half was read from the titration curve.
- the acid value of the resin having an ionic functional group is determined by the above-mentioned ⁇ Measurement of pKa of resin having an ionic functional group>.
- the amount of the neutralizing agent that can neutralize all the resin acid values was 100%.
- the amount of neutralizing agent necessary for 100% neutralization is 17.8 mL for a 1.0 mol / L-KOH aqueous solution, The amount required for summing is 8.9 mL.
- Measurement device FTNMR device JNM-EX400 (manufactured by JEOL Ltd.) ⁇ Measurement frequency: 400MHz ⁇ Pulse condition: 5.0 ⁇ s ⁇ Frequency range: 10500Hz Accumulation count: The molar ratio of each monomer component is determined from the integral value of the spectrum obtained 64 times, and based on this, the content of the monovalent group represented by the above formula (1) contained in the polymer A (Mol%) was calculated.
- the pKa of polymer 1 is shown in Table 1.
- the pKa of polymer 2 is shown in Table 1.
- Polymers 3 to 5 were obtained in the same manner as in Polymer 2 except that the following changes were made.
- Table 1 shows the pKa values of the polymers 3 to 5.
- Example 1 (Production Example of Resin Particle 1)
- MEK methyl ethyl ketone
- the obtained emulsion was distilled under reduced pressure to remove the solvent, and ion-exchanged water was added to prepare the resin concentration to be 20%, whereby an aqueous dispersion of resin particles 1 was obtained.
- Example 19 (Production Example of Resin Particle 19) In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200.0 parts of methyl ethyl ketone was added, and 100.0 parts of polymer 1 was added and dissolved.
- the solution 1 was added to 500.0 parts of ion-exchanged water, and the solution was separated into two phases.
- the obtained emulsion was distilled under reduced pressure to remove the solvent, and ion-exchanged water was added to prepare a resin concentration of 20%, whereby an aqueous dispersion of resin particles 19 was obtained.
- Table 3 shows the physical property values of the aqueous dispersions of the obtained resin particles 1 to 27.
- Toner Production Example 1 (Manufacture of toner mother particles) 850.0 parts of a 0.1 mol / L Na 3 PO 4 aqueous solution was added to a container equipped with a high-speed stirring device (trade name: CLEARMIX) manufactured by M Technique, and the number of revolutions was adjusted to 15000 rpm. Warmed to ° C. Here was added CaCl 2 aqueous solution 68.0 parts of 1.0 mol / L, to prepare an aqueous medium containing Ca 3 (PO 4) 2 is a fine sparingly water-soluble dispersing agent.
- CLEARMIX high-speed stirring device manufactured by M Technique
- the polymerizable monomer composition is charged into the aqueous medium, and a high-speed stirring device (trade name: CLEARMIX) manufactured by M Technique is operated at 60 ° C. at a rotational speed of 15000 rpm for 15 minutes. Then, particles of the polymerizable monomer composition were formed (granulated).
- a high-speed stirring device (trade name: CLEARMIX) manufactured by M Technique is operated at 60 ° C. at a rotational speed of 15000 rpm for 15 minutes. Then, particles of the polymerizable monomer composition were formed (granulated).
- the temperature of the dispersion of the toner base particles to which the resin particles adhered was kept at 80 ° C. (heating temperature), and stirring was continued for 1 hour. Thereafter, the dispersion was cooled to 20 ° C., 10% hydrochloric acid was added until the pH reached 1.5, and the mixture was stirred for 2 hours. Furthermore, after sufficiently washing with ion-exchanged water, it was filtered, dried and classified to obtain toner particles 1.
- the obtained toner particles 1 had a weight average particle diameter of 6.1 ⁇ m.
- Toner 1 100.0 parts of the above toner particles 1 and 1.0 part of hydrophobized silica fine particles as a fluidity improver were mixed for 15 minutes using a Henschel mixer manufactured by Mitsui Miike Co., Ltd. at a rotational speed of 3000 rpm. (External addition), Toner 1 was obtained.
- silica fine particles those treated with dimethyl silicone oil (20% by mass) were used, the number average particle size of the primary particles was 10 nm, and the BET specific surface area was 170 m 2 / g.
- Toners 2 to 27 were obtained in the same manner as in Toner Production Example 1 except that the aqueous dispersion of resin particles 1 was changed to use the aqueous dispersion of resin particles 2 to 27.
- a color laser beam printer (trade name: LBP7600C) manufactured by Canon Inc. was used as an evaluation machine. The remodeling point is that the peripheral speed of the photosensitive drum is 250 mm / second.
- LBP7600C (trade name) is a color laser printer (image forming apparatus (electrophotographic apparatus)) using a one-component developing system.
- a laser beam printer paper (trade name: CS-680, 68 g / m 2 ) manufactured by Canon Inc. was used as the paper (recording medium).
- the product toner was extracted from the cyan cartridge for the color laser printer, the interior was cleaned by air blow, and 150 g of toner 1 was filled.
- product toner was extracted, and magenta, yellow, and black cartridges with the remaining toner amount detection mechanism disabled were inserted.
- a solid image was output so that the applied toner amount was 0.5 mg / cm 2 in an N / N environment. 10,000 images with a printing area (area on which the toner is placed) of 10% were output, and then a solid image was output. The initial image density and the image density after outputting 10,000 sheets were measured, and the difference between the initial image density and the image density after outputting 10,000 sheets was calculated, and ranked A to D according to the following criteria.
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Abstract
Description
本発明は、
イオン性官能基を有するpKaが6.0以上9.0以下である樹脂、
該樹脂を溶解しうる溶解度パラメーターが12.0以下の有機溶剤、
水、および、
該イオン性官能基の50mol%以上90mol%以下を中和しうる量の中和剤を用いて調製された液を用い、該樹脂を含有する粒子を製造する樹脂粒子の製造方法であって、
該中和剤が、pKaが3.0以下の酸およびpKbが3.0以下の塩基からなる群より選択される少なくとも1種を含む
ことを特徴とする樹脂粒子の製造方法である。
イオン性官能基を有するpKa(酸解離定数のこと。)が6.0以上9.0以下である樹脂、
該樹脂を溶解しうる溶解度パラメーターが12.0以下の有機溶剤、
水、および、
該イオン性官能基の50mol%以上90mol%以下を中和しうる量の中和剤を用いて調製された液を用い、該樹脂を含有する粒子を製造する樹脂粒子の製造方法であって、
該中和剤が、pKaが3.0以下の酸およびpKb(塩基解離定数のこと。)が3.0以下の塩基からなる群より選択される少なくとも1種を含む
ことを特徴とする樹脂粒子の製造方法である。
式(1)
R11およびR12におけるアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、s-ブチル基、tert-ブチル基などが挙げられる。また、アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基などが挙げられる。
水中でのpKaが3.0以下の酸としては、例えば、塩酸、臭酸、ヨウ素酸、過臭素酸、メタ過ヨウ素酸、過マンガン酸、チオシアン酸、硫酸、硝酸、ホスホン酸、リン酸、二リン酸、ヘキサフルオロリン酸、テトラフルオロホウ酸、トリポリリン酸、アスパラギン酸、o-アミノ安息香酸、p-アミノ安息香酸、イソニコチン酸、オキサロ酢酸、クエン酸、2-グリセリンリン酸、グルタミン酸、シアノ酢酸、シュウ酸、トリクロロ酢酸、o-ニトロ安息香酸、ニトロ酢酸、ピクリン酸、ピコリン酸、ピルビン酸、フマル酸、フルオロ酢酸、ブロモ酢酸、o-ブロモ安息香酸、マレイン酸、マロン酸などが挙げられる。これらの酸は、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
樹脂粒子を製造するためには、以下の(1)~(4)の工程をこの順序で行うことが好ましい。
(1)イオン性官能基を有するpKaが6.0以上9.0以下である樹脂と該樹脂を溶解しうる溶解度パラメーターが12.0以下の有機溶媒とを混合して、該樹脂が該有機溶媒に溶解した樹脂溶解液を得る工程。
(2)該樹脂溶解液と上述の中和剤とを混合し、該樹脂の有する該イオン性官能基の50mol%以上90mol%以下が該中和剤によって中和された混合液を得る中和剤混合工程。
(3)該混合液の粒子が水中に分散した分散液を得る造粒工程。
(4)該分散液から該有機溶媒を除去する工程。
造粒工程においては、転相乳化を利用して造粒を行っても良く、あるいは、攪拌によって造粒を行ってもよい。
樹脂粒子の体積基準のメジアン径(Dv50)および個数基準のメジアン径(Dn50)は、MALVERN社製のゼータサイザーNano-ZS(商品名)を用い、動的光散乱法(DLS:Dynamic Light Scattering)を利用し、粒径を測定することによって算出した。
Material:Polystyrene latex(RI:1.59、Absorption:0.01)
Dispersant:Water(Temperature:25℃、Viscosity:0.8872cP、RI:1.330)
Temperature:25.0℃
Cell:Clear disposable zetacell
Measurement duration:Automatic
試料は、0.50質量%となるように水で希釈して調製し、ディスポーザブルキャピラリーセル(DTS1060)に充填し、セルを装置のセルホルダーに装入した。
トナーの重量平均粒径(D4)および個数平均粒径(D1)は、以下のようにして算出した。
酸価は、試料1gに含まれる酸を中和するために必要な水酸化カリウムのmg数である。本発明における酸価は、JISK0070-1992に準じて測定される。具体的には、以下の手順に従って測定した。
・電極:複合ガラス電極ダブルジャンクション型(京都電子工業(株)製)
・滴定装置用制御ソフトウェア:AT-WIN
・滴定解析ソフト:Tview
滴定時における滴定パラメーターならびに制御パラメーターは以下のように行った。
滴定パラメーター
滴定モード:ブランク滴定
滴定様式:全量滴定
最大滴定量:20mL
滴定前の待ち時間:30秒
滴定方向:自動
制御パラメーター
終点判断電位:30dE
終点判断電位値:50dE/dmL
終点検出判断:設定しない
制御速度モード:標準
ゲイン:1
データ採取電位:4mV
データ採取滴定量:0.1mL
測定サンプル0.100gを250mLのトールビーカーに精秤し、トルエン/エタノール(3:1)の混合溶液150mLを加え、1時間かけて溶解させた。上記電位差滴定装置を用い、上記水酸化カリウムエチルアルコール溶液を用いて滴定した。
試料を用いない(すなわちトルエン/エタノール(3:1)の混合溶液のみとする)以外は、上記操作と同様の滴定を行った。
A=[(C-B)×f×5.611]/S
(上記式中、Aは、試料の酸価(mgKOH/g)を示す。Bは、空試験の水酸化カリウムエチルアルコール溶液の添加量(mL)を示す。Cは、本試験の水酸化カリウムエチルアルコール溶液の添加量(mL)を示す。fは、水酸化カリウム溶液のファクターを示す。Sは、試料の質量(g)を示す。)
測定サンプル0.100gを250mLのトールビーカーに精秤し、テトラヒドロフラン150mLを加え、30分かけて溶解した。この溶液にpH電極を入れ、サンプルのテトラヒドロフラン溶液のpHを読み取った。その後、0.1mol/L水酸化カリウムエチルアルコール溶液(キシダ化学(株)製)を10μLずつ添加し、その都度pHを読み取り、滴定を行った。pHが10以上となり、30μL添加してもpHの変化がなくなるまで0.1mol/L水酸化カリウムエチルアルコール溶液を加えた。得られた結果から0.1mol/L水酸化カリウムエチルアルコール溶液添加量に対するpHをプロットし、滴定曲線を得た。得られた滴定曲線からpH変化の傾きが一番大きいところを中和点とし、添加した水酸化カリウム量から酸価(mgKOH/g)を算出した。pKaは中和点までに必要とした0.1mol/L水酸化カリウムエチルアルコール溶液量の半分量でのpHと同じ値であるため、滴定曲線から半分量でのpHを読み取った。
前述した<イオン性官能基を有する樹脂のpKaの測定>で、イオン性官能基を有する樹脂の酸価が求められる。この樹脂酸価を全て中和できる量の中和剤の量を100%とした。
例えば、酸価が10mgKOH/gの樹脂100gの場合、100%中和するために必要な中和剤の量は、1.0mol/L-KOH水溶液であれば17.8mLであり、50%中和するために必要な量は8.9mLである。
<NMRの測定>
重合体Aに含まれる上記式(1)で示される1価の基の含有量は核磁気共鳴分光分析(1H-NMR)[400MHz、CDCl3、室温(25℃)]により求めた。
・測定周波数:400MHz
・パルス条件:5.0μs
・周波数範囲:10500Hz
・積算回数:64回
得られたスペクトルの積分値から各単量体成分のmol比を求め、これを基に重合体Aに含まれる上記式(1)で示される1価の基の含有量(mol%)を算出した。
(工程1)
2,5-ジヒドロキシ安息香酸100gと80%硫酸1441gとを50℃に加熱混合し、分散液を得た。この分散液にtert-ブチルアルコール144gを加えて50℃で30分間撹拌した。その後、この分散液にtert-ブチルアルコール144gを加え、30分間撹拌する操作を3回行い、反応液を得た。反応液を室温まで冷却し、氷水1kgにゆっくり注ぎ、析出物を得た。析出物を濾過し、水洗し、ヘキサンで洗浄した。析出物をメタノール200mLに溶解させ、水3.6L中で再沈殿させた。これを濾過した後、濾物を80℃にて乾燥させることによって、下記式(4)で示されるサリチル酸中間体74.9gを得た。
工程1で得られたサリチル酸中間体25.0gをメタノール150mLに溶解させ、炭酸カリウム36.9gを加えて65℃に加熱し、反応液を得た。この反応液に4-(クロロメチル)スチレン18.7gとメタノール100mLの混合液を滴下し、65℃にて3時間反応させ、反応液を得た。反応液を冷却した後、濾過し、濾液を濃縮して粗生成物を得た。粗生成物をpH2の水1.5Lに分散させ、酢酸エチルを加えて抽出した。その後、抽出物を水洗し、硫酸マグネシウムを用いて乾燥させ、減圧下、酢酸エチルを留去して析出物を得た。析出物をヘキサンで洗浄した後、トルエンと酢酸エチルを用いて再結晶化させることで精製することによって、下記式(5)で示される重合性単量体M-1を20.1g得た。
上記式(4)で示されるサリチル酸中間体を2,4-ジヒドロキシ安息香酸18gに変更した以外は、重合性単量体M-1の合成例と同様にして、下記式(6)で示される重合性単量体M-2を得た。
上記式(4)で示されるサリチル酸中間体を2,3-ジヒドロキシ安息香酸18gに変更した以外は、重合性単量体M-1の合成例と同様にして、下記式(7)で示される重合性単量体M-3を得た。
構造式(4)で示されるサリチル酸中間体を2,6-ジヒドロキシ安息香酸18gに変更した以外は、重合性単量体M-1の合成例と同様にして、下記式(8)で示される重合性単量体M-4を得た。
式(8)
上記式(5)で示される重合性単量体M-1の9.9gとスチレン60.1gをDMF42.0mLに溶解させ、窒素バブリングをしながら1時間撹拌した後、110℃まで加熱した。この反応液に、重合開始剤としてtert-ブチルパーオキシイソプロピルモノカルボネート(商品名:パーブチルI、日本油脂(株)製)4.62gとトルエン42mLの混合液を滴下した。さらに110℃にて4時間反応した。その後、冷却し、メタノール1Lに滴下し、析出物を得た。得られた析出物をテトラヒドロフラン120mLに溶解させた後、この溶解液をメタノール1.80Lに滴下し、白色析出物を析出させ、濾過し、減圧下90℃にて乾燥させることによって、重合体1を57.6g得た。得られた重合体1のNMRと酸価を測定し、重合体単量体M-1に由来する成分の含有量を確認した。
撹拌機、コンデンサー、温度計および窒素導入管を備えた反応容器にキシレン200gを入れ、窒素気流下で還流した。
以下の変更を行った以外は重合体2の合成例と同様に合成を行い、重合体3~5を得た。
重合体3:
5-ビニルサリチル酸9.0gをフタル酸-1-ビニル5.3gに変更した。
重合体4:
5-ビニルサリチル酸9.0gをビニル安息香酸8.1gに変更した。
重合体5:
5-ビニルサリチル酸9.0gを1-ビニルナフタレン-2-カルボン酸10.9gに変更した。
重合体3~5のpKaを表1に示す。
原料の使用量を表2に示すように変更した以外は、重合体1の合成例と同様にして重合体6~9を得た。
重合体6~9のpKaを表1に示す。
撹拌機、コンデンサー、温度計および窒素導入管を備えた反応容器にキシレン200gを入れ、窒素気流下で還流した。
重合体10のpKaを表1に示す。
窒素導入管、脱水管、撹拌器および熱電対を取り付けた反応容器にビスフェノールAプロピレンオキサイド2モル付加物500g、テレフタル酸154g、フマル酸45g、オクチル酸スズ2gを入れ、230℃で8時間の重縮合反応を行った。その後、さらに、8kPaで1時間にわたって重縮合反応を継続した。その後、160℃に冷却することにより、ポリエステルを合成した。次いで、160℃の状態でアクリル酸10gを投入し、混合させて15分間保持した後、スチレン142g、n-ブチルアクリレート35g、重合開始剤(ジ-tert-ブチルペルオキサイド)10gの混合物を滴下ロートにより1時間かけて滴下した。その後、160℃を維持した状態で1時間にわたって付加重合反応を行った後、200℃に昇温させ、10kPaで1時間保持することにより、重合体11を得た。
重合体11のpKaを表1に示す。
撹拌機、コンデンサー、温度計、窒素導入管を備えた反応容器に、メチルエチルケトン(MEK)(溶解度パラメーター:9.3)200.0部を入れ、重合体1の100.0部を加えて溶解させた(樹脂溶解液を得る工程)。
重合体と、中和剤の種類、量を表3に示すように変更した。
撹拌機、コンデンサー、温度計、窒素導入管を備えた反応容器に、メチルエチルケトン200.0部を入れ、重合体1を100.0部加えて溶解させた。
(トナー母粒子の製造)
エム・テクニック社製の高速撹拌装置(商品名:クレアミックス)を備えた容器中に0.1mol/LのNa3PO4水溶液850.0部を添加し、回転数を15000rpmに調整し、60℃に加温した。ここに1.0mol/LのCaCl2水溶液68.0部を添加し、微細な難水溶性分散剤であるCa3(PO4)2を含む水系媒体を調製した。
・n-ブチルアクリレート 30.0部
・飽和ポリエステル(テレフタル酸-プロピレンオキサイド変性ビスフェノールA共重合体、酸価:13mgKOH/g、重量平均分子量(Mw):14500) 3.0部
次に、上記溶解液に以下の材料を添加して、混合液を調製した。
・エステルワックス(主成分:C21H43COOC22H45、融点:72.5℃)12.0部
その後、混合液を60℃に加温した後、特殊機化工業(株)製のTK式ホモミキサーにて、回転数9000rpmの条件で撹拌し、上記材料を溶解させ、分散させた。
還流冷却管、撹拌機および温度計を備えた反応容器に上記トナー母粒子の分散液500.0部(固形分100.0部)を入れ、撹拌しながら、水酸化カリウム水溶液を加え、pHを8.5に調整した(pH調整)。ここに、樹脂粒子1の水分散体5.0部(固形分1.0部)を22℃で(添加温度)緩やかに添加し、回転数200rpmの条件で15分間撹拌を行った。
トナー製造例1において、樹脂粒子1の水分散体を、樹脂粒子2~27の水分散体を用いるように変更した以外は、同様にしてトナー2~27を得た。
トナー1~27について、以下の方法に従って性能の評価を行った。結果を表4に示す。
23℃/50%RHの環境(N/N環境)下で、トナー載り量0.5mg/cm2となるようにベタ画像を出力した。
ベタ部分の画像の濃度を、マクベス社製のマクベス反射濃度計(商品名:RD918)を用いて測定した。
A:0.00以上0.05未満
B:0.05以上0.10未満
C:0.10以上0.20未満
D:0.20以上
N/N環境下でトナー載り量0.5mg/cm2となるようにベタ画像を出力した。印字面積(トナーが載る面積)10%の画像を10000枚出力し、その後、ベタ画像を出力した。
初期および10000枚画像出力後の画像の濃度を測定し、初期の画像の濃度と10000枚画像出力後の画像の濃度の差を算出し、以下の基準でA~Dにランク付けした。
A:0.00以上0.05未満
B:0.05以上0.10未満
C:0.10以上0.20未満
D:0.20以上
Claims (12)
- イオン性官能基を有するpKaが6.0以上9.0以下である樹脂、
該樹脂を溶解しうる溶解度パラメーターが12.0以下の有機溶剤、
水、および、
該イオン性官能基の50mol%以上90mol%以下を中和しうる量の中和剤
を用いて調製された液を用い、該樹脂を含有する粒子を製造する樹脂粒子の製造方法であって、
該中和剤が、pKaが3.0以下の酸およびpKbが3.0以下の塩基からなる群より選択される少なくとも1種を含む
ことを特徴とする樹脂粒子の製造方法。 - 前記中和剤が、前記pKbが3.0以下の塩基を含む請求項1に記載の樹脂粒子の製造方法。
- [規則91に基づく訂正 06.10.2015]
前記pKbが3.0以下の塩基が、Liを有する塩基、Naを有する塩基およびKを有する塩基からなる群より選択される少なくとも1種を含む請求項2に記載の樹脂粒子の製造方法。 - [規則91に基づく訂正 06.10.2015]
前記pKbが3.0以下の塩基が、LiOH、NaOHおよびKOHからなる群より選択される少なくとも1種を含む請求項3に記載の樹脂粒子の製造方法。 - 前記樹脂のpKaが、7.0以上8.5以下である請求項1~4のいずれか1項に記載の樹脂粒子の製造方法。
- 前記イオン性官能基が、芳香環に結合したカルボキシ基である請求項1~5のいずれか1項に記載の樹脂粒子の製造方法。
- 前記樹脂が、ビニル系重合体である請求項1~6のいずれか1項に記載の樹脂粒子の製造方法。
- 着色剤、結着樹脂およびワックスを含むトナー母粒子を製造する工程と、
請求項1~7のいずれか1項に記載の製造方法を用いて樹脂粒子を製造する工程と、
該トナー母粒子に該樹脂粒子を固着させてトナー粒子を得る工程と、
を有することを特徴とするトナー粒子の製造方法。 - 前記樹脂粒子の体積基準のメジアン径(Dv50)が、5nm以上200nm以下である請求項8に記載のトナー粒子の製造方法。
- 前記樹脂粒子の体積基準のメジアン径(Dv50)と、個数基準のメジアン径(Dn50)の比である、Dv50/Dn50が、2.5以下である請求項8または9に記載のトナー粒子の製造方法。
- イオン性官能基を有するpKaが6.0以上9.0以下である樹脂と該樹脂を溶解しうる溶解度パラメーターが12.0以下の有機溶媒とを混合して、該樹脂が該有機溶媒に溶解した樹脂溶解液を得る工程、
該樹脂溶解液と中和剤とを混合し、該樹脂の有する該イオン性官能基の50mol%以上90mol%以下が該中和剤によって中和された混合液を得る中和剤混合工程、
該混合液の粒子が水中に分散した分散液を得る造粒工程、及び、
該分散液から該有機溶媒を除去する工程
を有する樹脂粒子の製造方法であって、
該中和剤が、pKaが3.0以下の酸およびpKbが3.0以下の塩基からなる群より選択される少なくとも1種を含む、
ことを特徴とする樹脂粒子の製造方法。 - 該造粒工程が、転相乳化あるいは攪拌によって造粒する工程である請求項11に記載の樹脂粒子の製造方法。
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