WO2016194969A1 - トナー用バインダー樹脂、トナーおよびその製造方法 - Google Patents
トナー用バインダー樹脂、トナーおよびその製造方法 Download PDFInfo
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- WO2016194969A1 WO2016194969A1 PCT/JP2016/066250 JP2016066250W WO2016194969A1 WO 2016194969 A1 WO2016194969 A1 WO 2016194969A1 JP 2016066250 W JP2016066250 W JP 2016066250W WO 2016194969 A1 WO2016194969 A1 WO 2016194969A1
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- toner
- polyester resin
- resin
- binder resin
- structural unit
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
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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
- G03G9/081—Preparation methods by mixing the toner components in a liquefied state; melt kneading; reactive mixing
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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
- G03G9/0815—Post-treatment
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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
- G03G9/0819—Developers with toner particles characterised by the dimensions of the 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
- G03G9/0821—Developers with toner particles characterised by physical parameters
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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
- G03G9/08784—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
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/09758—Organic compounds comprising a heterocyclic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a binder resin for toner, a toner, and a method for producing the same.
- This application is based on Japanese Patent Application No. 2015-111332 filed in Japan on June 1, 2015, Japanese Patent Application No. 2015-249773 filed in Japan on December 22, 2015, and December 22, 2015. Furthermore, priority is claimed based on Japanese Patent Application No. 2015-249774 filed in Japan, the contents of which are incorporated herein by reference.
- a method for obtaining an image by an electrophotographic printing method or an electrostatic charge developing method fixing is performed after developing an electrostatic charge image formed on a photosensitive member with toner charged in advance by friction.
- the toner needs to hold a stable charge amount first, and then needs to be fixed to paper.
- an apparatus used for obtaining an image by an electrophotographic printing method or an electrostatic charge developing method has a fixing portion that is a heating body, and the temperature in the apparatus rises, so that toner does not block, that is, Storage stability is required.
- the temperature of the fixing unit has been lowered from the viewpoint of energy saving, and the toner has been strongly required to have a low temperature fixing property.
- the binder resin for toner has a great influence on the toner characteristics as described above, and polystyrene resin, styrene acrylic resin, polyester resin, epoxy resin, polyamide resin and the like are known. Recently, polyester resins have attracted particular attention because they are excellent in storage stability, low-temperature fixability, non-offset properties, durability, grindability during toner production, etc., and have a good performance balance.
- Patent Document 1 proposes a toner having excellent low-temperature fixability, hot offset resistance, glossiness, durability, and storage stability.
- Examples of the toner production method using a polyester resin include a pulverization method and a chemical method.
- the pulverization method is a method for obtaining a toner by melting and kneading a polyester resin, a pigment (colorant), a release agent, and the like, and finely pulverizing the obtained kneaded material with a pulverizer or the like, and classifying it. Widely used.
- energy and time required for pulverization increase, the manufacturing process becomes complicated, and the yield further decreases. For this reason, attention has been focused on chemical methods that can reduce the particle size more efficiently.
- a material containing a polyester resin and other toner compound is dissolved or dispersed in an organic solvent in which the polyester resin can be dissolved, and the liquid is dispersed in an aqueous medium containing a dispersion stabilizer. After granulation, the organic solvent is removed, and the resulting particles are separated, washed, and dried to obtain toner particles; the polyester resin is dissolved in the organic solvent, and the liquid is dispersed as necessary. Emulsified in an aqueous medium containing a stabilizer to remove the organic solvent to obtain a resin emulsion, finely disperse other toner compound in the aqueous medium, mix with the resin emulsion, and agglomerate and heat-fuse the fine particles. And a method of obtaining toner particles by separating, washing, and drying the obtained particles.
- Patent Document 2 proposes a toner using a binder resin for toner containing plant-derived raw material components.
- Patent Document 1 the resin for toner disclosed in Patent Document 1 is not easily broken when pulverized and has insufficient pulverizability. Moreover, solvent solubility may become inadequate.
- the toner described in Patent Document 2 has insufficient storage stability, particularly storage stability under high humidity conditions.
- the present invention relates to a binder resin for a toner that has a good grindability and solvent solubility and is excellent in storage stability, low-temperature fixability, non-offset property and durability, and toner and toner production using the same It aims to provide a method.
- polyester resin (A) one or both of a trivalent or higher polyvalent carboxylic acid and a trivalent or higher polyhydric alcohol is used in an amount of 0.1 to 80 with respect to the total number of moles of all acid components.
- the ratio of the number of carbon atoms contained in the structural unit derived from isosorbide to the total number of carbon atoms contained in the polyester resin (B) is less than 1%, according to any one of [1] to [4] Binder resin for toner.
- the method for producing a toner according to [7] A method for producing toner, comprising a step of dissolving the binder resin for toner in an organic solvent.
- a binder resin for a toner that provides a toner having good pulverization and solvent solubility and excellent storage stability, low-temperature fixability, non-offset property and durability, and toner and toner using the same Can be provided.
- the binder resin for toner of the present invention contains a polyester resin (A) and a polyester resin (B).
- the binder resin for toner of the present invention may further contain a binder resin other than the polyester resin (A) and the polyester resin (B) as long as the effects of the present invention are not impaired.
- the “polyester resin” is a polycondensate of a monomer mixture containing a polyvalent carboxylic acid and a polyhydric alcohol, and includes a structural unit derived from a polyvalent carboxylic acid and a structural unit derived from a polyhydric alcohol.
- the polyester resin (A) contains at least a structural unit derived from isosorbide as a structural unit derived from a polyhydric alcohol. Thereby, the grindability and solvent solubility of the binder resin for toner are improved.
- polyvalent carboxylic acid in the structural unit derived from the polyvalent carboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, and dibutyl isophthalate.
- Aromatic dicarboxylic acids such as esters and acid anhydrides thereof; aliphatic dicarboxylic acids such as sebacic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, adipic acid, succinic acid, and esters and acid anhydrides thereof Acid; trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic , Polycarboxylic acids trivalent or more such as their esters and anhydrides; and the like.
- polyvalent carboxylic acid aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and trivalent or higher polyvalent carboxylic acids are preferable. Trimellitic acid or its acid anhydride is preferred as the trivalent or higher polyvalent carboxylic acid.
- the polyester resin (A) may contain other polyhydric alcohol-derived structural units other than isosorbide-derived structural units as long as the effects of the present invention are not impaired.
- Other polyhydric alcohols include, for example, ethylene glycol, neopentyl glycol, polyethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,4 -Aliphatic diols such as cyclohexanedimethanol and erythritan; polyoxypropylene (2.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4 -Hydroxyphenyl) propane, polyoxypropylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -polyoxyethylene (2.0) -2,2- Bis (4-hydroxyphenyl) propane, polyoxypropylene (6) 2,
- polystyrene resin may be plant-derived substances or petroleum-derived substances, and any one of them may be used alone or in combination of two or more.
- numerical value in the parenthesis attached after polyoxyethylene or polypropylene shows the average added mole number of an oxyethylene group or an oxypropylene group.
- Other polyhydric alcohols include ethylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, polyoxyethylene (2.
- the polyester resin (A) may further contain a structural unit derived from a monohydric alcohol, a structural unit derived from a monovalent carboxylic acid, or the like as long as the effects of the present invention are not impaired. When these monovalent structural units are included, these monovalent structural units are likely to be present at the ends of the molecular chains of the polyester resin. Including a monovalent alcohol-derived structural unit or a carboxylic acid-derived structural unit at the polymer terminal improves the dispersibility with the toner member, and improves the moisture absorption resistance of the resin by adjusting the carboxylic acid value and the hydroxyl value. It is effective to improve the toner chargeability and thereby stabilize the chargeability of the toner.
- monohydric alcohols include aromatic monoalcohols having 30 or less carbon atoms such as benzyl alcohol; aliphatic monoalcohols having 30 or less carbon atoms such as oleyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol; Monovalent carboxylic acids include aromatic monocarboxylic acids having 30 or less carbon atoms such as benzoic acid, p-methylbenzoic acid and cinnamic acid; carbon numbers such as stearic acid, behenic acid, oleic acid, linoleic acid and linolenic acid. 30 or less aliphatic carboxylic acid; and the like.
- the content of the structural unit derived from isosorbide is the ratio of the number of carbon atoms contained in the structural unit derived from isosorbide to the total number of carbon atoms contained in the polyester resin (A) (hereinafter referred to as “isosorbide-derived carbon atom”).
- the ratio is also preferably within a range of 0.1 to 30%.
- the proportion of carbon atoms derived from isosorbide is more preferably from 0.1 to 20%, particularly preferably from 0.5 to 15%. If the isosorbide-derived carbon atom ratio is equal to or higher than the lower limit, the pulverizability and solvent solubility of the binder resin for toner are more excellent.
- the isosorbide carbon atom ratio is not more than the above upper limit, the durability of the binder resin for toner, the storage stability of the toner under high humidity, and the fixing property are further improved.
- the content of structural units derived from isosorbide in the polyester resin (A) is preferably 0.1 mol% or more based on the total number of moles of structural units derived from all polycarboxylic acids, 50 mol% is more preferable, 3 to 40 mol% is more preferable, and 5 to 30 mol% is particularly preferable.
- the content of the constituent unit derived from isosorbide is not less than the lower limit, the pulverizability and solvent solubility of the binder resin for toner are more excellent.
- the content of the constituent unit derived from isosorbide is not more than the above upper limit value, the durability of the binder resin for toner, the storage stability of the toner under high humidity, and the fixing property are further improved.
- the polyester resin (A) preferably contains one or both of a structural unit derived from a trivalent or higher polyvalent carboxylic acid and a structural unit derived from a trivalent or higher polyhydric alcohol.
- a structural unit derived from a trivalent or higher polyvalent carboxylic acid and a structural unit derived from a trihydric or higher polyhydric alcohol in the polyester resin (A) (hereinafter collectively referred to as “trivalent or higher monomer derived”).
- trivalent or higher monomer derived Is preferably in the range of 0.1 to 80 mol% with respect to the total number of moles (100 mol%) of all polyvalent carboxylic acid-derived structural units. ⁇ 60 mol% is more preferred, and 1 ⁇ 50 mol% is particularly preferred.
- the offset resistance on the high temperature side of the toner is more excellent.
- the content of the structural unit derived from a trivalent or higher monomer is equal to or less than the upper limit, the formation of gel (solvent insoluble matter) can be suppressed, and the solvent solubility is more excellent. Further, the glossiness when used for color toners is also good.
- the content of the structural unit derived from the trivalent or higher polyvalent carboxylic acid in the polyester resin (A) is 0.1 mol% based on the total number of moles (100 mol%) of the structural units derived from all the polyvalent carboxylic acids.
- the above is preferable, 0.1 to 80 mol% is more preferable, 1 to 60 mol% is further preferable, and 1 to 50 mol% is particularly preferable. If the content of the structural unit derived from a trivalent or higher polyvalent carboxylic acid is not less than the lower limit, the offset resistance on the high temperature side of the toner is more excellent.
- the content of the structural unit derived from a trivalent or higher polyvalent carboxylic acid is not more than the above upper limit, the formation of gel (solvent insoluble matter) can be suppressed, and the solvent solubility is more excellent. Further, the glossiness when used for color toners is also good.
- the content of the structural unit derived from the trihydric or higher polyhydric alcohol in the polyester resin (A) is 0.1 mol% or more with respect to the total number of moles (100 mol%) of the structural units derived from all the polycarboxylic acids. It is preferably 0.1 to 80 mol%, more preferably 1 to 60 mol%, particularly preferably 1 to 50 mol%.
- the content of the structural unit derived from a trihydric or higher polyhydric alcohol is not less than the lower limit, the offset resistance on the high temperature side of the toner is more excellent.
- the content of the structural unit derived from a trihydric or higher polyhydric alcohol is not more than the above upper limit, the formation of gel (solvent insoluble matter) can be suppressed, and the solvent solubility is more excellent. Further, the glossiness when used for color toners is also good.
- the softening temperature of the polyester resin (A) is 120 ° C. or lower.
- the softening temperature of the polyester resin (A) is 120 ° C. or lower, the low-temperature fixability of the toner and the solvent solubility of the binder resin for toner are excellent.
- the softening temperature of the polyester resin (A) is preferably 75 ° C. or higher, and more preferably 80 ° C. or higher. Therefore, the softening temperature of the polyester resin (A) is preferably 75 ° C. or higher and 120 ° C. or lower, and more preferably 80 ° C. or higher and 120 ° C. or lower.
- the softening temperature of the polyester resin is measured by the method described in Examples described later.
- the softening temperature of the polyester resin can be adjusted by the degree of polymerization, the raw material composition and the ratio thereof. For example, increasing the degree of polymerization tends to have a higher softening temperature.
- the glass transition temperature (Tg) of the polyester resin (A) is preferably 35 to 85 ° C, more preferably 35 to 82 ° C. If Tg is not less than the lower limit of the range, the storage stability of the toner is more excellent, and if it is not more than the upper limit of the range, the low-temperature fixability of the toner is more excellent.
- the Tg of the polyester resin is measured by the method described in Examples described later.
- the Tg of the polyester resin can be adjusted by the raw material composition, its ratio, the degree of polymerization, and the like. For example, Tg tends to be higher when more of the structural units derived from isosorbide are included.
- the acid value of the polyester resin (A) is preferably 0.1 to 60 mgKOH / g, more preferably 0.1 to 50 mgKOH / g. If the acid value of the polyester resin (A) is not less than the lower limit of the above range, the productivity of the resin tends to be improved. If the acid value is not more than the upper limit of the above range, the resin has excellent moisture resistance and the toner is used. Difficult to be affected by the environment. The acid value of the polyester resin is measured by the method described in Examples described later.
- the weight average molecular weight (Mw) of the polyester resin (A) is preferably 500 to 1,000,000, and more preferably 500 to 800,000. If the Mw of the polyester resin (A) is not less than the lower limit value of the above range, the durability of the toner is more excellent, and if it is not more than the upper limit value of the above range, the low temperature fixability of the toner is more excellent.
- the number average molecular weight (Mn) of the polyester resin (A) is preferably 500 to 100,000, and more preferably 500 to 50,000.
- the peak top molecular weight (Mp) of the polyester resin (A) is preferably 500 to 100,000, and more preferably 500 to 50,000.
- Mw, Mn, and Mp of the polyester resin are values in terms of standard polystyrene measured by a gel permeation chromatography method. In detail, it measures by the method as described in the Example mentioned later.
- the polyester resin (A) preferably has an insoluble content of tetrahydrofuran (THF) of 0 to 40% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 10% by mass.
- THF tetrahydrofuran
- the THF-insoluble matter of the polyester resin is measured by the measuring method described in the examples described later.
- the polyester resin (A) can be obtained by polycondensing a monomer mixture containing a polyvalent carboxylic acid and a polyhydric alcohol.
- the polyhydric alcohol contains at least a substance containing a structural unit derived from isosorbide, and may contain a polyhydric alcohol other than the substance containing a structural unit derived from isosorbide.
- the substance containing a structural unit derived from isosorbide is a divalent alcohol containing the structure shown in Formula 1, and examples thereof include isosorbide and an alkylene oxide adduct of isosorbide.
- the monomer mixture may further contain a monohydric alcohol, a monovalent carboxylic acid, or the like, if necessary.
- Content of each monomer in a monomer mixture is set according to content of the structural unit derived from each monomer of a polyester resin (A).
- the composition of the monomer mixture ratio of each monomer to the total amount of all monomers
- the composition of the polyester resin obtained from this monomer mixture (of each structural unit relative to the total amount of all structural units) Ratio) is almost the same.
- the ratio of the substance containing the structural unit derived from isosorbide to the total number of moles of all the acid components in the monomer mixture is 0.1 mol% or more
- the structural unit derived from isosorbide is derived from all polycarboxylic acids.
- a polyester resin containing 0.1 mol% or more with respect to the total number of moles of the structural unit is obtained.
- the ratio of the number of carbon atoms contained in the substance containing the structural unit derived from isosorbide to the total number of carbon atoms contained in the monomer mixture is 0.1-30%, the ratio of carbon atoms derived from isosorbide is 0.1-30. % Polyester resin is obtained.
- the content (mol%) of the trivalent or higher monomer component with respect to the total number of moles (100 mol%) of all acid components in the monomer mixture is the structural unit derived from all polyvalent carboxylic acids in the obtained polyester resin. Is substantially equivalent to the content (mol%) of the structural unit derived from a trivalent or higher monomer with respect to the total number of moles of (100 mol%).
- the “total acid component” is the sum of all polyvalent carboxylic acids.
- the polycondensation of the monomer mixture can be performed by a known method and is not particularly limited.
- Examples of the polycondensation method include a method in which the monomer mixture is charged into a reaction vessel and polymerized through an esterification reaction or a transesterification reaction and a condensation polymerization reaction.
- the polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C to 280 ° C. When the polymerization temperature is 180 ° C. or higher, the productivity tends to be good, and when it is 280 ° C. or lower, the decomposition of the resin and the by-product of volatile components that cause odor tend to be suppressed.
- the lower limit of the polymerization temperature is more preferably 200 ° C. or higher, and particularly preferably 220 ° C. or higher.
- the upper limit of the polymerization temperature is more preferably 270 ° C. or less.
- the polycondensation of the monomer mixture may be performed in the presence of a polymerization catalyst.
- the polymerization catalyst include titanium tetraalkoxide, titanium oxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide, magnesium acetate, calcium acetate and the like.
- titanium tetraalkoxide is preferable because it has a particularly large effect of increasing the reaction rate.
- the amount of the polymerization catalyst added during the polycondensation is preferably 0 to 0.2 parts by mass with respect to 100 parts by mass of all raw materials.
- the polycondensation of the monomer mixture may be performed in the presence of a release agent. Performing polycondensation in the presence of a release agent tends to improve toner fixability and wax dispersibility.
- a mold release agent the thing similar to what is mentioned as another component mentioned later is mentioned, Any 1 type can be used individually or in combination of 2 or more types.
- the amount of the release agent added during the polycondensation can be appropriately set within a range not impairing the effects of the present invention.
- the contents are discharged in a lump from the apparatus, and are subjected to a pulverization step as necessary. Thereby, a polyester resin (A) is obtained. Since the polyester resin (A) in the present invention has good grindability, it can be efficiently ground to a fine particle size.
- concentration of the biomass ratio can be specified by the method of performing the measurement at, etc.
- the polyester resin (B) is a polyester resin different from the polyester resin (A).
- the polyester resin (B) typically has a softening temperature, a content of a structural unit derived from isosorbide, a structural unit derived from a trivalent or higher polyvalent carboxylic acid and / or a structural unit derived from a trivalent or higher polyhydric alcohol. At least one of the contents of is different from the polyester resin (A).
- the polyester resin (B) includes a structural unit derived from a polyvalent carboxylic acid and a structural unit derived from a polyhydric alcohol.
- the polyester resin (B) may further contain a structural unit derived from a monohydric alcohol, a structural unit derived from a monovalent carboxylic acid, and the like as long as the effects of the present invention are not impaired.
- Examples of the polyvalent carboxylic acid, polyhydric alcohol, monohydric alcohol, and monovalent carboxylic acid are the same as those described for the polyester resin (A), and preferred embodiments are also the same.
- the polyester resin (B) may or may not contain a structural unit derived from isosorbide as a structural unit derived from a polyhydric alcohol.
- the content of the structural unit derived from isosorbide is the isosorbide-derived carbon atom ratio, that is, the ratio of the number of carbon atoms contained in the structural unit derived from isosorbide to the total number of carbon atoms contained in the polyester resin (B). Is preferably in the range of less than 1%.
- the isosorbide-derived carbon atom ratio of the polyester resin (B) is more preferably less than 0.3%, and may be 0%. When the isosorbide carbon atom ratio is not more than the above upper limit, the durability of the toner and the storage stability under high humidity are further improved.
- the polyester resin (B) does not contain a structural unit derived from isosorbide, or is derived from isosorbide within a range where the isosorbide-derived carbon atom ratio is more than 0% and less than 1% (more preferably more than 0% and less than 0.3%). It is preferable that the structural unit is included.
- Content of the structural unit derived from isosorbide in the polyester resin (B) is less than 0.1 mol% with respect to the total number of moles of the structural unit derived from the polyvalent carboxylic acid and the structural unit derived from the polyhydric alcohol. Is preferable, and may be 0 mol%. That is, the polyester resin (B) does not contain a structural unit derived from isosorbide, or a structural unit derived from isosorbide exceeds 0.1 mol% with respect to the total number of moles of structural units derived from all polycarboxylic acids. It is preferable to contain less than mol%. As a result, it is possible to suppress a decrease in toner durability and storage stability under high humidity.
- the polyester resin (B) is one or both of a structural unit derived from a trivalent or higher monomer, that is, a structural unit derived from a trivalent or higher polyvalent carboxylic acid and a structural unit derived from a trivalent or higher polyhydric alcohol. Is included, the content of the structural unit derived from the trivalent or higher monomer in the polyester resin (B) is 0 with respect to the total number of moles (100 mol%) of the structural units derived from all the polyvalent carboxylic acids. The range is preferably from 1 to 80 mol%, more preferably from 1 to 45 mol%, particularly preferably from 1 to 40 mol%.
- the offset resistance on the high temperature side of the toner is more excellent.
- the content of the structural unit derived from a trivalent or higher monomer is equal to or less than the upper limit, the formation of gel (solvent insoluble matter) can be suppressed, and the solvent solubility is more excellent. Further, the glossiness when used for color toners is also good.
- the content of the structural unit derived from the trivalent or higher polyvalent carboxylic acid in the polyester resin (B) is 0.1 mol% with respect to the total number of moles (100 mol%) of all the structural units derived from the polyvalent carboxylic acid.
- the above is preferable, 0.1 to 80 mol% is more preferable, 1 to 45 mol% is further preferable, and 1 to 40 mol% is particularly preferable. If the content of the structural unit derived from a trivalent or higher polyvalent carboxylic acid is not less than the lower limit, the offset resistance on the high temperature side of the toner is more excellent.
- the content of the structural unit derived from a trivalent or higher polyvalent carboxylic acid is not more than the above upper limit, the formation of gel (solvent insoluble matter) can be suppressed, and the solvent solubility is more excellent. Further, the glossiness when used for color toners is also good.
- the content of the structural unit derived from the trihydric or higher polyhydric alcohol in the polyester resin (B) is 0.1 mol% or more with respect to the total number of moles (100 mol%) of the structural units derived from all the polycarboxylic acids. It is preferably 0.1 to 80 mol%, more preferably 1 to 45 mol%, particularly preferably 1 to 40 mol%.
- the content of the structural unit derived from a trihydric or higher polyhydric alcohol is not less than the lower limit, the offset resistance on the high temperature side of the toner is more excellent.
- the content of the structural unit derived from a trihydric or higher polyhydric alcohol is not more than the above upper limit, the formation of gel (solvent insoluble matter) can be suppressed, and the solvent solubility is more excellent. Further, the glossiness when used for color toners is also good.
- the polyester resin (A) and the polyester resin (B) are derived from polyvalent carboxylic acids having three or more valences. It is preferable that the content of the structural unit and / or the structural unit derived from a trihydric or higher polyhydric alcohol is different.
- the softening temperature of the polyester resin (B) is not particularly limited, and may be higher than 120 ° C. or 120 ° C. or lower.
- the softening temperature of the polyester resin (B) is preferably 120 ° C. or less, and more preferably 119 ° C. or less, from the viewpoint of low-temperature fixability of the toner and solvent solubility of the binder resin for toner.
- the softening temperature of the polyester resin (B) is preferably 75 ° C. or higher, and more preferably 80 ° C. or higher. Therefore, the softening temperature of the polyester resin (B) is preferably 75 to 120 ° C, more preferably 80 to 120 ° C.
- the polyester resin (A) and the polyester resin (B) preferably have different softening temperatures.
- the glass transition temperature (Tg) of the polyester resin (B) is preferably 35 to 85 ° C, more preferably 35 to 82 ° C. If Tg is not less than the lower limit of the range, the storage stability of the toner is more excellent, and if it is not more than the upper limit of the range, the low-temperature fixability of the toner is more excellent.
- the acid value of the polyester resin (B) is preferably 0.1 to 60 mgKOH / g, more preferably 0.1 to 50 mgKOH / g. If the acid value of the polyester resin (B) is not less than the lower limit of the above range, the reactivity of the resin tends to be improved, and if it is not more than the upper limit of the above range, the moisture resistance is more excellent.
- the weight average molecular weight (Mw) of the polyester resin (B) is preferably 500 to 1,000,000, and more preferably 500 to 800,000. If the Mw of the polyester resin (B) is not less than the lower limit of the above range, the durability is more excellent, and if it is not more than the upper limit of the above range, the pulverizability and solvent solubility of the toner binder resin are more excellent.
- the number average molecular weight (Mn) of the polyester resin (B) is preferably 500 to 100,000, and more preferably 500 to 50,000.
- the peak top molecular weight (Mp) of the polyester resin (B) is preferably 500 to 100,000, and more preferably 500 to 50,000.
- the THF-insoluble content of the polyester resin (B) is preferably 0 to 40% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 10% by mass.
- the polyester resin (B) can be produced by the same method as the polyester resin (A).
- binder resin other than the polyester resin (A) and the polyester resin (B) examples include polyester resins other than the polyester resin (A) and the polyester resin (B), cyclic olefin resins, styrene resins, and styrene- An acrylic resin, an acrylic resin, an epoxy resin, etc. are mentioned. Any of these may be used alone or in admixture of two or more. By using these resins and polyester resins in combination, the fixability tends to be improved.
- the mass ratio of the polyester resin (A) to the polyester resin (B) is 5:95 to 95: 5. 10:90 to 90:10 are more preferable, 25:75 to 75:25 are more preferable, and 40:60 to 60:40 are particularly preferable.
- the ratio of the polyester resin (A) is 5% by mass or more based on the total of the polyester resin (A) and the polyester resin (B)
- the toner binder resin tends to have better grindability and solvent solubility. In the case of 95% by mass or less, the storage stability of the toner under high humidity tends to be better.
- the content of the other binder resin is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, particularly preferably 20 parts by mass or less, with respect to 100 parts by mass in total of the polyester resin (A) and the polyester resin (B). preferable. If content of other binder resin is below the said upper limit, the effect by a polyester resin (A) and a polyester resin (B) will fully be exhibited.
- the hygroscopicity index of the binder resin for toner of the present invention is 2 or less, more preferably 1.8 or less, and particularly preferably 1.6 or less.
- the hygroscopicity index is less than or equal to the above upper limit value, the storage stability of the toner binder resin under high humidity conditions is excellent.
- the hygroscopic index is a value determined by the following measuring method.
- the polyester resin (A) and the polyester resin (B) are each pulverized to obtain a pulverized product.
- the pulverized product is sieved, passed through a 16 mesh (1.0 mm aperture) sieve, and 22 mesh (0. Particles that do not pass through a 71 mm) sieve are collected and dried in a vacuum dryer at 40 ° C. for 4 hours or more. After drying, each particle is dry blended at the same mass ratio as the polyester resin (A) and the polyester resin (B) in the toner binder resin, and the resulting mixture is weighed (X (g)).
- the hygroscopicity index of the binder resin for toner is adjusted by the content of structural units derived from isosorbide (isosorbide-derived carbon atom ratio) in the polyester resin (A), the mass ratio of the polyester resin (A) and the polyester resin (B), etc. it can.
- the binder resin for toner of the present invention has a THF insoluble content of 5% by mass or less, preferably 4% by mass or less, and particularly preferably 3% by mass or less. If the THF-insoluble content is less than or equal to the above upper limit, the solvent solubility of the binder resin for toner in an organic solvent (THF or the like) generally used for dissolving the polyester resin by a chemical method or the like is excellent. The lower the THF-insoluble content of the binder resin for toner, the better. The lower limit is not particularly limited. In the present invention, the THF-insoluble content is a value determined by the measurement method described in the examples described later.
- the THF-insoluble content of the binder resin for toner is the content of a structural unit derived from a trivalent or higher polyvalent carboxylic acid and / or a structural unit derived from a trihydric or higher polyhydric alcohol in each of the polyester resins (A) and (B).
- the degree of polymerization can be adjusted. For example, the lower the content of a structural unit derived from a trivalent or higher polyhydric carboxylic acid and / or a structural unit derived from a trivalent or higher polyhydric alcohol, there is a tendency for the THF-insoluble matter to decrease.
- the toner binder resin of the present invention described above has good pulverizability when the toner is produced through the pulverization step.
- the polyester resin (A) does not contain a structural unit derived from isosorbide. There is a tendency that a finer pulverized product is obtained. Therefore, when the toner is manufactured by the pulverization method, the pulverization energy necessary for miniaturization can be reduced.
- the time required for the dissolution can be reduced by previously pulverizing and refining the binder resin or the like to be dissolved in a solvent. Therefore, toner productivity is improved.
- the mixture containing the polyester resin (A) and the polyester resin (B) was melt-kneaded and thus obtained. The method of including the process of grind
- pulverizing a kneaded material is mentioned.
- the toner binder resin of the present invention has good solvent solubility when the toner is manufactured through the solvent dissolution step, and the gel (solvent insoluble) when the toner binder resin is dissolved in the organic solvent. Min) can be suppressed.
- the solvent solubility is better than when the polyester resin (A) does not contain a structural unit derived from isosorbide. Tend to be. Therefore, toner productivity is improved.
- a preferred embodiment of a toner production method using the toner binder resin of the present invention includes a method including a step of dissolving the toner binder resin of the present invention in an organic solvent.
- An example of a method including such a process is a chemical method.
- the toner obtained using the binder resin for toner of the present invention has excellent storage stability and is difficult to block even under high humidity conditions. According to the binder resin for toner of the present invention, the toner can be excellent in all of storage stability, low-temperature fixability, non-offset property and durability.
- the toner of the present invention contains the above-described binder resin for toner of the present invention.
- the toner of the present invention may further contain other components than the binder resin, if necessary.
- binder resin examples include a colorant, a charge control agent, a release agent, other additives other than these, and a magnetic material.
- the colorant is not particularly limited, but carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow, rhodamine dye, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo And disazo dyes, condensed azo dyes or pigments. These colorants can be used alone or in admixture of two or more. In the case of a full-color toner, benzidine yellow, monoazo dyes, condensed azo dyes, etc. can be used as yellow, quinacridone, rhodamine dyes, monoazo dyes, etc. as magenta, phthalocyanine blue, etc. as cyan. .
- the charge control agent is not particularly limited, but is a positive charge control agent such as a quaternary ammonium salt, a basic or electron donating organic substance; a metal chelate, a metal-containing dye, an acidic or electron withdrawing organic substance, etc. And a negative charge control agent.
- a positive charge control agent such as a quaternary ammonium salt, a basic or electron donating organic substance; a metal chelate, a metal-containing dye, an acidic or electron withdrawing organic substance, etc.
- a negative charge control agent In the case of a color toner, it is preferable that the charge control agent is colorless or light color from the viewpoint that there is no color tone problem on the toner.
- Examples of such a charge control agent include salicylic acid or alkylsalicylic acid chromium, zinc, aluminum And metal salts, metal complexes, amide compounds, phenol compounds, naphthol compounds, and the like.
- the release agent is not particularly limited, and can be appropriately selected from known release agents in consideration of toner releasability, storage stability, fixability, color developability, and the like.
- Examples of the release agent include carnauba wax, rice wax, beeswax, polypropylene wax, polyethylene wax, synthetic ester wax, paraffin wax, fatty acid amide, and silicone wax. Any of these may be used alone or in combinations of two or more.
- the melting point of the release agent is not particularly limited, and can be appropriately selected and used in consideration of the toner performance.
- additives include, but are not limited to, fluidity improvers (fluidity modifiers) such as fine powdered silica, alumina, titania; magnetite, ferrite, cerium oxide, strontium titanate, conductive titania, etc. Inorganic fine powders; Resistance adjusting agents such as styrene resins and acrylic resins; lubricants; These may be included as an internal additive or may be included as an external additive.
- fluidity improvers fluidity modifiers
- fluidity modifiers such as fine powdered silica, alumina, titania
- Inorganic fine powders Resistance adjusting agents such as styrene resins and acrylic resins
- lubricants These may be included as an internal additive or may be included as an external additive.
- the toner of the present invention can be used as any one of a magnetic one-component developer, a non-magnetic one-component developer, and a two-component developer.
- the toner of the present invention preferably contains a magnetic substance.
- the magnetic material include ferromagnetic alloys including iron, cobalt, nickel and the like, including ferrite and magnetite.
- the content of the binder resin for toner of the present invention is such that the total amount of the polyester resin (A) and the polyester resin (B) is 20% by mass or more based on the total amount of the toner (100% by mass). It is preferable that the amount is as follows.
- the total amount of the polyester resin (A) and the polyester resin (B) is more preferably 22% by mass or more, and further preferably 25% by mass or more.
- the total amount of the polyester resin (A) and the polyester resin (B) is equal to or more than the lower limit value, the effect as a binder resin for fixing the toner to the paper is sufficiently exerted, and the toner pulverization property, Storage stability, low-temperature fixability, non-offset property, and durability are improved.
- the upper limit of the content of the binder resin for toner of the present invention with respect to the total amount of toner can be appropriately set according to the content of other components optionally contained, and is not particularly limited, but is typically 95% by mass.
- the content thereof is not particularly limited, but it is 2 to 10% by mass with respect to the total amount of toner from the viewpoint of toner color tone, image density, and thermal characteristics. preferable.
- the content is not particularly limited, but it is preferably 0.5 to 5% by mass with respect to the total amount of toner.
- the content of the charge control agent is 0.5% by mass or more, the charge amount of the toner tends to be a sufficient level, and when the content is 5% by mass or less, a decrease in the charge amount due to aggregation of the charge control agent is suppressed. It tends to be.
- the content is not particularly limited, but from the viewpoint of the toner performance described above, it is preferably 0.3 to 15% by mass with respect to the total amount of toner.
- the lower limit of the content of the release agent is more preferably 1% by mass, and particularly preferably 2% by mass.
- the upper limit of the content of the release agent is more preferably 13% by mass, and particularly preferably 12% by mass. Therefore, the content of the release agent is more preferably 1 to 13% by mass, and particularly preferably 2 to 12% by mass with respect to the total amount of toner.
- the content is not particularly limited, but is preferably 0.05 to 10% by mass with respect to the total amount of the toner.
- the content of other additives is 0.05% by mass or more, a toner performance-modifying effect tends to be sufficiently obtained, and when it is 10% by mass or less, the image stability of the toner tends to be good. is there.
- the content is not particularly limited, but it greatly affects the pulverizability, and is preferably 3 to 70% by mass with respect to the total amount of toner.
- the content of the magnetic material is 3% by mass or more, the charge amount of the toner tends to be at a sufficient level, and when it is 70% by mass or less, the fixability and grindability of the toner tend to be good.
- the upper limit of the content of the magnetic material is more preferably 60% by mass, and particularly preferably 50% by mass. Therefore, the content of the magnetic substance is more preferably 3 to 60% by mass, and particularly preferably 3 to 50% by mass with respect to the total amount of toner.
- the average particle size of the toner of the present invention is not particularly limited, but is preferably 1 to 10 ⁇ m, and more preferably 3 to 8 ⁇ m. If the average particle diameter is not less than the lower limit of the above range, the toner productivity is excellent, and if it is not more than the upper limit, the image quality is improved. In addition, in this specification, an average particle diameter is a value measured with the measuring method mentioned later.
- the method for producing the toner of the present invention is not particularly limited, and a known method such as a pulverization method or a chemical method can be used.
- a step of melt-kneading a mixture containing the polyester resin (A) and the polyester resin (B) and pulverizing the obtained kneaded product (toner lump) is performed.
- the manufacturing method containing is mentioned.
- the mixture may contain other binder resins, colorants, charge control agents, release agents, other additives, magnetic materials, and the like.
- Melt kneading can be performed using a known kneader such as a twin screw extruder. The melt-kneading is typically performed under conditions of a set temperature of 100 to 200 ° C.
- the kneaded product can be pulverized using a known pulverizer such as a jet mill.
- the pulverization may be performed stepwise, such as coarse pulverization and then fine pulverization, or may be performed in one step.
- the obtained pulverized product may be classified.
- external addition treatment of inorganic particles or the like may be performed as necessary. Thereby, the toner of the present invention is obtained.
- a polyester resin (A), a polyester resin (B), and if necessary, other binder resins, colorants, charge control agents, release agents, Other additives, magnetic substances, etc. are dissolved or dispersed in an organic solvent, granulated in an aqueous medium, then the solvent is removed, washed and dried to obtain toner particles, and if necessary inorganic particles
- a method for obtaining a toner by performing an external addition treatment, etc. a polyester emulsion (A) and a polyester resin (B) are dissolved in a solvent, neutralized, then finely dispersed in water, and the solvent is removed to remove the solvent.
- ком ⁇ онентs Prepare other binder resin, colorant, charge control agent, release agent, aqueous fine dispersion of other additives as necessary, mix with these, agglomerate, coalesce, dehydrate, wash, Dry to obtain toner particles, and add inorganic particles as required.
- the solvent include tetrahydrofuran, ethyl acetate, methyl ethyl ketone, isopropyl alcohol and the like.
- the aqueous medium include water.
- a step of melting and kneading a mixture containing the polyester resin (A) and the polyester resin (B) and pulverizing the obtained kneaded product may be performed prior to dissolution or dispersion in a solvent.
- the polyester resin (A) and the polyester resin (B) are separately melt-kneaded before being dissolved or dispersed in a solvent, and then the obtained kneaded materials are mixed and the resulting mixture is pulverized. You may go.
- the toner production method of the present invention was obtained by melt-kneading a mixture containing the polyester resin (A) and the polyester resin (B) in view of the usefulness of excellent crushability of the binder resin for toner.
- a method including a step of pulverizing the kneaded product is preferable.
- a method including a step of dissolving the binder resin for toner in an organic solvent is preferable.
- the binder resin for toner of the present invention since the binder resin for toner of the present invention has excellent pulverizability, it has a small particle size and can efficiently dissolve the solvent. When the binder resin for toner is dissolved in the solvent, other components other than the binder resin may be dissolved or dispersed in the solvent.
- the toner of the present invention described above includes the binder resin for toner of the present invention, as described above, it is excellent in grindability, storage stability, low-temperature fixability, non-offset property and durability.
- the pulverizability of the kneaded product is good.
- the toner binder resin has good solubility in an organic solvent. Therefore, it is excellent in productivity in both processes.
- the toner of the present invention is suitably used for developing an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording method, electrostatic printing method and the like.
- the toner of the present invention can be used as any one of a magnetic one-component developer, a non-magnetic one-component developer, and a two-component developer. If the toner of the present invention contains a magnetic material, the toner of the present invention can be used as it is as a magnetic one-component developer. If the toner of the present invention does not contain a magnetic material, the toner of the present invention can be used as it is as a non-magnetic one-component developer. Further, if the toner of the present invention does not contain a magnetic material and a carrier is used in combination, it can be used as a two-component developer.
- a magnetic substance such as iron powder, magnetite powder or ferrite powder, those having a resin coating on the surface thereof, or a known material such as a magnetic carrier
- a coating resin for the resin coating carrier generally known styrene resins, acrylic resins, styrene acrylic copolymer resins, silicone resins, modified silicone resins, fluorine resins, mixtures of these resins, etc. Can be used.
- Glass transition temperature (Tg) Glass transition temperature
- 10 ⁇ 0.5 mg is filled in an aluminum cell, heated on a hot plate at 100 ° C. for 10 minutes, and the cell is brought into close contact with dry ice and rapidly cooled to 0 ° C. or lower.
- Intersection between the baseline on the low temperature side of the chart and the tangent line of the endothermic curve near the glass transition temperature when measured with a differential scanning calorimeter DSC-60 manufactured at a rate of 5 ° C / min. was determined, and the temperature was defined as Tg.
- Softening temperature Using a polyester resin as a measurement sample, a flow tester CFT-500 manufactured by Shimadzu Corporation was used and measured with a nozzle of 1 mm ⁇ ⁇ 10 mm at a constant rate of temperature increase with a load of 294 N (30 kgf) and a temperature increase rate of 3 ° C./min. Do. 1.0 g of the measurement sample is prepared. The temperature when the measurement sample was distilled 4 mm from the baseline was determined, and the temperature was defined as the softening temperature.
- Sample concentration 4 mg / 10 mL.
- Filtration conditions Filter sample solution with 0.45 ⁇ m Teflon (registered trademark) membrane filter. Flow rate: 1 mL / min. Injection volume: 0.1 mL.
- Detector Differential refractive index (RI) detector.
- THF insoluble matter of polyester resin About 100 g of polyester resin was weighed into a 100 mL Erlenmeyer flask (D (g)), 50 mL of THF was added, and the polyester resin was dissolved in a water bath set at 70 ° C. for 3 hours to prepare a THF solution. On the other hand, Celite 545 was tightly packed into the glass filter 1GP100 from the 6th to the 7th minute, dried for 3 hours or more in a dryer at 105 ° C., and weighed (E (g)). Subsequently, the THF solution in which the polyester resin was dissolved was transferred into the dried glass filter, and suction filtered.
- the polyester resin (A) and the polyester resin (B) are each pulverized to obtain a pulverized product.
- the pulverized product is sieved, passed through a 16 mesh (1.0 mm aperture) sieve, and 22 mesh (0. 71 mm) particles that do not pass through the sieve were collected and dried in a vacuum dryer at 40 ° C. for 4 hours or more. After drying, each particle was dry blended at the same mass ratio as that of the polyester resin (A) and the polyester resin (B) in the toner binder resin of each Example and Comparative Example, and the resulting mixture was weighed ( X (g)).
- THF-insoluble matter of the toner binder resin A 1 ⁇ A 2/100 + B 1 ⁇ B 2/100
- a 1 and B 1 represent the THF-insoluble content (mass%) of the polyester resin (A) and the polyester resin (B), respectively
- a 2 and B 2 represent the polyester resin (A) and the polyester resin, respectively.
- the ratio (mass%) of each of the polyester resin (A) and the polyester resin (B) when the total of (B) is 100 mass% is shown.
- ⁇ Toner Evaluation Method> Storage stability, condition 1, low humidity
- Storage stability condition 1, low humidity
- About 5 g of toner is weighed and placed in a sample bottle, which is left in a dryer maintained at 35 ° C. and 50% humidity for about 24 hours, and the degree of aggregation of the toner is evaluated for storage stability (blocking resistance). It was used as an index.
- the evaluation criteria were as follows. ⁇ (Very good): Disperse just by inverting the sample bottle. ⁇ (Good): Disperse when the sample bottle is turned upside down and tapped 2-3 times. ⁇ (Available): Disperse when the sample bottle is inverted and tapped 4-5 times.
- X Inferior: The sample bottle is inverted and does not disperse when tapped 5 times.
- ⁇ Toner Evaluation Method> Storage stability, condition 2, high humidity
- Storage stability condition 2, high humidity
- About 5 g of toner is weighed and placed in a sample bottle, which is left in a dryer maintained at 35 ° C. and humidity of 85% for about 24 hours, and the degree of toner aggregation is evaluated for storage stability (blocking resistance). It was used as an index.
- the evaluation criteria were as follows. ⁇ (Very good): Disperse just by inverting the sample bottle. ⁇ (Good): Disperse when the sample bottle is turned upside down and tapped 2-3 times.
- ⁇ (Available) Disperse when the sample bottle is inverted and tapped 4-5 times.
- X Inferior: The sample bottle is inverted and does not disperse when tapped 5 times.
- Hot offset resistance Using a printer that has a fixing roller not coated with silicone oil and that can change the roller temperature set at a roller speed of 30 mm / s, the test pattern has a toner concentration of 0.5 mg / cm 2 and a length of 4.5 cm.
- X A solid image of 15 cm in width was printed every 5 ° C of roller temperature.
- the minimum temperature at which the toner moves to the fixing roller due to the hot offset phenomenon during fixing is defined as the hot offset occurrence temperature, and the hot offset resistance (non-offset property) is determined using the following criteria.
- the pulverizability was evaluated by determining the residual ratio of the powder remaining on the mesh in the following procedure for the pulverized product obtained by finely pulverizing the toner soul to a particle size of 10 ⁇ m or less during the production of the toner.
- the pulverized product was sieved to obtain a powder that passed through 16 mesh but did not pass 22 mesh. 10.00 g (G (g)) of this classified powder was precisely weighed, ground for 10 minutes with a trioblender grinder (manufactured by Trio Science), and then passed through a 30-mesh sieve.
- the particle size and particle size distribution of the particles were measured using a laser diffraction type particle size measuring device (trade name: “LA-920” manufactured by Horiba, Ltd.). According to the operation manual of the measuring machine, using a measurement flow cell, add distilled water into the cell, select and set the relative refractive index to 1.20, set the particle size standard as the volume standard, adjust the optical axis, Fine adjustment and blank measurement were performed. Next, an aqueous dispersion of particles was added to a concentration ranging from 70 to 90%, and sonication was performed for 1 minute at an intensity of 5 to measure the particle size distribution of the particles. From the measured particle size distribution, the particle diameter (median diameter) corresponding to 50% of the cumulative volume distribution standard was taken as the average particle diameter.
- a laser diffraction type particle size measuring device trade name: “LA-920” manufactured by Horiba, Ltd.
- the condensation reaction was carried out while distilling the diol component from the reaction system.
- the viscosity of the reaction system increased with the reaction, the degree of vacuum was increased with the increase of the viscosity, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating a desired softening temperature. Then, when the predetermined torque was exhibited, stirring was stopped, the reaction system was returned to normal pressure, and the reaction product was taken out by pressurizing with nitrogen to obtain polyester resins A to E.
- Table 1 shows the physical property values of the obtained polyester resins A to E.
- the preparation composition of polyhydric carboxylic acid and polyhydric alcohol shown in Table 1 is a mole part of each component when the total number of moles of all acid components (all polyvalent carboxylic acids) is 100 mole parts.
- the “bisphenol A PO adduct” polyoxypropylene (2.3) -2,2-bis (4-hydroxyphenyl) propane was used.
- the isosorbide-derived carbon atom ratio is the ratio (%) of the number of carbon atoms contained in the structural unit derived from isosorbide to the total number of carbon atoms contained in the polyester resin.
- the content of the trivalent or higher monomer component with respect to the isosorbide-derived carbon atom ratio and the total number of moles of all acid components was calculated from the charged composition.
- Example 1 89 parts by mass of a polyester resin, 7 parts by mass of a quinacridone pigment (Clarient's HOSTAPARM PIN E, CI No .: Pigment Red 122), 3 parts by mass of Carnauba Wax No. 1 (manufactured by Toyo Adre), negative chargeability 1 part by weight of a charge control agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) was mixed with a Henschel mixer for 5 minutes to obtain a mixture.
- the obtained mixture was melt-kneaded with a biaxial kneader.
- the melt kneading was performed by setting the barrel 1 to 30 ° C., the barrel 2 to 60 ° C., the barrel 3 to 100 ° C., and the barrel 4 and the subsequent temperatures to 120 ° C.
- the toner soul was obtained by cooling.
- the obtained toner mass was pulverized to a particle size of 10 ⁇ m or less with a jet mill pulverizer to obtain a pulverized product.
- fine particles having a particle size of 3 ⁇ m or less were cut with a classifier to adjust the average particle size to 4 ⁇ m or more and 9 ⁇ m or less.
- Examples 2 to 3 Comparative Examples 1 to 4> A toner was obtained in the same manner as in Example 1 except that the composition of the binder resin for toner (the type of polyester resin and the ratio to the total mass (mass%)) was changed as shown in Table 2. The obtained toner was evaluated by the above-described evaluation method. The results are shown in Table 2.
- the toners of Examples 1 to 3 have good pulverization properties, and the pulverization properties of the binder resin for toner used for each toner were good. Further, these binder resins for toner had a THF insoluble content of 5% by mass and were excellent in solvent solubility. The toners of Examples 1 to 3 were excellent in storage stability, low-temperature fixability, hot offset resistance, and durability. In contrast, in Comparative Example 1, polyester resin A having a softening temperature exceeding 120 ° C. is used as a polyester resin containing an isosorbide component, and the THF-insoluble content of the toner binder resin is more than 5% by mass. The solvent solubility of the binder resin was poor.
- the grindability was inferior compared with Examples 1 to 3.
- Comparative Example 2 since the polyester resins D and E that do not contain an isosorbide component were combined, the pulverizability of the toner binder resin was poor.
- Comparative Example 3 the polyester resin A containing an isosorbide component and having a softening temperature of 120 ° C. or less is used alone, and the toner binder resin has a high hygroscopicity index, so that the storage stability of the toner under high humidity conditions is improved. It was bad.
- Comparative Example 4 since the polyester resin D not containing an isosorbide component was used alone, the grindability was poor.
- the toner binder resin of the present invention is used in the production of toner. According to the binder resin for toner of the present invention, a toner excellent in storage stability, low-temperature fixability, non-offset property, and durability can be obtained. Further, since the grindability and solvent solubility are excellent, the productivity of the toner can be increased.
- the toner of the present invention can be used for developing an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording method, electrostatic printing method and the like.
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Abstract
Description
本願は、2015年6月1日に、日本に出願された特願2015-111332号、2015年12月22日に、日本に出願された特願2015-249773号、および2015年12月22日に、日本に出願された特願2015-249774号に基づき優先権を主張し、その内容をここに援用する。
また、電子写真印刷法や静電荷現像法により画像を得るために用いられる装置は、加熱体である定着部を有し、装置内での温度が上昇するため、トナーは、ブロッキングしないこと、つまり保存安定性が必要である。
特にヒートローラーを用いる定着方式においては、省エネ化の観点から定着部の低温化が進み、トナーには、低温定着性が強く求められるようになってきた。加えて、装置のコンパクト化が進み、オイルを塗布しないローラーが用いられるようになってきており、トナーにはヒートローラーとの剥離性、つまり非オフセット性への要求が高まっている。
また、連続印刷時においても装置の汚れや印刷時へのカブリなどが見られないこと、すなわちトナーの耐久性が必要である。
例えば特許文献1には、低温定着性、耐ホットオフセット性、光沢性、耐久性および貯蔵安定性に優れたトナーが提案されている。
例えば特許文献2には、植物由来の原料成分を含むトナー用バインダー樹脂を用いたトナーが提案されている。
[1]イソソルバイド由来の構成単位を含み軟化温度が120℃以下であるポリエステル樹脂(A)と、前記ポリエステル樹脂(A)とは異なるポリエステル樹脂(B)とを含み、吸湿性指数が2以下、テトラヒドロフラン不溶分が5質量%以下である、トナー用バインダー樹脂。
[2]前記ポリエステル樹脂(A)に含まれる全炭素原子数に対するイソソルバイド由来の構成単位に含まれる炭素原子数の比率が0.1~30%である、[1]記載のトナー用バインダー樹脂。
[3]前記ポリエステル樹脂(A)が、三価以上の多価カルボン酸および三価以上の多価アルコールのいずれか一方または両方を、全酸成分の総モル数に対して0.1~80モル%の範囲で含む単量体混合物の重縮合物である、[1]または[2]に記載のトナー用バインダー樹脂。
[4]前記ポリエステル樹脂(B)の軟化温度が120℃以下である、[1]~[3]のいずれかに記載のトナー用バインダー樹脂。
[5]前記ポリエステル樹脂(B)に含まれる全炭素原子数に対するイソソルバイド由来の構成単位に含まれる炭素原子数の比率が1%未満である、[1]~[4]のいずれかに記載のトナー用バインダー樹脂。
[6]前記ポリエステル樹脂(A)と前記ポリエステル樹脂(B)との質量比が5:95~95:5である、[1]~[5]のいずれかに記載のトナー用バインダー樹脂。
[7]前記[1]~[6]のいずれかに記載のトナー用バインダー樹脂を含むトナー。
[8]前記[7]に記載のトナーの製造方法であって、
前記トナー用バインダー樹脂を有機溶剤に溶解する工程を含む、トナーの製造方法。
本発明のトナー用バインダー樹脂は、ポリエステル樹脂(A)と、ポリエステル樹脂(B)とを含む。
本発明のトナー用バインダー樹脂は、本発明の効果を損なわない範囲で、ポリエステル樹脂(A)およびポリエステル樹脂(B)以外の他のバインダー樹脂をさらに含んでもよい。
「ポリエステル樹脂」は、多価カルボン酸と多価アルコールとを含む単量体混合物の重縮合物であり、多価カルボン酸由来の構成単位と、多価アルコール由来の構成単位とを含む。
ポリエステル樹脂(A)は、多価アルコール由来の構成単位として、少なくともイソソルバイド由来の構成単位を含む。これにより、トナー用バインダー樹脂の粉砕性、溶剤溶解性が良好となる。
多価カルボン酸としては、テレフタル酸、イソフタル酸等の芳香族ジカルボン酸、三価以上の多価カルボン酸が好ましい。三価以上の多価カルボン酸としてはトリメリット酸またはその酸無水物が好ましい。
他の多価アルコールとしては、例えば、エチレングリコール、ネオペンチルグリコール、ポリエチレングリコール、1,2-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ジエチレングリコール、トリエチレングリコール、1,4-シクロヘキサンジメタノール、エリスリタン等の脂肪族ジオール;ポリオキシプロピレン(2.3)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシエチレン(2.0)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(2.0)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(2.2)-ポリオキシエチレン(2.0)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(6)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(2.4)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(3.3)-2,2-ビス(4-ヒドロキシフェニル)プロパン等の芳香族ジオール;ソルビトール、1,2,3,6-ヘキサテトラロール、1,4-ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、1,2,4-ブタントリオール、1,2,5-ペンタントリオール、グリセロール、2-メチル-1,2,3-プロパントリオール、2-メチル-1,2,4-ブタントリオール、トリメチロールプロパン、1,3,5-トリヒドロキシメチルベンゼン等の三価以上のアルコール;等が挙げられる。これらは植物由来物質、石油由来物質のいずれでもよく、いずれか1種を単独でまたは2種以上を組み合わせて使用することができる。
なお、ポリオキシエチレンまたはポリプロピレンの後に付された括弧内の数値は、オキシエチレン基またはオキシプロピレン基の平均付加モル数を示す。
他の多価アルコールとしては、エチレングリコール、ネオペンチルグリコール、1,2-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、1,4-シクロヘキサンジメタノール、ポリオキシエチレン(2.0)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(2.3)-2,2-ビス(4-ヒドロキシフェニル)プロパン、三価以上のアルコールが好ましい。三価以上のアルコールとしてはグリセリン、トリメチロールプロパンが好ましい。
一価アルコールとしては、ベンジルアルコール等の炭素数30以下の芳香族モノアルコール;オレイルアルコール、ラウリルアルコール、セチルアルコール、ステアリルアルコール、ベヘニルアルコール等の炭素数30以下の脂肪族モノアルコール;等が挙げられる。
一価のカルボン酸としては、安息香酸、p-メチル安息香酸、桂皮酸等の炭素数30以下の芳香族モノカルボン酸;ステアリン酸、ベヘン酸、オレイン酸、リノール酸、リノレン酸等の炭素数30以下の脂肪族カルボン酸;等が挙げられる。
トナーの保存安定性の観点から、ポリエステル樹脂(A)の軟化温度は、75℃以上が好ましく、80℃以上がより好ましい。
したがって、ポリエステル樹脂(A)の軟化温度は、75℃以上120℃以下が好ましく、80℃以上120℃以下がより好ましい。
ポリエステル樹脂の軟化温度は、後述する実施例に記載の方法により測定される。ポリエステル樹脂の軟化温度は、重合度、原料組成物やその比率等により調整できる。例えば重合度を高める方が、軟化温度が高い傾向がある。
ポリエステル樹脂のTgは、後述する実施例に記載の方法により測定される。ポリエステル樹脂のTgは、原料組成物やその比率、重合度等により調整できる。例えば、イソソルバイド由来の構成単位を多く含むほうが、Tgが高い傾向がある。
ポリエステル樹脂の酸価は、後述する実施例に記載の方法により測定される。
ポリエステル樹脂(A)の数平均分子量(Mn)は、500~100,000であることが好ましく、500~50,000がより好ましい。
ポリエステル樹脂(A)のピークトップ分子量(Mp)は、500~100,000であることが好ましく、500~50,000がより好ましい。
ポリエステル樹脂のMw、Mn、Mpはそれぞれ、ゲルパーミエーションクロマトグラフィー法により測定される標準ポリスチレン換算の値である。詳しくは、後述する実施例に記載の方法により測定される。
ポリエステル樹脂のTHF不溶分は、後述する実施例に記載の測定方法により測定される。
例えば単量体混合物中の全酸成分の総モル数に対するイソソルバイド由来の構成単位を含む物質の割合を0.1モル%以上とすれば、イソソルバイド由来の構成単位を、全ての多価カルボン酸由来の構成単位の総モル数に対して0.1モル%以上含むポリエステル樹脂が得られる。単量体混合物に含まれる全炭素原子数に対するイソソルバイド由来の構成単位を含む物質に含まれる炭素原子数の比率を0.1~30%とすれば、イソソルバイド由来炭素原子比率が0.1~30%であるポリエステル樹脂が得られる。
単量体混合物における全酸成分の総モル数(100モル%)に対する三価以上の単量体成分の含有量(モル%)は、得られるポリエステル樹脂における全ての多価カルボン酸由来の構成単位の総モル数(100モル%)に対する三価以上の単量体由来の構成単位の含有量(モル%)とほぼ同等である。
「全酸成分」とは、全ての多価カルボン酸の合計である。
重合温度は、特に制限されないが、180℃~280℃の範囲とするのが好ましい。重合温度が180℃以上の場合に、生産性が良好となる傾向にあり、280℃以下の場合に、樹脂の分解や、臭気の要因となる揮発分の副生成を抑制できる傾向にある。重合温度の下限値は200℃以上がより好ましく、220℃以上が特に好ましい。重合温度の上限値は270℃以下がより好ましい。
重合触媒としては、例えば、チタンテトラアルコキシド、酸化チタン、ジブチルスズオキシド、酢酸スズ、酢酸亜鉛、二硫化スズ、三酸化アンチモン、二酸化ゲルマニウム、酢酸マグネシウム、酢酸カルシウム等が挙げられる。これらのうち、チタンテトラアルコキシドは、特に反応速度を速める効果が大きいため、好ましい。
重縮合時における重合触媒の添加量は、全原料100質量部に対して0~0.2質量部が好ましい。
離型剤としては、後述する他の成分として挙げるものと同様のものが挙げられ、いずれか1種を単独でまたは2種以上を組み合わせて使用することができる。
重縮合時における離型剤の添加量は、本発明の効果を損なわない範囲で適宜設定できる。
重合終了後、内容物は装置から塊状で排出され、必要に応じて粉砕工程を経る。これにより、ポリエステル樹脂(A)が得られる。本発明におけるポリエステル樹脂(A)は粉砕性が良いため、効率よく細粒径まで粉砕することができる。
ポリエステル樹脂(B)は、ポリエステル樹脂(A)とは異なるポリエステル樹脂である。
ポリエステル樹脂(B)は、典型的には、軟化温度、イソソルバイド由来の構成単位の含有量、三価以上の多価カルボン酸由来の構成単位および/または三価以上の多価アルコール由来の構成単位の含有量のうち少なくとも1つがポリエステル樹脂(A)とは異なる。
多価カルボン酸、多価アルコール、一価アルコール、一価カルボン酸はそれぞれポリエステル樹脂(A)で挙げたものと同様のものが挙げられ、好ましい態様も同様である。ただしポリエステル樹脂(B)は、多価アルコール由来の構成単位として、イソソルバイド由来の構成単位を含んでもよく、含まなくてもよい。
したがって、ポリエステル樹脂(B)は、イソソルバイド由来の構成単位を含まない、またはイソソルバイド由来炭素原子比率が0%超1%未満(より好ましくは0%超0.3%未満)となる範囲でイソソルバイド由来の構成単位を含むものであることが好ましい。
ポリエステル樹脂(B)の軟化温度は、トナーの低温定着性およびトナー用バインダー樹脂の溶剤溶解性の観点から、120℃以下が好ましく、119℃以下がより好ましい。
ポリエステル樹脂(B)の軟化温度は、保存安定性の観点から、75℃以上が好ましく、80℃以上がより好ましい。
したがって、ポリエステル樹脂(B)の軟化温度は、75~120℃が好ましく、80~120℃がより好ましい。
ポリエステル樹脂(B)の数平均分子量(Mn)は、500~100,000であることが好ましく、500~50,000がより好ましい。
ポリエステル樹脂(B)のピークトップ分子量(Mp)は、500~100,000であることが好ましく、500~50,000がより好ましい。
ポリエステル樹脂(B)のTHF不溶分は、0~40質量%であることが好ましく、0~20質量%がより好ましく、0~10質量%がさらに好ましい。
ポリエステル樹脂(A)およびポリエステル樹脂(B)以外の他のバインダー樹脂としては、例えば、ポリエステル樹脂(A)およびポリエステル樹脂(B)以外の他のポリエステル樹脂、環状オレフィン樹脂、スチレン系樹脂、スチレン-アクリル系樹脂、アクリル系樹脂、エポキシ樹脂等が挙げられる。これらはいずれか1種を単独でまたは2種以上を混合して使用できる。これらの樹脂とポリエステル樹脂とを併用して使用することにより、定着性を向上させることができる傾向にある。
本発明のトナー用バインダー樹脂中、ポリエステル樹脂(A)とポリエステル樹脂(B)との質量比(ポリエステル樹脂(A):ポリエステル樹脂(B))は、5:95~95:5であることが好ましく、10:90~90:10がより好ましく、25:75~75:25がさらに好ましく、40:60~60:40が特に好ましい。ポリエステル樹脂(A)の比率が、ポリエステル樹脂(A)とポリエステル樹脂(B)の合計に対して5質量%以上の場合に、トナー用バインダー樹脂の粉砕性および溶剤溶解性がより良好となる傾向にあり、95質量%以下の場合に、トナーの高湿度下保存安定性がより良好となる傾向にある。
本発明のトナー用バインダー樹脂の吸湿性指数は、2以下であり、1.8以下がより好ましく、1.6以下が特に好ましい。吸湿性指数が前記上限値以下であれば、トナー用バインダー樹脂の高湿度条件下での保存安定性が優れる。
トナー用バインダー樹脂の粉砕性指数は低いほど好ましく、下限は特に限定されない。
(吸湿性指数の測定方法)
ポリエステル樹脂(A)およびポリエステル樹脂(B)を各々粉砕して粉砕物を得て、前記粉砕物を篩いにかけ、16メッシュ(目開き1.0mm)の篩を通過し22メッシュ(目開き0.71mm)の篩を通過しない粒子を分取し、40℃の真空乾燥機で4時間以上乾燥する。乾燥後、各粒子を、トナー用バインダー樹脂におけるポリエステル樹脂(A)とポリエステル樹脂(B)との質量比と同じ質量比でドライブレンドし、得られた混合物を秤量(X(g))する。前記混合物を、35℃、相対湿度85%の恒温恒湿機にて48時間放置した後、秤量(Y(g))し、以下の式により吸湿率(%)を算出する。以上の操作を3回行い、求めた吸湿率(%)の平均値を吸湿性指数とする。
吸湿率(%)=(Y-X)/X×100
本発明のトナー用バインダー樹脂のTHF不溶分は5質量%以下であり、4質量%以下が好ましく、3質量%以下が特に好ましい。THF不溶分が前記上限値以下であれば、ケミカル法等で一般にポリエステル樹脂の溶解に用いられている有機溶剤(THF等)に対するトナー用バインダー樹脂の溶剤溶解性が優れる。
トナー用バインダー樹脂のTHF不溶分は低いほど好ましく、下限は特に限定されない。
本発明において、THF不溶分とは、後述する実施例に記載の測定方法により求められる値である。
以上説明した本発明のトナー用バインダー樹脂にあっては、粉砕工程を経てトナーを製造する場合に、粉砕性が良好である。例えばポリエステル樹脂(A)とポリエステル樹脂(B)とを含む混合物を溶融混練し、得られた混練物を粉砕したときに、ポリエステル樹脂(A)がイソソルバイド由来の構成単位を含まない場合に比べて、より微細な粉砕物が得られる傾向がある。そのため、粉砕法によりトナーを製造する場合には、微細化のために必要な粉砕エネルギーを低減できる。また、ケミカル法によりトナーを製造する場合にも、溶剤に溶解させるバインダー樹脂等を予め粉砕して微細化しておくことで、その溶解に要する時間を低減できる。そのため、トナーの生産性が向上する。
上記効果を奏することから、本発明のトナー用バインダー樹脂を用いたトナーの製造方法の好ましい一態様として、ポリエステル樹脂(A)とポリエステル樹脂(B)とを含む混合物を溶融混練し、得られた混練物を粉砕する工程を含む方法が挙げられる。
上記効果を奏することから、本発明のトナー用バインダー樹脂を用いたトナーの製造方法の好ましい一態様として、本発明のトナー用バインダー樹脂を有機溶剤に溶解する工程を含む方法が挙げられる。このような工程を含む方法として、例えばケミカル法が挙げられる。
本発明のトナー用バインダー樹脂によれば、前記トナーを、保存安定性、低温定着性、非オフセット性および耐久性の全てに優れたものとすることもできる。
本発明のトナーは、前述の本発明のトナー用バインダー樹脂を含む。
本発明のトナーは、必要に応じて、バインダー樹脂以外の他の成分をさらに含んでもよい。
バインダー樹脂以外の他の成分としては、例えば、着色剤、荷電制御剤、離型剤、それら以外の他の添加剤、磁性体等が挙げられる。
離型剤の融点は特に制限されず、上記トナー性能を考慮して適宜選択して使用できる。
磁性1成分現像剤として用いられる場合には、本発明のトナーは、磁性体を含有することが好ましい。
磁性体としては、例えば、フェライト、マグネタイト等をはじめとする、鉄、コバルト、ニッケル等を含む強磁性の合金が挙げられる。また、その他、化合物や強磁性元素を含まないが、適当に熱処理することによって強磁性を表すようになる合金、例えば、マンガン-銅-アルミニウム、マンガン-銅-スズ等のマンガンと銅とを含む所謂ホイスラー合金、二酸化クロム等が挙げられる。
本発明のトナー中、本発明のトナー用バインダー樹脂の含有量は、ポリエステル樹脂(A)とポリエステル樹脂(B)との合計量が、トナーの全量(100質量%)に対して20質量%以上となる量であることが好ましい。ポリエステル樹脂(A)とポリエステル樹脂(B)との合計量は、22質量%以上がより好ましく、25質量%以上がさらに好ましい。ポリエステル樹脂(A)とポリエステル樹脂(B)との合計量が前記下限値以上であれば、紙にトナーが定着するためのバインダー樹脂としての効果が充分に発揮されるとともに、トナーの粉砕性、保存安定性、低温定着性、非オフセット性、耐久性がより優れたものとなる。
トナーの全量に対する本発明のトナー用バインダー樹脂の含有量の上限は、任意に含まれる他の成分の含有量に応じて適宜設定でき、特に限定されないが、典型的には95質量%である。
本発明のトナーの製造方法は、特に限定されず、粉砕法、ケミカル法等の公知の方法を利用できる。
前記混合物は、他のバインダー樹脂、着色剤、荷電制御剤、離型剤、他の添加剤、磁性体等を含んでもよい。溶融混練は、2軸押出機等の公知の混練機を用いて行うことができる。溶融混練は、典型的には、設定温度100~200℃の条件下で行われる。混練物の粉砕は、ジェットミル等の公知の粉砕機を用いて行うことができる。粉砕は、粗粉砕し、次いで微粉砕する等、段階的に行ってもよく、一段階で行ってもよい。粉砕後、得られた粉砕物を分級してもよい。粉砕または分級の後、必要に応じて、無機粒子の外添処理等を行ってもよい。これにより、本発明のトナーが得られる。
溶剤としては、例えばテトラヒドロフラン、酢酸エチル、メチルエチルケトン、イソプロピルアルコール等が挙げられる。水系媒体としては、例えば水等が挙げられる。
溶剤への溶解または分散の前に、ポリエステル樹脂(A)とポリエステル樹脂(B)とを含む混合物を溶融混練し、得られた混練物を粉砕する工程を行ってもよい。または溶剤への溶解または分散の前に、ポリエステル樹脂(A)およびポリエステル樹脂(B)を別々に溶融混練した後、得られた各々の混練物を混合し、得られた混合物を粉砕する工程を行ってもよい。
トナー用バインダー樹脂の溶剤溶解性が優れることの有用性の点では、トナー用バインダー樹脂を有機溶剤に溶解する工程を含む方法が好ましい。加えて、本発明のトナー用バインダー樹脂は粉砕性が優れるため小粒径であり、溶剤溶解を効率よく行うことができる。
トナー用バインダー樹脂を溶剤に溶解する際、バインダー樹脂以外の他の成分を溶剤に溶解または分散させてもよい。
以上説明した本発明のトナーにあっては、本発明のトナー用バインダー樹脂を含むため、上述したように、粉砕性、保存安定性、低温定着性、非オフセット性および耐久性に優れる。また、トナー用バインダー樹脂等を溶融混練し、得られた混練物を粉砕する工程を経てトナーを製造する場合に、混練物の粉砕性が良好である。加えて、ケミカル法において、トナー用バインダー樹脂を溶剤に溶解する工程を経てトナーを製造する場合に、トナー用バインダー樹脂の有機溶剤への溶解性が良好である。そのため、両工程において生産性に優れる。
本発明のトナーは、電子写真法、静電記録法や静電印刷法等において、静電荷像または磁気潜像の現像に好適に用いられる。
本発明のトナーは、磁性1成分現像剤、非磁性1成分現像剤、2成分現像剤の何れの現像剤としても使用できる。本発明のトナーが磁性体を含有していれば、本発明のトナーをそのまま磁性1成分現像剤として用いることができる。本発明のトナーが磁性体を含有していなければ、本発明のトナーをそのまま非磁性1成分現像剤として用いることができる。また、本発明のトナーとして磁性体を含有していないものと、キャリアとを併用すれば、2成分現像剤として用いることができる。
後述の各例で用いた評価方法は以下の通りである。
(ガラス転移温度(Tg))
ポリエステル樹脂について、アルミニウム製セルに10±0.5mgを充填し、100℃のホットプレート上にて10分間加熱させ、セルをドライアイスに密着させて0℃以下に急速冷却した後、島津製作所(株)製示差走差熱量計DSC-60を用い、昇温速度5℃/分で測定を行った時のチャートの低温側のベースラインと、ガラス転移温度近傍にある吸熱カーブの接線との交点の温度を求め、その温度をTgとした。
ポリエステル樹脂を測定サンプルとし、島津製作所(株)製フローテスターCFT-500を用い、1mmφ×10mmのノズルにより、荷重294N(30kgf)、昇温速度3℃/分の等速昇温下で測定を行う。測定サンプルは1.0g準備する。測定サンプルがベースラインより4mm留出したときの温度を求め、その温度を軟化温度とした。
ポリエステル樹脂約0.2gを枝付き三角フラスコ内に精秤し(A(g))、ベンジルアルコール20mLを加え、窒素雰囲気下として230℃のヒーターにて15分間加熱してポリエステル樹脂を溶解した。室温まで放冷後、クロロホルム20mL、フェノールフタレイン溶液数滴を加え、0.02規定のKOHベンジルアルコール溶液にて滴定した(滴定量=B(mL)、KOH溶液の力価=p)。ブランク測定を同様に行い(滴定量=C(mL))、以下の式に従ってポリエステル樹脂の酸価を算出した。
酸価(mgKOH/g)=(B-C)×0.02×56.11×p÷A
以下の条件で、ゲルパーミエーションクロマトグラフィー法により溶出曲線を得て、得られた溶出曲線のピーク値に相当する保持時間から、標準ポリスチレン換算により平均分子量(Mw、Mn、Mp)および分子量分散度(Mw/Mn)を求めた。
装置:東洋ソーダ工業(株)製、HLC8020。
カラム:東洋ソーダ工業(株)製、TSKgel(登録商標)GMHXL(カラムサイズ:7.8mm(内径)×30.0cm(長さ))を3本直列に連結したもの。
オーブン温度:40℃。
溶解液:テトラヒドロフラン(THF)。
試料濃度:4mg/10mL。
濾過条件:0.45μmテフロン(登録商標)メンブレンフィルターで試料溶液を濾過。
流速:1mL/分。
注入量:0.1mL。
検出器:示差屈折率(RI)検出器。
100mL三角フラスコにポリエステル樹脂を約0.5g秤量し(D(g))、THFを50mL加え、70℃に設定したウォーターバスに3時間浸けて前記ポリエステル樹脂を溶解し、THF溶液を調製した。一方、ガラスフィルター1GP100に6~7分目までセライト545をきつく充填し、105℃の乾燥機で3時間以上乾燥して秤量した(E(g))。
続いて、この乾燥したガラスフィルター内に、上記のポリエステル樹脂を溶解したTHF溶液を移して吸引ろ過した。アセトンを用いて三角フラスコの壁に残存した内容物をすべてガラスフィルター内に移し、ガラスフィルター内はアセトンを流して可溶分は吸引瓶に落とし、フィルター内に溶剤が残らないよう吸引を続けたのち、80℃の真空乾燥機で3時間以上乾燥して秤量した(F(g))。以下の式にてTHF不溶分(質量%)を算出した。
THF不溶分(質量%)=(F-E)/D ×100
ポリエステル樹脂(A)およびポリエステル樹脂(B)を各々粉砕して粉砕物を得て、前記粉砕物を篩いにかけ、16メッシュ(目開き1.0mm)の篩を通過し22メッシュ(目開き0.71mm)の篩を通過しない粒子を分取し、40℃の真空乾燥機で4時間以上乾燥した。乾燥後、各粒子を、各実施例および比較例のトナー用バインダー樹脂におけるポリエステル樹脂(A)とポリエステル樹脂(B)との質量比と同じ質量比でドライブレンドし、得られた混合物を秤量(X(g))した。前記混合物を、35℃、相対湿度85%の恒温恒湿機にて48時間放置した後、秤量(Y(g))し、以下の式により吸湿率(%)を算出した。以上の操作を3回行い、求めた吸湿率(%)の平均値を吸湿性指数とした。
吸湿率(%)=(Y-X)/X×100
各実施例および比較例で用いたポリエステル樹脂(A)およびポリエステル樹脂(B)それぞれのTHF不溶分(質量%)およびそれらの質量比から、以下の式によりトナー用バインダー樹脂のTHF不溶分(質量%)を算出した。
トナー用バインダー樹脂のTHF不溶分=A1×A2/100+B1×B2/100
ここで、A1およびB1はそれぞれ、ポリエステル樹脂(A)およびポリエステル樹脂(B)それぞれのTHF不溶分(質量%)を示し、A2およびB2はそれぞれ、ポリエステル樹脂(A)およびポリエステル樹脂(B)の合計を100質量%としたときのポリエステル樹脂(A)およびポリエステル樹脂(B)それぞれの割合(質量%)を示す。
(保存安定性、条件1、低湿度)
トナーを約5g秤量してサンプル瓶に投入し、これを35℃、湿度50%に保持された乾燥機に約24時間放置し、トナーの凝集程度を評価して保存安定性(耐ブロッキング性)の指標とした。評価基準を以下の通りとした。
◎(非常に良好):サンプル瓶を逆さにするだけで分散する。
○(良好) :サンプル瓶を逆さにし、2~3回叩くと分散する。
△(使用可能) :サンプル瓶を逆さにし、4~5回叩くと分散する。
×(劣る) :サンプル瓶を逆さにし、5回叩いた際に分散しない。
(保存安定性、条件2、高湿度)
トナーを約5g秤量してサンプル瓶に投入し、これを35℃、湿度85%に保持された乾燥機に約24時間放置し、トナーの凝集程度を評価して保存安定性(耐ブロッキング性)の指標とした。評価基準を以下の通りとした。
◎(非常に良好):サンプル瓶を逆さにするだけで分散する。
○(良好) :サンプル瓶を逆さにし、2~3回叩くと分散する。
△(使用可能) :サンプル瓶を逆さにし、4~5回叩くと分散する。
×(劣る) :サンプル瓶を逆さにし、5回叩いた際に分散しない。
シリコーンオイルが塗布されていない定着ローラーを有し、ローラー速度100mm/秒に設定した温度変更可能であるプリンター(カシオ計算機(株)製SPEEDIA(登録商標)N4-614)を用いて印刷を行い、低温定着性の評価を行った。具体的には、トナーを紙に定着させたときに、トナーが紙に定着し始めるときの最終温度を定着温度とし、次の基準で判定した。
◎(非常に良好):定着温度が140℃未満。
〇(良好) :定着温度が140℃以上150℃未満。
△(使用可能) :定着温度が150℃以上160℃未満。
×(劣る) :定着温度が160℃以上。
シリコーンオイルが塗布されていない定着ローラーを有し、ローラー速度30mm/sに設定したローラー温度変更可能であるプリンターを用いて、テストパターンとして0.5mg/cm2のトナー濃度にて縦4.5cm×横15cmのベタ画像を、ローラー温度5℃毎に印刷した。その際、定着時にホットオフセット現象により定着ローラーにトナーが移行するときの最低温度をホットオフセット発生温度と定め、以下の基準を用いて耐ホットオフセット性(非オフセット性)を判断した。
◎(非常に良好):ホットオフセット発生温度が200℃以上。
○(良好) :ホットオフセット発生温度が180℃以上200℃未満。
△(使用可能) :ホットオフセット発生温度が170℃以上180℃未満。
×(劣る) :ホットオフセット発生温度が170℃未満。
耐ホットオフセット性の評価と同様の方法にてテストパターンの印刷を一万枚行った後、ブレード癒着、印字面のカブリにより、以下の基準を用いて耐久性を評価した。
◎(非常に良好):ブレード癒着やカブリは認められない。
〇(良好) :ブレード癒着やカブリはごくわずかに見られる程度。
△(使用可能) :ブレード癒着やカブリは若干認められるが添加剤などにより改良可能。
×(劣る) :ブレード癒着やカブリが大いに見られる。
粉砕性は、トナーの製造時、トナー魂を粒子径10μm以下に微粉砕して得られた粉砕物について、以下の手順で、メッシュ上に残る粉体残存率を求めることで評価した。
粉砕物を篩いにかけ、16メッシュを通過し22メッシュを通過しない粉体を得た。この分級された粉体を10.00g(G(g))精秤し、トリオブレンダー粉砕器(トリオサイエンス社製)にて10分間粉砕した後、30メッシュの篩いにかけた。30メッシュの篩いを通過しない粉体の質量(H(g))を精秤し、次式により残存率を算出した。この操作を3回行い、それらを平均した値を、各例のトナーにおける残存率とした。
残存率(%)=(H/G)×100
◎(非常に良好):55%未満の残存率
〇(良好) :55%以上65%未満の残存率
△(使用可能) :65%以上75%未満の残存率
×(劣る) :75%以上の残存率
粒子の粒子径および粒度分布は、レーザ回折型粒径測定機((株)堀場製作所製、商品名:「LA-920」)を用いて測定した。該測定機の操作マニュアルに従い、測定用フローセルを用いて、セル内に蒸留水を加え、相対屈折率を1.20に選択設定し、粒径基準を体積基準にし、光軸の調整、光軸の微調整、ブランク測定を実施した。次に透過率70~90%の範囲になる濃度まで粒子の水分散液を添加し、超音波処理を強度5で1分間実施し、粒子の粒度分布測定を実施した。測定した粒度分布から、体積分布基準の累積50%に相当する粒子径(メジアン径)を平均粒子径とした。
表1に示す多価カルボン酸、多価アルコール、および全酸成分に対して500ppmのチタニウムアルコキサイドを、蒸留塔備え付けの反応容器に投入した。
次いで、反応容器中の攪拌翼の回転数を120rpmに保ち、昇温を開始し、反応系内の温度が265℃になるように加熱し、この温度を保持してエステル化反応を行った。エステル化反応が終了し反応系からの水の留出がなくなった後、反応系内の温度を下げて245℃に保ち、反応容器内を約40分かけて減圧し、真空度を133Paとし、反応系からジオール成分を留出させながら縮合反応を行った。
反応とともに反応系の粘度が上昇し、粘度上昇とともに真空度を上昇させ、攪拌翼のトルクが所望の軟化温度を示す値となるまで縮合反応を実施した。そして、所定のトルクを示した時点で撹拌を停止し、反応系を常圧に戻し、窒素により加圧して反応物を取り出し、ポリエステル樹脂A~Eを得た。得られたポリエステル樹脂A~Eの物性値を表1に示す。
「ビスフェノールA PO付加物」としては、ポリオキシプロピレン(2.3)-2,2-ビス(4-ヒドロキシフェニル)プロパンを使用した。
イソソルバイド由来炭素原子比率は、ポリエステル樹脂に含まれる全炭素原子数に対するイソソルバイド由来の構成単位に含まれる炭素原子数の比率(%)である。
イソソルバイド由来炭素原子比率、全酸成分の総モル数に対する三価以上の単量体成分の含有量はそれぞれ、仕込み組成から算出した。
ポリエステル樹脂89質量部と、キナクリドン顔料(クラリアント社製HOSTAPARM PINK E、C.I.番号:Pigment Red 122)7質量部と、カルナバワックス1号(東洋アドレ社製)3質量部と、負帯電性の荷電制御剤(日本カーリット社製LR-147)1質量部とを、ヘンシェルミキサーで5分間混合して混合物を得た。ポリエステル樹脂としては、上記で製造したポリエステル樹脂Aとポリエステル樹脂Dとを、A:D=50:50の質量比で使用した。すなわち、トナー用バインダー樹脂の総質量に対するポリエステル樹脂Aの比率を50質量%、ポリエステル樹脂Fの比率を50質量%とした。
得られたトナーについて、前述の評価方法による評価を行った。結果を表2に示す。
トナー用バインダー樹脂の組成(ポリエステル樹脂の種類と総質量に対する比率(質量%))を表2に示すとおりに変更した以外は、実施例1と同様の方法でトナーを得た。
得られたトナーについて、前述の評価方法による評価を行った。結果を表2に示す。
これに対し、比較例1では、イソソルバイド成分を含むポリエステル樹脂として軟化温度が120℃超のポリエステル樹脂Aを用いており、トナー用バインダー樹脂のTHF不溶分が5質量%超であるため、トナー用バインダー樹脂の溶剤溶解性が不良であった。また、実施例1~3に比べて粉砕性が劣っていた。
比較例2では、共にイソソルバイド成分を含まないポリエステル樹脂D、Eを組み合わせたため、トナー用バインダー樹脂の粉砕性が不良であった。
比較例3では、イソソルバイド成分を含み軟化温度が120℃以下のポリエステル樹脂Aを単独で用いており、トナー用バインダー樹脂の吸湿性指数が高いため、トナーの高湿度条件下での保存安定性が不良であった。
比較例4では、イソソルバイド成分を含まないポリエステル樹脂Dを単独で用いたため、粉砕性が不良であった。
本発明のトナーは、電子写真法、静電記録法や静電印刷法等において、静電荷像または磁気潜像の現像に用いることができる。
Claims (8)
- イソソルバイド由来の構成単位を含み軟化温度が120℃以下であるポリエステル樹脂(A)と、前記ポリエステル樹脂(A)とは異なるポリエステル樹脂(B)とを含み、吸湿性指数が2以下、テトラヒドロフラン不溶分が5質量%以下である、トナー用バインダー樹脂。
- 前記ポリエステル樹脂(A)に含まれる全炭素原子数に対するイソソルバイド由来の構成単位に含まれる炭素原子数の比率が0.1~30%である、請求項1記載のトナー用バインダー樹脂。
- 前記ポリエステル樹脂(A)が、三価以上の多価カルボン酸および三価以上の多価アルコールのいずれか一方または両方を、全酸成分の総モル数に対して0.1~80モル%の範囲で含む単量体混合物の重縮合物である、請求項1または2に記載のトナー用バインダー樹脂。
- 前記ポリエステル樹脂(B)の軟化温度が120℃以下である、請求項1~3のいずれか一項に記載のトナー用バインダー樹脂。
- 前記ポリエステル樹脂(B)に含まれる全炭素原子数に対するイソソルバイド由来の構成単位に含まれる炭素原子数の比率が1%未満である、請求項1~4のいずれか一項に記載のトナー用バインダー樹脂。
- 前記ポリエステル樹脂(A)と前記ポリエステル樹脂(B)との質量比が5:95~95:5である、請求項1~5のいずれか一項に記載のトナー用バインダー樹脂。
- 請求項1~6のいずれか一項に記載のトナー用バインダー樹脂を含むトナー。
- 請求項7に記載のトナーの製造方法であって、
前記トナー用バインダー樹脂を有機溶剤に溶解する工程を含む、トナーの製造方法。
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