WO2015182707A1 - ポリエステル樹脂、ポリエステル樹脂を含むトナー、およびポリエステル樹脂の製造方法 - Google Patents
ポリエステル樹脂、ポリエステル樹脂を含むトナー、およびポリエステル樹脂の製造方法 Download PDFInfo
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- WO2015182707A1 WO2015182707A1 PCT/JP2015/065417 JP2015065417W WO2015182707A1 WO 2015182707 A1 WO2015182707 A1 WO 2015182707A1 JP 2015065417 W JP2015065417 W JP 2015065417W WO 2015182707 A1 WO2015182707 A1 WO 2015182707A1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- WRYWBRATLBWSSG-UHFFFAOYSA-N naphthalene-1,2,4-tricarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 WRYWBRATLBWSSG-UHFFFAOYSA-N 0.000 description 1
- LATKICLYWYUXCN-UHFFFAOYSA-N naphthalene-1,3,6-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 LATKICLYWYUXCN-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WDAISVDZHKFVQP-UHFFFAOYSA-N octane-1,2,7,8-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)CCCCC(C(O)=O)CC(O)=O WDAISVDZHKFVQP-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
- G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
- G03G15/0822—Arrangements for preparing, mixing, supplying or dispensing developer
- G03G15/0865—Arrangements for supplying new developer
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a polyester resin used for developing an electrostatic charge image or a magnetic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, a toner containing the polyester resin, and a method for producing the polyester resin.
- the electrostatic charge image formed on the photosensitive member is developed with toner charged in advance by friction and then fixed.
- the fixing method there are a heat roller method in which a toner image obtained by development is fixed using a pressurized and heated roller, and a non-contact fixing method in which fixing is performed using an electric oven or flash beam light.
- the toner needs to maintain a stable charge amount first, and then needs to have good fixability to paper.
- the apparatus has a fixing unit which is a heating body, and the temperature in the apparatus rises, so that it is necessary that the toner does not block. Further, even during continuous printing, it is necessary that the apparatus is not soiled or fogged on the printing surface, that is, the durability of the toner 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 the ability to fix on a paper at a lower temperature, that is, the low temperature fixing property.
- a roller that does not apply a release agent is used, and there is an increasing demand for toner to be peelable from the heat roller, that is, offset resistance.
- Binder resin for toner has a great influence on the above-mentioned toner characteristics
- polystyrene resin, styrene-acrylic resin, polyester resin, epoxy resin, polyamide resin, etc. are known.
- a polyester resin which is excellent in fixing property at a low temperature and has a good performance balance has attracted attention.
- polyester resin for toner is desired to have both low temperature fixability and high temperature hot offset resistance.
- a trivalent or higher carboxylic acid component or alcohol component is used.
- the resin is designed to have a branched or crosslinked structure.
- polyester resins it has been studied to prevent resin coloring by using a metal-containing compound as a polymerization catalyst.
- Patent Document 1 discloses a polyester resin produced from a trivalent or higher carboxylic acid component, an alcohol component, a divalent carboxylic acid, an aromatic diol and an aliphatic diol, and the polyester resin by controlling the degree of vacuum. A method of manufacturing is described.
- Patent Document 2 describes that the metal content is reduced in order to prevent coloring of the polyester resin.
- the polyester resin described in Patent Document 1 uses a large amount of a bisphenol A derivative component, which is disadvantageous in terms of cost reduction. Moreover, in the method of patent document 1, since polycondensation time became long, productivity was inadequate.
- An object of the present invention is to solve the above-mentioned problems and to provide a crosslinked polyester resin having a raw material structure that is environmentally friendly and low in cost, in which the amount of bisphenol A derivative component is reduced.
- Another object of the present invention is to solve the problems in the conventional production method, and provide a polyester resin that is excellent in productivity, and that provides a toner having excellent storage stability, hot offset resistance, low-temperature fixability, and image stability. It is to provide a method of manufacturing.
- the gist of the present invention includes a trivalent or higher acid-derived component and a component derived from a bisphenol A alkylene oxide adduct, and 0.01 to 0.35 of a component derived from a bisphenol A alkylene oxide adduct with respect to 1 mol of all acid-derived components.
- a polyester resin, and a polyhydric alcohol and a polycarboxylic acid, in which the molar ratio is such that the ratio of acid value (mgKOH / g) to hydroxyl value (mgKOH / g) is acid value: hydroxyl value 1: 3 to 1:26
- a method for producing a polyester resin comprising polycondensing a monomer mixture containing an acid, wherein the monomer mixture comprises 0.01 to 0.35 mol of trivalent or higher acid component and 1 mol of total acid component.
- the number of carboxyl groups in the monomer mixture at the time of charging, and the hydroxyl acid in the monomer mixture at the time of charging .
- the ratio of the number of carboxyl groups: hydroxyl number 1: 1.13 to 1: 1.30, in the production method of the polyester resin.
- polyester resin according to [1] or [2], wherein the metal content derived from the polymerization catalyst is 20 ppm or less.
- a toner comprising the polyester resin according to any one of [1] to [3].
- the polyester resin of the present invention By using the polyester resin of the present invention, it is possible to provide an environmentally friendly and low-cost raw material polyester resin in which the amount of components derived from the bisphenol A alkylene oxide adduct is reduced, and a toner including the same.
- the production method of the present invention can provide a polyester resin from which a toner excellent in productivity, storage stability, hot offset resistance, low-temperature fixability, and image stability can be obtained.
- the polyester resin of the present invention is (i) a trivalent or higher acid-derived component and a bisphenol A alkylene oxide adduct-derived component; (ii) 0.01 to 0.35 mol of a component derived from a bisphenol A alkylene oxide adduct with respect to 1 mol of the total acid-derived component, (iii)
- the “trivalent or higher acid-derived component” of the polyester resin of the present invention is a component in the resin derived from the “trivalent or higher acid” used as a raw material, and the acid forms an ester bond with the alcohol component. Means a residue excluding the group leaving from the acid.
- the trivalent or higher acid is a trivalent carboxylic acid (R (—COOH) 3 ) and all carboxylic acids form an ester bond, (R— (CO) 3 ) Is a “trivalent or higher acid-derived component” in the resin.
- the “trivalent or higher acid” component that gives a “trivalent or higher acid-derived component” is an acid component having three or more hydrogens that can be released as H + in one molecule, or an ester or acid thereof.
- the acid is preferably a trivalent or higher aliphatic or aromatic carboxylic acid or an ester or acid anhydride thereof, preferably a trivalent or higher and a hexavalent or lower, more preferably a trivalent or tetravalent.
- the trivalent or higher aliphatic carboxylic acid may be linear, branched or cyclic, and examples thereof include aliphatic carboxylic acids having 1 to 10 carbon atoms.
- Examples of the aromatic carboxylic acid include aromatic carboxylic acids having 6 to 18 carbon atoms.
- trimellitic acid 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid or these Examples thereof include pyromellitic acid, 1,2,7,8-octanetetracarboxylic acid, and esters or acid anhydrides thereof. Trimellitic acid or its acid anhydride is preferred because it is easily available industrially. In the polyester resin of the present invention, by containing a trivalent or higher acid-derived component, the fixability and hot offset resistance of the toner containing the obtained polyester resin are improved.
- the amount of the trivalent or higher acid-derived component relative to 1 mol of the total acid-derived component of the polyester resin of the present invention is preferably 0.01 to 0.30 mol.
- the upper limit of the amount of the trivalent or higher acid-derived component relative to 1 mol of the total acid-derived component is more preferably 0.25 mol or less.
- the polyester resin of the present invention may further contain other polycarboxylic acid-derived components other than trivalent or higher acid-derived components.
- polyvalent carboxylic acids that give other polycarboxylic acid-derived components include terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, dibutyl isophthalate, Or aromatic dicarboxylic acid components such as these acid anhydrides; aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, or esters or acid anhydrides thereof An acid component or the like can be used.
- the amount of aromatic dicarboxylic acid used is not particularly limited, but it is preferably 0.6 to 0.9 mol per 1 mol of all acid components.
- the amount of the aromatic dicarboxylic acid used is 0.6 mol or more, the storage stability of the toner tends to be good and the resin strength tends to be improved.
- the lower limit of the usage-amount of aromatic dicarboxylic acid 0.7 mol or more is more preferable.
- Terephthalic acid and isophthalic acid are preferable in terms of handling properties and cost.
- the “bisphenol A alkylene oxide adduct-derived component” of the polyester resin of the present invention is a component in the resin derived from “bisphenol A alkylene oxide adduct” used as a raw material, and the alcohol has an ester bond with an acid component. It means a residue excluding a hydrogen atom that is eliminated during formation.
- the “bisphenol A alkylene oxide adduct” giving the “bisphenol A alkylene oxide adduct-derived component” is not particularly limited, and examples thereof include a propylene oxide adduct or an ethylene oxide adduct of bisphenol A. 6 is preferred.
- the polyester resin of the present invention contains 0.01 to 0.35 mol of a bisphenol A alkylene oxide adduct-derived component with respect to 1 mol of all the acid-derived components described above.
- the bisphenol A alkylene oxide adduct component is contained in an amount of 0.1 to 0.32 mol relative to 1 mol of the total acid-derived component, and more preferably, the bisphenol A alkylene oxide adduct is added to 1 mol of the total acid-derived component. Contains 0.15 to 0.3 moles of derived components.
- the polyester resin of the present invention may further contain other polyhydric alcohol-derived components derived from the bisphenol A alkylene oxide adduct-derived components.
- An aliphatic diol or the like can be used as the polyhydric alcohol that gives other polyhydric alcohol-derived components.
- Aliphatic diols include ethylene glycol, neopentyl glycol, propylene glycol, butanediol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, Examples include isosorbide. These can be used alone or in combination of two or more, and can also be used in combination of an aliphatic diol and an aromatic diol.
- trihydric or higher polyhydric alcohols can be used as long as the effects of the present invention are not impaired.
- a trihydric or higher polyhydric alcohol is preferable, and a trivalent or tetravalent polyhydric alcohol is more preferable.
- trihydric or higher polyhydric alcohol examples include sorbitol, 1,2,3,6-hexatetralol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolpropane, 1,3,5-trihydroxymethyl
- the softening temperature of the polyester resin of the present invention is preferably 120 to 150 ° C.
- the toner obtained when the softening temperature is 120 ° C. or higher tends to have good hot offset resistance. Further, when the softening temperature is 150 ° C. or lower, the toner fixing property tends to be good, and 145 ° C. or lower is more preferable.
- the polyester resin of the present invention is preferably amorphous in consideration of the performance of the toner as a binder resin. Therefore, it is preferable to adjust appropriately the kind and ratio of each raw material component.
- the polyester resin of the present invention preferably has a metal content derived from the polymerization catalyst of 20 ppm or less. Such a polyester resin can be obtained by polymerization without using a polymerization catalyst or by using a very small amount of polymerization catalyst.
- the glass transition temperature (hereinafter referred to as Tg) of the polyester resin of the present invention is not particularly limited, but is preferably 45 to 65 ° C.
- Tg is 45 ° C. or higher, the blocking resistance of the toner tends to be good, and when it is 65 ° C. or lower, the fixability of the toner tends to be good.
- the lower limit of Tg 48 degreeC or more is more preferable.
- the glass transition temperature is obtained by using a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation and a graph showing an endothermic curve near the glass transition temperature and the baseline of the chart when measured at a heating rate of 5 ° C./min. The temperature at the intersection with the tangent was determined.
- the acid value of the amorphous polyester resin for toner of the present invention is not particularly limited, but is preferably 20 mgKOH / g or less. When the acid value is 20 mgKOH / g or less, the image density of the toner tends to be stable.
- the upper limit of the acid value of the polyester resin is more preferably 15 mgKOH / g or less, and particularly preferably 12 mgKOH / g or less.
- the hydroxyl value of the amorphous polyester resin for toner of the present invention is not particularly limited, but is preferably 70 mgKOH / g or less. This is because if it exceeds 70 mgKOH / g, storage stability and hot offset resistance tend to be lowered.
- the hydroxyl value is a value measured as follows. About 0.5 g of sample is precisely weighed into a 100 ml conical stoppered flask (Wg), 20 ml of acetylating agent (5 ml of acetic anhydride mixed with 500 ml of pyridine) is added, and immersed in a water bath at 95 ° C. or higher for 1 hour. The sample was heated to acetylate the hydroxyl group in the sample.
- the method for producing a polyester resin of the present invention comprises polycondensing a monomer mixture containing a polyhydric alcohol and a polycarboxylic acid, and the monomer mixture is composed of a trivalent or higher acid component and 1 mol of the total acid component.
- the ratio of the number of carboxyl groups in the monomer mixture at the time of charging to the number of hydroxyl groups in the monomer mixture at the time of charging is 0.01 to 0.35 mol of bisphenol A alkylene oxide adduct. The number is 1: 1.13 to 1: 1.30.
- polyhydric alcohol polyhydric alcohol
- polycarboxylic acid trivalent or higher acid component
- bisphenol A alkylene oxide adduct in the production method of the present invention are as described above for the polyester resin.
- the monomer mixture in the method for producing a polyester resin of the present invention contains 0.01 to 0.35 mol of a bisphenol A alkylene oxide adduct with respect to 1 mol of the total acid component.
- the bisphenol A alkylene oxide adduct component is contained in an amount of 0.1 to 0.32 mol per mol of the total acid component, and more preferably, the bisphenol A alkylene oxide adduct component is 0 mol per mol of the total acid component. .Contains 15 to 0.3 mol.
- the ratio of the number of carboxyl groups in the monomer mixture at the time of charging to the number of hydroxyl groups in the monomer mixture at the time of charging is 1.13 to 1.30.
- the number of carboxyl groups is calculated in the same manner as when the acid anhydride is used, as well as when the acid anhydride is not used. Further, the number of hydroxyl groups does not include an OH group present in the carboxyl group.
- the number of hydroxyl groups is 1.13 or more when the number of carboxyl groups is 1, the gelation during the polycondensation reaction can be easily controlled and the fixability of the obtained toner tends to be good. Further, when it is 1.30 or less, the reactivity tends to be good and the storage stability of the obtained toner tends to be good. 1.28 or less is more preferable.
- the amount of the trivalent or higher acid component relative to 1 mol of the total acid component is preferably 0.01 to 0.30 mol.
- the amount is 0.01 mol or more, the fixability and hot offset resistance of the obtained toner are good, and when the amount is 0.30 mol part or less, the preservability is good and the gelation occurs during the polycondensation reaction. This is because the reaction can be easily controlled.
- the upper limit of the quantity of the trivalent or more acid component with respect to 1 mol of all the acid components 0.25 mol or less is more preferable.
- the amount of the bisphenol A alkylene oxide adduct in the monomer mixture is 3 mol with respect to 100 mol parts of the monomer mixture from the viewpoint of storage stability, durability, and crystallinity suppression. In terms of reactivity and cost, the amount is preferably 15 parts by mole or less, and more preferably 13 parts by mole or less.
- the lower limit of the amount of the bisphenol A alkylene oxide adduct in 100 mole parts of the monomer mixture is more preferably 5 mole parts or more, and still more preferably 8 mole parts or more.
- the amount of the aromatic dicarboxylic acid used is not particularly limited, but it is preferably 0.06 to 0.090 mol based on 1 mol of the total acid component.
- the amount of the aromatic dicarboxylic acid used is 0.06 mol or more, the storage stability of the toner tends to be good and the resin strength tends to be improved.
- the lower limit of the usage-amount of aromatic dicarboxylic acid 0.07 mol or more is more preferable.
- Terephthalic acid and isophthalic acid are preferable in terms of handling properties and cost.
- a known method may be used as a polymerization reaction method in the method for producing a polyester resin of the present invention.
- a monomer mixture containing a polyhydric alcohol, a polyvalent carboxylic acid and a lower alkyl ester thereof is charged into a reaction vessel, There is a method in which water or lower alkyl alcohol is distilled off by esterification reaction or transesterification reaction, and then the degree of polymerization is increased while removing glycol by polycondensation reaction to obtain a resin.
- the esterification reaction or transesterification temperature is preferably 240 ° C. to 280 ° C. It is because productivity improves by setting it as 240 degreeC or more, and 255 degreeC or more is more preferable. Moreover, when it is 280 degrees C or less, it exists in the tendency which can suppress decomposition
- the temperature of the polycondensation reaction is preferably 220 ° C to 250 ° C. This is because when the temperature of the polycondensation reaction is 220 ° C. or higher, the productivity tends to be good. When the temperature is 250 ° C. or lower, the decomposition of the resin can be suppressed, and the productivity can be improved. This is because there is a tendency to suppress the by-product of volatile matter that is a factor.
- the polycondensation reaction temperature in consideration of the raw material composition ratio and the like.
- Polycondensation reaction in the case of a composition ratio with a superior reactivity, such as a small amount of bisphenol A alkylene oxide adduct, a large amount of trivalent or higher acid component, and a small number of hydroxyl groups when the number of carboxyl groups is 1. If the composition ratio is low and the composition ratio is inferior in reactivity, it is effective to set the polycondensation reaction temperature high.
- titanium catalyst such as titanium tetraalkoxide, titanium oxide, tin catalyst such as dibutyltin oxide, stannous oxide, tin 2-ethylhexanoate, tin acetate, tin disulfide, zinc acetate, trioxide
- a catalyst such as antimony, germanium dioxide, or magnesium acetate can be used.
- a polymerization catalyst it is preferably carried out in an amount of 20 ppm or less, more preferably 15 ppm or less, based on the amount of the monomer mixed substance.
- the reactivity during the polycondensation reaction can be ensured without using a polymerization catalyst, and the desired polycondensation time is in the range of 20 to 120 minutes. This resin can be obtained.
- the polyester resin of the present invention can be used as a main component of the toner binder or blended with other toner binder resins.
- a binder resin other than the polyester resin of the present invention for example, a polyester resin other than the polyester resin of the present invention, a styrene resin, a styrene-acrylic resin, a cyclic olefin resin, a methacrylic acid resin, an epoxy Resin etc. can be mentioned, and can be used individually or in mixture of 2 or more types in the range which does not impair the effect of this invention.
- colorant at the time of toner formation carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dye, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, Examples thereof include monoazo, disazo, condensed azo dyes and pigments. These dyes and pigments can be used alone or in admixture of two or more. In the case of a full color toner, yellow includes benzidine yellow, monoazo dyes and dyes, condensed azo dyes and the like, magenta includes quinacridone, rhodamine dyes and monoazo dyes, and cyan includes phthalocyanine blue and the like.
- the content of the colorant is preferably 2 to 10% by mass in the toner from the viewpoint of toner color tone, image density, and thermal characteristics.
- the charge control agent examples include a quaternary ammonium salt as a positive charge control agent and a basic or electron donating organic substance, and as a negative charge control agent, a metal chelate, a metal-containing dye, an acid or electron withdrawing property. Organic materials and the like.
- the charge control agent is colorless or light color and does not cause any color tone problems on the toner.
- Examples include metal salts, metal complexes, amides of salicylic acid or alkylsalicylic acid with chromium, zinc, aluminum, etc. A compound, a phenol compound, a naphthol compound, etc. are mentioned.
- a vinyl polymer having a styrene, acrylic acid, methacrylic acid or sulfonic acid group may be used as the charge control agent.
- the content of the charge control agent is preferably 0.5 to 5% by mass in the 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 release agent to be added to the toner include carnauba wax, rice wax, montan wax, beeswax, polypropylene wax, polyethylene wax, synthetic ester wax, paraffin wax, fatty acid amide, silicone wax and the like. Each can be used alone or in combination of two or more.
- the content of the releasing agent is preferably 0.3 to 15% by mass in the toner because it affects the releasing effect of the toner, storage stability, fixing property, color developing property and the like.
- the lower limit of the content of the release agent is more preferably 1% by mass or more, and particularly preferably 2% by mass or more.
- the upper limit value of the content of the release agent is more preferably 13% by mass or less, and particularly preferably 10% by mass or less.
- additives such as flow modifiers include fine powder silica, alumina, titania and other fluidity improvers, magnetite, ferrite, cerium oxide, strontium titanate, conductive fine titanic inorganic powder, styrene resin, Examples thereof include resistance adjusting agents such as acrylic resins, lubricants, and the like, and these are used as an internal additive or an external additive.
- the content of these additives is not particularly limited, but is preferably 0.05 to 10% by mass in the toner.
- the content of these 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 evaluation method of resin shown by a present Example is as follows.
- 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 hit 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.
- the density measurement part is vertically valley-folded, and a protective paper is placed on the folded part, and a 1 kg weight is slid to the folding part 5 times to make a crease, followed by a mountain fold at the same crease, and then folded from above A 1 kg weight was slid to the part 5 times.
- the test paper was stretched, cellophane tape (Nitto Denko CS System No. 29) was affixed to the bent part, traced 5 times, and then slowly peeled off, and the image density was measured with a Macbeth image densitometer.
- Fixing rate image density after test / image density before test ⁇ 100 (%) ⁇ (Very good): Fixing rate of 85% or more ⁇ (Good): Fixing rate of 75% or more and less than 85% x (Inferior): Fixation rate of less than 75% or an offset phenomenon occurs at 145 ° C and cannot be measured
- Hot offset resistance 0.5 mg / cm 2 toner as a test pattern using a printer having a fixing roller not coated with silicone oil and capable of changing the roller temperature set to a roller speed of 30 mm / s
- 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.
- the hot-offset resistance was judged using the above criteria. ⁇ (Very good): Hot offset does not occur at 200 ° C ⁇ (Good): Hot offset generation temperature exceeds 185 ° C and 200 ° C or less x (Inferior): Hot offset generation temperature is 185 ° C or less
- Example 1 Polyhydric carboxylic acid and polyhydric alcohol having the charge composition shown in Table 1 were charged into a reaction vessel equipped with a distillation column. Subsequently, the rotation speed of the stirring blade in the reaction vessel was maintained at 200 rpm, and the temperature increase was started. The temperature in the reaction system was heated to 265 ° C. to maintain this temperature. The esterification reaction was carried out until no water was distilled from the reaction system.
- the temperature in the reaction system is lowered and adjusted to the polycondensation temperature shown in Table 1, the degree of vacuum is reduced to 1 kPa or less over the reaction vessel over about 20 minutes, and the condensation polymerization reaction is conducted while distilling the diol component from the reaction system. Went.
- the reaction was continued while maintaining a high vacuum state, and the polycondensation reaction was carried out until the viscosity of the reaction system increased as the degree of polymerization increased, and the torque of the stirring blade reached a value indicating the desired softening temperature. And stirring was stopped when the predetermined torque was shown.
- the reaction system was returned to normal pressure by introducing nitrogen, pressurized with nitrogen, the reaction product was taken out from the bottom of the reactor, and cooled to obtain a polyester resin.
- the characteristic values of the obtained polyester resin are shown in Table 1.
- Example 2 (Example 2) to (Example 7), (Comparative Example 3) A polyester resin was obtained in the same manner as in Example 1 except that the components charged in the reaction vessel were changed as shown in Table 1. The characteristic values and evaluation results of the obtained resin are shown in Table 1.
- polyester resin when a polyester resin is produced by setting the ratio of the number of carboxyl groups in the monomer mixture at the time of charging to the number of hydroxyl groups in the monomer mixture at the time of charging from 1: 1.13 to 1: 1.30, the polyester resin is stored.
- the stability, low-temperature fixing, hot offset resistance, and image stability were all usable or good (Examples 1 to 7).
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Abstract
Description
〔1〕
三価以上の酸由来成分およびビスフェノールAアルキレンオキサイド付加物由来成分を含み、
全酸由来成分1モルに対してビスフェノールAアルキレンオキサイド付加物由来成分を0.01~0.35モル含み、
酸価(mgKOH/g)と水酸基価(mgKOH/g)の比が、酸価:水酸基価=1:3~1:26である、ポリエステル樹脂。
〔2〕
前記三価以上の酸由来成分の含有量が、全酸由来成分1モル中0.01~0.30モルである、前記〔1〕記載のポリエステル樹脂。
〔3〕
重合触媒由来の金属含有量が20ppm以下である、前記〔1〕または〔2〕記載のポリエステル樹脂。
〔4〕
前記〔1〕から〔3〕のいずれかに記載のポリエステル樹脂を含むトナー。
〔5〕
多価アルコールと多価カルボン酸を含むモノマー混合物を重縮合する事を含むポリエステル樹脂の製造方法であって、
前記モノマー混合物が、三価以上の酸成分と、全酸成分1モルに対して0.01~0.35モルのビスフェノールAアルキレンオキサイド付加物を含み、
仕込み時の前記モノマー混合物中のカルボキシル基数と水酸基数との比が、カルボキシル基数:水酸基数=1:1.13~1:1.30である、ポリエステル樹脂の製造方法。
〔6〕
前記三価以上の酸成分の含有量が、全酸成分1モル中に0.01~0.30モルである、前記〔5〕記載のポリエステル樹脂の製造方法。
〔7〕
重合触媒20ppm以下の条件で重合する、前記〔5〕または〔6〕に記載のポリエステル樹脂の製造方法。
また、本発明の製造方法により、生産性に優れ、保存安定性、耐ホットオフセット性、低温定着性、画像安定性に優れたトナーが得られるポリエステル樹脂を得ることができる。
本発明のポリエステル樹脂は、
(i) 三価以上の酸由来成分およびビスフェノールAアルキレンオキサイド付加物由来成分を含み、
(ii) 全酸由来成分1モルに対してビスフェノールAアルキレンオキサイド付加物由来成分を0.01~0.35モル含み、
(iii) 酸価(mgKOH/g)と水酸基価(mgKOH/g)の比が、酸価:水酸基価=1:3~1:26である。
「三価以上の酸由来成分」を与える「三価以上の酸」成分とは、1分子中にH+として放出することができる水素を3個以上持っている酸成分またはこれらのエステルもしくは酸無水物である。酸としては三価以上の脂肪族あるいは芳香族カルボン酸またはこれらのエステルもしくは酸無水物が好ましく、三価以上六価以下であることが好ましく、三価あるいは四価であることがさらに好ましい。三価以上の脂肪族カルボン酸としては、直鎖、分岐鎖あるいは環状のいずれであってもよく、炭素数1~10の脂肪族カルボン酸を挙げることができる。芳香族カルボン酸としては炭素数6~18の芳香族カルボン酸を挙げることができる。
具体例としては、トリメリット酸、1,2,4-シクロヘキサントリカルボン酸、2,5,7-ナフタレントリカルボン酸、1,2,4-ナフタレントリカルボン酸、1,2,5-ヘキサントリカルボン酸またはこれらのエステルもしくは酸無水物等、ピロメリット酸、1,2,7,8-オクタンテトラカルボン酸、またはこれらのエステルもしくは酸無水物等が挙げられる。工業的に入手が容易な点でトリメリット酸またはその酸無水物が好ましい。
本発明のポリエステル樹脂においては、三価以上の酸由来成分を含むことで、得られたポリエステル樹脂を含むトナーの定着性、耐ホットオフセット性が良好となる。
水酸基価は次のとおり測定した値である。サンプル約0.5gを100mlの共栓付三角フラスコに精秤し(Wg)、アセチル化剤(無水酢酸5mlをピリジン500mlに混合したもの)20mlを加え、95℃以上の水浴に浸して1時間加熱しサンプル中の水酸基をアセチル化した。続いて、水浴から出して放冷し、残った無水酢酸を分解するために水5mlを加えた。指示薬としてフェノールフタレインを数滴加え、0.2N KOHにて滴定し、薄くピンク色に着色した滴定量を記録した(As(ml))。ブランクとして、サンプルを加えない以外は同様に測定を行って滴定量を記録し(Ab(ml))、次式に基づいて水酸基価を求めた。
〔式1〕
f:0.2N KOHのファクター
本発明のポリエステル樹脂の製造方法は、多価アルコールと多価カルボン酸を含むモノマー混合物を重縮合することを含み、前記モノマー混合物が、三価以上の酸成分と、全酸成分1モルに対して0.01~0.35モルのビスフェノールAアルキレンオキサイド付加物を含み、仕込み時の前記モノマー混合物中のカルボキシル基数と、仕込み時の前記モノマー混合物中の水酸基数との比が、カルボキシル基数:水酸基数=1:1.13~1:1.30である、製造方法である。
前記モノマー混合物100モル部中のビスフェノールAのアルキレンオキサイド付加物の量の下限値は5モル部以上がより好ましく、8モル部以上がさらに好ましい。
上述の組成においては、重縮合反応の温度を適切に設定することで、重合触媒を用いずとも重縮合反応時の反応性を確保することができ、重縮合時間20~120分の範囲で所望の樹脂を得ることができる。
次に、本発明のポリエステル樹脂を含むトナーについて説明する。
トナー化の際に添加する離型剤としては、カルナバワックス、ライスワックス、モンタンワックス、蜜蝋、ポリプロピレン系ワックス、ポリエチレン系ワックス、合成エステル系ワックス、パラフィンワックス、脂肪酸アミド、シリコーン系ワックス等を挙げることができ、それぞれ単独でまたは2種以上を組み合わせて使用することができる。
(A)樹脂の評価方法
(1)ガラス転移温度(Tg)
島津製作所(株)製示差走差熱量計DSC-60を用いて、昇温速度5℃/分で測定した時のチャート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た。
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した時、サンプル1.0g中の1/2が流出した温度を求めた。
サンプル約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分加熱し樹脂を溶解した。室温まで放冷後、クロロホルム20ml、指示薬としてクレゾールレッド溶液数滴を加え、0.02規定のKOH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))、以下の式に従って算出した。
酸価(mgKOH/g)=(B-C)×0.02×56.11×p÷A
サンプル約0.5gを100mlの共栓付三角フラスコに精秤し(Wg)、アセチル化剤(無水酢酸5mlをピリジン500mlに混合したもの)20mlを加え、95℃以上の水浴に浸して1時間加熱しサンプル中の水酸基をアセチル化した。続いて、水浴から出して放冷し、残った無水酢酸を分解するために水5mlを加えた。指示薬としてフェノールフタレインを数滴加え、0.2N KOHにて滴定し、薄くピンク色に着色した滴定量を記録した(As(ml))。ブランクとして、サンプルを加えない以外は同様に測定を行って滴定量を記録し(Ab(ml))、次式に基づいて水酸基価を求めた。
〔式2〕
f:0.2N KOHのファクター
(5)保存安定性
トナーを約5g秤量してサンプル瓶に投入し、これを50℃に保温された乾燥機に24時間放置し、トナーの凝集の程度を評価して耐ブロッキング性の指標とした。評価基準は以下のとおりとした。
◎(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、ローラー速度を100mm/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のベタ画像を作成し、定着ローラーの温度を145℃に設定して定着させた。このテストパターン画像に対し、マクベス社製画像濃度計にて画像濃度を測定して記録した。
定着率=試験後の画像濃度/試験前の画像濃度 ×100 (%)
◎(非常に良好):85%以上の定着率
○(良好):75%以上85%未満の定着率
×(劣る):75%未満の定着率または145℃でオフセット現象が発生し測定不可
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を判断した。
◎(非常に良好) :200℃でホットオフセットが発生しない
○(良好) :ホットオフセット発生温度が185℃を超え200℃以下
×(劣る) :ホットオフセット発生温度が185℃以下
25℃、80RH%の環境下において、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のベタ画像を定着温度170℃で連続印刷し、1枚目と5000枚目の画像の変化を目視にて以下の条件で評価した。
○(良好) :画像濃度に変化がない、または影響が少ない。
△(使用可能限界):画像濃度に変化があり、添加剤による改良で使用できる限界である。
×(劣る) :画像濃度が大きく変化する。
表1に示す仕込み組成の多価カルボン酸、多価アルコール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200rpm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た。反応系から水の留出がなくなるまでエステル化反応を行った。
反応容器に仕込む成分を表1に示すとおりに変更した以外は実施例1と同様の方法でポリエステル樹脂を得た。得られた樹脂の特性値および評価結果を表1に示す。
表1に示す仕込み組成の多価カルボン酸、多価アルコール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200rpm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た。エステル化反応末期、反応系から水の留出がなくなるより前にゲル化反応が進行して反応系のトルクが上昇をはじめ、その後加速度的にトルク上昇が見られたため、エステル化反応終了前であったが、撹拌を停止し、窒素により加圧して反応装置底部より内容物を取り出した。取り出し途中にも内容物の増粘が進み、一部は反応装置内で固化し取り出すことができなかった。また取り出すことのできた樹脂には未反応の粉体原料が粒子状に残存していた。
表1に示す仕込み組成の多価カルボン酸、多価アルコール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200rpm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た。反応系から水の留出がなくなるまでエステル化反応を行った。
また、仕込み時の前記モノマー混合物中のカルボキシル基数と、仕込み時の前記モノマー混合物中の水酸基数との比を1:1.13~1:1.30としてポリエステル樹脂を製造した場合には、保存安定性、低温定着し、耐ホットオフセット性、画像安定性のいずれにおいても使用可能あるいは良好な結果であった(実施例1~7)。
Claims (7)
- 三価以上の酸由来成分およびビスフェノールAアルキレンオキサイド付加物由来成分を含み、
全酸由来成分1モルに対してビスフェノールAアルキレンオキサイド付加物由来成分を0.01~0.35モル含み、
酸価(mgKOH/g)と水酸基価(mgKOH/g)の比が、酸価:水酸基価=1:3~1:26である、ポリエステル樹脂。 - 前記三価以上の酸由来成分の含有量が、全酸由来成分1モル中0.01~0.30モルである、請求項1記載のポリエステル樹脂。
- 重合触媒由来の金属含有量が20ppm以下である、請求項1または2記載のポリエステル樹脂。
- 請求項1から3のいずれかに記載のポリエステル樹脂を含むトナー。
- 多価アルコールと多価カルボン酸を含むモノマー混合物を重縮合することを含むポリエステル樹脂の製造方法であって、
前記モノマー混合物が、三価以上の酸成分と、全酸成分1モルに対して0.01~0.35モルのビスフェノールAアルキレンオキサイド付加物を含み、
仕込み時の前記モノマー混合物中のカルボキシル基数と水酸基数との比が、カルボキシル基数:水酸基数=1:1.13~1:1.30である、ポリエステル樹脂の製造方法。 - 前記三価以上の酸成分の含有量が、全酸成分1モル中に0.01~0.30モルである、請求項5記載のポリエステル樹脂の製造方法。
- 重合触媒20ppm以下の条件で重合する、請求項5または6に記載のポリエステル樹脂の製造方法。
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KR1020167033383A KR101837334B1 (ko) | 2014-05-30 | 2015-05-28 | 폴리에스테르 수지, 폴리에스테르 수지를 포함하는 토너, 및 폴리에스테르 수지의 제조 방법 |
US15/314,661 US9971259B2 (en) | 2014-05-30 | 2015-05-28 | Polyester resin, toner containing polyester resin, and method for manufacturing polyester resin |
CN201580025823.2A CN106459393B (zh) | 2014-05-30 | 2015-05-28 | 聚酯树脂、包含聚酯树脂的调色剂以及聚酯树脂的制造方法 |
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JPH0656974A (ja) | 1992-08-10 | 1994-03-01 | Toray Ind Inc | トナーバインダー用ポリエステル樹脂の製造方法 |
CN100454149C (zh) * | 2002-12-20 | 2009-01-21 | 三菱丽阳株式会社 | 调色剂用聚酯树脂组合物及调色剂 |
JP4758749B2 (ja) * | 2005-12-12 | 2011-08-31 | 花王株式会社 | トナー用ポリエステルの製造方法 |
JP2011028170A (ja) | 2009-07-29 | 2011-02-10 | Sanyo Chem Ind Ltd | トナーバインダー及びトナー組成物 |
DE102011013315B4 (de) * | 2010-03-08 | 2024-05-08 | Kao Corporation | Verfahren zur Herstellung eines Harzbindemittels für Toner, damit erhältliches Harzbindemittel, Verfahren zur Herstellung eines Toners sowie damit erhältlicher Toner |
KR20130133057A (ko) * | 2011-03-29 | 2013-12-05 | 캐논 가부시끼가이샤 | 토너 |
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JPH1160703A (ja) * | 1997-08-07 | 1999-03-05 | Mitsubishi Rayon Co Ltd | トナー用ポリエステル樹脂、その製造方法およびそれを用いたトナー |
JP2001305790A (ja) * | 2000-04-18 | 2001-11-02 | Mitsubishi Rayon Co Ltd | トナー用高軟化温度ポリエステル樹脂および高軟化温度ポリエステル系トナー |
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US20170192369A1 (en) | 2017-07-06 |
CN106459393A (zh) | 2017-02-22 |
KR101837334B1 (ko) | 2018-03-09 |
KR20170002507A (ko) | 2017-01-06 |
JPWO2015182707A1 (ja) | 2017-04-20 |
US9971259B2 (en) | 2018-05-15 |
JP6536822B2 (ja) | 2019-07-03 |
CN106459393B (zh) | 2018-09-21 |
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