WO2017155123A1 - Method for producing polyether-modified polyester resin for electrophotography toner and electrophotography toner containing said resin - Google Patents

Method for producing polyether-modified polyester resin for electrophotography toner and electrophotography toner containing said resin Download PDF

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Publication number
WO2017155123A1
WO2017155123A1 PCT/JP2017/009999 JP2017009999W WO2017155123A1 WO 2017155123 A1 WO2017155123 A1 WO 2017155123A1 JP 2017009999 W JP2017009999 W JP 2017009999W WO 2017155123 A1 WO2017155123 A1 WO 2017155123A1
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Prior art keywords
resin
molecular weight
polyester resin
average molecular
toner
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PCT/JP2017/009999
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French (fr)
Japanese (ja)
Inventor
勝 脇坂
登欽 楊
珮宜 呉
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東邦塗料工業股▲分▼有限公司
勝 脇坂
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Publication of WO2017155123A1 publication Critical patent/WO2017155123A1/en

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    • 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
    • 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

Definitions

  • the present invention relates to a toner resin as a binder (binder) in an electrophotographic toner excellent in low-temperature fixability and offset resistance, a method for producing the same, and electrophotographic toner including the resin and excellent in blocking resistance and the like. It relates to toner.
  • iron powder is added to a toner fine powder containing carbon black, a colorant such as a pigment, and other additives in a toner resin as a binder.
  • a triboelectric developer (toner) mixed with a carrier such as glass beads.
  • an electrostatic latent image is usually formed on a photosensitive member, a triboelectric toner image is transferred from the electrostatic latent image to a sheet, and a releasable hot pressure roller or flash light source is used. Fix to a permanent visible image. In order to carry out these processes without problems, the toner is required to have a stable charge amount and to have a good fixability to paper.
  • the toner resin that plays the role of a binder in the toner is required to exhibit proper melting characteristics when fixing the toner, not to be offset to the heat roll, and not to aggregate when stored (blocking resistance).
  • Pigments), charge control agents, performance as a dispersion medium such as wax, and good pulverization efficiency into fine powders are also required.
  • toner resins include styrene acrylic resin, polyester resin, epoxy resin, and the like, each of which has both advantages and disadvantages.
  • Polyester resins have been increasingly used as toner resins in recent years.
  • Patent Documents 1 and 2 describe toner resin compositions comprising polyester resins crosslinked by adding an epoxy compound.
  • An object of the present invention is to obtain an electrophotographic toner that achieves both low-temperature fixability and offset resistance, provides an image with good color reproducibility and gloss, and is excellent in charging stability and storage stability. It is an object to provide a resin composition and an electrophotographic toner using the composition.
  • the present inventors prepared a polyester resin having predetermined characteristics as the first stage, reacted the polyester resin with an epoxy compound as the second stage, and It has been found that a polyether-modified polyester resin produced by reacting with a monovalent carboxylic acid or a monohydric phenol, and more preferably extending the chain length of the epoxy moiety with a dihydric phenol, can exhibit the desired properties, thereby completing the present invention. It was.
  • the present invention includes (1) a step of preparing a polyester resin (A) by condensation polymerization of a polybasic acid and a polyhydric alcohol, and (2) the polyester resin (A), an epoxy compound, a monovalent carboxylic acid or
  • a method for producing a toner resin for electrophotography comprising the step of preparing a polyether-modified polyester resin (AB) by copolymerizing monohydric phenol and preferably dihydric phenol.
  • the present invention also provides an electrophotographic toner resin produced by the production method and an electrophotographic toner composition containing the toner resin.
  • the present invention is a method for producing a polyether-modified polyester resin by copolymerizing a polyester resin with an epoxy compound, a monovalent carboxylic acid or a monohydric phenol, and preferably a dihydric phenol.
  • the polyether-modified polyester resin can be used as a toner resin constituting an electrophotographic toner having toughness, excellent storage stability, fixing property, offset resistance, image stability, and good color reproducibility.
  • the charge ratio of the epoxy compound to be copolymerized with the polyester resin is changed in the range of 5 to 95 parts of the epoxy compound with respect to 100 parts of the polyester resin, depending on the required characteristics. Thus, a toner resin having desired characteristics can be obtained.
  • Epoxy equivalent (hydrochloric acid-dioxane method) A resin sample of 5.0 g is precisely weighed in a 300 ml Erlenmeyer flask, and 25 ml of dioxane is added to dissolve the sample. Add 25 ml of N / 5 dioxane hydrochloride solution with a whole pipette, seal tightly, mix well, and let stand for 30 minutes. Next, 50 ml of a toluene / ethanol mixed solution (2: 3 volume ratio) is added, and titrated with an aqueous N / 10 normal sodium hydroxide solution using cresol red as an indicator.
  • the epoxy equivalent (g / equivalent) is calculated according to the following formula (A).
  • EEW (g / equivalent) 1000 ⁇ W / [(BS) ⁇ N ⁇ F] (A) here, EEW: Epoxy equivalent W: Sampling amount
  • B Amount of aqueous sodium hydroxide solution required for the blank test (ml)
  • S Amount of sodium hydroxide aqueous solution required for the sample (ml)
  • N normality of aqueous sodium hydroxide solution
  • F titer of aqueous sodium hydroxide solution
  • Molecular weight 100 mg of a resin sample is dissolved in 10 ml of tetrahydrofuran (THF) to prepare a sample solution, 100 ⁇ l of this sample solution is injected into a column, and the retention time is measured under the following conditions.
  • a calibration curve is prepared by measuring the retention time using polystyrene having a known average molecular weight as a standard substance. From this calibration curve, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the resin sample are determined in terms of polystyrene.
  • Measuring device Tosoh Corporation HLC-8320GPC Column: Tskel G 5000 + 4000 + 3000 + 2500HXL 4 column temperature: 40 ° C.
  • Detector RI detector used
  • Tg method Glass transition temperature The measurement is performed under the following conditions using a differential scanning calorimeter (METTLER TOLEDO DSC-1 STAR System). Measurement condition: Temperature range: 20-200 ° C Temperature increase rate: 10 ° C / min Sample amount: 10mg
  • Drop point / softening temperature Measurement is performed under the following conditions using an automatic dropping point / softening point measuring apparatus (METTLERTOLEDO DP70). Measurement condition: Measurement start temperature: Start at a temperature 15 ° C. lower than the expected softening temperature Temperature rising rate: 1 ° C./min
  • Acid value Measured by the following method using potentiometric titration.
  • a polyhydric alcohol (a1) and a polybasic acid (a2) are reacted in the presence of a catalyst to produce a polyester resin (A).
  • the polyhydric alcohol (a1) used as a raw material is selected from dihydric or higher alcohols and may be used alone or in combination of two or more. Specific examples include bisphenol A or a derivative thereof (for example, polyoxyalkylene adduct of bisphenol A), ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, pentamethylene glycol, glycerin and the like. For example, but not limited to.
  • the polybasic acid is selected from carboxylic acids having two or more carboxyl groups and may be used alone or in combination of two or more. Specific examples include, but are not limited to, aromatic compounds such as terephthalic acid, isophthalic acid, trimellitic acid and pyromellitic acid, and aliphatic compounds such as maleic acid / fumaric acid and succinic acid derivatives.
  • the charge ratio of each monomer raw material is calculated based on the OH / COOH equivalent ratio, and ranges from 0.6 to 1.0, preferably from 0.65 to 0.98, more preferably from 0.71 to 0.96.
  • the condensation polymerization reaction is preferably performed by solution polymerization or bulk polymerization.
  • the polymerization reaction is performed by dissolving each monomer in a solvent at an appropriate ratio as necessary, and adding an appropriate polymerization initiator (for example, a tin compound, a zinc compound, a titanium compound, a zirconium compound, etc.).
  • an appropriate polymerization initiator for example, a tin compound, a zinc compound, a titanium compound, a zirconium compound, etc.
  • a monobasic acid may be added to the reaction mixture as necessary.
  • the polyester resin (A) is reacted with the epoxy compound (b1), the monovalent carboxylic acid (b2) or the monovalent phenol (b3), and preferably the divalent phenol (b4) in the presence of a catalyst.
  • the epoxy compound (b1) can be selected from epoxy compounds having a molecular weight of about 300 to about 5000, preferably 340 to 4800 and an epoxy equivalent of about 150 to about 2500, preferably 170 to 2400. Specific examples include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol AD diglycidyl ether, phenol novolac glycidyl ether, novolac glycidyl ether, and the like.
  • Examples of monovalent carboxylic acids (b2) include aliphatic carboxylic acids such as propionic acid, butyric acid, caproic acid, cabrylic acid and stearic acid, and aromatics such as benzoic acid, toluic acid, ⁇ -naphthoic acid and phenylacetic acid. Examples thereof include monovalent carboxylic acids.
  • Examples of the monohydric phenol (b3) include phenol, cresol, isopropylphenol, octylphenol, t-butylphenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol, ⁇ -naphthol, ⁇ -naphthol and the like.
  • Examples of the dihydric phenol (b4) include bisphenol A, bisphenol AD, bisphenol F, phenol novolak, orthocresol novolak, and the like.
  • the reaction (second reaction) for adding an epoxy compound to the polyester resin (A) includes the polyester resin (A) and each raw material compound (b1, b2, b3 and b4), and an optional catalyst (for example, sodium hydroxide, water).
  • Alkali metal hydroxides such as potassium oxide and lithium hydroxide; tertiary amines such as N, N-dimethylbenzylamine, triethylamine and pyridine; quaternary ammonium salts such as tetramethylammonium chloride and benzyltriethylammonium chloride;
  • An organic phosphorus compound such as phenylphosphine or triethylphosphine, or an alkali metal salt such as lithium chloride) is heated as necessary.
  • each raw material of the polyaddition reaction (second reaction) for adding an epoxy moiety to the polyester resin (A) satisfies the following formulas (1) and (2).
  • X and Y are determined by solving the simultaneous equations of the above formulas (1) and (2), and the raw material charge is determined.
  • the composition ratio (%) of the polyester part (A) and the epoxy part (B) can be appropriately changed within the range of 5 to 90 parts of the epoxy part (B) with respect to 100 parts of the polyester resin (A).
  • the polyether-modified polyester resin (AB) produced by the method of the present invention is preferably prepared so as to have the following characteristics. Dropping point / softening temperature: 70-150 ° C Glass transition temperature: 50-70 ° C Number average molecular weight (Mn): 2700 to 10,000, preferably 3000 to 10,000 Weight average molecular weight (Mw): 10000-30000 Molecular weight distribution (Mw / Mn): 2.0 to 5.0
  • the present invention further provides an electrophotographic toner composition (toner) containing the polyether-modified polyester resin as a binder (toner resin).
  • a colorant is blended as an essential component.
  • the colorant can be selected from colorants commonly used in electrophotographic developers (toners), and is not particularly limited.
  • a conventionally known black colorant can be used.
  • Specific examples of the black colorant include carbon black.
  • toner composition other than black such as a yellow, magenta or cyan primary color toner composition
  • conventionally known colorants can be used, and there is no particular limitation.
  • a colorant used when preparing a yellow toner composition chrome yellow, quinoline yellow, and the like can be given.
  • examples of the colorant used when preparing a magenta toner composition include DuPont oil red and rose bengal. Further, examples of the colorant used when preparing a cyan toner composition include aniline blue, methylene blue chloride, and phthalocyanine blue.
  • the combination of colorants in the composition of the present invention is determined according to the required color and the like.
  • the blending amount of the colorant is usually about 0.1 to 10% by weight with respect to the total amount of the toner composition.
  • magnetic powder is blended as an essential component in the toner composition.
  • the magnetic powder used include iron oxides such as ferrite and magnetite, and metals such as iron, cobalt, and nickel. These may be used alone or in combination of two or more.
  • the magnetic powder is preferably a fine powder having a particle size of 1 ⁇ m or less.
  • the blending ratio is 50 to 200 parts by weight with respect to 100 parts by weight of the toner resin (binder resin).
  • the toner composition of the present invention may contain various compounding agents commonly used in conventional electrophotographic toner compositions, if necessary, in addition to the toner resin, the colorant and the magnetic powder.
  • a styrene acrylic resin, a polyester resin, an epoxy resin or the like that is commonly used as a toner resin can be further blended.
  • a charge control agent, a plasticizer, a low molecular weight polyethylene, a low molecular weight polypropylene, a mold release agent such as paraffin wax, amide wax, and silicone oil, and a fluidity improver such as silica can be blended.
  • the blending amount of these optional components is limited to a range that does not hinder the effects of the present invention.
  • composition of the present invention is usually provided in the form of a particle aggregate having an average particle size of 5 to 15 ⁇ m.
  • the toner composition of the present invention comprises a toner resin (binder resin) and a colorant, and further a magnetic powder in the case of a magnetic toner as a one-component developer, and if necessary, a charge adjusting agent, a wax, other Arbitrary additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then melt-mixed using a heating mixer such as a heating roll, a kneader, or an extruder. Next, after cooling and solidification, it can be produced by pulverization and classification using a jet mill or the like.
  • a mixer such as a Henschel mixer or a ball mill
  • Example 1 Bisphenol A propylene oxide adduct (P-RA-FBH hydroxyl value 314 KOHmg / g, manufactured by Chunichi Gosei Co., Ltd.) in a 1000 ml round bottom separable flask equipped with a stirrer, thermometer, nitrogen inlet and reflux tube 388. 9 g, 210.8 g of isophthalic acid, 3.02 g of dibutyltin oxide, and 30.0 g of xylene were charged and the temperature was raised. The top temperature at the beginning of the reaction was heated so as not to exceed 100 ° C., and a dehydration reaction was carried out.
  • P-RA-FBH hydroxyl value 314 KOHmg / g manufactured by Chunichi Gosei Co., Ltd.
  • the temperature in the reaction system was lowered to about 150 ° C., and 102.8 g of a bisphenol A type liquid epoxy resin (manufactured by Changchun Kako, BE188EL, epoxy equivalent 189 g / eq), benzoic acid 18.6 g, stearic acid 18.6 g, xylene 77 0.7 g was charged and 600 ppm of tetramethylammonium chloride was added.
  • a bisphenol A type liquid epoxy resin manufactured by Changchun Kako, BE188EL, epoxy equivalent 189 g / eq
  • the pressure reduction line was started, and the pressure reduction was started.
  • the pressure reached 1.33 Kpa (10 mmHg) or less, stirred for 1 hour, returned to normal pressure, and the reaction was continued at 160 ° C.
  • Sampling was performed after reaction at 160 ° C. for 8 hours, and the epoxy equivalent was measured. After confirming that the epoxy equivalent was 20000 or more, the produced polyether-modified polyester resin was extracted from the flask.
  • the obtained polyether-modified polyester resin had the following characteristics. Epoxy equivalent: 20000 or more, softening point: 123 ° C., glass transition temperature: 60 ° C., number average molecular weight (Mn): 6280, weight average molecular weight (Mw): 20300, weight average molecular weight (Mn) and number average molecular weight (Mw) Ratio (distribution Mw / Mn): 3.2.
  • Example 2 Bisphenol A propylene oxide adduct (P-RA-FBH hydroxyl value 318 KOHmg / g manufactured by Chunichi Gosei Co., Ltd.) in a 1000 ml round bottom separable flask equipped with a stirrer, thermometer, nitrogen inlet and reflux tube 350. 9 g, 26.3 g of diethylene glycol, 227.5 g of isophthalic acid, 3.04 g of dibutyltin oxide, and 25.2 g of xylene were charged and heated so that the initial top temperature of the reaction did not exceed 100 ° C., and a dehydration reaction was performed. . Sampling was performed during the reaction, and the acid value was measured.
  • the reflux tube was changed to a vacuum device: condenser, and the degree of vacuum was gradually increased at 240 ° C. to distill off water and unreacted substances.
  • the degree of vacuum reached 1.33 Kpa (10 mmHg) or less, and after stirring for 3 to 6 hours, sampling was performed to measure the acid value.
  • the temperature in the reaction system was lowered to about 150 ° C., 99.6 g of a bisphenol A type liquid epoxy resin (Changchun Kako, BE188EL, epoxy equivalent 189 g / eq), bisphenol A 11.3 g, benzoic acid 29.1 g, xylene 77. 7 g was charged, and 600 ppm of tetramethylammonium chloride was added.
  • a bisphenol A type liquid epoxy resin (Changchun Kako, BE188EL, epoxy equivalent 189 g / eq)
  • the pressure reduction line was started, and the pressure reduction was started.
  • the pressure reached 1.33 Kpa (10 mmHg) or less, stirred for 1 hour, returned to normal pressure, and the reaction was continued at 160 ° C.
  • Sampling was performed after reaction at 160 ° C. for 8 hours, and the epoxy equivalent was measured. After confirming that the epoxy equivalent was 20000 or more, the produced polyether-modified polyester resin was extracted from the flask.
  • the obtained polyether-modified polyester resin had the following characteristics. Epoxy equivalent: 20000 or more, softening point: 116 ° C., glass transition temperature: 59 ° C., number average molecular weight (Mn): 4550, weight average molecular weight (Mw): 18900, weight average molecular weight (Mn) and number average molecular weight (Mw) Ratio (distribution Mw / Mn): 4.2.
  • Example 3 Into a 1000 ml round bottom separable flask equipped with a stirrer, thermometer, nitrogen inlet and reflux tube, bisphenol A propylene oxide adduct (P-RA-FBH hydroxyl value 314 KOHmg / g manufactured by Chunichi Gosei Co., Ltd.) 366. 2 g, 17.1 g of triethylene glycol, 217.8 g of isophthalic acid, 3.02 g of dibutyltin oxide, and 25.0 g of xylene are heated and heated so that the initial top temperature of the reaction does not exceed 100 ° C. Carried out. Sampling was performed during the reaction, and the acid value was measured. When the theoretical acid value was approached, the reflux tube was changed to a vacuum device: condenser, and the degree of vacuum was gradually increased at 240 ° C. to distill off water and unreacted substances.
  • the degree of vacuum reached 1.33 Kpa (10 mmHg) or less, and after stirring for 3 hours, sampling was performed to measure the acid value.
  • the temperature in the reaction system was lowered to about 150 ° C., bisphenol A type liquid epoxy resin (Changchun Kako, BE188EL, epoxy equivalent 189 g / eq) 101.8 g, bisphenol A 9.1 g, benzoic acid 29.1 g, xylene 77. 7 g was charged and 600 ppm of tetramethylammonium chloride was added.
  • the pressure reduction line was started, and the pressure reduction was started.
  • the pressure reached 1.33 Kpa (10 mmHg) or less, stirred for 1 hour, returned to normal pressure, and the reaction was continued at 160 ° C.
  • Sampling was performed after reaction at 160 ° C. for 8 hours, and the epoxy equivalent was measured. After confirming that the epoxy equivalent was 20000 or more, the produced polyether-modified polyester resin was extracted from the flask.
  • the obtained polyether-modified polyester resin had the following characteristics. Epoxy equivalent: 20000 or more, softening point: 116 ° C., glass transition temperature: 59 ° C., number average molecular weight (Mn): 5300, weight average molecular weight (Mw): 19000, weight average molecular weight (Mn) and number average molecular weight (Mw) Ratio (distribution Mw / Mn): 3.6.
  • Example 4 Bisphenol A propylene oxide adduct (P-RA-FBH hydroxyl value 314 KOHmg / g, manufactured by Chunichi Gosei Co., Ltd.) in a 1000 ml round bottom separable flask equipped with a stirrer, thermometer, nitrogen inlet and reflux tube 219. 4 g, 219.4 g of isophthalic acid, and 3.28 g of dibutyltin oxide were charged, and the temperature was raised. The top temperature of the reaction was heated so as not to exceed 100 ° C., and a dehydration reaction was performed.
  • P-RA-FBH hydroxyl value 314 KOHmg / g manufactured by Chunichi Gosei Co., Ltd.
  • the temperature in the reaction system was lowered to about 150 ° C., and bisphenol A type liquid epoxy resin (Changchun Kako, BE188EL, epoxy equivalent 189 g / eq) 97.5 g, bisphenol A 34.1 g, benzoic acid 18.4 g, wax (day WE-10 manufactured by Oil Co., Ltd., 83.3 g and 93 g of xylene were charged, and 500 ppm of tetramethylammonium chloride was added.
  • the pressure reduction line was started and the pressure reduction was started.
  • the pressure reached 1.33 Kpa (10 mmHg)
  • the mixture was stirred for 1 hour and returned to normal pressure.
  • the reaction was continued at 160 ° C. Sampling was performed after reaction at 160 ° C. for 8 hours, and the epoxy equivalent was measured. After confirming that the epoxy equivalent was 20000 or more, the produced polyether-modified polyester resin was extracted from the flask.
  • the obtained polyether-modified polyester resin had the following characteristics. Softening point: 110 ° C., glass transition temperature: 58 ° C., number average molecular weight (Mn): 2790, weight average molecular weight (Mw): 10370, ratio of weight average molecular weight (Mn) to number average molecular weight (Mw) (distribution Mw / Mn): 3.7.
  • the obtained polyester resin had the following characteristics. Acid value: 32.7 KOH mg / g, softening point: 122 ° C., glass transition temperature: 74 ° C., number average molecular weight (Mn): 1510, weight average molecular weight (Mw): 6410, weight average molecular weight (Mn) and number average molecular weight Ratio of (Mw) (distribution Mw / Mn): 3.2.
  • the epoxy equivalent of the obtained epoxy resin is 1110 g / eq, softening point: 64.5 ° C., glass transition temperature: 24 ° C., number average molecular weight (Mn): 1410, weight average molecular weight (Mw): 2740, weight average molecular weight ( Mn) to number average molecular weight (Mw) (distribution Mw / Mn): 2.0.
  • a toner composition was prepared by adding a colorant, magnetic powder, and the like, and the following evaluation was performed.
  • ⁇ Fixability test> Using an electrophotographic copying machine modified so that the surface temperature of the fixing heat roller of the electrophotographic copying machine can be changed, the surface temperature of the fixing heat roller is changed in the range of 100 to 200 ° C. A copy was made. The density change in the copy image when the resulting copy image was rubbed with an eraser was visually observed. The surface temperature of the fixing heat roller was increased from 110 ° C. in increments of 5 ° C., and the temperature when the fixing rate exceeded 85% was defined as the minimum fixing temperature. Further, the test was conducted by raising the temperature, and the temperature at which the electrophotographic developer powder began to adhere to the heat roller was defined as the offset start temperature.
  • an electrophotographic composition powder is prepared by the above-described method, and the results of blocking resistance test and fixability test are shown in Table 1 together with the physical properties of each resin. Moreover, the comparison with a comparative example was also implemented.
  • the resin of Example 5 was produced according to the production method of the present invention.
  • the resin of Comparative Example 3 was produced by a production method different from the present invention.
  • Example 5 The resin of Comparative Example 3 had the physical property values shown in Table 3. Next, the melting points and softening temperatures of these resins were measured (results are shown in Table 4).
  • the specific measurement method is as follows.
  • Comparative Example 3 had a melting point of 94.1 ° C. to 116.1 ° C., whereas Example 5 was as low as 88.3 ° C. to 106.7 ° C. ing.
  • the softening temperature was 114 ° C. to 129 ° C. in Comparative Example 3, whereas Example 5 was as low as 101 ° C. to 111 ° C., and the softening time was shortened.
  • the thermal characteristics such as melting point and softening temperature contribute to low-temperature fixability when toner resin is used. More specifically, the low melting point and softening temperature mean that, at the time of thermal transfer by a heating roll, melting at a lower temperature starts transfer to paper. Therefore, it can be said that the resin of the present invention (Example 5) is superior in low-temperature fixability as a toner resin as compared with Comparative Example 3.

Abstract

The objective of the present invention is to provide a toner resin which can be used to prepare an electrophotography toner excelling in charge stability and storage stability, which realizes both low-temperature fixability and anti-offset properties, and with which an image having good color reproducibility and glossiness can be obtained. The present invention pertains to a method for producing an electrophotography toner resin, a resin produced by said production method, and an electrophotography toner composition comprising said resin; said production method comprising: (1) a step for subjecting a polybasic acid and a polyhydric alcohol to condensation polymerization to prepare a polyester resin (A); and (2) a step for copolymerizing the polyester resin (A), an epoxy compound, a monovalent carboxylic acid or monohydric phenol, and preferably dihydric phenol to prepare a polyether-modified polyester resin (AB) having a dripping point - softening temperature of 70 to 150℃, a glass transition temperature of 50 to 70℃, a number average molecular weight (Mn) of 2700 to 10,000, a weight average molecular weight (Mw) of 10,000 to 30,000, and a molecular weight distribution (Mw/Mn) of 2.0 to 5.0.

Description

電子写真用トナーのためのポリエーテル変性ポリエステル樹脂の製造方法及びその樹脂を含む電子写真用トナーMethod for producing polyether-modified polyester resin for electrophotographic toner and electrophotographic toner containing the resin
　本発明は、低温定着性と耐オフセット性に優れた電子写真用トナーにおけるバインダー（結着剤）となるトナー樹脂及びその製造方法、並びにその樹脂を含み耐ブロッキング性等にも優れた電子写真用トナーに関する。 The present invention relates to a toner resin as a binder (binder) in an electrophotographic toner excellent in low-temperature fixability and offset resistance, a method for producing the same, and electrophotographic toner including the resin and excellent in blocking resistance and the like. It relates to toner.
　複写機、ファックス、プリンター等の電子写真においては、静電画像を得る方法として、バインダーとなるトナー樹脂にカーボンブラック及び顔料等の着色剤、その他の添加剤を含有させたトナー微粉末に鉄粉やガラスビーズ等のキャリアーを混合した摩擦帯電現像剤（トナー）が用いられる。 In electrophotography such as copying machines, fax machines, and printers, as a method for obtaining an electrostatic image, iron powder is added to a toner fine powder containing carbon black, a colorant such as a pigment, and other additives in a toner resin as a binder. Or a triboelectric developer (toner) mixed with a carrier such as glass beads.
　複写物を得るには通常、感光体上に静電潜像を形成し、この静電潜像から摩擦帯電性のトナー像を用紙に転写し、離型性を有する熱圧ローラーまたはフラッシュ光源で定着させて永久可視像とする。これらのプロセスを問題なく実施するために、トナーには安定した帯電量を保持する事や紙への定着性が良好である事が求められる。 To obtain a copy, an electrostatic latent image is usually formed on a photosensitive member, a triboelectric toner image is transferred from the electrostatic latent image to a sheet, and a releasable hot pressure roller or flash light source is used. Fix to a permanent visible image. In order to carry out these processes without problems, the toner is required to have a stable charge amount and to have a good fixability to paper.
　トナーにおいてバインダーの役割を果たすトナー樹脂には、トナー定着時に適正な溶融特性を示し、かつヒートロールにオフセットしないこと、トナー保存時に凝集しないこと（耐ブロッキング性）等が要求され、さらに着色剤（顔料）、帯電制御剤、ワックス等の分散媒としての性能や微粉状への良好な粉砕効率も求められる。 The toner resin that plays the role of a binder in the toner is required to exhibit proper melting characteristics when fixing the toner, not to be offset to the heat roll, and not to aggregate when stored (blocking resistance). Pigments), charge control agents, performance as a dispersion medium such as wax, and good pulverization efficiency into fine powders are also required.
　従来のトナー樹脂としては、スチレンアクリル樹脂、ポリエステル樹脂及びエポキシ樹脂等が用いられているが、これらの樹脂は 各々長所と短所を併せ持っている。
　ポリエステル樹脂は、近年トナー樹脂としての使用が増加してきており、例えば、特許文献１及び２には、エポキシ化合物を添加することにより架橋させたポリエステル樹脂からなるトナー樹脂組成物が記載されている。 Conventional toner resins include styrene acrylic resin, polyester resin, epoxy resin, and the like, each of which has both advantages and disadvantages.
Polyester resins have been increasingly used as toner resins in recent years. For example, Patent Documents 1 and 2 describe toner resin compositions comprising polyester resins crosslinked by adding an epoxy compound.
　近年のプリンター等の高速化、小型化、省エネルギー化等により、保存性、低温定着性、耐オフセット性、耐ブロッキング性等の特性を更に向上させたトナー樹脂が求められている。 In recent years, there has been a demand for a toner resin having further improved characteristics such as storage stability, low-temperature fixability, offset resistance, and blocking resistance due to speeding up, downsizing, energy saving, and the like of printers.
特許第５７４８１１５号公報Japanese Patent No. 5748115 特開２０１１－１８６２０６号公報JP 2011-186206 A
　本発明における課題は、低温定着性と耐オフセット性を両立し、色再現性、光沢性が良好な画像が得られ、且つ帯電安定性、保存安定性にも優れる電子写真用トナーが得られるトナー樹脂組成物及びこの組成物を用いた電子写真用トナーを提供することにある。 An object of the present invention is to obtain an electrophotographic toner that achieves both low-temperature fixability and offset resistance, provides an image with good color reproducibility and gloss, and is excellent in charging stability and storage stability. It is an object to provide a resin composition and an electrophotographic toner using the composition.
　上記の課題を解決すべき鋭意検討した結果、本発明者等は、第１段階として所定の特性を持つポリエステル樹脂を調製し、第２段階として前記ポリエステル樹脂を、エポキシ化合物と反応させ、更に一価カルボン酸又は一価フェノールと反応させ、更に好ましくは二価フェノールでエポキシ部の鎖長延長を行い製造したポリエーテル変性ポリエステル樹脂が所望の特性を発揮できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors prepared a polyester resin having predetermined characteristics as the first stage, reacted the polyester resin with an epoxy compound as the second stage, and It has been found that a polyether-modified polyester resin produced by reacting with a monovalent carboxylic acid or a monohydric phenol, and more preferably extending the chain length of the epoxy moiety with a dihydric phenol, can exhibit the desired properties, thereby completing the present invention. It was.
　即ち、本発明は、（１）多塩基酸及び多価アルコールを縮合重合させてポリエステル樹脂（Ａ）を調製する工程、及び（２）前記ポリエステル樹脂（Ａ）、エポキシ化合物、一価カルボン酸又は一価フェノール、及び好ましくは二価フェノールを共重合させることによりポリエーテル変性ポリエステル樹脂（ＡＢ）を調製する工程、を含む、電子写真用トナー樹脂の製造方法を提供する。
　また本発明は、前記製造方法で製造された電子写真用トナー樹脂、並びに、当該トナー樹脂を含有する電子写真用トナー組成物を提供する。 That is, the present invention includes (1) a step of preparing a polyester resin (A) by condensation polymerization of a polybasic acid and a polyhydric alcohol, and (2) the polyester resin (A), an epoxy compound, a monovalent carboxylic acid or There is provided a method for producing a toner resin for electrophotography comprising the step of preparing a polyether-modified polyester resin (AB) by copolymerizing monohydric phenol and preferably dihydric phenol.
The present invention also provides an electrophotographic toner resin produced by the production method and an electrophotographic toner composition containing the toner resin.
　本発明は、ポリエステル樹脂を、エポキシ化合物、一価カルボン酸又は一価フェノール、及び好ましくは二価フェノールと共重合することによりポリエーテル変性ポリエステル樹脂を製造する方法であり、当該方法で製造されたポリエーテル変性ポリエステル樹脂は、強靭性が付与され、保存性、定着性、耐オフセット性、画像安定性に優れ、なおかつ色再現性の良い電子写真用トナーを構成するトナー樹脂として使用できる。
　また、本発明の製造方法においては、要求される特性に応じて、共重合させるエポキシ化合物とポリエステル樹脂との仕込み割合を、ポリエステル樹脂１００部に対してエポキシ化合物５～９５部の範囲で変化させることにより、所望の特性を有するトナー樹脂を得る事が出来る。 The present invention is a method for producing a polyether-modified polyester resin by copolymerizing a polyester resin with an epoxy compound, a monovalent carboxylic acid or a monohydric phenol, and preferably a dihydric phenol. The polyether-modified polyester resin can be used as a toner resin constituting an electrophotographic toner having toughness, excellent storage stability, fixing property, offset resistance, image stability, and good color reproducibility.
In the production method of the present invention, the charge ratio of the epoxy compound to be copolymerized with the polyester resin is changed in the range of 5 to 95 parts of the epoxy compound with respect to 100 parts of the polyester resin, depending on the required characteristics. Thus, a toner resin having desired characteristics can be obtained.
　以下、本発明について詳述する。
　なお、本明細書中で使用される「エポキシ当量」、「分子量」、「分子量分布」、「ガラス転移温度」、「滴点・軟化温度」、及び「酸価」の値は、下記の方法に従って測定した値を意味するものとする。 Hereinafter, the present invention will be described in detail.
The values of “epoxy equivalent”, “molecular weight”, “molecular weight distribution”, “glass transition temperature”, “drop point / softening temperature”, and “acid value” used in the present specification are the following methods Means the value measured according to
１．エポキシ当量（塩酸－ジオキサン法）
　３００ｍｌの三角フラスコに樹脂試料５．０ｇを精秤し、ジオキサン２５ｍｌを加え試料を溶解させる。Ｎ／５塩酸ジオキサン溶液２５ｍｌをホールピペットで加え密栓して十分混合後３０分間静置する。
　次に、トルエン／エタノール混合溶液（２：３容量比）５０ｍｌを加えた後、クレゾールレッドを指示薬としてＮ／１０規定水酸化ナトリウム水溶液で滴定する。滴定結果に基づき下記式（イ）に従ってエポキシ当量（ｇ／当量）を計算する。
　ＥＥＷ（ｇ／当量）＝１０００×Ｗ／〔（Ｂ－Ｓ）×Ｎ×Ｆ〕　　（イ）
　ここで、
　ＥＥＷ：エポキシ当量
　Ｗ：試料採取量
　Ｂ：空試験に要した水酸化ナトリウム水溶液の量（ｍｌ）
　Ｓ：試料に要した水酸化ナトリウム水溶液の量（ｍｌ）
　Ｎ：水酸化ナトリウム水溶液の規定度
　Ｆ：水酸化ナトリウム水溶液の力価
　である。 1. Epoxy equivalent (hydrochloric acid-dioxane method)
A resin sample of 5.0 g is precisely weighed in a 300 ml Erlenmeyer flask, and 25 ml of dioxane is added to dissolve the sample. Add 25 ml of N / 5 dioxane hydrochloride solution with a whole pipette, seal tightly, mix well, and let stand for 30 minutes.
Next, 50 ml of a toluene / ethanol mixed solution (2: 3 volume ratio) is added, and titrated with an aqueous N / 10 normal sodium hydroxide solution using cresol red as an indicator. Based on the titration result, the epoxy equivalent (g / equivalent) is calculated according to the following formula (A).
EEW (g / equivalent) = 1000 × W / [(BS) × N × F] (A)
here,
EEW: Epoxy equivalent W: Sampling amount B: Amount of aqueous sodium hydroxide solution required for the blank test (ml)
S: Amount of sodium hydroxide aqueous solution required for the sample (ml)
N: normality of aqueous sodium hydroxide solution F: titer of aqueous sodium hydroxide solution
２．分子量（ＧＰＣ法）
　樹脂試料１００ｍｇをテトラヒドロフラン（ＴＨＦ）１０ｍｌに溶解して試料液を調整し、この試料液１００μｌをカラムに注入し、下記の条件で保持時間の測定を行う。平均分子量既知のポリスチレンを標準物質として用いて保持時間を測定して検量線を作成する。この検量線から、樹脂試料の数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）をポリスチレン換算により求める。
　測定装置：東ソー株式会社　ＨＬＣ－８３２０ＧＰＣ
　カラム：ＴｓｋｇｅｌＧ　５０００＋４０００＋３０００＋２５００ＨＸＬの４連
　カラム温度：４０℃
　移動層（流量）：ＴＨＦ（１ｍｌ／ｍｉｎ）
　検出器：ＲＩ検出器使用 2. Molecular weight (GPC method)
100 mg of a resin sample is dissolved in 10 ml of tetrahydrofuran (THF) to prepare a sample solution, 100 μl of this sample solution is injected into a column, and the retention time is measured under the following conditions. A calibration curve is prepared by measuring the retention time using polystyrene having a known average molecular weight as a standard substance. From this calibration curve, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the resin sample are determined in terms of polystyrene.
Measuring device: Tosoh Corporation HLC-8320GPC
Column: Tskel G 5000 + 4000 + 3000 + 2500HXL 4 column temperature: 40 ° C.
Moving bed (flow rate): THF (1 ml / min)
Detector: RI detector used
３．ガラス転移温度（Ｔｇ法）
　示差走査型熱量計（ＭＥＴＴＬＥＲ　ＴＯＬＥＤＯ　ＤＳＣ－１　ＳＴＡＲ　Ｓｙｓｔｅｍ）を用いて下記条件により測定する。
　測定条件：
　温度範囲：２０～２００℃
　昇温速度：１０℃／ｍｉｎ
　サンプル量：１０ｍｇ 3. Glass transition temperature (Tg method)
The measurement is performed under the following conditions using a differential scanning calorimeter (METTLER TOLEDO DSC-1 STAR System).
Measurement condition:
Temperature range: 20-200 ° C
Temperature increase rate: 10 ° C / min
Sample amount: 10mg
４．滴点・軟化温度（ＳＰ法）
　自動滴点・軟化点測定装置（ＭＥＴＴＬＥＲＴＯＬＥＤＯ　ＤＰ７０）を用いて下記の条件により測定する。
　測定条件：
　測定開始温度：予測される軟化温度より１５℃低い温度より開始
　昇温速度：１℃／ｍｉｎ 4). Drop point / softening temperature (SP method)
Measurement is performed under the following conditions using an automatic dropping point / softening point measuring apparatus (METTLERTOLEDO DP70).
Measurement condition:
Measurement start temperature: Start at a temperature 15 ° C. lower than the expected softening temperature Temperature rising rate: 1 ° C./min
５．酸　価
　電位差滴定法を用いて下記の方法により測定する。
１５０ｍｌのビーカーに樹脂試料１．０ｇ（想定される酸価により変動する）を精秤し、キシレン／ジメチルホルムアミド＝１／１を５０ｍｌ加えて試料を溶解させる。溶解後、ビーカーを測定装置にセットして測定を開始する。結果は自動計算（下記式（ロ））により算出される。
　酸価（ＫＯＨｍｇ／ｇ）＝（Ｓ－Ｂ）×Ｆ×Ｎ×５６．１／Ｗ　　（ロ）
　ここで、
　Ｗ：試料採取量
　Ｂ：空試験に要した水酸化カリウム－エタノール溶液の量（ｍｌ）
　Ｓ：試料に要した水酸化カリウム－エタノール溶液の量（ｍｌ）
　Ｎ：水酸化カリウム－エタノール溶液の規定度
　Ｆ：水酸化カリウム－エタノール溶液の力価
　である。 5. Acid value Measured by the following method using potentiometric titration.
In a 150 ml beaker, 1.0 g of a resin sample (which varies depending on the assumed acid value) is precisely weighed, and 50 ml of xylene / dimethylformamide = 1/1 is added to dissolve the sample. After dissolution, set the beaker on the measuring device and start measurement. The result is calculated by automatic calculation (the following formula (b)).
Acid value (KOHmg / g) = (SB) × F × N × 56.1 / W (b)
here,
W: Sampling amount B: Amount of potassium hydroxide-ethanol solution required for the blank test (ml)
S: Amount of potassium hydroxide-ethanol solution required for the sample (ml)
N: Normality of potassium hydroxide-ethanol solution F: Potency of potassium hydroxide-ethanol solution
　本発明のポリエーテル変性ポリエステル樹脂の製造方法では、まず第一段反応として、多価アルコール（ａ１）と、多塩基酸（ａ２）とを触媒の存在下で反応させてポリエステル樹脂（Ａ）を調製する。 In the method for producing a polyether-modified polyester resin of the present invention, first, as a first-stage reaction, a polyhydric alcohol (a1) and a polybasic acid (a2) are reacted in the presence of a catalyst to produce a polyester resin (A). Prepare.
　原料となる多価アルコール（ａ１）は、二価以上のアルコール類から選択され、単独で使用しても、２種以上のものを併用しても差し支えない。
　具体例としては、ビスフェノールＡ又はその誘導体（例えば、ビスフェノールＡのポリオキシアルキレン付加物）、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ペンタメチレングリコール、グリセリン等が挙げられるが、これらに限定されない。 The polyhydric alcohol (a1) used as a raw material is selected from dihydric or higher alcohols and may be used alone or in combination of two or more.
Specific examples include bisphenol A or a derivative thereof (for example, polyoxyalkylene adduct of bisphenol A), ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, pentamethylene glycol, glycerin and the like. For example, but not limited to.
　多塩基酸は、２以上のカルボキシル基を有するカルボン酸類から選択され、単独で使用しても、２種以上のものを併用しても差し支えない。
　具体例としては、テレフタル酸、イソフタル酸、トリメリット酸、ピロメリット酸等の芳香族化合物、マレイン酸／フマル酸、コハク酸誘導体等の脂肪属化合物が挙げられるが、これらに限定されない。 The polybasic acid is selected from carboxylic acids having two or more carboxyl groups and may be used alone or in combination of two or more.
Specific examples include, but are not limited to, aromatic compounds such as terephthalic acid, isophthalic acid, trimellitic acid and pyromellitic acid, and aliphatic compounds such as maleic acid / fumaric acid and succinic acid derivatives.
　各モノマー原料の仕込み割合は、ＯＨ／ＣＯＯＨ当量比に基づいて計算して、０．６～１．０、好ましくは０．６５～０．９８、より好ましくは０．７１～０．９６の範囲とする。 The charge ratio of each monomer raw material is calculated based on the OH / COOH equivalent ratio, and ranges from 0.6 to 1.0, preferably from 0.65 to 0.98, more preferably from 0.71 to 0.96. And
　縮合重合反応は、溶液重合又は塊状重合で行うのが好ましい。重合反応は、各モノマーを必要に応じて適切な割合で溶媒に溶解し、適当な重合開始剤（例えば、錫化合物、亜鉛化合物、チタン化合物、ジルコニウム化合物等）を加えて行う。必要に応じて、反応混合液に一塩基酸を添加してもよい。 The condensation polymerization reaction is preferably performed by solution polymerization or bulk polymerization. The polymerization reaction is performed by dissolving each monomer in a solvent at an appropriate ratio as necessary, and adding an appropriate polymerization initiator (for example, a tin compound, a zinc compound, a titanium compound, a zirconium compound, etc.). A monobasic acid may be added to the reaction mixture as necessary.
　本発明におけるポリエステル樹脂（Ａ）は、以下の特定を持つように調製するのが好ましい。
　酸価：５～４０ＫＯＨｍｇ／ｇ
　数平均分子量：Ｍｎ＝１０００～５０００
　重量平均分子量：Ｍｗ＝３０００～３００００ The polyester resin (A) in the present invention is preferably prepared so as to have the following specifications.
Acid value: 5-40 KOHmg / g
Number average molecular weight: Mn = 1000 to 5000
Weight average molecular weight: Mw = 3000-30000
　次いで、上記ポリエステル樹脂（Ａ）を、エポキシ化合物（ｂ１）と、一価カルボン酸（ｂ２）又は一価フェノール（ｂ３）と、及び好ましくは二価フェノール（ｂ４）とを触媒の存在下で反応させる。 Next, the polyester resin (A) is reacted with the epoxy compound (b1), the monovalent carboxylic acid (b2) or the monovalent phenol (b3), and preferably the divalent phenol (b4) in the presence of a catalyst. Let
　エポキシ化合物（ｂ１）は、分子量が約３００～約５０００、好ましくは３４０～４８００で、エポキシ当量が約１５０～約２５００、好ましくは１７０～２４００のエポキシ化合物の中から選択できる。具体例としては、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、ビスフェノールＡＤジグリシジルエーテル、フェノールノボラック型グリシジルエーテル、ノボラック型グリシジルエーテル等が挙げられる。 The epoxy compound (b1) can be selected from epoxy compounds having a molecular weight of about 300 to about 5000, preferably 340 to 4800 and an epoxy equivalent of about 150 to about 2500, preferably 170 to 2400. Specific examples include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol AD diglycidyl ether, phenol novolac glycidyl ether, novolac glycidyl ether, and the like.
　一価カルボン酸（ｂ２）の例としては、プロピオン酸、酪酸、カプロン酸、カブリル酸、ステアリン酸等の脂肪族カルボン酸、及び安息香酸、トルイル酸、α-ナフトエ酸、フェニル酢酸等の芳香族含有一価カルボン酸等が挙げられる。
　一価フェノール（ｂ３）の例としては、フェノール、クレゾール、イソプロピルフェノール、オクチルフェノール、t-ブチルフェノール、ノニルフェノール、ドデシルフェノール、キシレノール、ｐ－クミルフェノール、α-ナフトール、β-ナフトール等が挙げられる。
　二価フェノール（ｂ４）の例としては、ビスフェノールＡ、ビスフェノールＡＤ、ビスフェノールＦ、フェノールノボラック、オルソクレゾールノボラック等が挙げられる。 Examples of monovalent carboxylic acids (b2) include aliphatic carboxylic acids such as propionic acid, butyric acid, caproic acid, cabrylic acid and stearic acid, and aromatics such as benzoic acid, toluic acid, α-naphthoic acid and phenylacetic acid. Examples thereof include monovalent carboxylic acids.
Examples of the monohydric phenol (b3) include phenol, cresol, isopropylphenol, octylphenol, t-butylphenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol, α-naphthol, β-naphthol and the like.
Examples of the dihydric phenol (b4) include bisphenol A, bisphenol AD, bisphenol F, phenol novolak, orthocresol novolak, and the like.
　ポリエステル樹脂（Ａ）にエポキシ化合物を付加する反応（第二反応）は、ポリエステル樹脂（Ａ）及び各原料化合物（ｂ１、ｂ２、ｂ３及びｂ４）、並びに任意の触媒（例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等のアルカリ金属水酸化物、Ｎ，Ｎ－ジメチルベンジルアミン、トリエチルアミン、ピリジン等の第三級アミン、テトラメチルアンモニウムクロリド、ベンジルトリエチルアンモニュウムクロリド等の第四級アンモニウム塩、トリフェニルフォスフィン、トリエチルフォスフィン等の有機リン化合物、塩化リチウム等のアルカリ金属塩）を必要に応じて加熱して行う。 The reaction (second reaction) for adding an epoxy compound to the polyester resin (A) includes the polyester resin (A) and each raw material compound (b1, b2, b3 and b4), and an optional catalyst (for example, sodium hydroxide, water). Alkali metal hydroxides such as potassium oxide and lithium hydroxide; tertiary amines such as N, N-dimethylbenzylamine, triethylamine and pyridine; quaternary ammonium salts such as tetramethylammonium chloride and benzyltriethylammonium chloride; An organic phosphorus compound such as phenylphosphine or triethylphosphine, or an alkali metal salt such as lithium chloride) is heated as necessary.
　ポリエステル樹脂（Ａ）にエポキシ部を付加する重付加反応（第二反応）の各原料の使用割合は、以下の（１）式及び（２）式を満たすことが好ましい。
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000002
 It is preferable that the use ratio of each raw material of the polyaddition reaction (second reaction) for adding an epoxy moiety to the polyester resin (A) satisfies the following formulas (1) and (2).
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000002
　即ち、本発明の製造方法においては、上記（１）式及び（２）式の連立方程式を解いてＸ、Ｙを求め、原料仕込み量を決定する。
　ポリエステル部（Ａ）とエポキシ部（Ｂ）との構成比率（％）は、ポリエステル樹脂（Ａ）１００部に対してエポキシ部（Ｂ）５～９０部の範囲内で適宜変更が可能である。 That is, in the production method of the present invention, X and Y are determined by solving the simultaneous equations of the above formulas (1) and (2), and the raw material charge is determined.
The composition ratio (%) of the polyester part (A) and the epoxy part (B) can be appropriately changed within the range of 5 to 90 parts of the epoxy part (B) with respect to 100 parts of the polyester resin (A).
　本発明の方法によって製造されるポリエーテル変性ポリエステル樹脂（ＡＢ）は、以下の特性を有するように調製するのが好ましい。
　滴点・軟化温度：７０～１５０℃ 
　ガラス転移温度：５０～７０℃
　数平均分子量（Ｍｎ）：２７００～１００００、好ましくは３０００～１００００
　重量平均分子量（Ｍｗ）：１００００～３００００
　分子量分布（Ｍｗ／Ｍｎ）：２．０～５．０ The polyether-modified polyester resin (AB) produced by the method of the present invention is preferably prepared so as to have the following characteristics.
Dropping point / softening temperature: 70-150 ° C
Glass transition temperature: 50-70 ° C
Number average molecular weight (Mn): 2700 to 10,000, preferably 3000 to 10,000
Weight average molecular weight (Mw): 10000-30000
Molecular weight distribution (Mw / Mn): 2.0 to 5.0
　本発明は更に、前記ポリエーテル変性ポリエステル樹脂をバインダー（トナー樹脂）として含有する電子写真用トナー組成物（トナー）を提供する。 The present invention further provides an electrophotographic toner composition (toner) containing the polyether-modified polyester resin as a binder (toner resin).
　本発明のトナー組成物には着色剤が必須成分として配合される。着色剤は、電子写真用現像剤（トナー）に常用されている着色剤から選択することができ、特に制限されない。
　例えば、黒色のトナー組成物を調整する場合は、従来公知の黒色の着色剤を使用する事ができる。黒色の着色剤の具体例として、カーボンブラックを挙げることができる。 In the toner composition of the present invention, a colorant is blended as an essential component. The colorant can be selected from colorants commonly used in electrophotographic developers (toners), and is not particularly limited.
For example, when preparing a black toner composition, a conventionally known black colorant can be used. Specific examples of the black colorant include carbon black.
　黒色以外のトナー組成物、例えばイエロー、マゼンダまたはシアンの三原色トナー組成物を調製する場合は、それぞれ従来公知の着色剤を使用することができ、特に制限されない。例えばイエローのトナー組成物を調製する場合に用いられる着色剤として、クロームイエロー、キノリンイエロー等が挙げられる。 In the case of preparing a toner composition other than black, such as a yellow, magenta or cyan primary color toner composition, conventionally known colorants can be used, and there is no particular limitation. For example, as a colorant used when preparing a yellow toner composition, chrome yellow, quinoline yellow, and the like can be given.
　また、マゼンダのトナー組成物を調製する場合に用いられる着色剤として、例えばデュポンオイルレッド、ローズベンガル等が挙げられる。さらにシアンのトナー組成物を調製する場合に用いられる着色剤として、例えばアニリンブルー、メチレンブルーククロライド、フタロシアニンブルーが挙げられる。 Further, examples of the colorant used when preparing a magenta toner composition include DuPont oil red and rose bengal. Further, examples of the colorant used when preparing a cyan toner composition include aniline blue, methylene blue chloride, and phthalocyanine blue.
　本発明の組成物における着色剤の組み合わせは、求められる色彩等に応じて決められる。また、着色剤の配合量は、トナー組成物の全量に対して、通常は０．１～１０重量％程度となる量である。 The combination of colorants in the composition of the present invention is determined according to the required color and the like. The blending amount of the colorant is usually about 0.1 to 10% by weight with respect to the total amount of the toner composition.
　本発明のトナー組成物を１成分系現像剤である磁性トナーとして用いる場合には、トナー組成物には磁性粉が必須成分として配合される。用いられる磁性粉としては、例えばフェライト、マグネタイト等の酸化鉄、鉄、コバルト、ニッケル等の金属からなるものが挙げられ、これらは１種単独でも２種以上を組み合わせてもよい。 When the toner composition of the present invention is used as a magnetic toner which is a one-component developer, magnetic powder is blended as an essential component in the toner composition. Examples of the magnetic powder used include iron oxides such as ferrite and magnetite, and metals such as iron, cobalt, and nickel. These may be used alone or in combination of two or more.
　また、この磁性粉は粒径１μｍ以下の微粉末である事が好ましい。本発明のトナー組成物が磁性粉を含有する磁性トナーである場合、その配合割合はトナー樹脂（結着樹脂）１００重量部に対して５０～２００重量部の割合である。 The magnetic powder is preferably a fine powder having a particle size of 1 μm or less. When the toner composition of the present invention is a magnetic toner containing magnetic powder, the blending ratio is 50 to 200 parts by weight with respect to 100 parts by weight of the toner resin (binder resin).
　さらに本発明のトナー組成物は、前記のトナー樹脂、着色剤、及び磁性粉以外に、必要に応じて、従来の電子写真用トナー組成物に常用される各種配合剤を配合することができる。例えば、トナー樹脂として常用されているスチレンアクリル樹脂、ポリエステル樹脂、エポキシ樹脂等を更に配合することができる。また必要に応じて、荷電調整剤、可塑剤、低分子量ポリエチレン、低分子量ポリプロピレン、パラフィンワックス、アミドワックス、シリコーンオイル等の離型剤、シリカ等の流動性向上剤などを配合することもできる。
　ただし、これら任意成分の配合量は、本発明の効果を妨げない範囲に限られる。 Further, the toner composition of the present invention may contain various compounding agents commonly used in conventional electrophotographic toner compositions, if necessary, in addition to the toner resin, the colorant and the magnetic powder. For example, a styrene acrylic resin, a polyester resin, an epoxy resin or the like that is commonly used as a toner resin can be further blended. Further, if necessary, a charge control agent, a plasticizer, a low molecular weight polyethylene, a low molecular weight polypropylene, a mold release agent such as paraffin wax, amide wax, and silicone oil, and a fluidity improver such as silica can be blended.
However, the blending amount of these optional components is limited to a range that does not hinder the effects of the present invention.
　本発明の組成物は通常、平均粒径５～１５μｍの粒子集合体の形態で提供される。 The composition of the present invention is usually provided in the form of a particle aggregate having an average particle size of 5 to 15 μm.
　本発明のトナー組成物は、トナー樹脂（結着樹脂）及び着色剤、更に１成分系現像剤である磁性トナーとする場合には磁性粉、そして必要に応じて荷電調整剤、ワックス、その他の任意の添加剤を、ヘンシェルミキサー、ボールミル等の混合機によって十分混合した後、加熱ロール、ニーダー、押し出し機等の加熱混合機を用いて溶融混合する。次に冷却固化後、ジェットミル等を用いて粉砕および分級を行って製造することができる。 The toner composition of the present invention comprises a toner resin (binder resin) and a colorant, and further a magnetic powder in the case of a magnetic toner as a one-component developer, and if necessary, a charge adjusting agent, a wax, other Arbitrary additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then melt-mixed using a heating mixer such as a heating roll, a kneader, or an extruder. Next, after cooling and solidification, it can be produced by pulverization and classification using a jet mill or the like.
　以下に具体例を挙げて本発明を更に詳細に説明するが、本発明の技術範囲は以下の実施例によって限定されるものではなく、添付の特許請求の範囲によって確定されるものである。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the technical scope of the present invention is not limited by the following examples, but is defined by the appended claims.
（実施例１）
　攪拌装置、温度計、窒素導入口及び還流管を備えた容量１０００ｍｌ丸底セパラブルフラスコに、ビスフェノールＡプロピレンオキシド付加体（中日合成社製Ｐ－ＲＡ－ＦＢＨ　水酸基価　３１４　ＫＯＨｍｇ／ｇ）　３８８．９ｇ、イソフタル酸２１０．８ｇ、ジブチルチンオキサイド３．０２ｇ、キシレン３０．０ｇを仕込み昇温を行い、反応開始当初トップ温度を１００℃を超えないよう加熱し、脱水反応を実施した。 Example 1
Bisphenol A propylene oxide adduct (P-RA-FBH hydroxyl value 314 KOHmg / g, manufactured by Chunichi Gosei Co., Ltd.) in a 1000 ml round bottom separable flask equipped with a stirrer, thermometer, nitrogen inlet and reflux tube 388. 9 g, 210.8 g of isophthalic acid, 3.02 g of dibutyltin oxide, and 30.0 g of xylene were charged and the temperature was raised. The top temperature at the beginning of the reaction was heated so as not to exceed 100 ° C., and a dehydration reaction was carried out.
　反応途中でサンプリングを行い、酸価の測定を行い、理論酸価値に近づいたら還流管を減圧装置：コンデンサーに変え、２４０℃で減圧度を除々に高め水、未反応物を留去した。減圧度は１．３３Ｋｐａ（１０ｍｍＨｇ）以下に達し３～６時間攪拌後サンプリングを行い酸価の測定を行った。反応系内の温度を１５０℃程度まで降温し、ビスフェノールＡ型液状エポキシ樹脂（長春化工製、ＢＥ１８８ＥＬ、エポキシ当量１８９ｇ／ｅｑ）１０２．８ｇ、安息香酸１８．６ｇ、ステアリン酸１８．６ｇ、キシレン７７．７ｇを仕込み、テトラメチルアンモニウムクロリドを６００ｐｐｍ加えた。 Sampling was performed during the reaction, and the acid value was measured. When the theoretical acid value was approached, the reflux tube was changed to a pressure reducing device: condenser, and the degree of vacuum was gradually increased at 240 ° C. to distill off water and unreacted substances. The degree of vacuum reached 1.33 Kpa (10 mmHg) or less, and after stirring for 3 to 6 hours, sampling was performed to measure the acid value. The temperature in the reaction system was lowered to about 150 ° C., and 102.8 g of a bisphenol A type liquid epoxy resin (manufactured by Changchun Kako, BE188EL, epoxy equivalent 189 g / eq), benzoic acid 18.6 g, stearic acid 18.6 g, xylene 77 0.7 g was charged and 600 ppm of tetramethylammonium chloride was added.
　１６０℃で２時間反応後、減圧ラインとした後減圧を開始し減圧度１．３３Ｋｐａ（１０ｍｍＨｇ）以下に達し、１時間攪拌後常圧に戻し、１６０℃で引き続き反応を継続する。１６０℃で８時間反応後サンプリングを行い、エポキシ当量を測定し、エポキシ当量が２００００以上であることを確認した後、生成したポリエーテル変性ポリエステル樹脂をフラスコから抜き出した。 After the reaction at 160 ° C. for 2 hours, the pressure reduction line was started, and the pressure reduction was started. The pressure reached 1.33 Kpa (10 mmHg) or less, stirred for 1 hour, returned to normal pressure, and the reaction was continued at 160 ° C. Sampling was performed after reaction at 160 ° C. for 8 hours, and the epoxy equivalent was measured. After confirming that the epoxy equivalent was 20000 or more, the produced polyether-modified polyester resin was extracted from the flask.
　得られたポリエーテル変性ポリエステル樹脂は、次の特性を有していた。
　エポキシ当量：２００００以上、軟化点：１２３℃、ガラス転移温度：６０℃、数平均分子量（Ｍｎ）：６２８０、重量平均分子量（Ｍｗ）：２０３００、重量平均分子量（Ｍｎ）と数平均分子量（Ｍｗ）の比（分布Ｍｗ／Ｍｎ）：３．２。 The obtained polyether-modified polyester resin had the following characteristics.
Epoxy equivalent: 20000 or more, softening point: 123 ° C., glass transition temperature: 60 ° C., number average molecular weight (Mn): 6280, weight average molecular weight (Mw): 20300, weight average molecular weight (Mn) and number average molecular weight (Mw) Ratio (distribution Mw / Mn): 3.2.
（実施例２）
　攪拌装置、温度計、窒素導入口及び還流管を備えた容量１０００ｍｌ丸底セパラブルフラスコに、ビスフェノールＡプロピレンオキシド付加体（中日合成社製Ｐ－ＲＡ－ＦＢＨ　水酸基価　３１８　ＫＯＨｍｇ／ｇ）　３５０．９ｇ、ジエチレングリコール２６．３ｇ、イソフタル酸２２７．５ｇ、ジブチルチンオキサイド３．０４ｇ、キシレン２５．２ｇを仕込み昇温を行い、反応初期トップ温度を１００℃を超えないよう加熱し、脱水反応を実施した。反応途中でサンプリングを行い、酸価の測定を行い、理論酸価値に近づいたら還流管を減圧装置：コンデンサーに変え、２４０℃で減圧度を除々に高め水、未反応物を留去した。減圧度は１．３３Ｋｐａ（１０ｍｍＨｇ）以下に達し３～６時間攪拌後サンプリングを行い酸価の測定を行った。 (Example 2)
Bisphenol A propylene oxide adduct (P-RA-FBH hydroxyl value 318 KOHmg / g manufactured by Chunichi Gosei Co., Ltd.) in a 1000 ml round bottom separable flask equipped with a stirrer, thermometer, nitrogen inlet and reflux tube 350. 9 g, 26.3 g of diethylene glycol, 227.5 g of isophthalic acid, 3.04 g of dibutyltin oxide, and 25.2 g of xylene were charged and heated so that the initial top temperature of the reaction did not exceed 100 ° C., and a dehydration reaction was performed. . Sampling was performed during the reaction, and the acid value was measured. When the theoretical acid value was approached, the reflux tube was changed to a vacuum device: condenser, and the degree of vacuum was gradually increased at 240 ° C. to distill off water and unreacted substances. The degree of vacuum reached 1.33 Kpa (10 mmHg) or less, and after stirring for 3 to 6 hours, sampling was performed to measure the acid value.
　反応系内の温度を１５０℃程度まで降温し、ビスフェノールＡ型液状エポキシ樹脂（長春化工製、ＢＥ１８８ＥＬ、エポキシ当量１８９ｇ／ｅｑ）９９．６ｇ、ビスフェノールＡ１１．３ｇ、安息香酸２９．１ｇ、キシレン７７．７ｇを仕込み、テトラメチルアンモニウムクロラリドを６００ｐｐｍ加えた。 The temperature in the reaction system was lowered to about 150 ° C., 99.6 g of a bisphenol A type liquid epoxy resin (Changchun Kako, BE188EL, epoxy equivalent 189 g / eq), bisphenol A 11.3 g, benzoic acid 29.1 g, xylene 77. 7 g was charged, and 600 ppm of tetramethylammonium chloride was added.
　１６０℃で２時間反応後、減圧ラインとした後減圧を開始し減圧度１．３３Ｋｐａ（１０ｍｍＨｇ）以下に達し、１時間攪拌後常圧に戻し、１６０℃で引き続き反応を継続する。１６０℃で８時間反応後サンプリングを行い、エポキシ当量を測定し、エポキシ当量が２００００以上であることを確認した後、生成したポリエーテル変性ポリエステル樹脂をフラスコから抜き出した。 After the reaction at 160 ° C. for 2 hours, the pressure reduction line was started, and the pressure reduction was started. The pressure reached 1.33 Kpa (10 mmHg) or less, stirred for 1 hour, returned to normal pressure, and the reaction was continued at 160 ° C. Sampling was performed after reaction at 160 ° C. for 8 hours, and the epoxy equivalent was measured. After confirming that the epoxy equivalent was 20000 or more, the produced polyether-modified polyester resin was extracted from the flask.
　得られたポリエーテル変性ポリエステル樹脂は、次の特性を有していた。
　エポキシ当量：２００００以上、軟化点：１１６℃、ガラス転移温度：５９℃、数平均分子量（Ｍｎ）：４５５０、重量平均分子量（Ｍｗ）：１８９００、重量平均分子量（Ｍｎ）と数平均分子量（Ｍｗ）の比（分布Ｍｗ／Ｍｎ）：４．２。 The obtained polyether-modified polyester resin had the following characteristics.
Epoxy equivalent: 20000 or more, softening point: 116 ° C., glass transition temperature: 59 ° C., number average molecular weight (Mn): 4550, weight average molecular weight (Mw): 18900, weight average molecular weight (Mn) and number average molecular weight (Mw) Ratio (distribution Mw / Mn): 4.2.
（実施例３）
　攪拌装置、温度計、窒素導入口及び還流管を備えた容量１０００ｍｌ丸底セパラブルフラスコに、ビスフェノールＡプロピレンオキシド付加体（中日合成社製Ｐ－ＲＡ－ＦＢＨ　水酸基価　３１４　ＫＯＨｍｇ／ｇ）　３６６．２ｇ、トリエチレングリコール１７．１ｇ、イソフタル酸２１７．８ｇ、ジブチルチンオキサイド３．０２ｇ、キシレン２５．０ｇを仕込み昇温を行い、反応初期トップ温度を１００℃を超えないよう加熱し、脱水反応を実施した。反応途中でサンプリングを行い、酸価の測定を行い、理論酸価値に近づいたら還流管を減圧装置：コンデンサーに変え、２４０℃で減圧度を除々に高め水、未反応物を留去した。 (Example 3)
Into a 1000 ml round bottom separable flask equipped with a stirrer, thermometer, nitrogen inlet and reflux tube, bisphenol A propylene oxide adduct (P-RA-FBH hydroxyl value 314 KOHmg / g manufactured by Chunichi Gosei Co., Ltd.) 366. 2 g, 17.1 g of triethylene glycol, 217.8 g of isophthalic acid, 3.02 g of dibutyltin oxide, and 25.0 g of xylene are heated and heated so that the initial top temperature of the reaction does not exceed 100 ° C. Carried out. Sampling was performed during the reaction, and the acid value was measured. When the theoretical acid value was approached, the reflux tube was changed to a vacuum device: condenser, and the degree of vacuum was gradually increased at 240 ° C. to distill off water and unreacted substances.
　減圧度は１．３３Ｋｐａ（１０ｍｍＨｇ）以下に達し３時間攪拌後サンプリングを行い酸価の測定を行った。
　反応系内の温度を１５０℃程度まで降温し、ビスフェノールＡ型液状エポキシ樹脂（長春化工製、ＢＥ１８８ＥＬ、エポキシ当量１８９ｇ／ｅｑ）１０１．８ｇ、ビスフェノールＡ９．１ｇ、安息香酸２９．１ｇ、キシレン７７．７ｇを仕込み、テトラメチルアンモニウムクロライドを６００ｐｐｍ加えた。 The degree of vacuum reached 1.33 Kpa (10 mmHg) or less, and after stirring for 3 hours, sampling was performed to measure the acid value.
The temperature in the reaction system was lowered to about 150 ° C., bisphenol A type liquid epoxy resin (Changchun Kako, BE188EL, epoxy equivalent 189 g / eq) 101.8 g, bisphenol A 9.1 g, benzoic acid 29.1 g, xylene 77. 7 g was charged and 600 ppm of tetramethylammonium chloride was added.
　１６０℃で２時間反応後、減圧ラインとした後減圧を開始し減圧度１．３３Ｋｐａ（１０ｍｍＨｇ）以下に達し、１時間攪拌後常圧に戻し、１６０℃で引き続き反応を継続する。１６０℃で８時間反応後サンプリングを行い、エポキシ当量を測定し、エポキシ当量が２００００以上であることを確認した後、生成したポリエーテル変性ポリエステル樹脂をフラスコから抜き出した。 After the reaction at 160 ° C. for 2 hours, the pressure reduction line was started, and the pressure reduction was started. The pressure reached 1.33 Kpa (10 mmHg) or less, stirred for 1 hour, returned to normal pressure, and the reaction was continued at 160 ° C. Sampling was performed after reaction at 160 ° C. for 8 hours, and the epoxy equivalent was measured. After confirming that the epoxy equivalent was 20000 or more, the produced polyether-modified polyester resin was extracted from the flask.
　得られたポリエーテル変性ポリエステル樹脂は、次の特性を有していた。
　エポキシ当量：２００００以上、軟化点：１１６℃、ガラス転移温度：５９℃、数平均分子量（Ｍｎ）：５３００、重量平均分子量（Ｍｗ）：１９０００、重量平均分子量（Ｍｎ）と数平均分子量（Ｍｗ）の比（分布Ｍｗ／Ｍｎ）：３．６。 The obtained polyether-modified polyester resin had the following characteristics.
Epoxy equivalent: 20000 or more, softening point: 116 ° C., glass transition temperature: 59 ° C., number average molecular weight (Mn): 5300, weight average molecular weight (Mw): 19000, weight average molecular weight (Mn) and number average molecular weight (Mw) Ratio (distribution Mw / Mn): 3.6.
（実施例４）
　攪拌装置、温度計、窒素導入口及び還流管を備えた容量１０００ｍｌ丸底セパラブルフラスコに、ビスフェノールＡプロピレンオキシド付加体（中日合成社製Ｐ－ＲＡ－ＦＢＨ　水酸基価　３１４　ＫＯＨｍｇ／ｇ）　２１９．４ｇ、イソフタル酸２１９．４ｇ、ジブチルチンオキサイド３．２８ｇを仕込み昇温を行い、反応初期トップ温度が１００℃を超えないよう加熱し、脱水反応を実施した。 (Example 4)
Bisphenol A propylene oxide adduct (P-RA-FBH hydroxyl value 314 KOHmg / g, manufactured by Chunichi Gosei Co., Ltd.) in a 1000 ml round bottom separable flask equipped with a stirrer, thermometer, nitrogen inlet and reflux tube 219. 4 g, 219.4 g of isophthalic acid, and 3.28 g of dibutyltin oxide were charged, and the temperature was raised. The top temperature of the reaction was heated so as not to exceed 100 ° C., and a dehydration reaction was performed.
　反応途中でサンプリングを行い、酸価の測定を行い、理論酸価値に近づいたら還流管を減圧装置：コンデンサーに変え、２４０℃で減圧度を除々に高め水、未反応物を留去した。減圧度は１．３３Ｋｐａ（１０ｍｍＨｇ）に達し３時間攪拌後サンプリングを行い酸価の測定を行う。反応系内の温度を１５０℃程度まで降温し、ビスフェノールＡ型液状エポキシ樹脂（長春化工製、ＢＥ１８８ＥＬ、エポキシ当量１８９ｇ／ｅｑ）９７．５ｇ、ビスフェノールＡ３４．１ｇ、安息香酸１８．４ｇ、ワックス（日油社製ＷＥ－１０）８３．３ｇ、キシレン９３ｇを仕込み、テトラメチルアンモニウムクロライドを５００ｐｐｍ加えた。１６０℃で２時間反応後、減圧ラインとした後減圧を開始し減圧度１．３３Ｋｐａ（１０ｍｍＨｇ）に達し１時間攪拌後常圧に戻し、１６０℃で引き続き反応を継続する。１６０℃で８時間反応後サンプリングを行い、エポキシ当量を測定し、エポキシ当量が２００００以上であることを確認した後、生成したポリエーテル変性ポリエステル樹脂をフラスコから抜き出した。 Sampling was performed during the reaction, and the acid value was measured. When the theoretical acid value was approached, the reflux tube was changed to a pressure reducing device: condenser, and the degree of vacuum was gradually increased at 240 ° C. to distill off water and unreacted substances. The degree of vacuum reaches 1.33 Kpa (10 mmHg), and after stirring for 3 hours, sampling is performed to measure the acid value. The temperature in the reaction system was lowered to about 150 ° C., and bisphenol A type liquid epoxy resin (Changchun Kako, BE188EL, epoxy equivalent 189 g / eq) 97.5 g, bisphenol A 34.1 g, benzoic acid 18.4 g, wax (day WE-10 manufactured by Oil Co., Ltd., 83.3 g and 93 g of xylene were charged, and 500 ppm of tetramethylammonium chloride was added. After the reaction at 160 ° C. for 2 hours, the pressure reduction line was started and the pressure reduction was started. The pressure reached 1.33 Kpa (10 mmHg), the mixture was stirred for 1 hour and returned to normal pressure. The reaction was continued at 160 ° C. Sampling was performed after reaction at 160 ° C. for 8 hours, and the epoxy equivalent was measured. After confirming that the epoxy equivalent was 20000 or more, the produced polyether-modified polyester resin was extracted from the flask.
　得られたポリエーテル変性ポリエステル樹脂は、次の特性を有していた。
　軟化点：１１０℃、ガラス転移温度：５８℃、数平均分子量（Ｍｎ）：２７９０、重量平均分子量（Ｍｗ）：１０３７０、重量平均分子量（Ｍｎ）と数平均分子量（Ｍｗ）の比（分布Ｍｗ／Ｍｎ）：３．７。 The obtained polyether-modified polyester resin had the following characteristics.
Softening point: 110 ° C., glass transition temperature: 58 ° C., number average molecular weight (Mn): 2790, weight average molecular weight (Mw): 10370, ratio of weight average molecular weight (Mn) to number average molecular weight (Mw) (distribution Mw / Mn): 3.7.
（比較例１）
　攪拌装置、温度計、窒素導入口及び還流管を備えた容量１０００ｍｌ丸底セパラブルフラスコに、ビスフェノールＡプロピレンオキシド付加体（中日合成社製Ｐ－ＲＡ－ＦＢＨ　水酸基価　３１４　ＫＯＨｍｇ／ｇ）　３８８．９ｇ、イソフタル酸２１０．８ｇ、ジブチルチンオキサイド３．０２ｇ、キシレン３０．０ｇを仕込み昇温を行い、トップ温度を１００℃を超えないよう加熱し、脱水反応を実施した。 (Comparative Example 1)
Bisphenol A propylene oxide adduct (P-RA-FBH hydroxyl value 314 KOHmg / g, manufactured by Chunichi Gosei Co., Ltd.) in a 1000 ml round bottom separable flask equipped with a stirrer, thermometer, nitrogen inlet and reflux tube 388. 9 g, 210.8 g of isophthalic acid, 3.02 g of dibutyltin oxide, and 30.0 g of xylene were charged, the temperature was raised, and the top temperature was heated so as not to exceed 100 ° C. to carry out a dehydration reaction.
　反応途中でサンプリングを行い、酸価の測定を行い、理論酸価値に近づいたら還流管を減圧装置：コンデンサーに変え、２４０℃で減圧度を除々に高め水、未反応物を留去した。減圧度は１．３３Ｋｐａ（１０ｍｍＨｇ）以下に達し３時間攪拌後サンプリングを行い酸価の測定を行い生成したポリエステル樹脂をフラスコから抜き出した。 Sampling was performed during the reaction, and the acid value was measured. When the theoretical acid value was approached, the reflux tube was changed to a pressure reducing device: condenser, and the degree of vacuum was gradually increased at 240 ° C. to distill off water and unreacted substances. The degree of vacuum reached 1.33 Kpa (10 mmHg) or less, and after stirring for 3 hours, sampling was performed to measure the acid value, and the produced polyester resin was extracted from the flask.
　得られたポリエステル樹脂は、次の特性を有していた。
　酸価：３２．７ＫＯＨｍｇ／ｇ、軟化点：１２２℃、ガラス転移温度：７４℃、数平均分子量（Ｍｎ）：１５１０、重量平均分子量（Ｍｗ）：６４１０、重量平均分子量（Ｍｎ）と数平均分子量（Ｍｗ）の比（分布Ｍｗ／Ｍｎ）：３．２。 The obtained polyester resin had the following characteristics.
Acid value: 32.7 KOH mg / g, softening point: 122 ° C., glass transition temperature: 74 ° C., number average molecular weight (Mn): 1510, weight average molecular weight (Mw): 6410, weight average molecular weight (Mn) and number average molecular weight Ratio of (Mw) (distribution Mw / Mn): 3.2.
（比較例２）
　攪拌装置、温度計、窒素導入口及び還流管を備えた容量１０００ｍｌ丸底セパラブルフラスコに、ビスフェノールＡ型液状エポキシ樹脂（長春化工製、ＢＥ１８８ＥＬ、エポキシ当量１８９ｇ／ｅｑ）４９７．０ｇ、ビスフェノールＡ５７．２ｇ、安息香酸１４５．８ｇ、キシレン７７．７ｇを仕込み、テトラメチルアンモニュウムクロライドを６００ｐｐｍ加えた。 (Comparative Example 2)
Into a 1000 ml round bottom separable flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux tube, 497.0 g of bisphenol A type liquid epoxy resin (manufactured by Changchun Kako, BE188EL, epoxy equivalent 189 g / eq) 57. 2 g, 145.8 g of benzoic acid, and 77.7 g of xylene were charged, and 600 ppm of tetramethylammonium chloride was added.
　１６０℃で２時間反応後、減圧ラインとした後減圧を開始し減圧度１．３３Ｋｐａ（１０ｍｍＨｇ）以下に達し、１時間攪拌後常圧に戻し、１６０℃で引き続き反応を継続する。１６０℃で８時間反応後生成したエポキシ樹脂をフラスコから抜き出した。 After the reaction at 160 ° C. for 2 hours, the pressure reduction line was started, and the pressure reduction was started. The pressure reached 1.33 Kpa (10 mmHg) or less, stirred for 1 hour, returned to normal pressure, and the reaction was continued at 160 ° C. The epoxy resin produced after the reaction at 160 ° C. for 8 hours was extracted from the flask.
　得られたエポキシ樹脂のエポキシ当量は１１１０ｇ／ｅｑ、軟化点：６４．５℃、ガラス転移温度：２４℃、数平均分子量（Ｍｎ）：１４１０、重量平均分子量（Ｍｗ）：２７４０、重量平均分子量（Ｍｎ）と数平均分子量（Ｍｗ）の比（分布Ｍｗ／Ｍｎ）：２．０であった。 The epoxy equivalent of the obtained epoxy resin is 1110 g / eq, softening point: 64.5 ° C., glass transition temperature: 24 ° C., number average molecular weight (Mn): 1410, weight average molecular weight (Mw): 2740, weight average molecular weight ( Mn) to number average molecular weight (Mw) (distribution Mw / Mn): 2.0.
　上記実施例１～４及び比較例１及び２で調製した樹脂を用い、着色剤、磁性粉末などを加えてトナー組成物を調製し、以下の評価を行った。 Using the resins prepared in Examples 1 to 4 and Comparative Examples 1 and 2, a toner composition was prepared by adding a colorant, magnetic powder, and the like, and the following evaluation was performed.
＜耐ブロッキング性＞
　７０ｍｌガラス製サンプル瓶に、各例のトナー組成物粉末１０ｇを入れ、５０℃、相対湿度３５％の恒温恒湿槽中に３時間放置した。その後室温まで冷却し、その凝集度を目視で観察し、以下の規準にて評価を行った。
　◎：サンプル瓶を逆さにしただけで現像剤組成物粉末が流出する。
　○：サンプル瓶を逆さにし、軽く振っただけで現像剤組成物粉末が流出する。
　△サンプル瓶を逆さにし、軽くたたくと現像剤組成物粉末が流出する。
　▲：サンプル瓶を逆さにし、強い振動を与えると現像剤組成物粉末が流出する。
　×：サンプル瓶を逆さにした時全く現像剤組成物粉末が流出せず固化状態である。 <Blocking resistance>
In a 70 ml glass sample bottle, 10 g of the toner composition powder of each example was placed and left in a constant temperature and humidity chamber at 50 ° C. and a relative humidity of 35% for 3 hours. Thereafter, the mixture was cooled to room temperature, the degree of aggregation was visually observed, and evaluation was performed according to the following criteria.
A: The developer composition powder flows out only by inverting the sample bottle.
○: The developer composition powder flows out simply by turning the sample bottle upside down and shaking it lightly.
Δ When the sample bottle is turned upside down and tapped, the developer composition powder flows out.
▲: When the sample bottle is turned upside down and a strong vibration is applied, the developer composition powder flows out.
X: When the sample bottle is turned upside down, the developer composition powder does not flow out and is solidified.
＜定着性試験＞
　電子写真複写機の定着用熱ローラーの表面温度を変更可能に改造した電子写真複写機を用いて、定着用熱ローラーの表面温度を１００～２００℃の範囲で変えて、電子写真現像剤粉末の複写を行った。得られる複写画像の消しゴムで摩擦したときの複写画像における濃度変化を目視で観察した。定着用熱ローラーの表面温度を１１０℃から５℃刻みで上げ、定着率８５％を超えた時の温度を最低定着温度とした。さらに温度を上げ試験を行い、該電子写真現像剤粉末が熱ローラーに付着し始めた温度をオフセット開始温度とした。 <Fixability test>
Using an electrophotographic copying machine modified so that the surface temperature of the fixing heat roller of the electrophotographic copying machine can be changed, the surface temperature of the fixing heat roller is changed in the range of 100 to 200 ° C. A copy was made. The density change in the copy image when the resulting copy image was rubbed with an eraser was visually observed. The surface temperature of the fixing heat roller was increased from 110 ° C. in increments of 5 ° C., and the temperature when the fixing rate exceeded 85% was defined as the minimum fixing temperature. Further, the test was conducted by raising the temperature, and the temperature at which the electrophotographic developer powder began to adhere to the heat roller was defined as the offset start temperature.
　実施例に記載のポリエーテル変性ポリエステル樹脂を用い、上記の方法にて電子写真組成物粉末を作成し、耐ブロッキング性試験、定着性試験結果を各樹脂物性値と合わせ表１に記載する。また、比較例との比較も合わせて実施した。 Using the polyether-modified polyester resin described in the examples, an electrophotographic composition powder is prepared by the above-described method, and the results of blocking resistance test and fixability test are shown in Table 1 together with the physical properties of each resin. Moreover, the comparison with a comparative example was also implemented.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　比較例１で合成したポリエステル樹脂と、比較例２で合成したエポキシ樹脂を用いて混合した場合と、反応を実施した場合の物性をエポキシ当量の測定、酸価の測定を行う事により、比較を実施した。 When the polyester resin synthesized in Comparative Example 1 and the epoxy resin synthesized in Comparative Example 2 were mixed and measured, the physical properties when the reaction was carried out were measured by measuring the epoxy equivalent and the acid value. Carried out.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表２の結果より、ポリエステル樹脂／エポキシ樹脂＝８／２の混合物のエポキシ当量（ＥＥＷ）は６２００、酸価（ＡＶ）は２６ＫＯＨｍｇ／ｇであるが、１６０℃で反応した場合は、ＥＥＷが２００００超と実質的にエポキシ基が存在しない事が確認され、ＡＶは１９となり、理論的にはエポキシ基がポリエステル樹脂のカルボキシル基と全て反応した場合１６．１ＫＯＨｍｇ／ｇとなる事からほぼ反応していることが確認できた。 From the results of Table 2, the mixture of polyester resin / epoxy resin = 8/2 has an epoxy equivalent (EEW) of 6200 and an acid value (AV) of 26 KOHmg / g, but when reacted at 160 ° C., the EEW is 20000. It is confirmed that there is substantially no epoxy group, and AV is 19. In theory, when all the epoxy groups react with the carboxyl groups of the polyester resin, it becomes 16.1 KOHmg / g. It was confirmed that
　同様にポリエステル樹脂／エポキシ樹脂＝６／４の混合物のエポキシ当量（ＥＥＷ）は３２００、酸価（ＡＶ）は１８ＫＯＨｍｇ／ｇであるが１６０℃で反応した場合は、ＥＥＷが２００００超と実質的にエポキシ基が存在しない事が確認され、ＡＶは２となり、反応していることが確認できた。 Similarly, the mixture of polyester resin / epoxy resin = 6/4 has an epoxy equivalent (EEW) of 3200 and an acid value (AV) of 18 KOH mg / g, but when reacted at 160 ° C., the EEW is substantially over 20000. It was confirmed that no epoxy group was present, AV was 2, and it was confirmed that the reaction occurred.
　本発明の製造方法に従って実施例５の樹脂を製造した。一方、本発明とは異なる製造方法で比較例３の樹脂を製造した。実施例５御比較例３の樹脂は、表３に示す物性値を有していた。次いで、これらの樹脂の融点及び軟化温度を測定した（結果を表４に示す）。具体的な測定方法は以下の通りである。 The resin of Example 5 was produced according to the production method of the present invention. On the other hand, the resin of Comparative Example 3 was produced by a production method different from the present invention. Example 5 The resin of Comparative Example 3 had the physical property values shown in Table 3. Next, the melting points and softening temperatures of these resins were measured (results are shown in Table 4). The specific measurement method is as follows.
［融点の測定方法］
　乾燥した試料を乳鉢中で細かく粉砕し、一端を封印した毛細管に約３ｍｍとなる量を均一に充填した。
　溶液は約１分間に３℃上昇するように加温し、充填した毛細管は予想する融点より約１０℃低い液浴中に挿入した。予想される融点より約５℃低い温度からは、１分間に１℃上昇するよう加熱した。試料が毛細管内で溶融して、固体を認めなくなった時の温度を読み取った。
　装置：ヤマト製ＭＰ－２１
　溶液：シリコーンオイルＫＦ－９６を使用 [Measuring method of melting point]
The dried sample was finely pulverized in a mortar, and a capillary tube sealed at one end was uniformly filled with an amount of about 3 mm.
The solution was warmed to rise 3 ° C for about 1 minute and the filled capillary tube was inserted into a liquid bath about 10 ° C below the expected melting point. From a temperature about 5 ° C. lower than the expected melting point, heating was performed to increase 1 ° C. per minute. The temperature at which the sample melted in the capillary tube and no solid was observed was read.
Equipment: MP-21 made by Yamato
Solution: Use silicone oil KF-96
［軟化温度の測定方法］
　ＤＰ－７０測定装置（メトラー社製）を使用し、１℃／ｍｉｎの昇温速度で以下に示す方法で測定した。
（ｉ）測定装置（ＤＰ－７０）のカップより出始めの温度を開始温度とし、出始めより１９ｍｍサンプルが移動した温度を終了温度とした。
（ｉｉ）上記カップの出始めから終了までの時間を軟化時間とした。 [Measurement method of softening temperature]
A DP-70 measuring apparatus (manufactured by Mettler) was used, and the measurement was carried out by the following method at a heating rate of 1 ° C./min.
(I) The temperature at which the measurement apparatus (DP-70) began to come out from the cup was taken as the start temperature, and the temperature at which the 19 mm sample moved from the start was taken as the end temperature.
(Ii) The time from the start to the end of the cup was defined as the softening time.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　上記の表３、４に示すように、比較例３は、融点が９４．１℃～１１６．１℃であったのに対し、実施例５は８８．３℃～１０６．７℃と低くなっている。軟化温度も、比較例３が１１４℃～１２９℃であったのに対し、実施例５は１０１℃～１１１℃と低く、軟化時間も短くなった。 As shown in Tables 3 and 4 above, Comparative Example 3 had a melting point of 94.1 ° C. to 116.1 ° C., whereas Example 5 was as low as 88.3 ° C. to 106.7 ° C. ing. The softening temperature was 114 ° C. to 129 ° C. in Comparative Example 3, whereas Example 5 was as low as 101 ° C. to 111 ° C., and the softening time was shortened.
　これらの測定結果は、実施例５と比較例３とは、ガラス転移温度（Ｔｇ）及び数平均分子量（Ｍｎ）においては大差が無いにも拘らず、重量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）が大きく相違し、これにより融点及び軟化温度が高くなったことを示唆している。 These measurement results show that the weight average molecular weight (Mw) and the molecular weight distribution (Mw) of Example 5 and Comparative Example 3 are not significantly different in glass transition temperature (Tg) and number average molecular weight (Mn). / Mn) is significantly different, suggesting that the melting point and softening temperature were increased.
　融点及び軟化温度という熱特性は、トナー樹脂とした場合の低温定着性に寄与している。より詳細には、融点及び軟化温度が低いことは、加熱ロールによる熱転写時に、より低い温度で溶融して紙への転写が開始することを意味する。従って、本発明の樹脂（実施例５）は、比較例３に比べて、トナー樹脂としての低温定着性において優れていると言うことができる。 The thermal characteristics such as melting point and softening temperature contribute to low-temperature fixability when toner resin is used. More specifically, the low melting point and softening temperature mean that, at the time of thermal transfer by a heating roll, melting at a lower temperature starts transfer to paper. Therefore, it can be said that the resin of the present invention (Example 5) is superior in low-temperature fixability as a toner resin as compared with Comparative Example 3.

Claims (5)

  1. （１）多塩基酸及び多価アルコールを縮合重合させてポリエステル樹脂（Ａ）を調製する工程、及び
    （２）前記ポリエステル樹脂（Ａ）、エポキシ化合物、一価カルボン酸又は一価フェノール、及び好ましくは二価フェノールを共重合させることにより、滴点・軟化温度が７０～１５０℃、ガラス転移温度が５０～７０℃、数平均分子量（Ｍｎ）が２７００～１００００、重量平均分子量（Ｍｗ）が１００００～３００００、分子量分布（Ｍｗ／Ｍｎ）が２．０～５．０であるポリエーテル変性ポリエステル樹脂（ＡＢ）を調製する工程、を含む電子写真用トナー樹脂の製造方法。     (1) a step of preparing a polyester resin (A) by condensation polymerization of a polybasic acid and a polyhydric alcohol, and (2) the polyester resin (A), an epoxy compound, a monovalent carboxylic acid or a monohydric phenol, and preferably Has a dropping point / softening temperature of 70 to 150 ° C., a glass transition temperature of 50 to 70 ° C., a number average molecular weight (Mn) of 2700 to 10,000, and a weight average molecular weight (Mw) of 10,000 by copolymerizing dihydric phenol. And a step of preparing a polyether-modified polyester resin (AB) having a molecular weight distribution (Mw / Mn) of 2.0 to 5.0.
  2. 前記（１）で調製されたポリエステル樹脂（Ａ）の酸価が５～４０ＫＯＨｍｇ／ｇ、数平均分子量（Ｍｎ）が１０００～５０００、重量平均分子量（Ｍｗ）が３０００～３００００である、請求項１に記載の製造方法。 The polyester resin (A) prepared in (1) has an acid value of 5 to 40 KOHmg / g, a number average molecular weight (Mn) of 1000 to 5000, and a weight average molecular weight (Mw) of 3000 to 30000. The manufacturing method as described in.
  3. 請求項１又は２に記載の製造方法により製造され、滴点・軟化温度が７０～１５０℃、ガラス転移温度が５０～７０℃、数平均分子量（Ｍｎ）が２７００～１００００、重量平均分子量（Ｍｗ）が１００００～３００００、分子量分布（Ｍｗ／Ｍｎ）が２．０～５．０である、ポリエーテル変性ポリエステル樹脂。 It is produced by the production method according to claim 1 and has a dropping point / softening temperature of 70 to 150 ° C., a glass transition temperature of 50 to 70 ° C., a number average molecular weight (Mn) of 2700 to 10000, a weight average molecular weight (Mw). Is a polyether-modified polyester resin having a molecular weight distribution (Mw / Mn) of 2.0 to 5.0.
  4. ポリエステル部（Ａ）とエポキシ部（Ｂ）との比率が、ポリエステル部（Ａ）１００部に対してエポキシ部（Ｂ）が５～９０部である、請求項３に記載のポリエーテル変性ポリエステル樹脂。 The polyether-modified polyester resin according to claim 3, wherein the ratio of the polyester part (A) to the epoxy part (B) is 5 to 90 parts in the epoxy part (B) with respect to 100 parts in the polyester part (A). .
  5. 請求項３又は４に記載のポリエーテル変性ポリエステル樹脂をトナー樹脂として含有する、電子写真用トナー組成物。 An electrophotographic toner composition comprising the polyether-modified polyester resin according to claim 3 or 4 as a toner resin.
PCT/JP2017/009999 2016-03-11 2017-03-13 Method for producing polyether-modified polyester resin for electrophotography toner and electrophotography toner containing said resin WO2017155123A1 (en)

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