JP2017015879A - Electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic toner that is excellent in low-temperature fixability, storage property in high temperature and high humidity, and durability, and a binder resin for an electrophotographic toner used for the toner.SOLUTION: There is provided an electrophotographic toner containing a binder resin that is obtained through condensation polymerization of an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound in the presence of a hydrogenated terpene phenol copolymer resin, where the amount of the hydrogenated terpene phenol copolymer resin is 1 part by mass or more and 25 parts by mass or less based on the total amount 100 parts by mass of the alcohol component and the carboxylic acid component. Also provided is a binder resin for an electrophotographic toner used for the toner.SELECTED DRAWING: None

Description

  The present invention relates to an electrophotographic toner used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method and the like, and a binder resin for an electrophotographic toner used in the toner.

  In the field of electrophotography, with the development of electrophotographic systems, development of toner for electrophotography corresponding to high image quality is required.

  For example, Patent Document 1 contains a polylactic acid-based biodegradable resin, a terpene phenol copolymer resin, and one or more types of wax, and the total amount of wax is 7.0 to 20% by weight with respect to toner particles. An electrophotographic toner is described in which at least one of the waxes has a melting point equal to or lower than the softening temperature of the terpene phenol copolymer resin.

  Patent Document 2 describes an electrophotographic toner characterized by containing a polylactic acid-based biodegradable resin and a terpene phenol copolymer.

JP 2003-248339 A JP 2001-166537 A

  In Patent Documents 1 and 2, although a terpene phenol copolymer resin is used, the terpene phenol copolymer resin is not used as a raw material for the polycondensation reaction and is not a hydrogenated product.

  The present invention relates to an electrophotographic toner excellent in low-temperature fixability, storage stability under high temperature and high humidity, and durability, and a binder resin for electrophotographic toner used in the toner.

The present invention
[1] A binder resin obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound in the presence of a hydrogenated terpene phenol copolymer resin. An electrophotographic toner containing a binder resin in which the amount of the polymer resin is 1 part by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component; ] A binder resin for an electrophotographic toner obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound in the presence of a hydrogenated terpene phenol copolymer resin, the hydrogenated terpene phenol copolymer resin The amount of the terpene phenol copolymer resin is 1 part by weight or more and 25 parts by weight or less with respect to a total of 100 parts by weight of the alcohol component and the carboxylic acid component. On Chakujushi.

  The electrophotographic toner of the present invention exhibits excellent effects in low-temperature fixability, storage stability under high temperature and high humidity, and durability.

The electrophotographic toner of the present invention is a binder resin obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound in the presence of a predetermined amount of a hydrogenated terpene phenol copolymer resin. (Hereinafter also referred to as binder resin R).
The reason why the electrophotographic toner of the present invention is excellent in low-temperature fixability, storage stability under high temperature and high humidity (hereinafter also simply referred to as heat and humidity resistance storage stability), and durability is not clear, but is considered as follows. It is done.

The hydrogenated terpene phenol copolymer resin has a hydrogenated terpene skeleton and a hydrogenated phenol skeleton having a hydroxyl group. Both structures are highly hydrophobic and have a three-dimensional bulky structure. Yes. Therefore, it is considered that the resin having these skeletons has a structure with low flexibility.
In the presence of this hydrogenated terpene phenol resin, a binder resin obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound is excellent in moisture resistance due to increased hydrophobicity, As a result, it is considered that the storage stability under high temperature and high humidity is excellent.
Further, since the flexibility of the binder resin is low and it becomes hard as a resin, it is considered to be excellent in durability. Further, since the flexibility of the binder resin is low, it is considered that the ester group is also partially exposed on the surface, which is considered to be excellent in low-temperature fixability.

  Hydrogenated terpene phenolic copolymer resin is a hydrogenated product of terpene compound and phenolic copolymer resin, and terpene phenolic copolymer resin, for example, the presence of Friedel-Crafts type catalyst for terpene compound and phenolic It can manufacture by making it react under.

  The terpene compound, which is a raw material for producing the terpene phenol copolymer resin, is preferably a cyclic terpene compound, and may be a monocyclic terpene compound or a bicyclic terpene compound. Specific examples thereof include α-pinene, β-pinene, dipentene, limonene, ferrandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1,4-cineole, terpineol, camphene, tricyclene. , Paramenten-1, paramenten-2, paramenten-3, paramentadienes, caren and the like. Among these, α-pinene, β-pinene, and limonene are preferable, and limonene is more preferable from the viewpoints of heat and humidity resistance storage stability and durability. These compounds may be used alone or in combination of two or more, but are not limited thereto.

  Preferred examples of the phenols as the other raw material for producing the terpene phenol copolymer resin include an aromatic compound having a hydroxyl group, which may have a hydrocarbon group having 1 to 6 carbon atoms, for example, , Phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2, Examples include 4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,6-xylenol, p-phenylphenol, p-methoxyphenol, m-methoxyphenol and the like. Among these, phenol is preferable from the viewpoint of high reactivity and excellent heat and moisture resistance storage stability and durability. These compounds may be used alone or in combination of two or more, but are not limited thereto.

  Examples of Friedel-Crafts-type catalysts include aluminum chloride, boron trifluoride, and complexes thereof.

  The copolymerization reaction of a terpene compound and phenols can be performed in a reaction solvent such as an aromatic hydrocarbon as necessary. The reaction temperature is preferably about 0 ° C. or more and 120 ° C. or less, and the reaction time is preferably about 1 hour or more and 10 hours or less.

  The molar ratio of the terpene compound and phenols in the terpene phenol copolymer resin to be subjected to hydrogenation, i.e., the hydrogenated terpene phenol copolymer resin, is 1 mol of phenols from the viewpoint of heat and moisture resistance storage resistance, low temperature fixability, and durability. The number of moles of the terpene compound to be added is preferably 1 mol or more, more preferably 5 mol or more, more preferably 10 mol or more, still more preferably 20 mol or more, from the viewpoint of the polycondensation reactivity with the carboxylic acid component. Therefore, it is preferably 100 mol or less, more preferably 70 mol or less, and still more preferably 50 mol or less.

JP, 2008-248215, A can be referred to for hydrogenation of terpene phenol copolymer resin. Specifically, a noble metal such as palladium, ruthenium, rhodium or the like supported on a carrier such as activated carbon, activated alumina or diatomaceous earth can be used as a catalyst. The amount of the catalyst used is preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the terpene phenol copolymer resin as the raw material. At the time of hydrogenation, the reaction solvent may not be used, but alcohols, ethers, esters, saturated hydrocarbons and the like may be used as appropriate. The reaction temperature during hydrogenation is usually about 20 to 300 ° C., and the hydrogen pressure during hydrogenation is usually preferably about 5 to 300 kg / cm ² (0.49 to 29.40 MPa).

  The hydrogenation rate of the hydrogenated terpene phenol copolymer resin is preferably 80% or more, more preferably 90% or more, preferably 100% or less, more preferably 100%. The hydrogenation rate can be determined from the intensity of IR-analyzed peak values of aromatic rings derived from phenol in the hydrogenated terpene phenol copolymer resin and the starting terpene phenol copolymer resin.

  The softening point of the hydrogenated terpene phenol copolymer resin is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, and still more preferably 100 ° C. or higher, from the viewpoints of heat and humidity resistance storage stability, durability, and low-temperature fixability. From the same viewpoint, it is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, further preferably 130 ° C. or lower, and further preferably 125 ° C. or lower.

  The glass transition temperature of the hydrogenated terpene phenol copolymer resin is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, from the viewpoints of heat and humidity resistance storage stability, durability, and low-temperature fixability. Preferably it is 70 degrees C or less, More preferably, it is 65 degrees C or less, More preferably, it is 60 degrees C or less, More preferably, it is 55 degrees C or less.

  The number average molecular weight of the hydrogenated terpene phenol copolymer resin is preferably 400 or more, more preferably 500 or more, still more preferably 600 or more, from the viewpoints of heat and humidity resistance storage stability, durability, and low-temperature fixability. From this viewpoint, it is preferably 1500 or less, more preferably 1000 or less, and still more preferably 800 or less.

  The hydroxyl value of the hydrogenated terpene phenol copolymer resin is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, from the viewpoint of heat and humidity resistance storage stability, durability, and low-temperature fixability, from the same viewpoint. , Preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, further preferably 30 mgKOH / g or less, and further preferably 20 mgKOH / g or less.

  The amount of the hydrogenated terpene phenol copolymer resin is 1 part by mass or more, preferably from the viewpoint of heat and humidity resistance storage stability, durability, and low-temperature fixability with respect to 100 parts by mass of the total amount of the carboxylic acid component and the alcohol component. 3 parts by mass or more, more preferably 5 parts by mass or more, further preferably 7 parts by mass or more, and from the same viewpoint, it is 25 parts by mass or less, preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

  The alcohol component preferably contains at least one diol A selected from aliphatic diols and aromatic diols having 2 to 6 carbon atoms from the viewpoint of low-temperature fixability, and from the viewpoint of heat and moisture resistance storage stability Therefore, it is more preferable to contain an aromatic diol.

  Examples of the aliphatic diol having 2 to 6 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol. 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 2,3-hexanediol, 3,4-hexanediol, 2,4-hexanediol, 2 1,5-hexanediol, 1,6-hexanediol and the like. It is preferable to use one or more of these.

  The carbon number of the aliphatic diol is preferably 2 or more, more preferably 3 or more from the viewpoint of hot offset resistance, and preferably 6 or less, more preferably 5 or less, and still more preferably from the viewpoint of low-temperature fixability. 4 or less, more preferably 3 or less.

  The aliphatic diol having 2 to 6 carbon atoms is preferably an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom from the viewpoint of hot offset resistance and low-temperature fixability. Preferable examples of such aliphatic diols include 1,2-propanediol and 2,3-butanediol. It is preferable to use one or more of these.

  As the aromatic diol, the formula (I):

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y are the average number of moles of alkylene oxide added, each being a positive number, The sum value is 1 or more, preferably 1.5 or more, 16 or less, preferably 8 or less, more preferably 4 or less)
An alkylene oxide adduct of bisphenol A represented by Examples of alkylene oxide adducts of bisphenol A represented by the formula (I) include polyoxypropylene adducts of 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) propane. Examples include polyoxyethylene adducts. It is preferable to use one or more of these.

  The content of the diol A is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and still more preferably 90 mol%, from the viewpoint of low temperature fixability and heat and humidity resistance storage stability in the alcohol component. It is at least mol%, more preferably at least 95 mol%, preferably at most 100 mol%, more preferably at least 100 mol%. Here, when the aliphatic diol having 2 to 6 carbon atoms and the aromatic diol are used in combination as the diol A, the content is the total content thereof.

  Examples of other alcohol components include trivalent or higher alcohols such as glycerin.

  The carboxylic acid component contains an aromatic dicarboxylic acid compound.

  Examples of the aromatic dicarboxylic acid compound include terephthalic acid, isophthalic acid, phthalic acid, furandicarboxylic acid, anhydrides of these acids, esters of these acids with alcohols having 1 to 3 carbon atoms, and the like. It is preferable to use one type or two or more types. Among these, from the viewpoint of charge build-up, selected from the group consisting of terephthalic acid, isophthalic acid, furandicarboxylic acid, anhydrides of these acids, and esters of these acids with alcohols having 1 to 3 carbon atoms. One or more of these are preferred, and terephthalic acid is more preferred.

  The content of the aromatic dicarboxylic acid compound is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 80, from the viewpoint of heat and humidity resistance storage stability, durability, and low-temperature fixability in the carboxylic acid component. More than mol%, More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more, Preferably it is 100 mol% or less, More preferably, it is 100 mol%.

  Examples of the other carboxylic acid component include trivalent or higher carboxylic acid compounds such as aliphatic dicarboxylic acid compounds and trimellitic acid.

  The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate.

  From the viewpoint of reactivity, the equivalent ratio of the carboxylic acid component to the alcohol component (COOH group / OH group) in the binder resin R is preferably 0.70 or more, more preferably 0.75 or more, preferably 0.90 or less, more preferably Is 0.85 or less.

  The polycondensation of the alcohol component and the carboxylic acid component in the presence of the hydrogenated terpene phenol copolymer resin can be performed, for example, in an inert gas atmosphere, if necessary, as an esterification catalyst, an esterification cocatalyst, polymerization In the presence of an inhibitor or the like, it can be carried out preferably at a temperature of about 180 ° C. or higher and 250 ° C. or lower. The hydrogenated terpene phenol copolymer resin is used together with the alcohol component and the carboxylic acid component and may be present in the reaction system from the start of the polycondensation reaction or may be added to the reaction system in the middle of the polycondensation reaction. From the viewpoint of wet heat resistance, the hydrogenated terpene phenol copolymer resin is preferably present as early as possible, more preferably from the start of the reaction.

  Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamate. The amount of the esterification catalyst used is preferably 0.01 parts by mass or more and 1.5 parts by mass or less, more preferably 0.1 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the esterification promoter include gallic acid. The amount of the esterification promoter used is preferably 0.001 to 0.5 parts by mass, more preferably 0.01 to 0.1 parts by mass, with respect to 100 parts by mass of the total amount of alcohol component and carboxylic acid component. Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 parts by mass or more and 0.5 parts by mass or less, more preferably 0.01 parts by mass or more and 0.1 parts by mass or less, with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

  The softening point of the binder resin R is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, more preferably 105 ° C. or higher from the viewpoint of durability, and preferably 130 ° C. or lower from the viewpoint of low-temperature fixability. More preferably, it is 125 ° C. or lower.

  The glass transition temperature of the binder resin R is preferably 53 ° C. or higher, more preferably 55 ° C. or higher, more preferably 58 ° C. or higher, from the viewpoint of durability and heat and moisture resistance storage stability, and from the viewpoint of low temperature fixability. Preferably it is 80 degrees C or less, More preferably, it is 75 degrees C or less.

  The acid value of the binder resin R is preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more from the viewpoint of low-temperature fixability, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH from the viewpoint of durability. / g or less, more preferably 20 mgKOH / g or less, more preferably 15 mgKOH / g or less.

  The hydroxyl value of the binder resin R is preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, and even more preferably 25 mgKOH / g or more, from the viewpoint of low-temperature fixability. Is not more than 50 mgKOH / g, more preferably not more than 45 mgKOH / g, still more preferably not more than 40 mgKOH / g, still more preferably not more than 35 mgKOH / g.

  The number average molecular weight of the binder resin R is preferably 1000 or more, more preferably 1500 or more, still more preferably 2000 or more from the viewpoint of durability, and preferably 5000 or less, more preferably from the viewpoint of low-temperature fixability. 4000 or less.

  In the toner of the present invention, a known resin other than the binder resin R may be used in combination as a binder resin within a range not impairing the effects of the present invention. The content of the binder resin R is as follows: In the binder resin, it is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, preferably 100% by mass or less, and more preferably 100% by mass.

  The toner of the present invention includes a colorant, a release agent, a charge control agent, magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, and a cleaning property improver. Additives may be contained, and it is preferable that a colorant, a release agent and a charge control agent are contained.

  As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used, and the toner of the present invention may be either a black toner or a color toner.

  The content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, preferably 100 parts by mass or more from the viewpoint of improving the toner image density and low-temperature fixability. It is 40 parts by mass or less, more preferably 10 parts by mass or less.

  Examples of mold release agents include polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, sazol wax, and other aliphatic hydrocarbon waxes and oxides thereof, carnauba wax. , Ester waxes such as montan wax and their deoxidized waxes, fatty acid ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc., which may be used alone or in combination of two or more. Can be used.

  The melting point of the release agent is preferably 60 ° C. or more, more preferably 70 ° C. or more from the viewpoint of low-temperature fixability and offset resistance of the toner, and preferably 160 ° C. or less, more preferably from the viewpoint of low-temperature fixability. Is below 150 ° C.

  The content of the release agent is preferably 0.5 parts by mass or more from the viewpoint of low-temperature fixability and offset resistance of the toner and dispersibility in the binder resin with respect to 100 parts by mass of the binder resin. The amount is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 7 parts by mass or less.

  The charge control agent is not particularly limited, and may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent.

  Examples of positively chargeable charge control agents include nigrosine dyes such as “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron N-01”, “Bontron N-04”, “Bontron N-07 ”,“ Bontron N-09 ”,“ Bontron N-11 ”(manufactured by Orient Chemical Co., Ltd.), etc .; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds such as“ Bontron P-51 "(manufactured by Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; polyamine resin such as" AFP-B "(manufactured by Orient Chemical Co., Ltd.), etc. Imidazole derivatives such as “PLZ-2001” and “PLZ-8001” (manufactured by Shikoku Kasei Kogyo Co., Ltd.); styrene-acrylic resins such as “FCA-701PT” (manufactured by Fujikura Kasei Co., Ltd.) And the like.

  In addition, as the negatively chargeable charge control agent, metal-containing azo dyes such as “Varifast Black 3804”, “Bontron S-31”, “Bontron S-32”, “Bontron S-34”, “Bontron S-36” (Above, made by Orient Chemical Co., Ltd.), “Eisenspiron Black TRH”, “T-77” (made by Hodogaya Chemical Co., Ltd.), etc .; metal compounds of benzylic acid compounds, for example, “LR-147” , “LR-297” (manufactured by Nippon Carlit Co., Ltd.), etc .; metal compounds of salicylic acid compounds such as “Bontron E-81”, “Bontron E-84”, “Bontron E-88”, “Bontron E-” 304 "(manufactured by Orient Chemical Co., Ltd.)," TN-105 "(manufactured by Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dyes; quaternary ammonium salts such as" COPY CHARGE NX VP434 "(manufactured by Clariant) , Nitroimidazole derivatives, etc .; organometallic compounds Etc. The.

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, preferably 10 parts by mass or less, with respect to 100 parts by mass of the binder resin, from the viewpoint of charging stability of the toner. More preferably, it is 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less.

  The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by a melt kneading method is preferred. In the case of pulverized toner by the melt-kneading method, for example, after a raw material such as a binder resin, a colorant, a release agent, and a charge control agent is uniformly mixed with a mixer such as a Henschel mixer, a hermetically sealed kneader, uniaxial or 2 It can be manufactured by melt-kneading with a shaft extruder, open roll type kneader or the like, cooling, pulverizing and classifying.

  In the toner of the present invention, an external additive is preferably used in order to improve transferability, and inorganic fine particles are preferably used as the external additive. Examples of the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide, zinc oxide and the like, and silica is preferable.

  Silica is preferably hydrophobic silica that has been subjected to a hydrophobic treatment, from the viewpoint of toner transferability.

  Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. It is done.

  The average particle diameter of the external additive is preferably 10 nm or more, more preferably 15 nm or more, preferably 250 nm or less, more preferably 200 nm or less, and still more preferably, from the viewpoint of toner chargeability, fluidity, and transferability. 90 nm or less.

  The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.3 parts by mass or more, preferably 100 parts by mass of the toner before being processed with the external additive. Is 5 parts by mass or less, more preferably 3 parts by mass or less.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 μm or more, more preferably 4 μm or more, preferably 15 μm or less, more preferably 10 μm or less. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size. When the toner is treated with an external additive, the volume median particle size of the toner particles before being treated with the external additive is defined as the volume median particle size of the toner.

  The toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties of the resin and the like were measured by the following method. The resin includes a hydrogenated terpene phenol copolymer resin and a binder resin.

[Softening point of resin]
Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger, with a diameter of 1 mm and a length of 1 mm. Extrude from nozzle. The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[Glass transition temperature of resin]
Using a differential scanning calorimeter “DSC210” (manufactured by Seiko Denshi Kogyo Co., Ltd.), 0.01 to 0.02 g of sample is weighed into an aluminum pan, heated up to 200 ° C., and from that temperature to 0 ° C. at a cooling rate of 10 ° C./min. Allow to cool. Next, the sample is heated at a heating rate of 10 ° C / min, and the temperature at the intersection of the base line extension below the endothermic peak temperature and the tangent that indicates the maximum slope from the peak rise to the peak apex is measured. The glass transition temperature is assumed.

[Acid value and hydroxyl value of resin]
Measured according to the method of JIS K 0070. However, only the measurement solvent is changed from the ethanol / ether mixed solvent specified in JIS K 0070 to the acetone / toluene mixed solvent (acetone: toluene = 1: 1 (volume ratio)).

[Number average molecular weight of resin]
The molecular weight distribution is measured by the gel permeation chromatography (GPC) method according to the following method to determine the number average molecular weight.
(1) Preparation of sample solution Dissolve the sample in tetrahydrofuran at 40 ° C so that the concentration is 0.5 g / 100 mL. Subsequently, this solution is filtered using a PTFE type membrane filter “DISMIC-25JP” (manufactured by Toyo Roshi Kaisha, Ltd.) having a pore size of 0.20 μm to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Using the following measuring device and analytical column, tetrahydrofuran is flowed as an eluent at a flow rate of 1 mL per minute, and the column is stabilized in a constant temperature bath at 40 ° C. Inject 100 μL of the sample solution into the sample and perform measurement. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. The calibration curve at this time includes several types of monodisperse polystyrene (A-500 (5.0 × 10 ² ), A-1000 (1.01 × 10 ³ ), A-2500 (2.63 × 10 ³ ), A -5000 (5.97 × 10 ³ ), F-1 (1.02 × 10 ⁴ ), F-2 (1.81 × 10 ⁴ ), F-4 (3.97 × 10 ⁴ ), F-10 (9.64 × 10 ⁴ ), F -20 (1.90 × 10 ⁵ ), F-40 (4.27 × 10 ⁵ ), F-80 (7.06 × 10 ⁵ ), F-128 (1.09 × 10 ⁶ )) prepared as standard samples are used. The molecular weight is shown in parentheses.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: TSKgel GMH _XL + TSKgel G3000H _XL (manufactured by Tosoh Corporation)

[Melting point of release agent]
Using a differential scanning calorimeter “DSC210” (manufactured by Seiko Denshi Kogyo Co., Ltd.), 0.01 to 0.02 g of sample is weighed into an aluminum pan, heated up to 200 ° C., and from that temperature to 0 ° C. at a cooling rate of 10 ° C./min. Allow to cool. Next, the sample is heated at a heating rate of 10 ° C./min, and the maximum peak temperature of the heat of fusion is taken as the melting point.

[Average particle diameter of external additive]
The volume average particle diameter of the primary particles is obtained from the following formula.
Average particle diameter (nm) = 6 / (ρ × specific surface area (m ² / g)) × 1000
In the formula, ρ is the true specific gravity of the external additive. For example, the true specific gravity of silica is 2.2. The specific surface area is a BET specific surface area determined by a nitrogen adsorption method.

[Volume-median particle diameter of toner (D ₅₀ )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter, Inc.)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (Polyoxyethylene lauryl ether, HLB (Griffin): 13.6), dissolved in electrolyte solution, adjusted to 5% by weight Dispersion condition: 10 mg of measurement sample in 5 mL of the dispersion Add and disperse for 1 minute with an ultrasonic disperser (machine name: US-1 manufactured by SND Co., Ltd., output: 80 W), then add 25 mL of the electrolyte, and further with an ultrasonic disperser Disperse for 1 minute to prepare a sample dispersion.
Measurement conditions: The sample dispersion was added to 100 mL of the electrolyte so that the particle size of 30,000 particles could be measured in 20 seconds, and 30,000 particles were measured. Determine the median particle size (D ₅₀ ).

Production Example of Hydrogenated Terpene Phenol Copolymer Resin YS Polystar T series or U series manufactured by Yashara Chemical Co., Ltd. was used as the terpene phenol copolymer resin, and the hydrogenation was carried out in the same manner as in Synthesis Example 2 of JP-A-2008-248215. The hydrogenated terpene phenol copolymer resins A to D shown in Table 1 were obtained. The hydrogenation rates of the hydrogenated terpene phenol copolymer resins A to D were all 80% or more.

  In addition, YS polystar which is a raw material of hydrogenated terpene phenol copolymer resins A to D is manufactured by Yasuhara Chemical Co., Ltd., and each is a copolymer of terpene compound (β-pinene, α-pinene, limonene, etc.) and phenol. The number of moles of the terpene compound added to 1 mole of phenol in the hydrogenated terpene phenol copolymer resins A to D calculated from the hydroxyl value, that is, the number of hydroxyl groups (mmol / g), is the copolymer resin A (YS polystar). T115) is 14.4 mol, copolymer resin B (YS Polystar T135) is 11.8 mol, copolymer resin A (YS Polystar U110) is 22.4 mol, and copolymer resin A (YS Polystar U130) is 31.4 mol.

Examples 1-6 and Comparative Examples 2, 5, 6
[Manufacture of binder resin]
Alcohol component, carboxylic acid component, and polycondensation resin shown in Tables 2 and 4, esterification catalyst (tin (2-ethylhexanoate) (II)) 5 g, esterification cocatalyst (gallic acid) 0.5 g, thermometer , Put into a 10 liter four-necked flask equipped with a stainless steel stirrer, fractionation tower, dehydration tube, cooling tube, and nitrogen introduction tube, heated to 235 ° C in a mantle heater in a nitrogen atmosphere, After reacting for 5 hours, it was confirmed that the reaction rate reached 95% at 235 ° C, and the reaction was performed at 5.3 kPa until the softening points shown in Tables 2 and 4 were reached. It was.

[Manufacture of toner for electrophotography]
100 parts by weight of the resulting binder resin, 5 parts by weight of colorant “Regal 330R” (Cabot, carbon black), 1 part by weight of negatively chargeable charge control agent “Bontron E-81” (manufactured by Orient Chemical Industries) , And 2 parts by weight of release agent “Mitsui High Wax NP055” (Mitsui Chemicals, Polypropylene wax, melting point: 125 ° C.) were thoroughly mixed with a Henschel mixer, and then the rotational speed of the roll using a co-rotating twin screw extruder It was melt-kneaded at a heating temperature of 80 ° C. in a roll at 200 r / min. The obtained melt-kneaded product was cooled and coarsely pulverized, then pulverized with a jet mill and classified to obtain toner particles having a volume median particle size (D ₅₀ ) of 8 μm.

  To 100 parts by mass of the toner particles obtained, 1.0 part by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: HMDS, average particle size: 30 nm) is added and mixed with a Henschel mixer. Thus, a toner was obtained.

Examples 7 to 14 and Comparative Examples 1 and 4
Alcohol component, carboxylic acid component, and polycondensation resin shown in Tables 2 to 4 and esterification catalyst (tin (2-ethylhexanoate tin (II))) 5 g were thermometer, stainless steel stirring rod, fractionation tower, dehydration Put into a 10-liter four-necked flask equipped with a tube, a cooling tube, and a nitrogen inlet tube, raise the temperature to 185 ° C in a mantle heater in a nitrogen atmosphere, react for 3 hours, and then to 220 ° C The temperature was raised stepwise at a rate of 5 ° C / h. After confirming that the reaction rate reached 95% at 220 ° C., the reaction was continued until the softening point shown in Tables 2 to 4 was reached while distilling off the alcohol component of the raw material monomer at 5.3 kPa. A landing resin was obtained.

  A toner was obtained using the obtained binder resin in the same manner as in Example 1.

Comparative Example 3
A toner was obtained by using the polylactic acid-based biodegradable resin A and the terpene phenol copolymer A used in the examples of Patent Document 1 by the following method.

・ Polylactic acid biodegradable resin A
(Synthesized based on the production example of JP 2008-250171 A)
... 44.7 parts by mass Molecular weight: Mw = 125,000, Mn = 57,000
Tg: 53.2 ° C
Ti / Tm: 153/170 ° C
L / D component molar ratio L (mol%) / D (mol%) = 91.8 (mol%) / 8.2 (mol%)
-Terpene phenol copolymer A (cyclic terpene phenol copolymer) 40.0 parts by mass Mighty Ace K-125 (manufactured by Yasuhara Chemical Co., Ltd.)
Molecular weight: Mw = 600
Tg: 69.5 ° C
Ti / Tm: 92/111 ° C
・ Magenta masterbatch: 13.3 parts by mass The magenta masterbatch is composed of 70 parts by mass of polylactic acid biodegradable resin A and 30 parts by mass of magenta pigment (Clariant Japan, trade name: Toner Magenta E02) using a two-roll disperser. It was prepared by heat dispersion.
・ Boron complex salt (manufactured by Nippon Carlit Co., Ltd., trade name: LR-147) ... 2.0 parts by mass

The above raw materials were mixed with a Henschel mixer, melt-kneaded and then classified by pulverization to obtain negatively chargeable toner particles having a volume median particle size (D ₅₀ ) of 10 μm.
To 100 parts by mass of the toner particles, 0.6 parts by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., trade name: R-972) was adhered to the surface by a Henschel mixer to obtain a toner. The melting start temperature of the obtained toner was 92 ° C.

Test Example 1 [Low-temperature fixability of toner]
Toner was installed in a machine that improved the fixing machine of the copier “AR-505” (manufactured by Sharp Corporation) so that it can be fixed outside the machine, and paper manufactured by Sharp Corporation [CopyBond SF-70NA ( 75 g / m ² )] was obtained in an unfixed state. Using a fixing machine (fixing speed 390mm / sec) adjusted so that the total fixing pressure becomes 40kgf, the fixing roller temperature is raised from 100 ° C to 240 ° C in 5 ° C increments, and the unfixed state at each temperature. The fixing test of the printed material was conducted. “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JISZ-1522) was attached to the fixed image, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. The optical reflection density before and after the tape was peeled off was measured using a reflection densitometer “RD-915” (manufactured by Macbeth), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The temperature of the fixing roller that exceeded the minimum fixing temperature. The results are shown in Tables 2-4. The lower the minimum fixing temperature, the better the low-temperature fixing property. The minimum fixing temperature is preferably 125 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 115 ° C. or lower.

Test Example 2 [heat and humidity resistance of toner]
4 g of toner was placed in a 220 mL container (diameter: about 3 cm) and left in a high temperature and high humidity (temperature 55 ° C., humidity 85%) environment for 60 hours. The occurrence of toner aggregation was visually observed every 12 hours, and the heat and humidity resistance storage stability was evaluated according to the following evaluation criteria. The results are shown in Tables 2-4.

〔Evaluation criteria〕
A +: No aggregation is observed after 84 hours.
A: Aggregation is not observed after 72 hours, but aggregation is observed after 84 hours.
A-: Aggregation is not observed after 60 hours, but aggregation is observed after 72 hours.
B +: Aggregation is not observed after 48 hours, but aggregation is observed after 60 hours.
B: Aggregation is not observed after 36 hours, but aggregation is observed after 48 hours.
B-: Aggregation is not observed after 24 hours, but aggregation is observed after 36 hours.
C: Aggregation is not observed after 12 hours, but aggregation is observed after 24 hours.
D: Aggregation is observed within 12 hours.

Test Example 3 [Toner durability]
Toner is mounted on a non-magnetic one-component printer "OKI Microline18" (Oki Data Co., Ltd.), and A4 size paper has diagonal stripes with a blackening rate of 5.5% under conditions of 30 ° C and 80% humidity. The pattern was printed continuously. The photoreceptor was visually observed every 50 sheets printed, and white spots caused by filming of toner on the photoreceptor were visually observed. In the test, the point in time when the generation of white spots was confirmed was regarded as the number of printing durability. The results are shown in Tables 2-4. The slower the occurrence of white spots, that is, the greater the number of printed sheets, the better the durability. The number of printed sheets is preferably 600 sheets or more, more preferably 800 sheets or more, and even more preferably 900 sheets or more.

It can be seen that the toners of Examples 1 to 14 have a good balance of low-temperature fixability, heat and moisture storage stability, and durability as compared with the toners of Comparative Examples 1 to 6.
From the comparison of each of Examples 1 to 4 and Examples 7 to 10, the toners of Examples 3, 4, 9 and 10 using a hydrogenated terpene phenol copolymer resin having a hydroxyl value of 12.7 to 17.8 mg KOH / g. However, it is understood that the heat resistance and humidity resistance storage stability, durability, and low temperature fixability are superior.
From the comparison between Examples 3 and 9 and Examples 4 and 10, the binder resin of Example 4 using an alkylene oxide adduct of bisphenol A as the alcohol component is more resistant to heat and moisture resistance, durability and low temperature fixability. It turns out that it is excellent.
From the comparison of Examples 4 to 5 and Comparative Example 6, the toner of Example 4 in which the amount of the hydrogenated terpene phenol copolymer is 10 parts by mass with respect to 100 parts by mass of the total amount of the carboxylic acid component and the alcohol component is It turns out that it is excellent by storage stability, durability, and low-temperature fixability.
Similarly, in the comparison between Example 10 and Example 14, the toner of Example 14 having a hydrogenated terpene phenol copolymerization amount of 10 parts by mass with respect to 100 parts by mass in total of the carboxylic acid component and the alcohol component is heat resistant. It can be seen that it is superior in moisture-resistant storage stability, durability, and low-temperature fixability.
From the comparison of Examples 4 and 6, it can be seen that the binder resin of Example 6 using 100 mol% of the aromatic dicarboxylic acid compound as the carboxylic acid component is superior in heat and moisture resistance storage resistance, durability, and low temperature fixability. .
In Comparative Examples 1 and 2, when a non-hydrogenated terpene phenol copolymer was used, the heat and moisture resistance storage stability, durability, and low-temperature fixability were lowered, but this is the reactivity of the hydroxyl group bonded to the aromatic ring. Is estimated to be low.

  The electrophotographic toner of the present invention is suitably used as a toner used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like.

Claims (6)

  A binder resin obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound in the presence of a hydrogenated terpene phenol copolymer resin, the hydrogenated terpene phenol copolymer resin An electrophotographic toner containing a binder resin having an amount of 1 to 25 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.   The toner for electrophotography according to claim 1, wherein the content of the aromatic dicarboxylic acid compound in the carboxylic acid component is 50 mol% or more.   The aromatic dicarboxylic acid compound is one or more selected from the group consisting of terephthalic acid, isophthalic acid, furandicarboxylic acid, anhydrides of these acids, and esters of these acids with alcohols having 1 to 3 carbon atoms The toner for electrophotography according to claim 1 or 2.   The electrophotographic toner according to claim 1, wherein the alcohol component contains one or more diols A selected from aliphatic diols having 2 to 6 carbon atoms and aromatic diols.   The hydrogenated terpene phenol copolymer resin is a hydrogenated product of a copolymer resin of at least one terpene compound selected from the group consisting of α-pinene, β-pinene, and limonene and a phenol. The toner for electrophotography according to any one of 1 to 4.   A binder resin for an electrophotographic toner obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound in the presence of a hydrogenated terpene phenol copolymer resin, the hydrogenated terpene A binder resin for electrophotographic toner, wherein the amount of the phenol copolymer resin is 1 part by mass or more and 25 parts by mass or less with respect to 100 parts by mass in total of the alcohol component and the carboxylic acid component.