JP2010210997A - Toner and production method of toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner capable of attaining compatibility of low-temperature fixability, blocking resistance and high-temperature offset resistance, and capable of suppressing changes in the image density, when used in a high-temperature and high-humidity environment at a low printing ratio. <P>SOLUTION: The toner contains at least a binder resin and wax, wherein the binder resin contains a resin A, having a polyester unit comprising an alcohol component essentially comprising an aromatic diol; a polyester resin B obtained by condensation polymerization of an alcohol component, essentially comprising an aliphatic diol with an acid component essentially comprising an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid; and an aliphatic conjugate diene resin C. The content a (mass%) of the resin A in the binder resin ranges from 50 mass% to 98 mass%; and if the content (mass%) of the resin B and the content (mass%) of the resin C in the binder resin are denoted by b and c, respectively, b/a and c/b indicate the relations expressed by 0.02≤b/a<1.00 and 0.05≤c/b≤0.30. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system, and a method for producing the toner.

  In recent years, with the widespread use of electrophotographic full-color copiers, the demand for energy saving has further increased. As a specific energy saving measure, in order to reduce power consumption in the fixing process, a technique for fixing at a lower fixing temperature has been studied.

  In order to achieve these, it is preferable to use a resin having a sharper melt property as the toner, and in recent years, a polyester resin has been used as the sharp melt resin.

  For example, Patent Document 1 contains a crystalline polyester obtained by polycondensing an alcohol component containing 80 mol% or more of a diol having 2 to 6 carbon atoms and a carboxylic acid component containing 80 mol% or more of fumaric acid. Toner has been proposed. Although the above toner has some effects on improving low temperature fixability, there are problems such as deterioration of high temperature offset resistance and blocking resistance. To achieve both low temperature fixability and blocking resistance yet Not enough.

Patent Document 2 proposes a toner containing a polyester resin and a styrene-butadiene resin. The toner is excellent in environmental stability, but has not yet achieved both low-temperature fixability and offset resistance.

  In addition, when any of the above toners is used at a low printing ratio in a high temperature and high humidity environment, the toner charge amount may decrease, resulting in a large density fluctuation in the image or fogging on the white background. . Such a toner cannot be said to sufficiently satisfy the durability stability in high-speed printing such as the POD printing market, and further improvement is required.

JP 2001-222138 A JP 2000-0197780 A

  An object of the present invention is to provide a toner that solves the above problems. Specifically, an object of the present invention is to provide a toner capable of achieving both low-temperature fixability, blocking resistance, high-temperature offset resistance, and suppressing image density fluctuation when used at a low printing ratio under high temperature and high humidity.

As a result of intensive studies, the present inventors have used the toner of the present invention to achieve both low-temperature fixability, blocking resistance, high-temperature offset resistance, and a low printing ratio under high temperature and high humidity. It has been found that it is possible to suppress the density fluctuation of the image at the time. That is, the present invention is as follows.
In a toner containing at least a binder resin and a wax,
The binder resin includes at least a resin A having a polyester unit composed of an alcohol component mainly containing an aromatic diol, an alcohol component mainly containing an aliphatic diol and an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid. Containing polyester resin B and aliphatic conjugated diene resin C obtained by polycondensing the acid component
The content a (mass%) of the resin A in the binder resin is 50 mass% or more and 98 mass% or less,
When the content of the resin B in the binder resin is b (mass%) and the content of the resin C is c (mass%), b / a and c / b have the following relationship: To the toner.
0.02 ≦ b / a <1.00
0.05 ≦ c / b ≦ 0.30

  By using the toner of the present invention, it is possible to achieve both low-temperature fixability, blocking resistance, and high-temperature offset resistance. In addition, it is possible to provide a toner capable of suppressing image density fluctuation when used at a low printing ratio under high temperature and high humidity.

1 is a schematic cross-sectional view of a surface treatment apparatus of the present invention.

Hereinafter, the best mode for carrying out the present invention will be described in detail.
The present invention relates to a toner containing at least a binder resin and a wax.
The binder resin includes at least a resin A having a polyester unit composed of an alcohol component mainly containing an aromatic diol, an alcohol component mainly containing an aliphatic diol and an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid. Containing polyester resin B and aliphatic conjugated diene resin C obtained by polycondensing the acid component
The content a (mass%) of the resin A in the binder resin is 50 mass% or more and 98 mass% or less,
When the content of the resin B in the binder resin is b (mass%) and the content of the resin C is c (mass%), b / a and c / b have the following relationship: And
0.02 ≦ b / a <1.00
0.05 ≦ c / b ≦ 0.30

  In the present invention, the resin A having a polyester unit, the resin B obtained by condensation polymerization of a specific alcohol component and an acidic component, and the aliphatic conjugated diene resin C in the above range, It is possible to obtain a toner having both blocking resistance and high temperature offset resistance, and it is possible to suppress fluctuations in the density of an image when it is endured with a low print ratio image under high temperature and high humidity.

  In the present invention, the main component refers to a component that is contained most among the components contained.

  The resin A is a resin having a polyester unit composed of an alcohol component mainly composed of an aromatic diol, and the polyester unit means a portion derived from polyester. Specifically, the component constituting the polyester unit is an acid monomer component such as a divalent or higher valent alcohol monomer component and a divalent or higher carboxylic acid, a divalent or higher carboxylic acid anhydride, and a divalent or higher carboxylic acid ester. The aromatic diol component is the main component of the alcohol component. The resin preferably used is a polyester resin having a polyester unit, or a hybrid resin having a polyester unit and a styrene polymer unit. By using such a resin, the low-temperature fixability of the toner can be improved.

  In the toner of the present invention, the low-temperature fixability is improved by setting the content a (mass%) of the resin A in the binder resin to 50 mass% or more and 98 mass% or less. The content a (% by mass) of the resin A in the binder resin is preferably 55% by mass or more and 95% by mass or less, and more preferably 60% by mass or more and 90% by mass or less. When the content a (% by mass) of the resin A in the binder resin exceeds 98% by mass, the effect of improving the low-temperature fixability is not manifested, and when it is less than 50% by mass, the resin B described later is used. When added, the offset resistance and blocking resistance deteriorate.

  The resin B is a polyester resin obtained by polycondensing an alcohol component mainly containing an aliphatic diol and an acid component mainly containing an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid. Since the polyester resin using such a monomer has high crystallinity, the low-temperature fixability of the toner is improved.

  In the toner of the present invention, the blending amount with the resin A is important, and 0.02 ≦ b / a <1.00, where b (mass%) is the content of the resin B in the binder resin. In this case, the low-temperature fixability is improved. Preferably, 0.03 ≦ b / a ≦ 0.70, and more preferably 0.05 ≦ b / a ≦ 0.50. When b / a is less than 0.02, the effect of improving the low-temperature fixability of resin B does not appear, and when b / a is 1.00 or more, the content of resin B is excessive with respect to resin A Thus, the offset resistance and the blocking resistance are deteriorated.

  The resin C is a copolymer having an aliphatic conjugated diene compound as a monomer unit. In the toner of the present invention, the blending amount with the resin B is important. When the content of the resin C is c (mass%), the presence of the resin B in the resin A is controlled by controlling c / b. It turns out that the state can be controlled. Therefore, when 0.05 ≦ c / b ≦ 0.30, a toner with improved blocking resistance and high-temperature offset resistance can be obtained. Furthermore, it is possible to suppress fluctuations in the density of the image when endured with a low print ratio image under high temperature and high humidity. Preferably it is 0.10 <= c / b <= 0.30, More preferably, it is 0.15 <= c / b <= 0.30. When c / b is less than 0.05, the resin B is easily compatible with the resin A, so that the offset resistance and the blocking resistance are deteriorated. Further, it is durable at a low printing ratio image under high temperature and high humidity. When this occurs, the charge amount of the toner decreases. As a result, the density fluctuation of the image becomes large. On the other hand, when c / b exceeds 0.30, the presence of the resin C is relatively increased, so that the low-temperature fixability is deteriorated.

  The reason why the toner of the present invention exhibits such excellent effects is not clear, but the inventors consider as follows. In the present invention, it is considered that the presence state of the resin B in the resin A can be controlled by containing the resin A, the resin B, and the resin C in the above range. This is because resin C is easier to disperse in resin B than resin A, so when these resins coexist, it is considered that resin B and resin C are dispersed in resin A. ing. As a result, the excessive plastic effect of the resin B can be suppressed, and the deterioration of the blocking resistance of the toner can be suppressed. In addition, since the resin B has a low volume resistance, when the resin B is present alone on the surface of the toner particles, the charge amount of the toner is reduced under high temperature and high humidity. Therefore, in the present invention, since the resin B does not exist alone on the surface of the toner particles, and the resin B and the resin C can exist in a mixed state, the charge amount of the toner is reduced under high temperature and high humidity. Can be suppressed. Therefore, it is possible to suppress image density fluctuation. Further, by containing the resin C, the stress resistance of the toner is improved, and the density fluctuation of the image when it is endured with a low print ratio image can be suppressed.

  In the present invention, as means for incorporating the resin B and the resin C into the toner, the resin B and the resin C may be mixed together with the resin A and other raw materials by a mixer or the like. Furthermore, it is preferable that the resin B and the resin C are mixed in advance. For example, the resin B and the resin C may be melt-kneaded in advance, and the obtained mixture may be further mixed with the resin A and other raw materials.

  As described above, in order to suppress the active fluctuation of the image when it is endured with a low print ratio image under high temperature and high humidity, the resin A and the resin B are compatible with low temperature fixing property, blocking resistance and high temperature offset resistance. It is necessary to adjust the resin C within the range of the present invention.

  As a component which forms the polyester unit which resin A contained in the toner of the present invention has, for example, as a dihydric alcohol monomer component, as an aromatic diol, polyoxypropylene (2.2) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane , Polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) Examples thereof include alkylene oxide adducts of bisphenol A such as propane, and other diols include ethylene glycol. Diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6 -Hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A and the like.

  Examples of the trivalent or higher alcohol monomer component include sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Is mentioned. In the present invention, the main component of the alcohol component constituting the resin A is the aromatic diol.

  Divalent carboxylic acid monomer components include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; And succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid, or anhydrides thereof. Of these, terephthalic acid, succinic acid, adipic acid, and fumaric acid are preferable.

  Examples of the trivalent or higher carboxylic acid monomer component include trimellitic acid, pyromellitic acid, polyvalent carboxylic acid such as benzophenone tetracarboxylic acid and its anhydride, and the like. Of these, trimellitic acid is preferable.

  Examples of other monomers include polyhydric alcohols such as oxyalkylene ethers of novolak type phenol resins.

The hybrid resin means a resin in which a styrene polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a styrene polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction. In addition, both reactive monomers capable of reacting with at least either a condensation polymerization monomer or an addition polymerization monomer (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, alkenyl succinic acid, mesacone) An unsaturated dibasic acid such as an acid; an unsaturated dibasic acid anhydride such as a maleic anhydride, a citraconic anhydride, an itaconic anhydride, or an alkenyl succinic anhydride). A product obtained by addition polymerization of a system polymerization monomer may also be used.

  Examples of the monomer used in the styrene polymer unit in the hybrid resin include the following.

  Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene derivatives such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; monoolefins such as ethylene, propylene, butylene and isobutylene; polyenes such as butadiene and isoprene; vinyl chloride and chloride Vinyl halides such as vinylidene, vinyl bromide and vinyl fluoride Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, Α-methylene aliphatic monocarboxylic acid esters such as 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, acrylic N-butyl acid, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenolic acrylate Acrylic acid esters such as: vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl compounds such as N-vinylindole and N-vinylpyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

The proportion of the polyester unit component in the resin A contained in the toner of the present invention is 50.
It is preferably at least 70% by mass, particularly preferably at least 70% by mass. When the ratio of the polyester unit component contained in the resin A is 50% by mass or more, the low temperature fixability may be improved, which is preferable.

  The acid value of the resin A contained in the toner of the present invention is preferably 1 mgKOH / g or more and 50 mgKOH / g or less. Preferably, they are 2 mgKOH / g or more and 40 mgKOH / g or less, More preferably, they are 5 mgKOH / g or more and 30 mgKOH / g or less. When the acid value of the resin A is 1 mgKOH / g or more and 50 mgKOH / g or less, it is preferable for controlling the mixing property of the resin B and the resin C, and when the durability is obtained in a low printing ratio image under high temperature and high humidity. This is preferable because a decrease in the charge amount of the toner can be suppressed. In addition, the said acid value can be made into said range by adjusting the kind and compounding quantity of the monomer used for resin. Specifically, the acid value can be controlled by adjusting the alcohol monomer component ratio / acid component ratio and molecular weight during resin production. Moreover, it can control to make terminal alcohol react with a polyvalent acid monomer (for example, trimellitic acid) after ester condensation polymerization.

  Further, in the molecular weight distribution measured by gel permeation chromatography (GPC) of the THF soluble content of the resin A contained in the toner of the present invention, the peak molecular weight (Mp) is 2,000 or more and 50,000 or less, several An average molecular weight (Mn) of 1,500 or more and 30,000 or less and a weight average molecular weight (Mw) of 2,000 or more and 1,000,000 or less are preferable in terms of low-temperature fixability and high-temperature offset resistance.

  Examples of the aliphatic diol used as the alcohol component of the resin B contained in the toner of the present invention include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,4-butane. Diol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, Neopentyl glycol and 1,5-pentanediol are mentioned, and the main component in the alcohol component is the diol. Further, the aliphatic diol is preferably contained in the alcohol component in a proportion of 60 mol% or more in order to increase the crystallinity of the resin B. The alcohol component other than the aliphatic diol constituting the resin B is not particularly limited.

  Examples of the aliphatic dicarboxylic acid used in the resin B contained in the toner of the present invention include alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or anhydrides thereof; an alkyl group having 6 to 18 carbon atoms; Succinic acid substituted with alkenyl groups or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;

Aromatic dicarboxylic acids include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, or anhydrides thereof. In order to improve the crystallinity of the resin B, the aliphatic dicarboxylic acid or aromatic dicarboxylic acid is preferably contained in the total acid monomer in a proportion of 60 mol% or more. More preferably, it is 70 mol% or more, and particularly preferably 90 mol% or more.

The resin B contained in the toner of the present invention has a maximum endothermic peak existing in the temperature range of 30 ° C. or more and 200 ° C. or less in the endothermic curve at the time of temperature rise of the resin B measured by a differential scanning calorimeter (DSC). The peak temperature is preferably 80 ° C. or higher and 150 ° C. or lower. More preferably, it is 80 degreeC or more and 140 degrees C or less, Most preferably, they are 80 degreeC or more and 130 degrees C or less. When the peak temperature of the maximum endothermic peak is 80 ° C. or higher and 150 ° C. or lower, it is preferable for improving the low-temperature fixability when applied to the toner of the present invention. The peak temperature of the maximum endothermic peak can be set to the above range by adjusting the type and blending amount of the monomer used for the resin and the polymerization conditions.

  Further, the resin B contained in the toner of the present invention has a number average molecular weight (Mn) of 1,500 to 20,000 and a weight average molecular weight (Mw) in a molecular weight distribution measured by THF soluble content GPC. It is preferable from a viewpoint of durability that they are 5,000 or more and 1,000,000 or less.

  Resin C contained in the toner of the present invention is an aliphatic conjugated diene resin. Examples of the aliphatic conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 2,3-dimethyl- 1,3-butadiene, 1,4-diphenyl-1,3-butadiene, 1,1,4,4-tetraphenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene 2-ethyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1 , 3-hexadiene, 2,5-dimethyl-2,4-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 2,3-dimethyl-1,3-heptadiene, 1,3-octadiene 2,4-octadiene, 2,3-dimethyl-1,3-octadiene, 3,4-diethyl-1,3-octadiene, 1,3-nonadiene, 2,4-nonadiene, 2,3-dimethyl-1, Examples include 3-nonadiene and derivatives thereof, and an aliphatic conjugated diene copolymer can be obtained by copolymerization with one or two or more combinations of vinyl monomers. Among these, as the vinyl monomer, it is preferable to copolymerize a combination of styrene compound, acrylonitrile, and aliphatic conjugated diene compound as 1,3-butadiene, 2-methyl-1,3-butadiene, and 1,3-pentadiene.

  The vinyl monomer / aliphatic conjugated diene compound is preferably copolymerized at a mass ratio of 65/35 to 98/2 from the viewpoint of blocking resistance.

  The resin C contained in the toner of the present invention preferably has a weight average molecular weight (Mw) of 150,000 or more, more preferably 200,000 or more in the molecular weight distribution measured by GPC of THF-soluble matter. It is. The weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 10.0 or more, more preferably 20.0 or more. When the weight average molecular weight (Mw) is 150,000 or more and the weight average molecular weight (Mw) / number average molecular weight (Mn) is 10.0 or more, the blocking resistance and the high temperature offset resistance are improved. This is preferable because fluctuations in the density of the image when the image is durable with a low printing ratio image can be suppressed. In addition, said Mn and Mw can be made said range by adjusting the kind and compounding quantity of a polymerization initiator, the kind and compounding quantity of an emulsifier, polymerization conditions, etc.

  Examples of the synthesis method of the resin C contained in the toner of the present invention include known solution polymerization methods, suspension polymerization methods, and emulsion polymerization methods. Among them, copolymerization can be performed by solution polymerization methods and emulsion polymerization methods. preferable.

  In the solution polymerization method, a known solvent such as isooctane, cyclohexane, n-hexane, benzene, toluene, xylene, ethylbenzene, cis-2-butene can be used as a polymerization solvent, and a Ti-based, Ni-based polymerization catalyst can be used. System, Li system, and Co system are mainly used.

  In the emulsion polymerization method, water, monomers, emulsifiers, electrolytes, polymerization initiators, reducing agents, chelating agents, activators, chain transfer agents, and other additives are used, and in the emulsified state, a temperature of 0 ° C. or higher and 100 ° C. or lower. Polymerization reaction is performed within the range, and a latex containing a copolymer can be obtained.

  As the emulsifier, soaps such as fatty acid soap and rosin acid soap can be used. Specifically, the fatty acid soap is a long chain fatty acid carboxylic acid having 12 to 18 carbon atoms, such as lauric acid, myristic acid, stearic acid, oleic acid and the like, and sodium salts of these mixed aliphatic carboxylic acids. Or a potassium salt is a main component. The rosin acid soap is mainly composed of sodium salt or potassium salt obtained by disproportionating or hydrogenating natural rosin such as gum rosin, wood rosin, or tall oil rosin. These natural rosins are mainly composed of abietic acid, levopimaric acid, parastrinic acid, dehydroabietic acid, tetrahydroabietic acid and neoabietic acid. Further, sodium alkylbenzene sulfonate, sodium alkyl sulfonate, sodium salt of higher alcohol monosulfate and the like are used. The amount of the emulsifier added is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the monomer.

  The electrolytes include tetrasodium pyrophosphate, tetrapotassium pyrophosphate, trisodium phosphate and tripotassium phosphate, dipotassium hydrogen phosphate and disodium hydrogen phosphate, potassium carbonate and ammonium carbonate, potassium bicarbonate and sodium bicarbonate, and Potassium sulfite and sodium sulfite are used. The amount of electrolyte added can be changed in a timely manner according to pH adjustment under reaction conditions.

  Polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate; azo compounds such as 2,2′-azobis (isobutyronitrile) and 4,4′-azobis (4-cyanovaleric acid); Organic peroxides such as oxide and methyl ethyl ketone peroxide; organic hydroperoxides such as diisopropylbenzene hydroperoxide, cumene hydroperoxide, paramentane hydroperoxide, tert-butylisopropylbenzene hydroperoxide and cyclohexylbenzene hydroperoxide; There is a redox-type initiator composed of a combination with a reducing agent. Examples of the reducing agent include formic acid, citric acid, metasilicic acid, ethylenediaminetetraacetic acid, ethylenedinitrotetraacetic acid or their sodium salt or potassium salt and a heavy metal such as iron, copper or chromium, ferrous sulfate or pyrophosphoric acid. Examples include ferrous iron.

  As the activator, sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and reducing sugar (dextrose, fructose, etc.) are used.

  As chain transfer agents, mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropyl Santogen disulfides such as xanthogen disulfide; Thiuram disulfides such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetrabutylthiuram disulfide; Halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide and ethylene bromide; Pentaphenyl Hydrocarbons such as ethane; and acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglyco , Terpinolene, α-terpinene, γ-terpinene, ditenpene, α-methylstyrene dimer, (2-4-diphenyl-4-methyl-1-pentene is preferably 50% by mass or more), 2,5- Dihydrofuran, 3,6-dihydro-2H-pin, phthalane, 1,2-butadiene, 1,4-hexadiene and the like are used.

  These addition amounts of the polymerization initiator, activator, and chain transfer agent are preferably used in an amount of 0.001 part by mass or more and 5 parts by mass or more with respect to 100 parts by mass of the monomer. This range is preferable because the molecular weight of the resulting copolymer can be adjusted.

  Examples of the polymerization terminator include aromatic dimethyl dithiocarbamate such as sodium dimethyldithiocarbamate, diethylhydroxylamine, hydroxyaminesulfonic acid and alkali metal salts thereof, hydroxydimethylbenzenedithiocarboxylic acid, hydroxydiethylbenzenedithiocarboxylic acid, and hydroxydibutylbenzenedithiocarboxylic acid. Examples include carboxylic acids and alkali metal salts thereof, hydroquinone derivatives and catechol derivatives. The addition amount of the polymerization terminator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the monomer.

  The latex obtained after the polymerization reaction is preliminarily treated with an alkali, coagulated with a coagulant, separated, washed with water, dehydrated and dried to obtain a copolymer.

  Acid / metal salts can be used as the coagulant. Examples of the acid include inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as acetic acid and formic acid. In addition, a polymer flocculant and the like can be used in combination. As the metal salt, metal salts of these acids can be used. Examples of the metal salt include sodium chloride, sodium bromide, potassium chloride, potassium bromide, calcium chloride, calcium nitrate, aluminum chloride, aluminum sulfate, and magnesium sulfate. As the polymer flocculant, polyamine, polyacrylate ester, polyacrylamide, quaternary ammonium salt, imidazoline derivative, chitosan and the like are used.

  The amount used is 100 parts by mass of latex (solid content 15-30%), the acid is 0.1 to 20 parts by mass, the alkali metal salt is 1 to 30 parts by mass, and the polymer. The flocculant is used in an amount of 0.01 parts by mass or more and 5 parts by mass or less.

  The resulting copolymer is added with a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerating aid, a deterioration preventing agent, a softening agent, etc. The coalescence can be made tough and stretchability and relaxation properties can be maintained.

  As the vulcanizing agent, powder sulfur, sulfur flower, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur are used in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the copolymer. The Further, vulcanization is carried out by using in combination with the following vulcanization accelerator and vulcanization acceleration aid.

  Vulcanization accelerators include diethyldithiocarbamide zinc, 4,4′-dithiodimorpholine, N, N-dimethyl-S-tert-butylsulfenyldithiocarbamate, tetramethylthiuram disulfide, 2,2′-dibenzothiazyl. Disulfide, butyraldehyde aniline mercaptobenzothiazole, N-oxydiethylene-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazylsulfenamide, 2- (4′-morpholinodithio) benzothiazole and the like are used. . As the vulcanization acceleration aid, zinc white, magnesium oxide, stearic acid and the like are used. Vulcanization accelerators and vulcanization accelerator assistants are often used in combination, and the addition amount for the vulcanization accelerator is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the copolymer. used.

  Deterioration inhibitors include monophenol, bisphenol, polyphenol, hydroquinone derivative, phosphite or ester, phosphate ester blend, thioester, naphthylamine, diphenylamine, other diarylamine derivatives, p-phenylenediamine, quinoline, blended amine It is. The deterioration preventing agent is used in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the copolymer.

Softeners include asphalt, aromatic extracted oils such as saturated and unsaturated hydrocarbons, petroleum softeners containing nitrogen base, coal tar, coumarone-indene resin, dibutyl phthalate,
Tricresyl phosphate or the like is used. The softener is used in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the copolymer.

  As the binder resin used in the toner of the present invention, in addition to the resins A, B and C, the following polymers can be added.

  For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer , Styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrenic copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, Acrylic resin, meta Lil resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone - indene resins, and petroleum resins.

Examples of the wax used in the toner of the present invention include the following. Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof; Waxes composed mainly of fatty acid esters such as carnauba wax, behenic acid behenate wax, and montanic acid ester wax; fatty acid esters such as deoxidized carnauba wax that have been partially or fully deoxidized.

  Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Saturated alcohols such as sil alcohols; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Esters with alcohols such as sil alcohols; Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Methylene bis stearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; Unsaturated fatty acid amides such as sebacic acid amides; aromatic bisamides such as m-xylene bis-stearic acid amide, N, N ′ distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts such as those commonly referred to as metal soaps; waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides Price Partial esters of Lumpur; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils.

In the present invention, the wax is preferably used in an amount of 0.5 to 20 parts by mass per 100 parts by mass of the binder resin. The peak temperature of the maximum endothermic peak of the wax is preferably 45 ° C. or higher and 140 ° C. or lower. This is preferable because both the storage stability of the toner and the hot offset property can be achieved.

Examples of the colorant that can be contained in the toner include the following.
Examples of the black colorant include carbon black; those prepared by using a yellow colorant, a magenta colorant, and a cyan colorant and adjusting the color to black. As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.

  Examples of the color pigment for magenta toner include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.

  Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the color pigment for cyan toner include the following. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of the coloring dye for cyan include C.I. I. There is Solvent Blue 70.

Examples of the color pigment for yellow include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20
Examples of the coloring dye for yellow include C.I. I. There is Solvent Yellow 162.

  The amount of the colorant used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner may contain a charge control agent as necessary. As the charge control agent contained in the toner, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.

Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, sulfonic acid or polymer compounds having carboxylic acid in the side chain, sulfonates or sulfonated products in the side chain. Examples thereof include a polymer compound having a carboxylate or a carboxylate ester compound in the side chain, a boron compound, a urea compound, a silicon compound, and a calixarene. Examples of the positive charge control agent include quaternary ammonium salts, polymer compounds having the quaternary ammonium salt in the side chain, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

  It is preferable that an external additive is added to the toner in order to improve fluidity and stabilize durability. As the external additive, inorganic fine powders such as silica, titanium oxide and aluminum oxide are preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As an external additive for improving fluidity, an inorganic fine powder having a specific surface area of 50 m ² / g or more and 400 m ² / g or less is preferable. For stabilization of durability, the specific surface area is 10 m ² / g or more and 50 m or less. An inorganic fine powder of ² / g or less is preferable. In order to achieve both improvement in fluidity and stabilization of durability, inorganic fine particles having a specific surface area in the above range may be used in combination.

  The external additive is preferably used in an amount of 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.

  In the present invention, in order to further improve the dot reproducibility, it is preferable to use it as a two-component developer by mixing with a magnetic carrier because a stable image can be obtained over a long period of time.

  Examples of the magnetic carrier include iron powder whose surface is oxidized, non-oxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth, and the like Magnetic material dispersed resin carriers (so-called resin carriers) containing magnetic materials such as alloy particles, oxide particles, ferrite, and the like, and magnetic materials and binder resins that hold the magnetic materials in a dispersed state are generally known. Things can be used.

  When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio at that time is 2% by mass to 15% by mass, preferably 4% as the toner concentration in the developer. When the content is from 13% by weight to 13% by weight, good results are usually obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  As a method for producing toner particles, for example, a pulverization method in which a binder resin and a wax are melt-kneaded and the kneaded product is cooled and then pulverized and classified; a solution in which the binder resin and the wax are dissolved or dispersed in a solvent Suspension granulation method in which toner particles are obtained by introducing into a water-based medium and suspending granulation, and removing the solvent; a monomer composition in which a wax or the like is uniformly dissolved or dispersed in a monomer is contained in a dispersion stabilizer Suspension polymerization method in which toner particles are produced by dispersing in a continuous layer (for example, an aqueous phase) and carrying out a polymerization reaction; a monomer that is soluble in monomers but insoluble when a polymer is formed, and an aqueous organic solvent. A dispersion polymerization method that directly produces toner particles using an aqueous organic solvent that is soluble in the monomer that directly produces toner particles but is insoluble in the resulting polymer; it is polymerized directly in the presence of a water-soluble polar polymerization initiator. An emulsion polymerization method for producing particles; an emulsion aggregation method obtained by aggregating at least polymer fine particles and wax to form fine particle aggregates and an aging step for causing fusion between the fine particles in the fine particle aggregates; and so on.

The toner production method of the present invention is a toner production method comprising a mixing step of mixing at least a binder resin and a wax, and a melt-kneading step of melt-kneading the mixture obtained in the mixing step. Among the binder resins, those having a pre-melt kneading step in which the resin B and the resin C are previously melt-kneaded are preferable. That is, as described above, a method in which the resin B and the resin C are previously melt-kneaded and the obtained mixture is further mixed with the resin A and other raw materials is preferable.
This is preferable because the resin B can be dispersed in the resin B by melt-kneading the resin B and the resin C in advance, so that the compatibility of the resin B with the resin A can be further suppressed.

Hereinafter, a toner manufacturing procedure using the pulverization method will be described.
In the raw material mixing step, as a material constituting the toner particles, for example, a predetermined amount of other components such as a binder resin and a wax and, if necessary, a colorant and a charge control agent are weighed and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano hybrid (manufactured by Mitsui Mining Co., Ltd.).

  Next, the mixed material is melt-kneaded to disperse wax or the like in the binder resin. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer or a continuous kneader can be used, and a single-screw or twin-screw extruder has become the mainstream because of the advantage of continuous production. ing. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko), twin screw extruder (manufactured by KC K ), Ko Kneader (manufactured by Busus), Needex (manufactured by Mitsui Mining), and the like. Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

  Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization process, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill Finely pulverize with a turbomill (made by Turbo Industries) or air jet type fine pulverizer.

  Then, if necessary, classification such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classifier turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) The toner particles are obtained by classification using a machine or a sieving machine.

  In addition, if necessary, after pulverization, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechano-fusion system (manufactured by Hosokawa Micron), a faculty (manufactured by Hosokawa Micron), or Meteorbomb MR Type (manufactured by Nippon Pneumatic Co., Ltd.) is used. Thus, the toner particles can be subjected to a surface treatment such as a spheroidizing treatment.

  The toner particles used in the present invention are preferably obtained by obtaining the above pulverized product, performing surface treatment with hot air using, for example, a surface treatment apparatus shown in FIG. Alternatively, a pre-classified material may be subjected to surface treatment with hot air using the surface device shown in FIG. Thus, although it can be obtained by any method, the toner particles are more preferably particles obtained by performing a surface treatment with hot air.

  In the surface treatment with hot air, the toner is ejected by jetting from a high-pressure air supply nozzle, and the surface of the toner is treated by exposing the ejected toner to hot air. It is particularly preferable that the temperature be in the range of ° C or lower.

  Here, an outline of a surface treatment apparatus used for producing the toner of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view showing an example of a surface treatment apparatus according to the present invention. Toner 114 supplied from a toner supply port 100 is accelerated by injection air ejected from a high-pressure air supply nozzle 115 and is below the same. It heads for the airflow injection member 102. Diffusion air is ejected from the airflow ejecting member 102, and the toner diffuses outward by the diffusion air. At this time, the toner diffusion state can be controlled by adjusting the flow rate of the injection air and the flow rate of the diffusion air.

Further, a cooling jacket 106 is provided on the outer periphery of the toner supply port 100, the outer periphery of the surface treatment apparatus, and the outer periphery of the transfer pipe 116 for the purpose of preventing toner fusion. In addition, it is preferable to pass cooling water (preferably antifreeze such as ethylene glycol) through the cooling jacket.
The toner diffused by the diffusion air is processed on the surface of the toner by the hot air supplied from the hot air supply port 101. At this time, the temperature C (° C) in the hot air supply port is preferably 100 ° C or higher and 450 ° C or lower. More preferably, it is 100 degreeC or more and 400 degrees C or less.
When the temperature is lower than 100 ° C., the surface roughness of the toner particle surface may vary. Further, when the temperature exceeds 450 ° C., the toner may be coalesced due to excessive progress of the melted state, and the toner may be coarsened or fused.

  The toner whose surface has been treated with hot air is cooled by cold air supplied from a cold air supply port 103 provided on the outer periphery of the upper portion of the apparatus. At this time, cold air may be introduced from the second cold air supply port 104 provided on the side surface of the main body of the apparatus for the purpose of controlling the temperature distribution in the apparatus and controlling the surface state of the toner. The outlet of the second cold air supply port 104 can use a slit shape, a louver shape, a perforated plate shape, a mesh shape, etc., and the introduction direction can be selected according to the purpose, horizontal to the center direction and along the device wall surface It is.

At this time, the temperature E (° C.) in the cold air supply port and the second cold air supply port is preferably −50 ° C. or more and 10 ° C. or less. More preferably, it is -40 degreeC or more and 8 degrees C or less. The cold air is preferably dehumidified cold air. Specifically, the absolute water content is preferably 5 g / m ³ or less. More preferably, it is 3 g / m ³ or less.
When these cold air temperatures are lower than −50 ° C., the temperature in the apparatus is too low, and the heat treatment that is the original purpose is not sufficiently performed, and the toner may not be spheroidized. When the temperature exceeds 10 ° C., the control of the hot air zone in the apparatus becomes insufficient, the coalescence of the particles proceeds, and the powder particles may be coarsened.
Thereafter, the cooled toner is sucked by a blower and collected by a cyclone or the like through a transfer pipe 116.

  Further, if necessary, surface modification and spheronization may be further performed using, for example, a hybridization system manufactured by Nara Machinery Co., Ltd. or a mechano-fusion system manufactured by Hosokawa Micron. In such a case, if necessary, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Machine Co., Ltd.) may be used.

A method for measuring various physical properties of the toner and raw materials will be described below.
<Measurement of acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of the crushed binder resin sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (4: 1) is added and dissolved over 5 hours. . Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (4: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Measurement of resin molecular weight>
The molecular weight distribution of the THF soluble part of the resin is measured by gel permeation chromatography (GPC) as follows.
First, the toner is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measurement of maximum endothermic peak of resin and wax>
The peak temperature of the maximum endothermic peak of the resin and wax is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 10 mg of toner is precisely weighed, put in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the maximum endothermic peak of the endothermic curve in the DSC measurement of the toner of the present invention.

<Measurement of BET specific surface area of external additive>
The BET specific surface area of the external additive is measured according to JIS Z8830 (2001). A specific measurement method is as follows.
As the measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is defined as the BET specific surface area in the present invention.

The BET specific surface area is calculated as follows.
First, nitrogen gas is adsorbed on the external additive, and the equilibrium pressure P (Pa) in the sample cell at that time and the nitrogen adsorption amount Va (mol · g−1) of the external additive are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g−1) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g−1), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the external additive, is obtained by applying the following BET equation.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)
The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)
When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the above slope and intercept simultaneous equations using these values.
Furthermore, the BET specific surface area S (m ² / g) of the external additive is calculated from the calculated Vm and the molecular occupation cross-sectional area of the nitrogen molecule (0.162 nm ² ) based on the following formula.
S = Vm × N × 0.162 × 10−18
(N is Avogadro's number (mol-1).)

The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.
Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. Then, about 0.1 g of an external additive is put into the sample cell using a funnel.
The sample cell containing the external additive is set in a “pretreatment device Bacrepprep 061 (manufactured by Shimadzu Corporation)” connected to a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. . During vacuum deaeration, the external additive is gradually deaerated while adjusting the valve so that the external additive is not sucked into the vacuum pump. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the accurate mass of the external additive is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber plug during weighing so that the external additive in the sample cell is not contaminated by moisture in the atmosphere.
Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing the external additive. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impermeable material capable of sucking liquid nitrogen to a certain level by capillary action.
Subsequently, the free space of the sample cell including the connection tool is measured. The free space is measured by measuring the volume of the sample cell with helium gas at 23 ° C., and subsequently measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen using helium gas. Calculated from the difference in volume. Further, the saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.
Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules to the toner. At this time, the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, and the adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Further, using the value of Vm, the BET specific surface area of the external additive is calculated as described above.

<Method for Measuring Toner Weight Average Particle Size (D4)>
The weight average particle diameter (D4) of the toner is a precision particle size distribution measuring apparatus “Coulter Counter Multisizer by pore electrical resistance method equipped with an aperture tube of 100 μm.
3 ”(registered trademark, manufactured by Beckman Coulter) and attached dedicated software“ Beckman Coulter Multisizer 3 Version 3.51 ”(manufactured by Beckman Coulter, Inc.) for measurement condition setting and measurement data analysis, Measurement was performed with 25,000 effective measurement channels, and measurement data was analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

Prior to measurement and analysis, the dedicated software was set as follows.
In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic dispersion device “Ultrasonic Disposition System Tetora 150” (manufactured by Nikka Ki Bios Co., Ltd.) having an electrical output of 120 W A fixed amount of ion-exchanged water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measuring method of average circularity of toner>
The average circularity of the toner is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.
A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion liquid prepared according to the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. The binarization threshold at the time of particle analysis is set to 85%.

Here, by specifying the analysis particle size range, the average circularity of the range can be obtained.
For example, when obtaining an average circularity of an equivalent circle diameter of 0.500 μm or more and less than 1.985 μm, the analysis particle diameter range is limited to an equivalent circle diameter of 0.500 μm or more and less than 1.985 μm.
In measurement, automatic focus adjustment is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. The analysis particle size is the same as the equivalent circle diameter 0.500 μm or more, less than 1.985 μm, or 1.985 μm or more, and less than 39.69 μm. It was.

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

<Resin production example A-1>
As materials for the vinyl polymer unit, 7.6 parts by mass of styrene, 1.5 parts by mass of 2-ethylhexyl acrylate, 0.6 parts by mass of fumaric acid, 0.3 parts by mass of dimer of α-methylstyrene, dicumyl 0.02 part by mass of peroxide was placed in the dropping funnel. As a material of the polyester unit, 44.2 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4- Hydroxyphenyl) propane (20.6 parts by weight), terephthalic acid (10.0 parts by weight), trimellitic anhydride (7.3 parts by weight), fumaric acid (7.9 parts by weight) and titanium tetrabutoxide (0.2 parts by weight) were made of 4 liters of glass. Placed in a four-necked flask. A thermometer, a stirring rod, a condenser, and a nitrogen introducing tube were attached to the four-necked flask, and the four-necked flask was placed in a mantle heater. Next, after the inside of the four-necked flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and the monomer and polymerization of the vinyl polymer unit were performed from the previous dropping funnel while stirring at a temperature of 145 ° C. The initiator was added dropwise over 4 hours. Next, the obtained product was heated to 200 ° C. and reacted for 4 hours to obtain Resin A-1. The acid value of this resin A-1 is 10 mgKOH / g, and the molecular weight by GPC is as follows: the weight average molecular weight (Mw) is 400,000, the number average molecular weight (Mn) is 4,000, and the peak molecular weight (Mp) is 8, 000.

<Resin production example A-2>
71.0 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 28.0 parts by mass of terephthalic acid, 1.0 part by mass of trimellitic anhydride, and 0. 5 parts by mass were placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted at a temperature of 200 ° C. for 4 hours to obtain a binder resin A-2-1. The acid value of this resin A-2-1 is 15 mg KOH / g, and the molecular weight by GPC is as follows: weight average molecular weight (Mw) 80,000, number average molecular weight (Mn) 3,500, peak molecular weight (Mp) 5, 700.
Moreover, 70.0 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 20.0 parts by mass of terephthalic acid, 3.0 parts by mass of isophthalic acid, trimellitic anhydride 7 0.0 part by mass and 0.5 part by mass of titanium tetrabutoxide were placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted at 220 ° C. for 6 hours to obtain a binder resin A-2-2. The acid value of this resin A-2-2 is 5 mgKOH / g, and the molecular weight by GPC is as follows: weight average molecular weight (Mw) 120,000, number average molecular weight (Mn) 4,000, peak molecular weight (Mp) 10, 000.
The binder resin A-2-1, 50 parts by mass, and the binder resin A-2-2, 50 parts by mass were premixed with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.), and a melt kneader PCM30 (Ikegai Iron Works) Co., Ltd.) was melt blended under the conditions of a rotation speed of 3.3 s ⁻¹ and a kneading resin temperature of 150 ° C. to obtain a binder resin A-2. The acid value of this resin A-2 is 10 mgKOH / g, and the molecular weight by GPC is as follows: weight average molecular weight (Mw) 110,000, number average molecular weight (Mn) 3,800, peak molecular weight (Mp) 9,000 there were.

<Resin production example A-3>
Resin A-3 was obtained in the same manner as in Resin Production Example A-2 except that the amount of trimellitic anhydride added was adjusted so that the acid value of resin A-2-1 was 35 mgKOH / g. The acid value of this resin A-3 was 20 mgKOH / g, and the molecular weight by GPC was weight average molecular weight (Mw) 110,000, number average molecular weight (Mn) 3,800, and peak molecular weight (Mp) 9,000. It was.

<Resin production example A-4>
In Resin Production Example A-2, the amount of trimellitic anhydride added was adjusted so that the acid value of Resin A-2-1 was 60 mgKOH / g and the acid value of Resin A-2-2 was 30 mgKOH / g. Resin A-4 was obtained in the same manner as described above. The acid value of this resin A-4 is 45 mgKOH / g, and the molecular weight by GPC is weight average molecular weight (Mw) 110,000, number average molecular weight (Mn) 3,800, peak molecular weight (Mp) 9,000. there were.

<Resin production example A-5>
In Resin Production Example A-2, the amount of trimellitic anhydride added was adjusted so that the acid value of Resin A-2-1 was 70 mgKOH / g and the acid value of Resin A-2-2 was 40 mgKOH / g. Resin A-5 was obtained in the same manner as described above. The acid value of this resin A-5 is 55 mgKOH / g, and the molecular weight by GPC is as follows: weight average molecular weight (Mw) 110,000, number average molecular weight (Mn) 3,800, peak molecular weight (Mp) 9,000 there were.

  Table 1-A shows the physical properties of Resin A-1 to A-5 obtained in Resin Production Examples A-1 to A-5.

<Resin production example B-1>
Put 50 parts by mass of 1,4-butanediol, 25 parts by mass of terephthalic acid, 25 parts by mass of adipic acid, and 0.5 parts by mass of titanium tetrabutoxide in a 4-liter 4-necked flask made of glass, thermometer, stirring rod, condenser A nitrogen inlet tube was attached and placed in a mantle heater. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted at 200 ° C. for 1 hour to obtain Resin B-1. The maximum endothermic peak in DSC of Resin B-1 was 102.5 ° C., and the molecular weight by GPC was a number average molecular weight (Mn) of 4,200 and a weight average molecular weight (Mw) of 70,000.

<Resin production example B-2>
50 parts by mass of 1,4-butanediol, 35 parts by mass of terephthalic acid, 15 parts by mass of adipic acid, and 0.5 parts by mass of titanium tetrabutoxide were placed in a 4-liter 4-necked flask made of glass, a thermometer, a stirring rod, a condenser and A nitrogen inlet tube was installed and placed in the mantle heater. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted for 1 hour while stirring at a temperature of 200 ° C. to obtain Resin B-2. The maximum endothermic peak in DSC of Resin B-2 was 128.1 ° C., and the molecular weight by GPC was a number average molecular weight (Mn) of 4,400 and a weight average molecular weight (Mw) of 80,000.

<Resin production example B-3>
Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 7.5 parts by mass, 1,4-butanediol 42.5 parts by mass, terephthalic acid 40 parts by mass, adipic acid 10 parts by mass, 0.5 parts by mass of titanium tetrabutoxide was placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted for 1 hour while stirring at a temperature of 200 ° C. to obtain Resin B-3. The maximum endothermic peak in DSC of the resin B-3 was 135.2 ° C., and the molecular weight by GPC was a number average molecular weight (Mn) of 4,500 and a weight average molecular weight (Mw) of 77,000.

<Resin production example B-4>
12.5 parts by mass of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 37.5 parts by mass of 1,4-butanediol, 50 parts by mass of terephthalic acid, titanium tetrabutoxide 5 parts by mass were placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted for 1 hour while stirring at a temperature of 200 ° C. to obtain Resin B-4. The maximum endothermic peak in DSC of the resin B-4 was 148.2 ° C., and the molecular weight by GPC was a number average molecular weight (Mn) of 4,500 and a weight average molecular weight (Mw) of 77,000.

<Resin production example B-5>
17.5 parts by mass of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 32.5 parts by mass of 1,4-butanediol, 50 parts by mass of terephthalic acid, titanium tetrabutoxide. 5 parts by mass were placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted at a temperature of 200 ° C. for 1 hour to obtain Resin B-5. The maximum endothermic peak in DSC of the resin B-5 was 156.9 ° C., and the molecular weight by GPC was a number average molecular weight (Mn) of 4,500 and a weight average molecular weight (Mw) of 77,000.

<Resin production example B-6>
Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 22.5 parts by mass, 1,4-butanediol 27.5 parts by mass, terephthalic acid 50 parts by mass, titanium tetrabutoxide 0. 5 parts by mass were placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted for 1 hour while stirring at a temperature of 200 ° C. to obtain Resin B-6. The maximum endothermic peak in DSC of the resin B-6 was 161.2 ° C., and the molecular weight by GPC was a number average molecular weight (Mn) of 4,500 and a weight average molecular weight (Mw) of 77,000.

  Table 1-B shows the physical properties of Resins B-1 to B-6 obtained in Resin Production Examples B-1 to B-6.

<Resin production example C-1>
-Styrene 85 parts-1,3-butadiene 15 parts-Potassium rosinate 2 parts-Fatty acid potassium 2 parts-Tetrapotassium pyrophosphate 0.3 parts-Paramentane hydroperoxide 0.1 parts-Ethylenediamine Sodium tetraacetate 0.03 parts by mass, ferrous sulfate 0.01 parts by mass, sodium formaldehyde sulfoxylate 0.1 parts by mass, tert-dodecyl mercaptan 0.25 parts by mass The above components are added to 200 parts by mass of water. The polymerization reaction was started at a reaction temperature of 5 ° C. At a polymerization rate of 60%, 0.2 part by mass of sodium dimethyldithiocarbamate was added to terminate the polymerization. Thereafter, the remaining monomer was removed by heating to obtain a latex. The obtained latex is alkali-treated, 400 parts by mass of a 1% aluminum sulfate aqueous solution is added to 100 parts by mass of the latex, and the coagulated polymer is separated, washed with water, dehydrated and dried to obtain a copolymer (a). Got. Additives were added in the following composition to 100 parts by mass of the obtained copolymer (a), and the resin C-1 was obtained by heating at 160 ° C. for 20 minutes by a pressure press method. .
-Copolymer (a) 100 parts by mass-Zinc oxide 3 parts by mass-Stearic acid 2 parts by mass-Sulfur 1.5 parts by mass-N-cyclohexyl-2-benzothiazylsulfenamide 1.2 parts by mass The number average molecular weight (Mn) of the resin C-1 was 8900, the weight average molecular weight (Mw) was 240,000, and Mw / Mn = 27.0.

<Resin production example C-2>
In Production Example C-1, the same except that 0.1 part by mass of tert-dodecyl mercaptan, 1.0 part by mass of sulfur, and 0.8 part by mass of N-cyclohexyl-2-benzothiazylsulfenamide are changed. Thus, a resin C-2 having the following physical properties was obtained. Resin C-2 had Mn = 12,000, Mw = 180,000, and Mw / Mn = 15.0.

<Resin production example C-3>
In Production Example C-1, the same except that 0.2 parts by mass of tert-dodecyl mercaptan, 0.5 parts by mass of sulfur, and 0.4 parts by mass of N-cyclohexyl-2-benzothiazylsulfenamide are changed. Thus, a resin C-3 having the following physical properties was obtained. Resin C-3 had Mn = 10,000, Mw = 50,000, and Mw / Mn = 5.0.

Table 1-C shows the physical properties of Resins C-1 to C-3 obtained in Resin Production Examples C-1 to C-3.

(Toner production example 1)
-Resin B-1 8.0 parts by mass-Resin C-1 2.0 parts by mass After the above formulation was mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a biaxial kneader ( PCM-30 type (manufactured by Ikegai Iron Works Co., Ltd.) was melt-kneaded in advance at a rotation speed of 3.3 s ⁻¹ and a kneading resin temperature of 120 ° C. (preliminary melt-kneading step). The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product 1.
-Resin A-1 90 parts by mass-Crushed material 1 10 parts by mass-Fischer-Tropsch wax (peak temperature of maximum endothermic peak 105 ° C)
5 parts by mass / aluminum compound of 3,5-di-t-butylsalicylate 0.5 part by mass / C.I. I. Pigment Blue 15: 3 8 parts by mass After the above formulation was mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a twin-screw kneader (PCM-30 type, manufactured by Ikekai Iron Works Co., Ltd.) Were kneaded under conditions of a rotation speed of 3.3 s ⁻¹ and a kneading resin temperature of 150 ° C. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The obtained toner particles 1 had a weight average particle diameter (D4) of 5.8 μm.

The toner particles were subjected to a surface treatment by the surface treatment apparatus shown in FIG. The operating conditions were a feed amount = 5 kg / hr, a hot air temperature C = 250 ° C., and a hot air flow rate = 6 m ³ / min. Cold air temperature E = 5 ° C., cold air flow rate = 4 m ³ / min. , Cold air absolute water content = 3 g / m ³
, Blower airflow = 20 m ³ / min. Injection air flow rate = 1 m ³ / min. It was. The obtained treated toner particles 1 had an average circularity of 0.965 and a weight average particle diameter (D4) of 6.2 μm.

To 100 parts by mass of the obtained treated toner particles 1, 1.0 part by mass of titanium oxide fine particles having a BET specific surface area of 60 m ² / g surface-treated with 15% by mass of isobutyltrimethoxysilane and 20% by mass of hexamethyldisilazane are used. 0.8 parts by mass of treated hydrophobic silica fine particles with a BET specific surface area of 130 m ² / g and 1.0 parts by mass of hydrophobic silica fine particles with a BET specific surface area of 25 m ² / g surface-treated with 4% by mass of hexamethyldisilazane were added. The toner 1 was obtained by mixing with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). The composition of toner 1 is shown in Table 2.

<Example 1>
Magnetic ferrite carrier particles (number average particle size 35 μm) surface-coated with a silicone resin and toner 1 were mixed so that the toner concentration was 6% by mass to obtain a two-component developer 1.
The obtained two-component developer 1 was subjected to the following evaluation tests.

<Evaluation of fixability (low temperature fixability, high temperature offset resistance)>
The Canon full color copier imagePress C1 was modified so that the fixing temperature could be freely set, and the fixing temperature region test was conducted. The image was adjusted so that the amount of toner applied on the paper was 1.2 mg / cm ² in a single color mode in a normal temperature and normal humidity environment (23 ° C./50 to 60%), and an unfixed image was created. As the evaluation paper, color laser copier paper (A4, 81.4 g / m ² ) sold by Canon Marketing Japan Inc. was used, and an image was formed at an image area ratio of 25%. Thereafter, the fixing temperature was increased by 5 ° C. sequentially from 100 ° C. in a normal temperature and normal humidity environment (23 ° C./50 to 60%), and a temperature range where no offset or wrapping occurred was defined as a fixing possible region. The evaluation results are shown in Table 3.

<Blocking resistance>
Each of the toners was allowed to stand for 24 hours in a thermostatic chamber adjusted to 50 ° C., and the degree of blocking was evaluated.
(Evaluation criteria)
A: No agglomerates are generated at all, and the fluidity is very good. Excellent: B: The fluidity is slightly deteriorated but no agglomerates are generated. C: Some agglomerates are generated. However, it can be easily solved by applying a force. The present invention has a level that is not problematic in the present invention. D: Aggregates that cannot be easily solved even by applying a force are generated.

<Developability evaluation>
As an image forming apparatus, a Canon full-color copier imagePress C1 remodeling machine was used, and the two-component developer 1 was put in the developer at the cyan position and evaluated.
Durability image evaluation under normal temperature and humidity environment (23 ° C, 50% RH), normal temperature and low humidity environment (23 ° C, 5% RH), high temperature and high humidity environment (32.5 ° C, 80% RH) ( A4 horizontal, 1% printing ratio, 50,000 sheets). As the evaluation paper, color laser copier paper (A4, 81.4 g / m ² ) sold by Canon Marketing Japan Inc. was used. In the above evaluation environment, the amount of the FFH image (solid portion) on the paper was adjusted to 0.4 mg / cm ² . The FFH image is a value in which 256 gradations are displayed in hexadecimal, and 00H is the first gradation (white background), and FFH is the 256th gradation (solid part).

The items and evaluation criteria for the image output evaluation after the end of durability (first sheet) and after passing 50,000 sheets are shown below.
(Image density and fog after initial durability (first image) and after 50,000 images)
The development voltage was initially adjusted so that the applied amount of toner on the image was 0.4 mg / cm ² . X-
Using a Rite color reflection densitometer (500 series: manufactured by X-Rite), image density and fog were measured. The difference in image density after the initial durability (first sheet) and after 50,000 sheets was evaluated based on the following criteria.
(Evaluation criteria)
A: Less than 0.05 Very excellent B: 0.05 or more and less than 0.10 Good C: 0.10 or more and less than 0.20 It is a level that is not a problem in the present invention D: 0.20 or more In the present invention Is not acceptable

(Initial durability (first sheet) and fog after 50,000 sheets)
The average reflectance Dr (%) of plain paper before image printing was measured by a reflectometer (“REFLECTOMETER MODEL TC-6DS” manufactured by Tokyo Denshoku Co., Ltd.).
A solid white image (Vback: 150 V) was drawn on plain paper after 50,000 sheets in the initial durability. The reflectivity Ds (%) of the imaged solid white image was measured. The fog (%) was calculated from the obtained Dr and Ds (initial durability (first sheet) and after 50,000 sheets) using the following formula. The obtained fog was evaluated according to the following evaluation criteria.
Fog (%) = Dr (%)-Ds (%)
(Evaluation criteria)
A: Less than 0.5% Very good B: 0.5% or more, less than 1.0% Good C: 1.0% or more, less than 2.0% It is a level that is not a problem in the present invention. D : 2.0% or more Unacceptable in the present invention

  The evaluation results are shown in Tables 4-1 (room temperature and humidity environment (23 ° C., 50% RH)), Table 4-2 (room temperature and humidity environment (23 ° C., 5% RH)), and Table 4-3 (high temperature and high humidity). Shown in a wet environment (32.5 ° C., 80% RH).

<Examples 2 to 7 and Comparative Examples 1 to 8>
In Example 1, the types and contents of the resins A, B, and C were changed to the ratios of the toners shown in Table 2 below, and the other evaluations were performed in the same manner. Table 3, Table 4-1, Table 4-2, and Table 4-3 show the evaluation results.

<Example 8>
In Example 1, without carrying out the preliminary melt kneading step,
-Resin A-4 52.0 parts by mass-Resin B-3 44.0 parts by mass-Resin C-2 4.0 parts by mass-Fischer-Tropsch wax (peak temperature of maximum endothermic peak 105 ° C)
5 parts by mass / aluminum compound of 3,5-di-t-butylsalicylate 0.5 part by mass / C.I. I. Pigment Blue 15: 3 8 parts by mass After the above formulation was mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a twin-screw kneader (PCM-30 type, manufactured by Ikekai Iron Works Co., Ltd.) Were kneaded under conditions of a rotation speed of 3.3 s ⁻¹ and a kneading resin temperature of 150 ° C. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using a rotary classifier (200 TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 8. The obtained toner particles 8 had a weight average particle diameter (D4) of 5.8 μm.
To 100 parts by mass of the obtained toner particles 8, 1.2 parts by mass of titanium oxide fine particles having a BET specific surface area of 60 m ² / g surface-treated with 15% by mass of isobutyltrimethoxysilane and surface treatment with 20% by mass of hexamethyldisilazane. BET specific surface area ² surface-treated with 1.0 part by mass of hydrophobic silica fine particles having a BET specific surface area of 130 m ² / g and 4% by mass of hexamethyldisilazane
Toner 8 was obtained by adding 1.4 parts by mass of 5 m ² / g hydrophobic silica fine particles and mixing with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.).
The obtained toner 8 was evaluated in the same manner as in Example 1. Table 3, Table 4-1, Table 4-2, and Table 4-3 show the evaluation results.

<Examples 9 to 12>
In Example 8, the types and contents of the resins A, B, and C were changed to the ratio of the toner shown in Table 2 below, and evaluation was performed in the same manner except that. Table 3, Table 4-1, Table 4-2, and Table 4-3 show the evaluation results.

100: Toner supply port 101: Hot air supply port 102: Airflow jet member 103: Cold air supply port 104: Second cold air supply port 106: Cooling jacket 114: Toner 115: High pressure air supply nozzle 116: Transfer piping

Claims (7)

In a toner containing at least a binder resin and a wax,
The binder resin includes at least a resin A having a polyester unit composed of an alcohol component mainly containing an aromatic diol, an alcohol component mainly containing an aliphatic diol and an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid. Containing polyester resin B and aliphatic conjugated diene resin C obtained by polycondensing the acid component
The content a (mass%) of the resin A in the binder resin is 50 mass% or more and 98 mass% or less,
When the content of the resin B in the binder resin is b (mass%) and the content of the resin C is c (mass%), b / a and c / b have the following relationship: Toner.
0.02 ≦ b / a <1.00
0.05 ≦ c / b ≦ 0.30   The toner according to claim 1, wherein the resin B contains an aliphatic diol in the alcohol component of the resin B at a ratio of 60 mol% or more.   The resin B has a maximum endothermic peak peak temperature in the range of 30 ° C. to 200 ° C. in the endothermic curve at the time of temperature rise measured by a differential scanning calorimeter (DSC). The toner according to claim 1, wherein the toner is a toner.   The resin C has a weight average molecular weight (Mw) of 150,000 or more and a weight average molecular weight (Mw) / number average molecular weight (Mn) in a molecular weight distribution of THF-soluble matter measured by gel permeation chromatography (GPC). The toner according to claim 1, wherein the toner is 10.0 or more.   The toner according to any one of claims 1 to 4, wherein the resin A has an acid value of 1 mgKOH / g or more and 50 mgKOH / g or less.   The toner according to claim 1, wherein the toner is surface-treated with hot air. In a toner production method comprising: a mixing step of mixing at least a binder resin and a wax; and a melt-kneading step of melt-kneading the mixture obtained in the mixing step.
The binder resin includes at least a resin A having a polyester unit composed of an alcohol component mainly containing an aromatic diol, an alcohol component mainly containing an aliphatic diol and an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid. Containing polyester resin B and aliphatic conjugated diene resin C obtained by polycondensing the acid component
The mixing step includes a preliminary melt kneading step in which the resin B and the resin C are previously melt kneaded among the binder resins,
The content a (mass%) of the resin A in the binder resin is 50 mass% or more and 98 mass% or less,
When the content of the resin B in the binder resin is b (mass%) and the content of the resin C is c (mass%), b / a and c / b have the following relationship: Production method.
0.02 ≦ b / a <1.00
0.05 ≦ c / b ≦ 0.30

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