JP2018101069A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that achieves both low-temperature fixability and charge stability under high temperature and high humidity while reducing the occurrence of fogging during continuous printing.SOLUTION: A toner includes toner particles in each of which a surface of a particle containing a carboxyl group-containing crystalline resin is processed with a compound having a carbodiimide group or an epoxy group.SELECTED DRAWING: None

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.

In recent years, an image forming apparatus using an electrophotographic method is required to be faster and more reliable. In addition, there are high demands for power saving and shortened wait time, and in order to meet these demands, there is an increasing demand for low-temperature fixability as a toner.
In order to achieve low-temperature fixability, many proposals have been made to use not only amorphous resins but also crystalline resins as binder resins, and this is one of the effective means for achieving low-temperature fixability. It has become. However, in the high-speed developing system, the stress on the toner due to the developing roller, the regulating member, the stirring member, and the like in the developing device becomes larger. In particular, when a large number of sheets are continuously printed, the spacer particles are buried in the toner surface, and the effect of suppressing the cohesive force cannot be sufficiently exhibited, and it is difficult to maintain stable triboelectric charging characteristics. In particular, when the above-described crystalline resin is used for the purpose of promoting plasticization of an amorphous resin, the toughness of the toner is impaired, and these embedding phenomena are likely to occur. The toner in which the burying phenomenon has occurred tends to agglomerate with each other, so that triboelectric charging is less likely to occur, and the amount of charge decreases as printing is performed. Toner with reduced charge has a lower electrostatic binding force on the carrier, so the toner is scattered from the carrier due to the centrifugal force generated by the rotation of the developing support, and the toner is scattered on the non-image area and fogging occurs. (Patent Document 1).
In order to solve such problems, a method has been proposed in which the toner particle surface is cross-linked to form a shell on the toner particle surface, thereby reinforcing the toughness of the toner particle surface and preventing the spacer particles from being buried. (Patent Document 2). However, in the method disclosed in Patent Document 2, the toner particle surface is covered with a shell, so that low temperature fixability is sacrificed, and both low temperature fixability and charging stability during continuous paper feeding are extremely compatible. It was difficult.
On the other hand, it is known that a crystalline resin used for low-temperature fixability generally has a low resistance to an amorphous resin. If a low resistance component such as a crystalline resin is present on the surface of the toner particles, the charge obtained by frictional charging from the portion leaks to a member in contact with the toner particles and the charge is difficult to maintain. Also, in a high-temperature and high-humidity environment, leakage into the air increases, so in a copier placed in such an environment, the density of the first image produced after a long pause is darker than usual. There is a problem of being done. For example, Patent Document 3 proposes a method for controlling the compatibility of the crystalline resin in the amorphous polyester, but at the same time, the low-temperature fixability and the charging stability required in recent years are simultaneously realized. Is insufficient and there is room for improvement.

JP 2012-63718 A JP 2012-141523 A Japanese Patent Laying-Open No. 2015-82070

  The present invention has been made in view of the above problems, and is to provide a toner that achieves both low-temperature fixability and charging stability during continuous printing and under high temperature and high humidity.

The above problem can be solved by the following configuration.
That is, the present invention relates to a toner having toner particles obtained by treating the surface of particles containing a carboxyl group-containing crystalline resin with a compound having a carbodiimide group or an epoxy group.

  It is possible to provide a toner having both low-temperature fixability and charging stability at the time of continuous printing and under high temperature and high humidity.

It is explanatory drawing of the surface treatment apparatus suitable for the heat processing of the toner particle surface.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  The toner of the present invention has toner particles obtained by treating the surface of particles containing a carboxyl group-containing crystalline resin with a compound having a carbodiimide group or an epoxy group.

  In other words, the present inventors treated the surface of particles containing a carboxy group-containing crystalline resin with a compound having a carbodiimide group or an epoxy group, thereby suppressing low-temperature fixability and occurrence of fogging during continuous printing. It has been found that a toner having both charging stability under high temperature and high humidity can be obtained.

  The present inventors consider the following effects of using the toner of the present invention having such a configuration.

  The crystalline resin in the present invention is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).

  In general, a crystalline resin has a characteristic that charging stability is inferior to that of an amorphous resin, and this characteristic appears remarkably in a high temperature and high humidity environment. When a crystalline resin having such characteristics exists on the surface of the toner particle, the charge generated on the surface of the toner particle due to the frictional power failure leaks from the crystalline resin portion on the surface, so the charge of the toner is reduced. It becomes difficult to maintain and causes a problem in charging stability.

  In the present invention, a crystalline resin containing a carboxyl group present on the surface of a particle containing a crystalline resin containing a carboxyl group is treated with a compound having an epoxy group or a carbodiimide group to thereby obtain a crystalline resin. The carboxyl groups contained in are bonded to each other. Therefore, the crystalline structure of the crystalline resin existing on the particle surface can be made amorphous. This can be confirmed from the decrease in the endothermic peak area (ΔH) of DSC before and after the treatment with the compound having an epoxy group or a carbodiimide group. As a result, only the crystalline resin on the particle surface is in an amorphous state, and the crystalline resin inside can form particles with a maintained crystal structure. Since the crystalline resin has regularly arranged molecules, it forms regular potential energy in the crystal. However, when the crystallinity is lost and the amorphous state is reached, the molecules are not regularly arranged, so that the potential energy becomes random and the electric charge becomes difficult to move. That is, it is considered that the resin that loses the crystallinity present on the surface of the toner particles and is in an amorphous state has a higher electrical resistance than the crystalline resin, and is therefore excellent in charging stability. As a result, leakage of charges from the crystalline resin on the surface of the toner particles can be suppressed, and the effect of high charging stability in a high temperature and high humidity environment without impairing the low temperature fixability of the crystalline resin inside the toner particles. It is thought that it was expressed. Furthermore, the crystalline resin that has lost crystallinity present on the surface of the toner particles has a structure in which the crystalline resins are cross-linked with each other, so that the toughness of the toner particle surface is increased, and the outer surface in the developing process of the electrophotographic process is increased. Suppresses toner degradation such as embedding additives. Therefore, the charging stability during continuous paper feeding can be maintained.

  In order to achieve the object in the present invention, a preferable toner configuration will be described in detail below.

  As the carboxyl group-containing crystalline resin which is also the binder resin (binder resin) of the toner of the present invention, a known polyester resin can be used (preferably containing 2 to 50 parts by mass per 100 parts by mass of particles). Polyester resin A, polyester resin B, or a mixture of these as described below is preferably used.

(Polyester resin A)
The polyester resin A used in the toner of the present invention is obtained by polycondensing an alcohol component mainly composed of an aromatic diol and a carboxylic acid component.

  The aromatic diol used in the polyester resin A is not particularly limited, and examples thereof include bisphenol derivatives represented by the following formula (a) and diols represented by the following formula (b).

（式中、Ｒはエチレン又はプロピレン基、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜７である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 7.)

  Examples of the bisphenol derivative represented by the above formula (a) include 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) propane, and the like. In some cases, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5 -Diols such as pentanediol, 1,6-hexanediol, and other diols such as bisphenol A and hydrogenated bisphenol A are bisphenol derivatives represented by the above formula (a) or diols represented by the above formula (b) Can also be used in combination.

  Other alcohol components that can be used for the polyester resin A 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, sorbit, 1,2,3 , 6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycine Phosphorus, 2-methylpropane triol, 2-methyl-1,2,4-butane triol, trimethylol ethane, trimethylol propane, 1,3,5-trihydroxy methyl benzene.

  As described above, the main component of the alcohol component constituting the polyester resin A is an aromatic diol. Here, in the alcohol component constituting the polyester resin A, the aromatic diol is contained in a proportion of 80 mol% or more and 100 mol% or less, and contained in a proportion of 90 mol% or more and 100 mol% or less. Is preferred.

  As the polyvalent carboxylic acid monomer used in the polyester unit of the polyester resin, the following polyvalent carboxylic acid monomers can be used.

  Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids and These lower alkyl esters are mentioned. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenyl succinic acid are preferably used.

  Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid. 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra ( Methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, acid anhydrides thereof, or lower alkyl esters thereof. Among these, in particular, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or its derivative, is inexpensive and easy to control, so that it is preferably used. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination.

  In the present invention, the polyester resin A may be a hybrid resin containing other resin components as long as the polyester resin is a main component. For example, a hybrid resin of a polyester resin and a vinyl resin can be given. As a method of obtaining a reaction product of a vinyl resin or a vinyl copolymer unit and a polyester resin, such as a hybrid resin, a monomer component capable of reacting with each of the vinyl resin, the vinyl copolymer unit and the polyester resin is included. Where a polymer is present, a method of performing a polymerization reaction of one or both resins is preferable.

  For example, among the monomers constituting the polyester resin component, those capable of reacting with the vinyl copolymer include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  In the present invention, as the polyester resin A, if a polyester resin is a main component, various resin compounds conventionally known as binder resins can be used in combination with the above-described vinyl resin. Examples of such resin compounds include phenol resin, natural resin-modified phenol resin, natural resin-modified male resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy Examples include resins, xylene resins, polyvinyl butyral, terpene resins, coumaroindene resins, petroleum resins, and the like.

  The polyester resin A in the present invention can be produced according to a normal polyester synthesis method. For example, the above-mentioned carboxylic acid monomer and alcohol monomer are esterified or transesterified, and then subjected to a polycondensation reaction in accordance with a conventional method under reduced pressure or by introducing nitrogen gas. A polyester resin can be obtained.

  The esterification or transesterification reaction can be performed using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and magnesium acetate, if necessary.

  The polycondensation reaction can be carried out using a conventional polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide. .

  The polyester resin A of the present invention may be used by mixing a high molecular weight polyester resin A (H) and a low molecular weight polyester resin A (L). The content ratio (H / L) of the high molecular weight polyester resin A (H) and the low molecular weight polyester resin A (L) is 10/90 or more and 60/40 or less on a mass basis, and low temperature fixability and hot resistance. It is preferable from the viewpoint of offset property.

  The peak molecular weight of the high molecular weight polyester resin A (H) is preferably 10,000 or more and 20,000 or less from the viewpoint of hot offset resistance. The acid value of the high molecular weight polyester resin A (H) is preferably 15 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment.

  The number average molecular weight of the low molecular weight polyester resin A (L) is preferably 1500 or more and 3500 or less from the viewpoint of low-temperature fixability. The acid value of the low molecular weight polyester resin A (L) is preferably 10 mgKOH / g or more and 25 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment. Furthermore, the hydroxyl value of the binder resin of the present invention is preferably 2 mgKOH / g or more and 20 mgKOH / g or less from the viewpoint of low-temperature fixability and storage stability.

(Polyester resin B)
The polyester resin B of the present invention has an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms in an amount of 80 mol% or more, preferably 85 mol% or more, and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms in an amount of 80 mol% or more, preferably Is obtained by polycondensation with a carboxylic acid component contained in an amount of 85 mol% or more.

  The aliphatic diol is not particularly limited, but is preferably a linear (more preferably linear) aliphatic diol, such as butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonanediol. And decanediol are preferably exemplified.

  In the present invention, if an aliphatic diol is a main component as an alcohol component of the polyester resin B, a polyhydric alcohol monomer other than the aliphatic diol can also be used. Among the polyhydric alcohol monomers, examples of the dihydric alcohol monomer include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like. Among the polyhydric alcohol monomers, trihydric or higher polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol. 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and the like Group alcohol and the like.

  Furthermore, in the present invention, if an aliphatic diol is a main component as an alcohol component of polyester B, a monovalent alcohol may be used together. Examples of the monovalent alcohol include monofunctional groups such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, and dodecyl alcohol. And alcohol.

  On the other hand, the aliphatic dicarboxylic acid is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, etc., and hydrolyzing these acid anhydrides or lower alkyl esters Also included.

  In the present invention, if an aliphatic dicarboxylic acid is a main component as the carboxylic acid component of the polyester resin B, a polyvalent carboxylic acid other than the aliphatic dicarboxylic acid can also be used. Among the other polyvalent carboxylic acid monomers, divalent carboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; n-dodecyl succinic acid, n-dodecenyl succinic aliphatic carboxylic acid; cyclohexane dicarboxylic acid Examples thereof include alicyclic carboxylic acids such as acids, and these acid anhydrides or lower alkyl esters are also included. Among the other carboxylic acid monomers, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, Aromatic carboxylic acids such as 2,4-naphthalenetricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2 -Aliphatic carboxylic acids such as methylenecarboxypropane, and derivatives of these acid anhydrides or lower alkyl esters are also included.

  Furthermore, in this invention, as long as aliphatic dicarboxylic acid is a main component as a carboxylic acid component of the polyester resin B, you may contain monovalent carboxylic acid together. Examples of the monovalent carboxylic acid include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, Examples thereof include monocarboxylic acids such as dodecanoic acid and stearic acid.

  The polyester resin B in the present invention can be produced according to a normal polyester synthesis method. For example, the above-mentioned carboxylic acid monomer and alcohol monomer are esterified or transesterified, and then subjected to a polycondensation reaction in accordance with a conventional method under reduced pressure or by introducing nitrogen gas. A polyester resin can be obtained.

  The esterification or transesterification reaction is carried out using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, manganese acetate, magnesium acetate, etc., if necessary. be able to.

  The polycondensation reaction is carried out using a conventional polymerization catalyst such as titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. Can be done using. The polymerization temperature and the catalyst amount are not particularly limited, and may be determined appropriately.

  In the esterification or transesterification reaction or polycondensation reaction, all the monomers may be charged all at once in order to increase the strength of the resulting polyester resin B. In order to reduce the low molecular weight component, a method in which a divalent monomer is first reacted and then a trivalent or higher monomer is added and reacted may be used.

  The molar ratio (carboxylic acid component / alcohol component) between the alcohol component and the carboxylic acid component, which are raw material monomers of the polyester resin B, is preferably 0.80 or more and 1.20 or less.

(Compound having epoxy group or carbodiimide group)
The toner according to the present invention is characterized by using a compound having an epoxy group or a carbodiimide group capable of reacting with a carboxyl group of a crystalline resin present on the surface of toner particles. The compound having an epoxy group or a carbodiimide group may be used alone or in combination with two or more compounds. The reaction of the compound having an epoxy group or a carbodiimide group can be reacted by heat in a wet or dry manner.

  In the wet reaction, after a fine particle dispersion containing a binder resin containing at least a crystalline resin in an aqueous dispersion medium is aggregated to the particle size of the toner, a compound having an epoxy group or a carbodiimide group is added, This is carried out by allowing the reaction with the crystalline resin to proceed. Therefore, it is desirable that the compound having an epoxy group or a carbodiimide group is water-soluble in a wet reaction. By using a compound having a water-soluble epoxy group or carbodiimide group, the reaction is likely to proceed only on the outermost surface of the toner particles, so that both low-temperature fixability and toughness of the toner particle surface are easily realized. The wet reaction temperature is desirably a temperature not higher than the melting point of the wax, and the reaction is desirably performed in a temperature range from room temperature to about 80 ° C. The reaction time is, for example, preferably from 30 minutes to 6 hours, and preferably from 1 hour to 3 hours. When the reaction time is short, the reaction does not proceed sufficiently and it is difficult to exhibit effects such as charging stability. On the other hand, if the reaction time is too long, the reaction proceeds excessively and the toughness of the toner particle surface increases, so that there is a possibility that sufficient low-temperature fixability cannot be obtained.

  In the dry reaction, for example, fine particles of a compound having an epoxy group or a carbodiimide group are fixed on the toner particle surface using a known mixer such as a Henschel mixer, and then instantaneously heated on the toner particle surface. The reaction can be carried out by performing a hot air treatment step in which the surface of the toner particles is modified by blowing hot air and immediately cooling the toner particles with cold air. Therefore, in the dry reaction, the compound having an epoxy group or a carbodiimide group is desirably a solid.

  The compound having an epoxy group or a carbodiimide group is a compound having a carbodiimide group or an epoxy group whose unit mass per carbodiimide group or epoxy group equivalent number is 1500 g / eq or less in consideration of low-temperature fixability and charge stability of the toner Is preferably treated at a treatment amount of 0.01 to 10 parts by mass per 100 parts by mass of the particles containing the crystalline resin.

  As the compound having an epoxy group, any compound that is liquid or solid at room temperature can be used. It is desirable to contain at least two epoxy groups per molecule of the compound, and the epoxy equivalent of the compound having an epoxy group is preferably 50 g / eq or more and 4000 g / eq or less, and 85 g / eq or more and 1500 g / eq or less. Is desirable.

  In order to efficiently perform the reaction with the compound containing an epoxy group, the acid value of the crystalline resin is preferably 3 mgKOH / g or more and 30 mgKOH / g or less, more preferably 8 mgKOH / g or more and 20 mgKOH / g or less.

  Although the compound which has an epoxy group used for this invention is not specifically limited, A typical thing is shown to following formula (c)-(i).

（式中、Ｒ₂は水素原子または一価の置換基を示す。）

(In the formula, R ₂ represents a hydrogen atom or a monovalent substituent.)

（式中、Ｒ₃はそれぞれ独立に、水素原子または一価の置換基を示す。ｎは０〜１０の整数を示す。）

(In the formula, each R ₃ independently represents a hydrogen atom or a monovalent substituent. N represents an integer of 0 to 10.)

（式中、Ｒ₄はそれぞれ独立に、水素原子または炭素数１〜１２の置換基を示す。Ｘは芳香環を含む二価の有機基を示す。ｎは１〜１０の整数を示す。）

(In the formula, each R ₄ independently represents a hydrogen atom or a substituent having 1 to 12 carbon atoms. X represents a divalent organic group containing an aromatic ring. N represents an integer of 1 to 10.)

（式中、Ｒ₅は水素原子または炭素数１〜１２の置換基を示す。）

(In the formula, R ₅ represents a hydrogen atom or a substituent having 1 to 12 carbon atoms.)

（式中、Ｒ₆はそれぞれ独立に、水素原子または炭素数１〜１２の置換基を示す。ｎは１〜１０の整数を示す。）

(In the formula, each R ₆ independently represents a hydrogen atom or a substituent having 1 to 12 carbon atoms. N represents an integer of 1 to 10.)

  In the present invention, a polymer obtained by polymerizing a compound having a glycidyl group and a vinyl group as one of monomers can also be used. Monomers that can be used include esters of glycidyl alcohol and unsaturated carboxylic acids, unsaturated glycidyl ethers, such as glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, allyl glycidyl ether. And allyl β-methylglycidyl ether.

  In particular, a glycidyl monomer represented by the following formula (j) is preferably used.

（式中、Ｒ₈はそれぞれ独立に、水素原子、アルキル基、アリール基、アラルキル基、カルボシキシル基及びアルコキシカルボニル基を示す。）

(In the formula, each R ₈ independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a carboxyl group, or an alkoxycarbonyl group.)

  The glycidyl group-containing vinyl resin can be obtained by copolymerizing such a monomer having a glycidyl group alone or mixed as a vinyl monomer by a known polymerization method.

  The vinyl resin having a glycidyl group preferably has a weight average molecular weight (Mw) of 2,000 to 10,000, more preferably 3,000 to 40,000. When the Mw is 2,000 or more, the toughness of the toner particle surface is maintained when treated with the vinyl resin, and the effect on development stability is sufficient. Further, when Mw is 100,000 or less, there is no adverse effect on the fixing property.

  The compound containing a carbodiimide group is desirably water-soluble or water-dispersible, and may be used alone or in combination of two or more. The carbodiimide equivalent of the compound having a carbodiimide group is desirably 100 g / eq or more and 1000 g / eq or less. The carbodiimide equivalent represents the chemical formula amount per 1 mol of the carbodiimide group.

  A compound containing a carbodiimide group can be produced by a condensation reaction involving decarbonization of an organic diisocyanate compound using a known phospholine catalyst. In some cases, a hydrophilic carbodiimide group-containing compound can be obtained by reacting a hydrophilic segment containing a functional group that reacts with an isocyanate group at the terminal.

  As the compound containing an isocyanate group, a known isocyanate compound is used. For example, aliphatic diisocyanate, aromatic diisocyanate. Examples thereof include alicyclic diisocyanates and mixtures thereof.

(wax)
The toner of the present invention can contain a wax if necessary. 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 mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax. 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; Of unsaturated fatty acid amides such as sebacic acid amide; 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 vinylic monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides Alcohol Partial ester; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils. Furthermore, an amide compound obtained by condensing an aliphatic monoamine and an aliphatic diamine with an aliphatic carboxylic acid and an aliphatic dicarboxylic acid is also used. Examples of the aliphatic monoamine include octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, aralkylamine, behenylamine, 2-ethylhexylamine, oleylamine, erucylamine and the like. Examples of the diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, hexamethylenediamine, metaxylenediamine, tolylenediamine, paraxylenediamine, phenylenediamine, isophoronediamine, 1,10-decanediamine, , 12-dodecanediamine, 4,4-diaminodicyclohexylmethane, 4,4-diaminodiphenylmethane, and the like.

  Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax or fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low-temperature fixability and hot offset resistance. In the present invention, a hydrocarbon wax is more preferable in that the hot offset resistance is further improved.

  The wax content is preferably 1.0 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the binder resin. When the content of the wax is within this range, it is easy to efficiently exhibit hot offset properties at high temperatures.

  Further, from the viewpoint of achieving both the storage stability of the toner and the high temperature offset resistance, in the endothermic curve at the time of temperature rise measured by a differential scanning calorimeter (DSC), the maximum existing in the temperature range of 30 ° C. to 200 ° C. The peak temperature of the endothermic peak is preferably 50 ° C. or higher and 110 ° C. or lower.

(Charge control agent)
In the present invention, the toner may contain a charge control agent for controlling the triboelectric charge amount as required. 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, polymeric compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonated compounds in the side chain. Examples thereof include a polymer compound, a polymer compound having a carboxylate or a carboxylic acid ester in the side chain, a boron compound, a urea compound, a silicon compound, and 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.

(Coloring agent)
Examples of the colorant that can be contained in the toner of the present invention 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 magenta colored pigment 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, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.

  Examples of the magenta coloring 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.

  The following are mentioned as a cyan coloring pigment. 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 cyan coloring dyes include C.I. I. There is Solvent Blue 70.

  The following are mentioned as a yellow coloring pigment. 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 yellow coloring dyes 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.

(Fluidity improver)
A fluidity improver such as an inorganic fine powder can be used in the toner of the present invention. Examples of the fluidity improver include the following. Fluorine-based resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; wet-process silica, fine-powder silica such as dry-process silica; these silicas as silane coupling agents, titanium coupling agents, or silicone oils, etc. Silica treated by surface treatment. A preferable fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is dry process silica or fumed silica.

  Among these, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is preferably used. The treated silica fine powder preferably has a degree of hydrophobicity of 30 or more and 98 or less titrated by a methanol titration test.

  Examples of the method for hydrophobizing the silica fine powder include a method of chemically treating with an organosilicon compound that reacts with the silica fine powder or an organosilicon compound that physically adsorbs the silica fine powder. A preferred method is a method in which a fine silica powder produced by vapor phase oxidation of a silicon halide compound is treated with an organosilicon compound. Examples of organosilicon compounds include the following. Hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α- Chlorethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1 -Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyl Rudisiloxane and dimethylpolysiloxane. These are used alone or in a mixture of two or more.

The silica fine powder may be treated with silicone oil, or may be treated with a combination of silicone oil and the organosilicon compound. As the silicone oil, those having a viscosity at 25 ° C. of 30 mm ² / s or more and 1000 mm ² / s or less are preferable. Examples thereof include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.

  Examples of the method for hydrophobizing the silica fine powder with silicone oil include the following methods. A method in which silica fine powder treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer; a method in which silicone oil is sprayed onto a silica fine powder as a base. Alternatively, after dissolving or dispersing silicone oil in an appropriate solvent, a fine silica powder is added and mixed to remove the solvent. The silicone oil-treated silica is more preferably obtained by heating the silica in an inert gas at a temperature of 200 ° C. or higher (more preferably 250 ° C. or higher) to stabilize the surface coating after the silicone oil treatment.

  The inorganic fine powder is preferably used in an amount of 0.1 to 8.0 parts by weight, more preferably 0.1 to 4.0 parts by weight with respect to 100.0 parts by weight of the toner particles.

(Other external additives)
In the present invention, other external additives may be added to improve fluidity and adjust the triboelectric charge amount.

  As the external additive, inorganic fine particles such as silica, titanium oxide, aluminum oxide, and strontium titanate are preferable. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used. However, the mixing is not particularly limited as long as the mixing is possible.

(Production method)
The toner production method of the present invention is not particularly limited as long as it is a conventionally known toner production method such as an emulsion aggregation method, a melt-kneading method, or a dissolution suspension method, but the emulsion aggregation method is preferable from the viewpoint of dispersibility of raw materials. Then, the crystalline resin containing a carboxyl group present on the surface of the obtained toner particles is treated with a compound containing an epoxy group or a carbodiimide group.

  For example, when producing by the emulsion aggregation method, first, sufficiently small resin fine particles are prepared in advance with respect to the target particle diameter, and the resin fine particles are aggregated in an aqueous medium to produce core particles. In the emulsion aggregation method, toner particles are produced through an emulsification step, aggregation step, fusion step, particle surface treatment step, cooling step, and washing and drying step of resin fine particles.

  Hereinafter, details of each process will be described in detail.

(Emulsification process of resin fine particles)
Resin fine particles mainly composed of a polyester resin can be prepared by a known method. For example, by dissolving the resin in an organic solvent and adding it to an aqueous medium, dispersing the particles in an aqueous medium with a dispersing agent such as a homogenizer together with a surfactant and a polymer electrolyte, and then removing the solvent by heating or decompressing, A resin particle dispersion can be prepared. Alternatively, a phase inversion emulsification method may be used. Any organic solvent can be used as long as it dissolves the resin, but tetrahydrofuran, ethyl acetate, chloroform and the like are preferable from the viewpoint of solubility.

  In addition, the resin, a surfactant, a base, and the like are added to an aqueous medium, and the mixture is emulsified and dispersed in an aqueous medium substantially free of an organic solvent by a disperser that applies high-speed shearing force such as CLEARMIX, homomixer, and homogenizer. Is preferable from the viewpoint of environmental load. In particular, the content of the organic solvent having a boiling point of 100 ° C. or lower is preferably 100 μg / g or lower. When the amount is outside the above range, a new process for removing and collecting the organic solvent is required when the toner is produced, which imposes a load on wastewater treatment measures. The content of the organic solvent in the aqueous medium can be measured using gas chromatography (GC).

  The surfactant used at the time of emulsification is not particularly limited, and examples thereof include anionic surfactants such as sulfate ester, sulfonate, carboxylate, phosphate, and soap; Examples thereof include cationic surfactants such as amine salt type and quaternary ammonium salt type; nonionic surfactants such as polyethylene glycol type, alkylphenol ethylene oxide adduct type, and polyhydric alcohol type. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

  The volume-based median diameter of the resin fine particles is preferably 0.005 μm to 1.0 μm, and more preferably 0.01 μm to 0.4 μm. When the particle size is 1.0 μm or less, toner particles having a volume-based median diameter of 4.0 μm or more and 7.0 μm or less that are suitable as toner particles can be easily obtained. The volume-based median diameter uses a dynamic light scattering particle size distribution analyzer (Nanotrack UPA-EX150: manufactured by Nikkiso Co., Ltd.), laser scattering method, centrifugal sedimentation method, field-flow fractionation method, electrical detector method, and the like. Can be measured.

  Moreover, the emulsification process of a mold release agent and the emulsification process of a coloring agent can be adjusted similarly to the emulsification process of resin fine particles.

(Aggregation process)
The agglomeration step refers to mixing the above-mentioned resin fine particles, colorant fine particles, and release agent fine particles as necessary to prepare a mixed solution, and then aggregating the particles contained in the prepared mixed solution, Is a step of forming. The method for forming the aggregate is not particularly limited. For example, a pH adjuster, a flocculant, and a dispersion stabilizer are added and mixed in the mixed solution, and the temperature, mechanical power, etc. are adjusted. The method of adding suitably can be illustrated suitably.

  The pH adjuster is not particularly limited, and examples thereof include alkalis such as ammonia and sodium hydroxide, and acids such as nitric acid and citric acid.

  Examples of the flocculant include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; metal salts of trivalent metals such as iron and aluminum.

  The dispersion stabilizer is not particularly limited, and examples thereof include water-soluble polymers such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, and sodium polyacrylate; sodium dodecylbenzenesulfonate, sodium octadecylsulfate, and sodium oleate. Anionic surfactants such as sodium laurate and potassium stearate; cationic surfactants such as laurylamine acetate and lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide; polyoxyethylene alkyl Nonionic surfactants such as ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine; tricalcium phosphate, aluminum hydroxide , Calcium sulfate, calcium carbonate, inorganic compounds such as barium carbonate.

  In addition, these may be used individually by 1 type and may be used in combination of 2 or more type as needed.

  The addition / mixing of the pH adjuster, the flocculant, the dispersion stabilizer and the like is preferably performed at a temperature not higher than the glass transition temperature (Tg) of the resin particles contained in the mixed solution. When the above mixing is performed under this temperature condition, aggregation proceeds in a stable state. The said mixing can be performed using a well-known mixing apparatus, a homogenizer, a mixer, etc.

  The weight average particle diameter of the aggregate formed here is not particularly limited, but is usually controlled to 4.0 μm or more and 7.0 μm or less so as to be the same as the weight average particle diameter of the toner particles to be obtained. Good. Control can be easily performed, for example, by appropriately setting and changing the temperature at the time of addition / mixing of the flocculant and the like and the conditions of the stirring and mixing. The particle size distribution of the toner particles can be measured with a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter, Inc.) using a Coulter method.

(Fusion process)
The fusing step is a step of producing particles in which the agglomerate surface is smoothed by heating and fusing the agglomerates above the glass transition point (Tg) of the resin. Before entering the primary fusing step, a chelating agent, a pH adjusting agent, a surfactant and the like can be appropriately added in order to prevent fusion between toner particles.

  Examples of chelating agents include alkali metal salts such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, sodium gluconate, sodium tartrate, potassium citrate and sodium citrate, both nitrotriacetate (NTA) salts, COOH and OH There are many water-soluble polymers (polyelectrolytes) that contain the following functionalities.

  The heating temperature may be between the glass transition temperature (Tg) of the resin contained in the aggregate and the temperature at which the resin is thermally decomposed. As the heating / fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the heating / fusion time depends on the temperature of heating and cannot be defined unconditionally, but is generally 10 minutes to 10 hours.

(Particle surface treatment process)
A compound containing an epoxy group or carbodiimide group is added to the dispersion of toner particles that have undergone the fusing process, and the carboxyl group of the crystalline resin present on the surface of the toner particles reacts with the epoxy group or carbodiimide group. The reaction temperature with the epoxy group or carbodiimide group is preferably from 50 ° C. to 100 ° C., more preferably from 60 ° C. to 90 ° C. The reaction time with the epoxy group or carbodiimide group is preferably 0.5 hours or more and 8 hours or less, and more preferably 2 hours or more and 5 hours or less.

(Cooling process)
The cooling step is a step of cooling the temperature of the aqueous medium containing the particles to a temperature lower than the glass transition point (Tg) of the core resin. If the cooling is not performed to a temperature lower than Tg, coarse particles are generated. The specific cooling rate is 0.1 ° C./min or more and 50 ° C./min or less.

<Washing and drying process>
The particles produced through the above steps are washed and filtered with ion-exchanged water whose pH is adjusted with sodium hydroxide or potassium hydroxide, and then washed and filtered a plurality of times with ion-exchanged water. Thereafter, it is dried to obtain emulsion aggregation toner particles.

  Furthermore, a shearing force is applied to the surface of the obtained toner particles by applying inorganic particles such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resin, polyester resin and silicone resin in a dry state. It may be added.

  The melt-kneading method will be described as another manufacturing method.

  The melt-kneading method is characterized in that a toner composition that is a raw material of toner particles is melt-kneaded, and the obtained kneaded product is pulverized. An example of the manufacturing method will be described.

  In the raw material mixing step, polyester resin A, polyester resin B as described above, and other components such as wax and colorant, if necessary, are weighed in a predetermined amount and mixed as materials constituting the toner particles. . 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 Nippon Coke Industries, Ltd.).

  Next, the mixed material is melt-kneaded to disperse other raw materials and 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. From the advantage that continuous production is possible, a single-screw or twin-screw extruder has become the mainstream. Yes. 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 K.C. ), Co-kneader (manufactured by Buss), kneedex (manufactured by Nippon Coke Industries Co., Ltd.), 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 step, 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 classification 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 the present invention, if necessary, additives such as inorganic fine powder and resin particles are added and mixed and dispersed on the surface of the toner particles obtained by the melt-kneading method or the emulsion aggregation method, and the dispersed state is obtained. It is preferable to perform a heat treatment step for fixing the additive to the toner particle surface by surface treatment with hot air.

  For example, the toner can be obtained by performing surface treatment with hot air using the surface treatment apparatus shown in FIG. 1 and classifying it as necessary.

  The mixture quantitatively supplied by the raw material quantitative supply means 1 is guided to the introduction pipe 3 installed on the vertical line of the raw material supply means by the compressed gas adjusted by the compressed gas adjusting means 2. The mixture that has passed through the introduction pipe is uniformly dispersed by a conical projection-like member 4 provided at the center of the raw material supply means, and is guided to a radially extending eight-direction supply pipe 5 where heat treatment is performed. Led to.

  At this time, the flow of the mixture supplied to the processing chamber is regulated by the regulating means 9 for regulating the flow of the mixture provided in the processing chamber. Therefore, the mixture supplied to the processing chamber is heat-treated while swirling in the processing chamber and then cooled.

  The heat for heat-treating the supplied mixture is supplied from the hot air supply means 7, distributed by the distribution member 12, and introduced into the processing chamber by swirling the hot air spirally by the swirling member 13 for swirling the hot air. Is done. As the structure, the turning member 13 for turning hot air has a plurality of blades, and the turning of hot air can be controlled by the number and angle of the blades. The temperature of the hot air supplied into the processing chamber is preferably 100 ° C. or higher and 300 ° C. or lower, more preferably 130 ° C. or higher and 170 ° C. or lower, at the outlet of the hot air supply means 7. If the temperature at the outlet of the hot air supply means is within the above range, it is possible to uniformly spheroidize the toner particles while preventing the toner particles from fusing and coalescing due to overheating of the mixture. Become. The circularity at this time is preferably 0.955 or more and 0.980 or less. Hot air is supplied from the hot air supply means outlet 11.

Further, the heat-treated toner particles subjected to the heat treatment are cooled by the cold air supplied from the cold air supply means 8, and the temperature supplied from the cold air supply means 8 is preferably -20 ° C to 30 ° C. If the temperature of the cold air is within the above range, the heat-treated toner particles can be efficiently cooled, and the heat-treated toner particles can be prevented from being fused and coalesced without hindering uniform spheroidization of the mixture. be able to. The absolute moisture content of the cold air is preferably 0.5 g / m ³ or more and 15.0 g / m ³ or less.

  Next, the cooled heat-treated toner particles are recovered by the recovery means 10 at the lower end of the processing chamber. In addition, a blower (not shown) is provided at the tip of the collecting means, and is thereby configured to be sucked and conveyed.

  The powder particle supply port 14 is provided so that the swirling direction of the supplied mixture and the swirling direction of the hot air are the same direction. It is provided in the outer peripheral part of a process chamber so that the turning direction may be maintained. Further, the cold air supplied from the cold air supply means 8 is configured to be supplied from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber in a horizontal and tangential direction. The swirling direction of the pre-heat treatment toner particles supplied from the powder supply port, the swirling direction of the cold air supplied from the cold air supplying means, and the swirling direction of the hot air supplied from the hot air supplying means are all the same direction. Therefore, turbulent flow does not occur in the processing chamber, the swirling flow in the apparatus is strengthened, a strong centrifugal force is applied to the toner particles before heat treatment, and the dispersibility of the toner particles before heat treatment is further improved, so there are few coalesced particles Thus, heat-treated toner particles having a uniform shape can be obtained.

  Thereafter, external additives such as inorganic fine powder and resin particles selected as necessary may be added to externally add other inorganic fine particles to improve fluidity and charge stability. 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 Nippon Coke Industries, Ltd.).

(Career)
The toner of the present invention is preferably mixed with a magnetic carrier and used as a two-component developer in that a stable image can be obtained over a long period of time.

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

  Next, methods for measuring physical properties related to the present invention will be described.

(Measurement method of softening point (Tm))
The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “flow characteristic evaluation device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). Then, the temperature of the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.

  As a measurement sample, about 1.0 g of resin is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

(Measurement of glass transition temperature (Tg))
The glass transition temperature of the resin is measured in accordance with 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 5 mg of resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rising rate is 10 ° C./min between a measurement range of 30 to 200 ° C. Measure with. The temperature is raised to 180 ° C. and held for 10 minutes, then the temperature is lowered to 30 ° C., and then the temperature is raised again. In the second temperature raising process, a specific heat change is obtained in the temperature range of 30 to 100 ° C. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature (Tg) of the resin.

(Measurement of number average molecular weight (Mn), weight average molecular weight (Mw))
The molecular weight distribution of the THF soluble part of the resin is measured by gel permeation chromatography (GPC) as follows.

The column is stabilized in a 40 ° C. heat chamber, and tetrahydrofuran (THF) is allowed to flow through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is suitably used. The detector uses an RI (refractive index) detector. In addition, as a column, it is good to combine several commercially available polystyrene gel columns, for example, the following combinations are mentioned. Combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P made by Showa Denko KK, TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ) made by Tosoh Corporation , G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), TSKgourd column combination.

  Moreover, a sample is produced as follows.

  Place 50 mg of the sample in 10 ml of THF, leave it at 25 ° C. for several hours, shake well, mix well with THF (until the sample is no longer integrated), and let stand for more than 12 hours. Note that the total standing time in THF is 24 hours. Then, a sample processing filter (pore size of 0.2 μm or more and 0.5 μm or less, for example, Myssho Disc H-25-2 (manufactured by Tosoh Corporation)) can be used as a GPC sample.

(Measurement of melting point (Tm))
The melting point of the crystalline polyester resin B and the wax is the DSC curve measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments). To do.

  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 2 mg of a sample is precisely weighed, placed 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 temperature of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the melting point.

(Measurement of endothermic amount (ΔH))
The peak temperature (Tp) of the maximum endothermic peak of the toner or the like (toner, crystalline polyester) in the present invention is measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions. Measurement is performed at a temperature rising rate of 10 ° C./min within a measurement temperature range of 30 to 200 ° C.

  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 5 mg of a sample is precisely weighed, placed in a silver pan, and measured once. A silver empty pan is used as a reference.

  When using toner as a sample, if the maximum endothermic peak (maximum endothermic peak derived from the binder resin) does not overlap with the endothermic peaks of resins other than wax and crystalline resin, the endothermic amount of the maximum endothermic peak obtained Is treated as the endothermic amount of the maximum endothermic peak derived from the crystalline resin as it is. On the other hand, when the toner is used as a sample, if the endothermic peak of the resin other than the wax and the binder resin overlaps with the maximum endothermic peak of the binder resin, the endothermic amount derived from the resin other than the wax and the binder resin is calculated. It is necessary to subtract from the endothermic amount of the maximum endothermic peak obtained.

  The maximum endothermic peak means a peak where the endothermic amount is maximum when there are a plurality of peaks. Further, the endothermic amount (ΔH) of the maximum endothermic peak is obtained from the peak area by calculation using analysis software attached to the apparatus.

(Measurement of acid value)
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 in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

  Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potential difference titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.). 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 0.100 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

The measurement conditions for the acid value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank titration Titration style: Total titration Maximum titration: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter end point judgment potential: 30 dE
End point determination differential value: 50 dE / dmL
End point detection range setting: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 mL

main exam;
0.100 g of a measurement sample is precisely weighed in a 250 mL tall beaker, and 150 mL of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.

Blank test;
Titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene / ethanol (3: 1) is used).

The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.611] / S
(In the formula, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in blank test (mL), C: addition amount of potassium hydroxide ethyl alcohol solution in this test (mL), f: Factor of potassium hydroxide solution, S: Sample (g))

(Measurement method of hydroxyl value)
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

  Add 25.0 g of special grade acetic anhydride to a 100 mL volumetric flask, add pyridine to bring the total volume to 100 mL, and shake well to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.

  Titration is performed using a 1.0 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Co., Ltd.). 100 mL of 1.00 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 1.00 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

The measurement conditions for the hydroxyl value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank titration Titration style: Total titration Maximum titration: 80 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter end point judgment potential: 30 dE
End point determination differential value: 50 dE / dmL
End point detection range setting: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.5 mL

main exam;
2.00 g of the pulverized measurement sample is precisely weighed into a 200 mL round bottom flask, and 5.00 mL of the acetylating reagent is accurately added to this using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.

  Place a small funnel in the mouth of the flask and immerse 1 cm of the bottom of the flask in a 97 ° C. glycerin bath and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.

  After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1.00 mL of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5.00 mL of ethyl alcohol.

  The obtained sample is transferred to a 250 mL tall beaker, and 100 mL of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.

Blank test;
Titration similar to the above operation is performed except that no sample is used.

The obtained results are substituted into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D
Here, A: hydroxyl value (mgKOH / g), B: addition amount (mL) of potassium hydroxide ethyl alcohol solution in blank test, C: addition amount (mL) of potassium hydroxide ethyl alcohol solution in final test, f : Factor of potassium hydroxide solution, S: Sample (g), D: Acid value of resin (mgKOH / g).

(Measurement of toner weight average particle diameter (D4))
The weight average particle diameter (D4) of the toner is determined based on the precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting and analyzing the measurement data, the measurement data is measured with 25,000 effective channels. Analyze and calculate. As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in deionized water to 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 is 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, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) 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 to 60 μm.

Specific measurement methods are as follows (1) to (7).
(1) About 200 ml of the electrolytic solution is placed in a 250 ml round bottom beaker made exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. The 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 placed in a glass 100 ml flat bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder having a pH of 7 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 cleaning precision instruments (made by Wako Pure Chemical Industries, Ltd.) 3 times by weight with deionized 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 disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkiki Bios) with an electrical output of 120 W. A fixed amount of deionized water is added, and about 2 ml of the contamination N is added to the 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) In the round bottom beaker (1) installed in the sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. 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).

(Measurement 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.

  The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is picked up by a CCD camera, and the picked-up image is image-processed at an image processing resolution of 512 × 512 pixels (0.37 × 0.37 μm per pixel), the contour of each particle image is extracted, and the particle image The projected area S, the peripheral length L, etc. are measured.

Next, the equivalent circle diameter and the circularity are obtained using the area S and the peripheral length L. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. And is calculated by the following formula.
Circularity C = 2 × (π × S) 1/2 / L

  When the particle image is circular, the circularity is 1.000, and the greater the degree of unevenness around the particle image, the smaller the circularity. After calculating the circularity of each particle, the range of the circularity of 0.200 to 1.000 is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity.

  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 put in, and about 2 ml of the contamination N is added to the 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 procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the total count mode in the HPF measurement mode. Then, by setting the binarization threshold at the time of particle analysis to 85% and specifying the analysis particle diameter, the number ratio (%) of particles in the range and the average circularity can be calculated. The average circularity of the toner was set to an equivalent circle diameter of 1.98 μm to 39.96 μm, and the average circularity of the toner was determined.

  In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “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 measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.98 μm or more and less than 39.69 μm.

(Measurement method of epoxy equivalent)
The basic operation conforms to JISK-7236.
(1) 0.1 g to 2.0 (g) of the sample is precisely weighed, and the weight of the sample is set to W (g).
(2) A sample is put into a 300 (ml) beaker and dissolved in 10 ml of chloroform and 20 ml of acetic acid.
(3) To this solution is added 10 ml of tetraethylammonium bromide acetic acid solution.
(4) Titrate with a potentiometric titrator using 0.1 mol / l perchloric acid acetic acid solution. (For example, it can be measured using a potentiometric titrator AT-400 (Winworkstation) manufactured by Kyoto Electronics Co., Ltd. and an ABP-410 electric burette.)
(5) The amount of perchloric acid acetic acid solution used at this time is S (ml), and a blank is measured at the same time. The amount of perchloric acid acetic acid solution used at this time is B (ml).
(6) The epoxy equivalent is calculated from the following formula. f is a factor of the perchloric acid acetic acid solution, K is a temperature correction value of the perchloric acid acetic acid solution, t is a liquid temperature of the perchloric acid acetic acid solution at the time of sample measurement, t ₀ is a liquid of the perchloric acid acetic acid solution at the time of standardization It is warm.
Epoxy equivalent (g / eq) = 1000 × W / (f × K × (SB))
Temperature correction value K = 1− (t−t ₀ ) / 1000

  Hereinafter, the present invention will be described with reference to production examples and examples.

(Production example of polyester resin A)
(Production Example 1 of Low Molecular Weight Polyester Resin A (L))
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 360.0 parts by mass (1.0 mol)
・ Terephthalic acid: 140.0 parts by mass (0.85 mol)
-Tin 2-ethylhexanoate (esterification catalyst): 2.5 parts by mass (0.006 mol)
The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).
Trimellitic anhydride: 9.6 parts by mass (0.05 mol)
-Tert-butylcatechol (polymerization inhibitor): 0.5 part by mass (0.003 mol)
Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was continued for 1 hour while maintaining the temperature at 180 ° C., and it was confirmed that the softening point measured according to ASTM D36-86 reached 94 ° C. Then, the temperature was lowered to stop the reaction (second reaction step) to obtain a low molecular weight polyester resin A (L) -1. The resulting low molecular weight polyester resin A (L) -1 had a softening point (Tm) of 94 ° C., a glass transition temperature (Tg) of 57 ° C., a number average molecular weight of 2500, and an acid value of 13 mgKOH / g.

(Production Example 2 of Low Molecular Weight Polyester Resin A (L))
In Production Example 1 of the low molecular weight polyester resin A (L), trimellitic anhydride: 9.6 parts by mass (0.05 mol) was changed to 4.8 parts by mass (0.025 mol) in the same manner. Low molecular weight polyester resin A (L) -2 was obtained. The obtained low molecular weight polyester resin A (L) -2 had a softening point (Tm) of 93 ° C., a glass transition temperature (Tg) of 56 ° C., a number average molecular weight of 2300, and an acid value of 7 mgKOH / g.

(Production Example 3 of Low Molecular Weight Polyester Resin A (L))
In Production Example 1 of low molecular weight polyester resin A (L), trimellitic anhydride: 9.6 parts by mass (0.05 mol) was changed to 15.4 parts by mass (0.08 mol) in the same manner. Low molecular weight polyester resin A (L) -3 was obtained. The resulting low molecular weight polyester resin A (L) -3 had a softening point (Tm) of 95 ° C., a glass transition temperature (Tg) of 58 ° C., a number average molecular weight of 2700, and an acid value of 18 mgKOH / g.

(Production Example 4 of Low Molecular Weight Polyester Resin A (L))
In Production Example 1 of low molecular weight polyester resin A (L), trimellitic anhydride: 9.6 parts by mass (0.05 mol) was changed to 19.2 parts by mass (0.1 mol) in the same manner. Low molecular weight polyester resin A (L) -4 was obtained. The resulting low molecular weight polyester resin A (L) -4 had a softening point (Tm) of 92 ° C., a glass transition temperature (Tg) of 55 ° C., a number average molecular weight of 2100, and an acid value of 2 mgKOH / g.

(Production Example 5 of Low Molecular Weight Polyester Resin A (L))
In Production Example 1 of low molecular weight polyester resin A (L), trimellitic anhydride: 9.6 parts by mass (0.05 mol) was changed to 0.96 parts by mass (0.005 mol) in the same manner. Low molecular weight polyester resin A (L) -5 was obtained. The obtained low molecular weight polyester resin A (L) -5 had a softening point (Tm) of 96 ° C., a glass transition temperature (Tg) of 59 ° C., a number average molecular weight of 3000, and an acid value of 25 mgKOH / g.

(Production Example 6 of Low Molecular Weight Polyester Resin A (L))
Low molecular weight polyester resin A (L) was prepared in the same manner as in Production Example 1 of low molecular weight polyester resin A (L), except that tin 2-ethylhexanoate: 0.01 mol was changed to dioctyl tin oxide: 0.01 mol. -6 was obtained. The obtained low molecular weight polyester resin A (L) -6 had a softening point (Tm) of 95 ° C., a glass transition temperature (Tg) of 58 ° C., a number average molecular weight of 2600, and an acid value of 15 mgKOH / g.

(Production Example 1 of High Molecular Weight Polyester Resin A (H))
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 360.0 parts by mass (1.0 mol)
・ Terephthalic acid: 91.3 parts by mass (0.55 mol)
・ Fumaric acid: 17.4 parts by mass (0.15 mol)
-Tin 2-ethylhexanoate (esterification catalyst): 2.5 parts by mass (0.006 mol)
The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure (first reaction step).
Trimellitic anhydride: 28.8 parts by mass (0.15 mol)
-Tert-butylcatechol (polymerization inhibitor): 0.5 part by mass (0.003 mol)
Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was continued for 15 hours while maintaining the temperature at 160 ° C., and the softening point measured according to ASTM D36-86 reached 132 ° C. Then, the temperature was lowered to stop the reaction (second reaction step) to obtain a high molecular weight polyester resin A (H) -1. The obtained high molecular weight polyester resin A (H) -1 had a softening point (Tm) of 132 ° C., a glass transition temperature (Tg) of 61 ° C., a peak molecular weight of 15000, and an acid value of 21 mgKOH / g.

(Production Example 1 of Polyester Resin B)
・ 1,6-hexanediol: 115.8 parts by mass (0.98 mol)
・ Dodecanedioic acid: 230.3 parts by mass (1.00 mol)
-Tin dioctylate: 8.10 parts by mass (0.02 mol)
The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, the reaction was performed for 6 hours while stirring at a temperature of 140 ° C., and then the reaction was performed while increasing the temperature to 200 ° C. at 10 ° C./hour. To obtain a polyester resin B-1. The obtained polyester resin B-1 had a weight-average molecular weight of 10,000, an acid value of 16 mgKOH / g, and a maximum endothermic peak at 55 ° C. in a DSC curve by differential scanning calorimetry.

(Production Examples 2 to 12 of polyester resin B)
The types of alcohol component and acid component were changed as shown in Tables 1 and 2, and polyester resins B-2 to B-12 were obtained in the same manner as in Production Example 1 except that. The physical properties of these polyester resins B are shown in Table 1.

(Production Example 13 of Polyester Resin B)
・ 1,6-Hexanediol: 147.5 parts by mass (1.25 mol)
・ Dodecanedioic acid: 230.3 parts by mass (1.00 mol)
-Tin dioctylate: 8.10 parts by mass (0.02 mol)
The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, the reaction was performed for 6 hours while stirring at a temperature of 140 ° C., and then the reaction was performed while increasing the temperature to 200 ° C. at 10 ° C./hour. I let you. Subsequently, after the temperature was lowered to 100 ° C., 20.4 parts by mass (0.20 mol) of 1-hexanol was added, the temperature was raised to 140 ° C., and the mixture was further reacted for 2 hours to obtain polyester resin B-13. . Table 1 shows the physical properties of the obtained polyester resin B-13.

(Example of production of crystalline resin C)
In a flask equipped with a thermometer, a water separator, and a stirrer, 60.0 parts by mass (1.0 mol) of ethylenediamine and 6.9 parts by mass (0.01 mol) of tris (nonylphenyl) phosphite in a nitrogen atmosphere And stirred at room temperature for 1 hour. Subsequently, 546.7 parts by mass (2.2 mol) of stearic acid was added, and the reaction was carried out at 190 ° C. for 5 hours while removing the reaction water. Thereafter, unreacted stearic acid was removed under reduced pressure to obtain Resin C. The obtained crystalline resin C had an acid value of 6.0 KOH / g and a melting point of 140 ° C.

(Example of production of carboxyl group-containing vinyl resin 1)
To a flask in a nitrogen atmosphere, 80 parts by mass of styrene, 19.5 parts by mass of n-butyl acrylate, 4.5 parts by mass of methacrylic acid, 0.7 parts by mass of tert-butyl peroxide, and 200 parts by mass of xylene were added, The reaction was carried out for 6 hours while refluxing xylene. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a carboxyl group-containing vinyl resin 1. The weight average molecular weight was 25,000, and the acid value was 30 KOH / g.

(Production example of epoxy resin 1)
To a flask equipped with a thermometer, a dropping funnel, a reflux condenser, and a stirrer was added 182.2 parts by mass (1.00 mol) of sorbitol, 5.0 parts by mass of benzyltriethylammonium chloride (0.02 mol), and methyl ethyl ketone. Methyl ethyl ketone was refluxed. Subsequently, 388.5 parts by mass (4.20 mol) of epichlorohydrin was added dropwise over 3 hours, and the mixture was stirred for 1 hour while maintaining the temperature. Then, 656 mass parts (4.10 mol) of 25% sodium hydroxide aqueous solution was dripped over 5 hours, and also it stirred for 1 hour. After completion of the reaction, the salt produced by the reaction was removed by filtration, washed with water three times to remove unreacted epichlorohydrin, and it was confirmed that the pH became neutral. Subsequently, after dehydrating by azeotropic distillation, the solvent was removed by distillation under reduced pressure to obtain 333.6 parts by mass of the desired epoxy resin 1. The epoxy equivalent was 102.0 g / eq. Water was added so that the epoxy resin 1 was 50% by mass to obtain an epoxy resin 1-containing solution.

(Production example of epoxy resin 2)
In a flask equipped with a thermometer, a dropping funnel, a reflux condenser and a stirrer, 62.0 parts by mass of monopropylene glycol (1.00 mol), 462.5 parts by mass of epichlorohydrin (5.00 mol), benzyltriethylammonium chloride 5 0.0 part by mass (0.02 mol) was added, and the mixture was stirred at 70 ° C. for 1 hour. Then, 352 mass parts (2.20 mol) of 25% sodium hydroxide aqueous solution was dripped over 5 hours, and also it stirred for 1 hour. After completion of the reaction, the salt produced by the reaction was removed by filtration, methyl ethyl ketone was added, washed with water three times to remove unreacted epichlorohydrin, and it was confirmed that the pH became neutral. Subsequently, after dehydrating by azeotropic distillation, the solvent was removed by distillation under reduced pressure to obtain 168.0 parts by mass of the desired epoxy resin 2. The epoxy equivalent was 92.0 g / eq. Water was added so that the epoxy resin 2 would be 50% by mass to obtain an epoxy resin 3 containing solution.

(Production example of epoxy resin 3)
In a flask equipped with a thermometer, dropping funnel, reflux condenser and stirrer, 62.0 parts by mass (1.00 mol) of monoethylene glycol, 462.5 parts by mass of epichlorohydrin (5.00 mol), benzyltriethylammonium chloride 5 0.0 part by mass (0.02 mol) was added, and the mixture was stirred at 70 ° C. for 1 hour. Then, 352 mass parts (2.20 mol) of 25% sodium hydroxide aqueous solution was dripped over 5 hours, and also it stirred for 1 hour. After completion of the reaction, the salt produced by the reaction was removed by filtration, methyl ethyl ketone was added, washed with water three times to remove unreacted epichlorohydrin, and it was confirmed that the pH became neutral. Subsequently, after dehydrating by azeotropic distillation, the solvent was removed by distillation under reduced pressure to obtain 155.0 parts by mass of the desired epoxy resin 3. The epoxy equivalent was 85.0 g / eq. Water was added so that the epoxy resin 3 was 50% by mass to obtain an epoxy resin 2 containing solution.

(Production example of epoxy resin 4)
While adding 70 parts by mass of styrene, 17 parts by mass of n-butyl acrylate, 13 parts by mass of glycidyl methacrylate, 7 parts by mass of tert-butyl peroxide, and 200 parts by mass of xylene, a flask having a nitrogen atmosphere was added while refluxing xylene. The reaction was performed for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain epoxy resin 4. The weight average molecular weight was 10,000 and the epoxy equivalent was 1500 g / eq.

(Production example of epoxy resin 5)
While adding 75 parts by mass of styrene, 20 parts by mass of n-butyl acrylate, 5 parts by mass of glycidyl methacrylate, 7 parts by mass of tert-butyl peroxide, and 200 parts by mass of xylene, a flask having a nitrogen atmosphere was added while refluxing xylene. The reaction was performed for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain epoxy resin 5. The weight average molecular weight was 12,000 and the epoxy equivalent was 2,000 g / eq.

  The obtained epoxy resin 5 was dissolved in tetrahydrofuran. While stirring this tetrahydrofuran solution at 10000 rpm for 30 minutes with a homogenizer (IKA Japan: Ultra Tarax) at room temperature, 5 parts by weight of potassium hydroxide and 10 parts by weight of sodium dodecylbenzene-sulfonate were added as surfactants. 1000 parts by mass of exchange water was dropped. The solid was collected and dried. Fine particles of epoxy resin 5 having a volume average particle diameter of 0.10 μm were obtained.

(Production example of carbodiimide resin 1)
In a flask equipped with a thermometer, a reflux machine and a stirrer, in a nitrogen atmosphere, 174.2 parts by mass (1.00 mol) of toluene diisocyanate, 4.00 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide Part (0.02 mol) was added and reacted at 70 ° C. for 3 hours. Subsequently, the temperature was lowered to 40 ° C., 100 parts by mass of polyethylene glycol monomethyl ether was added, the mixture was further stirred at the same temperature, and disappearance of the isocyanate group was confirmed by infrared absorption (IR) spectrum, and then the reaction was stopped. Water was added so that one component of the carbodiimide resin was 50% by mass to obtain a transparent solution containing the carbodiimide resin 1.

(Production example of carbodiimide resin 2)
A flask equipped with a thermometer, a reflux machine, and a stirrer was charged with 168.2 parts by mass (1.00 mol) of hexamethylene diisocyanate and 3-methyl-1-phenyl-2-phospholene-1-oxide under a nitrogen atmosphere. A part by mass (0.02 mol) was added and reacted at 170 ° C. for 5 hours. Subsequently, the temperature was lowered to 130 ° C., 100 parts by mass of polyethylene glycol monomethyl ether was added, the mixture was further stirred at the same temperature, and the disappearance of the isocyanate group was confirmed by infrared absorption (IR) spectrum, and then the reaction was stopped. Water was added so that the carbodiimide resin 2 component was 50% by mass to obtain a carbodiimide resin 2-containing transparent solution.

(Production Example of High Molecular Weight Polyester Resin A (H) Fine Particle Dispersion (1))
100 parts by mass of high molecular weight polyester resin A (H) -1 was dissolved in 150 parts by mass of tetrahydrofuran. An ion in which 5 parts by mass of potassium hydroxide and 10 parts by mass of sodium dodecylbenzene-sulfonate were added as surfactants while stirring this tetrahydrofuran solution at 10000 rpm for 30 minutes with a homogenizer (IKA Japan: Ultra Tarax) at room temperature. 1000 parts by mass of exchange water was dropped. The mixed solution was heated to about 75 ° C. to remove tetrahydrofuran. Then, it diluted with ion-exchange water so that solid content might be 8%, and obtained high molecular weight polyester resin A (H) fine particle dispersion (1) with a volume average particle diameter of 0.09 micrometer.

(Production example of low molecular weight polyester resin A (L) fine particle dispersions (1) to (6))
In the preparation of the high molecular weight polyester resin A (H) fine particle dispersion (1), the high molecular weight polyester resin A (H) -1 was changed to low molecular weight polyester resins A (H) -1 to 6 in the same manner. Thus, low molecular weight polyester resin A (L) fine particle dispersions (1) to (6) were obtained.

(Production Example of Polyester Resin B Fine Particle Dispersions (1) to (13))
Polyester resin B fine particles in the same manner except that the high molecular weight polyester resin A (H) -1 is changed to polyester resins B-1 to B-13 in the preparation of the high molecular weight polyester resin A (H) fine particle dispersion (1). Dispersions (1) to (13) were obtained.

(Production example of crystalline resin C fine particle dispersion)
In the preparation of the high molecular weight polyester resin A (H) fine particle dispersion (1), except that the high molecular weight polyester resin A (H) -1 is changed to the crystalline resin C, the crystalline resin C fine particle dispersion is similarly prepared. Got.

(Production example of carboxyl group-containing vinyl resin 1 fine particle dispersion)
Carboxyl group-containing vinyl resin in the same manner except that the high molecular weight polyester resin A (H) -1 is changed to carboxyl group-containing vinyl resin 1 in the preparation of the high molecular weight polyester resin A (H) fine particle dispersion (1). One fine particle dispersion was obtained.

(Production example of colorant fine particle dispersion)
Color material (cyan pigment: Pigment Blue 15: 3) 10 parts by weight anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.5 parts by weight ion-exchanged water 88.5 parts by weight The above is mixed and dissolved. Then, using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), dispersion was performed for about 1 hour to prepare an aqueous dispersion of color material fine particles in which the color material was dispersed. The volume-based median diameter was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.), and was 0.20 μm.

(Production Example of Release Agent Fine Particle Dispersion (1))
Fischer-Tropsch wax (peak temperature of maximum endothermic peak 90 ° C.) 5.0 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 part by weight ion-exchanged water 89 parts by weight After being put into the mixing container, the sample is heated to 90 ° C and circulated to Claremix W-Motion (M Technique Co., Ltd.). After stirring for 19000 r / min and screen rotation speed of 19000 r / min and dispersing for 60 minutes, the rotor rotation speed is 1000 r / min, screen rotation speed is 1000 r / min, and cooling speed is 10 ° C./min. By cooling to 40 ° C., an aqueous dispersion of release agent fine particles was obtained. The volume-based median diameter was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), and was 0.15 μm.

[Example 1]
(Production example of toner particle 1)
Low molecular weight polyester resin A (L) fine particle dispersion (1) 75.0 parts by mass (resin equivalent)
High molecular weight polyester resin A (H) fine particle dispersion (1) 25.0 parts by mass (equivalent to resin)
Polyester resin B fine particle dispersion (1) 25.0 parts by mass (resin equivalent)
Release agent fine particle dispersion (1) 5.0 parts by weight (equivalent to release agent)
Colorant fine particle dispersion 5.0 parts by weight (equivalent to colorant)
1.5 mass% magnesium sulfate aqueous solution 10.0 mass parts The above was disperse | distributed using the homogenizer (the IKA company_made: Ultra Turrax T50). Subsequently, the pH was adjusted to 8.1 with a 0.1N sodium hydroxide aqueous solution. Then, it heated, stirring with a stirring blade to 45 degreeC in the water bath for heating. After maintaining at 45 ° C. for 1 hour, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 5.5 μm were formed. After adding 40 parts by mass of a 5 mass% trisodium citrate aqueous solution, the temperature was raised to 85 ° C. while maintaining stirring, and maintained for 90 minutes to fuse the core particles. Next, while stirring was continued, water was placed in the water bath and cooled to 25 ° C. Further, when the particle size of the core particles was measured by a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter, Inc.) using a Coulter method, the volume-based median diameter was 5.6 μm.

  Thereafter, 1.25 parts by mass (epoxy resin 50%) of an epoxy resin 1-containing solution and 50 parts by mass of sodium dodecylbenzenesulfonate were added, and the mixture was heated to 75 ° C. and reacted for 2 hours. .

  Thereafter, after filtration and solid-liquid separation, 800 parts by mass of ion-exchanged water whose pH was adjusted to 8 with sodium hydroxide was added to the solid content, followed by stirring and washing for 30 minutes. Thereafter, filtration and solid-liquid separation were performed again. Subsequently, 800 parts by mass of ion-exchanged water was added to the solid content and washed with stirring for 30 minutes. Thereafter, filtration and solid-liquid separation were performed again, and this was repeated 5 times. Next, toner particles 1 were obtained by drying the obtained solid content.

To 100 parts by mass of the obtained toner particles 1, 1.0 part by mass of silica fine particles having a primary average particle diameter of 15.0 nm is added, and the rotation speed is 31.6 s ⁻¹ and the rotation time is measured with a Henschel mixer (FM-75 type). The mixture was mixed for 5 min and passed through an ultrasonic vibration sieve having an aperture of 54 μm to obtain toner 1.

(Production example of two-component developer 1)
The toner 1 and magnetic ferrite carrier particles (number average particle size 35 μm) coated with a silicone resin are used to form a toner concentration of 9% by mass with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.). The two-component developer 1 was obtained by mixing at 0.5 s ⁻¹ and a rotation time of 5 minutes.

  The performance of the toner was evaluated according to the following methods (1) to (3).

(1) Fixability evaluation A developer unit containing the above two-component developer is installed in the cyan station of a Canon full-color copier imagePRESS C800, and it has been modified so that an image can be formed with the fixing temperature removed. Formed. For the evaluation, Canon plain paper / white A4 (basis weight 73 g / m ² ) was used.

The development conditions are adjusted as appropriate so that the amount of FFH image (hereinafter, solid portion) toner is 1.3 mg / cm ^{2 on the} paper, 3 cm from the A4 evaluation paper tip, and 2 cm × 10 cm at the center of the evaluation paper. A solid unfixed image was formed. The unfixed image was conditioned for 24 hours in a low temperature and low humidity environment (15 ° C./10% RH).

  Take out the fixing unit from Canon full color copier imagePRESS C800 and prepare it in a low temperature and low humidity environment (15 ° C / 10% RH) using a fixing test jig modified so that the process speed and upper and lower fixing member temperatures can be controlled independently. did. With the process speed adjusted to 400 mm / sec and the lower belt temperature fixed at 90 ° C., the upper belt temperature of the fixing test jig was adjusted every 5 ° C. within the range of 100 to 200 ° C. The moisture-adjusted unfixed image was passed through. The fixed image that has passed through the fixing device is rubbed 5 times with a lens cleaning wiper (Dasper Ozu Sangyo Co., Ltd.) applied with a load of 4.9 kPa, and the density reduction rate of the image density before and after the rubbing is 10% or less. This point was taken as the fixing temperature. Based on the criterion that fixing was not possible when the density decreased over 10%, the lowest upper belt set temperature not exceeding 10% of the image density decreasing rate was set as the fixing start temperature, and evaluation was performed according to the following evaluation standards. . The evaluation results are shown in Table 3.

(Evaluation criteria: low temperature fixability)
A: Less than 115 ° C. (very good)
B: 115 ° C. or higher and lower than 135 ° C. (excellent)
C: 135 ° C. or higher and lower than 150 ° C. (slightly superior)
D: 150 ° C. or higher and lower than 170 ° C. (prior art level; acceptable level in the present invention)
E: 170 ° C. or higher (inferior to conventional; unusable level in the present invention)

(High humidity environment toner scattering evaluation)
The above two-component developer was placed in the cyan station of a Canon full-color copying machine imagePRESS C800, and toner scattering in the developing device was evaluated in a high-temperature and high-humidity environment (30 ° C., 80% RH). After outputting 20,000 images on a chart with an image ratio of 45%, only the developing device is rotated idly for 30 seconds in the main body of the image forming apparatus, and the toner adhering to the surface of the opposing photoreceptor is collected by taping. The amount was measured with a photovolt reflection densitometer (trade name: TC-6DS / A; manufactured by Tokyo Denshoku Co., Ltd.). Evaluation was performed according to the following evaluation criteria. The evaluation results are shown in Table 3.

(Evaluation criteria: Toner scattering fog)
A: Less than 5% (very good)
B: 5% or more and less than 20% (excellent)
C: 20% or more and less than 40% (somewhat better)
D: 40% or more and less than 50% (prior art level; acceptable level in the present invention)
E: 50% or more (inferior to the prior art; impractical level in the present invention)

(Chargeability, Q / M (mC / kg) maintenance rate evaluation after standing)
10.0 g of the above two-component developer is placed in a 50 cc plastic bottle, left in an environment of 32.5 ° C. and 80% RH for 24 hours, shaken with a Yayoi shaker at 200 rpm for 5 minutes in the environment, and then toner The initial charge amount (μC / g) of the charge amount was measured with an E-Spart Analyzer manufactured by Hosokawa Micron.

  The two-component developer in the plastic bottle subjected to the above evaluation was allowed to stand in the environment for 2 weeks, and the average charge amount (μC / g) after being allowed to stand using E-Spart Analyzer manufactured by Hosokawa Micron as described above. It was measured.

  From the relationship between the initial average charge amount and the average charge amount after standing, the maintenance rate of the average charge amount was calculated and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 3.

(Evaluation criteria: Q / M (mC / kg) maintenance rate evaluation after leaving)
A: 90% or more (very good)
B: Less than 90% and 80% or more (excellent)
C: Less than 80% and 70% or more (slightly superior)
D: Less than 70% and 60% or more (prior art level; acceptable level in the present invention)
E: Less than 60% (inferior to conventional; unusable level in the present invention)

[Examples 2 to 30 and 32]
The high molecular weight polyester resin A (H), the low molecular weight polyester resin A (L), the polyester resin B, and the epoxy group or carbodiimide group-containing resin were changed in the same manner as in Example 1 except that they were changed as shown in Table 2. Toners 2 to 30 and 32 were produced, and two-component developers 2 to 30 and 32 were produced in the same manner. Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 31
(Production example of toner 31)
Low molecular weight polyester resin A (L) -1 75.0 parts by mass Crystalline polyester resin B-12 60.0 parts by mass Fischer-Tropsch wax (maximum endothermic peak peak temperature 90 ° C.) 5.0 parts by mass I. Pigment Blue 15: 3 5.0 parts by mass After mixing the raw materials shown in the above prescription with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industries Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, It knead | mixed with the biaxial kneader (PCM-30 type | mold, Ikegai Co., Ltd.) set to the temperature of 125 degreeC. 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. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were classified at a classifying rotor rotational speed of 50.0 s ⁻¹ . The obtained toner particles had a weight average particle diameter (D4) of 5.8 μm.

12.0 parts by mass of epoxy resin 5 and 5.0 parts by mass of silica fine particles having a primary average particle size of 120 nm are added to 100 parts by mass of the obtained toner particles, and a Henschel mixer (FM-75 type, Nippon Coke Industries Co., Ltd.) is added. In the company) and mixed at a rotation speed of 30 s ⁻¹ and a rotation time of 5 min. Using the obtained mixture, heat treatment was performed by the surface treatment apparatus shown in FIG. 1 to obtain heat-treated toner particles. The operating conditions were a feed amount = 5 kg / hr, a hot air temperature = 220 ° C., and a hot air flow rate = 6 m ³ / min. Cold air temperature = 5 ° C., cold air flow rate = 4 m ³ / min. , Cold air absolute water content = 3 g / m ³ , blower air flow = 20 m ³ / min. Injection air flow rate = 1 m ³ / min. It was. The obtained treated toner particles had an average circularity of 0.963 and a weight average particle diameter (D4) of 6.2 μm.

  To 100.0 parts by mass of the obtained toner particles, 0.5 parts by mass of titanium oxide fine particles having a primary average particle diameter of 50 nm surface-treated with 15.0% by mass of isobutyltrimethoxysilane and 20.0% by mass of hexamethyldisilazane. 1.0 parts by mass of hydrophobic silica fine particles having a primary average particle diameter of 15 nm and surface-treated with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Kogyo Co., Ltd.) are mixed, and an ultrasonic vibrating sieve having an aperture of 54 μm is added. The toner 31 was passed through.

(Production example of two-component developer 31)
A V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) with the toner 31 and magnetic ferrite carrier particles (number average particle size 35 μm) coated with a silicone resin so that the toner concentration is 9% by mass. Was mixed for 0.5 s ^{−1 at} a rotation time of 5 min, and a two-component developer 31 was obtained. Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 33
A toner 33 was produced in the same manner as in Example 1 except that the polyester resin B and the epoxy group- or carbodiimide group-containing resin were changed as shown in Table 2, and a two-component developer 33 was produced in the same manner.

Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Comparative Examples 1 to 4]
Comparative toners 1 to 4 were prepared in the same manner as in Example 1 except that the polyester resin B and the epoxy group or carbodiimide group-containing resin were changed as shown in Table 2, and the comparative two-component developer 1 was similarly prepared. Thru 4 were produced. Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

  1. 1. Raw material quantitative supply means, 2. compressed gas flow rate adjusting means; 3. Introducing pipe, 4. Protruding member, 5. supply pipe, 6. processing chamber; Hot air supply means, 8. Cold air supply means, 9. Regulatory means, 10. Recovery means, 11. 11. Hot air supply means outlet, 12. distribution member; Swivel member, 14. Powder particle supply port

Claims (4)

  A toner having toner particles obtained by treating the surface of a particle containing a carboxyl group-containing crystalline resin with a compound having a carbodiimide group or an epoxy group.   The toner according to claim 1, wherein the crystalline resin is a crystalline polyester resin, and an acid value of the crystalline polyester resin is 3 mgKOH / g or more and 30 mgKOH / g or less.   The toner according to claim 2, wherein the crystalline polyester resin is contained in an amount of 2 to 50 parts by mass per 100 parts by mass of the particles.   The treatment amount of the compound having a carbodiimide group or epoxy group whose unit mass per carbodiimide group or epoxy group equivalent number is 1500 g / eq or less is 0.01 parts by mass or more per 100 parts by mass of particles containing the crystalline resin The toner according to claim 1, wherein the toner is 10 parts by mass or less.

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