JP6821442B2 - toner - Google Patents

Description

The present invention relates to toners used in electrophotographic methods, electrostatic recording methods, electrostatic printing methods, and toner jet methods.

In recent years, electrophotographic full-color copiers have become widespread and have begun to be applied to the printing market. In the printing market, high speed, high image quality, and high productivity are required while supporting a wide range of media (paper types). For example, even if the paper type is changed from thick paper to thin paper, printing can be continued without changing the process speed or the heating set temperature of the fuser according to the paper type, and media constant velocity is required. There is.
In order to support media constant velocity, toner is required to properly complete fixing in a wide fixing temperature range from low temperature to high temperature.
In order to properly fix the toner at a wide range of fixable temperatures, a crystalline resin with sharp melt properties is added to the toner to improve low temperature fixing performance, wax is contained in the toner, and the toner has releasability. There is a way to make it. In this case, the dispersed state of the crystalline resin and wax in the toner has a significant effect on the properties of the toner, and therefore it is desired that the toner is fine and uniform.
In order to control the dispersion state of the wax in the toner, a technique of incorporating a wax dispersant in the toner has been proposed (Patent Document 1).
Further, in order to improve low temperature fixability and offset resistance, a technique for adjusting the melt viscosity of toner and wax and the blending ratio of wax and wax dispersant has been proposed (Patent Document 2).
However, even if the dispersion state of the wax in the toner is controlled, if the toner is left under high temperature and high humidity or if post-treatment such as thermal spheroidization treatment is performed, the wax migrates and elutes near the toner surface. Therefore, the fluidity of the toner is deteriorated, and the chargeability may be inferior.
In addition, high-speed machines still lack fixability at low temperatures, and may cause blocking if left in a high-temperature and high-humidity environment for a long period of time. In particular, the melt-kneaded pulverized toner that has been melt-kneaded together with the crystalline resin has a low viscosity at the time of kneading, so that it is difficult to apply a sufficient kneading load at the time of kneading. Therefore, various materials in the toner such as wax may not be sufficiently dispersed, and the chargeability may be inferior.
As described above, there is still room for study in order to control the dispersed state of the wax in the toner and satisfy the chargeability, low temperature fixability, and blocking resistance (preservation property).

Japanese Unexamined Patent Publication No. 2007-271789 JP 2015-166766

An object of the present invention is to solve the above-mentioned problems, to have excellent wax dispersibility and low-temperature fixability, to maintain chargeability even in long-term image output under high temperature and high humidity, and to satisfy blocking resistance. To provide toner.

（式（４）中、Ｒ³は、水素原子又はメチル基を示し、Ｒ⁴は、飽和脂環式基を示す。） As a result of diligent studies, the present inventors have found that the relationship between a crystalline resin having a sharp melt property and a wax and a wax dispersant is important in order to provide a toner that solves the above problems. , The present invention has been reached.
That is, the present invention is a toner having toner particles containing an amorphous polyester resin, a crystalline polyester resin, a wax, and a wax dispersant.
The wax dispersant is a polymer having a styrene acrylic polymer moiety and a polyolefin moiety having a unit represented by the following formula (4).
The present invention relates to a toner characterized in that the wax is an ester compound represented by the following formula (1) or behenyl stearate .
R ^1- CO-O-R ² (1)
(In the formula (1), R ¹ and R ² each independently represent an alkyl group having 18 or more and 24 or less carbon atoms.)

(In formula (4), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a saturated alicyclic group.)

By using the toner of the present invention, it is possible to provide a toner which is excellent in wax dispersibility and low temperature fixability, maintains chargeability even in long-term image output under high temperature and high humidity, and can satisfy blocking resistance. it can.

It is a figure of the thermosphere processing apparatus used in this invention.

The toner of the present invention is a toner having toner particles containing an amorphous polyester resin, a crystalline polyester resin, a wax, and a wax dispersant.
The wax dispersant is a polymer having a styrene acrylic polymer moiety having a unit having a saturated alicyclic group and a polyolefin moiety.
The wax is an ester compound represented by the following formula (1).
R ^1- CO-O-R ² (1)
(In the formula (1), R ¹ and R ² each independently represent an alkyl group having 18 or more and 24 or less carbon atoms.)

In the present invention, the toner contains a crystalline polyester resin, a wax dispersant having a unit having a saturated alicyclic group , and an ester wax. In the wax dispersant used in the present invention, the wax is dispersed in the toner by the interaction of the ester wax with the polyolefin moiety. At the same time, the dispersant of the present invention also interacts with the crystalline polyester to improve the plasticizing effect of the crystalline polyester and improve the low temperature fixability. Further, since the wax dispersant used in this case has a unit having a saturated alicyclic group , it has high hydrophobicity, and the chargeability and blocking resistance under high temperature and high humidity are improved.

The ester wax used in the present invention has an alkyl group having 18 or more and 24 or less carbon atoms in R ¹ and R ^{2 in} the above formula (1), and thus has a sufficient plasticizing effect when interacting with crystalline polyester. It is demonstrated in. If the number of carbon atoms is smaller than the above, the plasticizing effect is too large and the chargeability is lowered, and if it is larger than the above, the plasticizing effect is not sufficiently exhibited.

The wax of the present invention is preferably an ester wax in which the proportion of the unreacted alcohol component in the ester compound is 1.5% or less. This is because, in the present invention, the proportion of the unreacted alcohol component in the ester compound is 1.5% or less, and the above-mentioned plastic effect is sufficiently exhibited by the small amount of impurities. If there is a large amount of unreacted alcohol component, water may be adsorbed on this portion and the chargeability under high temperature and high humidity may decrease.

In the wax dispersant of the present invention, it is preferable that the polyolefin moiety contains polypropylene and the melting point Mp (p) of the polypropylene satisfies the following formula (2).
70 ≤ Mp (p) ≤ 90 (2)

In the present invention, when the melting point Mp (p) of polypropylene in the wax dispersant is 70 ° C. or higher and 90 ° C. or lower, the wax becomes toner particles in a finely dispersed state.

In the toner of the present invention, since the wax and the dispersant are solidified in the same temperature range in the process of cooling after melt-kneading, it can be considered that the hydrocarbon wax and the wax dispersant are solidified in a close state. That is, it is considered that the wax dispersant is also solidified at the interface between the binder resin and the wax while maintaining the state in which the wax is finely dispersed.

The dispersant polypropylene used in the present invention has a melting point close to that of wax, but has a large molecular weight. Therefore, the dispersant itself does not easily migrate to the surface of the toner particles even if it is left in a high temperature and high humidity environment for a long period of time or is exposed to high temperature hot air because it is subjected to a thermal spheroidizing treatment. Therefore, it is presumed that the dispersant of the present invention serves as an anchor, suppresses the migration of the wax itself to the surface of the toner particles, and maintains the finely dispersed state.

If the melting point of the polypropylene portion of the dispersant exceeds 90 ° C., the softening point and molecular weight of polypropylene increase, and the viscosity of the dispersant increases. Therefore, the viscosity of the toner is also affected, and the fixability may be particularly deteriorated. Further, when the melting point of the polypropylene portion of the dispersant is lower than 70 ° C., when the toner receives heat, the viscosity of the dispersant becomes low and the molecular weight of polypropylene becomes small, so that the dispersant also adheres to the toner surface. It will be easier to migrate. Therefore, it becomes difficult for the effect of suppressing the transfer of the wax to the surface of the toner particles to be exhibited, which may affect the chargeability.

The crystalline polyester resin of the present invention is a resin obtained by polycondensation of an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid compound having 6 to 12 carbon atoms, and is the crystalline polyester. The content of the resin is preferably 3 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the amorphous polyester resin.

In the present invention, the crystalline polyester resin has an alcohol component containing an aliphatic diol having 6 or more and 12 or less carbon atoms and at least one compound selected from the group consisting of derivatives thereof, and 6 or more and 12 or less carbon atoms. It is a crystalline polyester resin obtained by shrink-polymerizing a carboxylic acid component containing at least one compound selected from the group consisting of the aliphatic dicarboxylic acid of the above and a compound thereof, that is low temperature fixability and blocking resistance. More preferable from the viewpoint of sex. Further, the content of the crystalline polyester is preferably 3 parts by mass or more and 15 parts by mass or less from the viewpoint of low temperature fixability and chargeability. That is, when it is 3 parts by mass or more, the low temperature fixability is improved, and when it is 15 parts by mass or less, the chargeability under high temperature and high humidity is maintained.

In the present invention, it is preferable that the content B (parts by mass) of the wax dispersant and the content W (parts by mass) of the wax satisfy the following formula (3).
B ≧ 1.5 × W (3)

By relation wax dispersant and a wax in the present invention satisfies the above formula (3), the hydrophobic effect of the wax dispersant is sufficiently exhibited, thereby improving the charging property at high temperature and high humidity.

In the present invention, the toner is preferably a pulverized toner produced by a step of cooling the melt-kneaded product and then heat-treating the resin particles obtained by pulverizing the melt-kneaded product. In the present invention, when the wax is transferred to the surface by heat treatment of the toner, the dispersant is also transferred to the surface of the toner, so that the hydrophobicity of the surface of the toner is improved and the chargeability at high temperature and high humidity is improved. Is improved.

The composition of the preferable toner in the present invention will be described in detail below.

<Crystalline polyester resin>
In the present invention, a crystalline polyester resin is contained as a binder resin, and the crystalline resin is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).

The crystalline polyester resin can be obtained by reacting a divalent or higher valent carboxylic acid with a diol. Among them, a resin obtained by polycondensation of an aliphatic diol and an aliphatic dicarboxylic acid is preferable because of its high crystallinity. Further, in the present invention, only one type of crystalline polyester resin may be used, or a plurality of types may be used in combination.

In the present invention, the crystalline polyester resin has an alcohol component containing an aliphatic diol having 6 or more and 12 or less carbon atoms and at least one compound selected from the group consisting of derivatives thereof, and 6 or more and 12 or less carbon atoms. It is a crystalline polyester resin obtained by shrink-polymerizing a carboxylic acid component containing at least one compound selected from the group consisting of the aliphatic dicarboxylic acid of the above and a compound thereof, that is low temperature fixability and blocking resistance. More preferable from the viewpoint of sex.

The aliphatic diol having 6 to 12 carbon atoms is not particularly limited, but is preferably a chain-like (preferably linear) aliphatic diol. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butadiene glycol, 1,5-pentanediol, Neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12 -Dodecanediol can be mentioned. Among these, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12 Linear aliphatic α, ω-diols such as −dodecanediol are preferably exemplified.

In the present invention, the derivative is not particularly limited as long as the same resin structure can be obtained by the above polycondensation. For example, a derivative obtained by esterifying the above diol can be mentioned.

In the present invention, in the alcohol component constituting the crystalline polyester resin, at least one compound selected from the group consisting of the above-mentioned aliphatic diols having 6 to 12 carbon atoms and derivatives thereof is used with respect to the total alcohol component. , 50% by mass or more, and more preferably 70% by mass or more.

In the present invention, polyhydric alcohols other than the above aliphatic diols can also be used.

Among the polyhydric alcohols, examples of diols other than the aliphatic diol include aromatic alcohols such as polyoxyethylene bisphenol A and polyoxypropylene bisphenol A; 1,4-cyclohexanedimethanol and the like.

Among the polyhydric alcohols, the trihydric or higher polyhydric alcohols include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4. -Butantriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and aliphatic alcohols such as trimethylrolpropane. Be done.

Further, in the present invention, a monohydric alcohol may be used to the extent that the characteristics of the crystalline polyester resin are not impaired. Examples of the monohydric alcohol include n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol, and benzyl alcohol.

On the other hand, the aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms is not particularly limited, but may be a chain (preferably linear) aliphatic dicarboxylic acid. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, undecandicarboxylic acid, dodecandicarboxylic acid, maleic acid , Fumaric acid, mesaconic acid, citraconic acid, itaconic acid. Hydrolyzed salts of these acid anhydrides or lower alkyl esters are also included.

In the present invention, the derivative is not particularly limited as long as the same resin structure can be obtained by the above polycondensation. Examples thereof include an acid anhydride of the dicarboxylic acid component, and a derivative obtained by methyl esterifying, ethyl esterifying, or acid chlorideizing the dicarboxylic acid component.

In the present invention, among the carboxylic acid components constituting the crystalline polyester resin, at least one compound selected from the group consisting of the above-mentioned aliphatic dicarboxylic acids having 6 or more and 12 or less carbon atoms and derivatives thereof is the total carboxylic acid component. On the other hand, it is preferably 50% by mass or more, and more preferably 70% by mass or more.

In the present invention, polyvalent carboxylic acids other than the above aliphatic dicarboxylic acids can also be used. Among the polyvalent carboxylic acids, the divalent carboxylic acid other than the above aliphatic dicarboxylic acid includes aromatic carboxylic acids such as isophthalic acid and terephthalic acid; and aliphatic carboxylic acids such as n-dodecylsuccinic acid and n-dodecenylsuccinic acid. Acids; Examples include alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, and these acid anhydrides or lower alkyl esters are also included.

Among other polyvalent carboxylic acids, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimelic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2, Aromatic carboxylic acids such as 4-naphthalentricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2- Examples thereof include aliphatic carboxylic acids such as methylenecarboxypropane, and derivatives such as these acid anhydrides or lower alkyl esters are also included.

Further, in the present invention, a monovalent carboxylic acid may be used to the extent that the characteristics of the crystalline polyester resin are not impaired. 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, and octanoic acid. ..

In the present invention, the crystalline polyester resin can be produced according to a usual polyester synthesis method. For example, a crystalline polyester resin can be obtained by subjecting the carboxylic acid component and the alcohol component to an esterification reaction or a transesterification reaction, and then carrying out a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. ..

The above esterification or transesterification reaction is carried out using a usual esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, tin 2-ethylhexanoate, dibutyltin oxide, manganese acetate, and magnesium acetate, if necessary. It can be carried out.

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

In the esterification or transesterification reaction, or polycondensation reaction, all the monomers are charged in a batch to increase the strength of the obtained crystalline polyester resin, or the divalent monomer is first reacted to reduce the low molecular weight component. After that, a method such as adding a monomer having a valence of 3 or more and causing the reaction may be used.

In the present invention, the reason why the low temperature fixability of the toner is improved by using the crystalline polyester resin is considered as follows.

The crystalline polyester resin and the amorphous polyester resin are compatible with each other to widen the interval between the molecular chains of the amorphous polyester resin and weaken the intermolecular force, thereby significantly lowering the glass transition temperature (Tg) of the toner. This is to keep the melt viscosity low.

In order to increase the compatibility between the crystalline polyester resin and the amorphous polyester resin, the carbon number of the aliphatic diol and / or the aliphatic dicarboxylic acid constituting the crystalline polyester resin is shortened, and the ester group concentration is increased. It is good to increase the polarity.

However, even for toner whose glass transition temperature (Tg) is significantly lowered, it is necessary to ensure blocking resistance during use and transportation in a high temperature and high humidity environment. For that purpose, when the toner is exposed to high temperature and high humidity, the crystalline polyester resin in the compatible toner is recrystallized, and the glass transition temperature (Tg) of the toner is set to the amorphous polyester resin. It is necessary to return to the vicinity of the glass transition temperature (Tg) of.

Here, if the ester group concentration of the crystalline polyester resin is high and the compatibility between the amorphous polyester resin and the crystalline polyester resin is too high, it becomes difficult to recrystallize the crystalline polyester resin, and the toner resistance The blocking property tends to decrease.

From the above, from the viewpoint of achieving both low-temperature fixability and blocking resistance, the aliphatic diol constituting the crystalline polyester resin has 6 or more and 12 or less carbon atoms, and the aliphatic dicarboxylic acid has 6 or more carbon atoms. It is preferably 12 or less.

Further, in the present invention, the low temperature fixability is further improved by using the wax dispersant and the crystalline polyester resin in combination.

In general, a plasticizer such as a crystalline polyester resin exhibits a plasticizing effect by preventing the amorphous polyester resin from being regularly oriented by entering the gaps of the amorphous polyester resin as described above. Therefore, plasticizers with bulky side chains often exhibit useful properties.

Since the wax dispersant of the present invention has a structural portion having a bulky saturated alicyclic group , the wax dispersant and the crystalline polyester resin interact with each other in the toner to form a bulky side chain. It is presumed that it is a plasticizer that can be used. Therefore, in the present invention, it is considered that the low temperature fixability is further improved by using the wax dispersant and the crystalline polyester resin in combination.

<Amorphous polyester resin>
The amorphous polyester resin used in the toner of the present invention needs to contain the polyester resin as a main component. The monomers used in the polyester unit of the polyester resin include polyhydric alcohol (dihydric or trihydric or higher alcohol), polyvalent carboxylic acid (divalent or trivalent or higher carboxylic acid), its acid anhydride or its lower grade. Alkyl esters are used. Here, when producing a branched polymer, it is effective to partially crosslink in the molecule of the binder resin, and for that purpose, it is preferable to use a polyfunctional compound having a valence of 3 or more. Therefore, it is preferable that the raw material monomer of the polyester unit contains a carboxylic acid having a valence of 3 or more, an acid anhydride thereof or a lower alkyl ester thereof, and / or an alcohol having a valence of 3 or more.

As the polyhydric alcohol monomer used in the polyester unit of the polyester resin, the following polyhydric alcohol monomer can be used.

The divalent alcohol component includes ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-Hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydride bisphenol A, bisphenol represented by the formula (A) and derivatives thereof;

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ及びｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０以上１０以下である。）
式（Ｂ）で示されるジオール類；

(In the formula, R is an ethylene or propylene group, x and y are integers of 0 or more, and the average value of x + y is 0 or more and 10 or less.)
Diols represented by the formula (B);

が挙げられる。

Can be mentioned.

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. , 1,2,5-pentantriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene Can be mentioned. Of these, glycerol, trimethylolpropane, and pentaerythritol are preferably used. These divalent alcohols and trihydric or higher alcohols can be used alone or in combination of two or more.

As the polyvalent carboxylic acid monomer used in the polyester unit of the polyester resin, the following polyvalent carboxylic acid monomer 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, sebatic acid, azelaic acid, and 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 Examples thereof include these lower alkyl esters. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenyl succinic acid are preferably used.

Examples of the trivalent or higher valent carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalentricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid. , 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra ( Methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimeric acid, acid anhydrides thereof or lower alkyl esters thereof. Of these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or a derivative thereof is preferably used because it is inexpensive and reaction control is easy. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination of two or more.

If the main component is a polyester resin, it may be a hybrid resin containing another resin component. For example, a hybrid resin of a polyester resin and a vinyl resin can be mentioned. As a method for obtaining a reaction product of a vinyl-based resin or a vinyl-based copolymerization unit and a polyester resin such as a hybrid resin, a monomer component capable of reacting with each of the vinyl-based resin, the vinyl-based copolymerization unit and the polyester resin is included. A method of polymerizing one or both resins in the presence of the polymer is preferable.

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

Further, in the present invention, if the polyester resin is the main component of the binder resin, various resin compounds conventionally known as the binder resin can be used in combination in addition to the vinyl-based resin described above. Examples of such resin compounds include phenol resin, natural resin modified phenol resin, natural resin modified malein resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, and epoxy. Examples thereof include resins, xylene resins, polyvinyl butyral, terpene resins, kumaroinden resins, petroleum resins and the like.

Further, the peak molecular weight of the binder resin of the present invention is preferably 5000 or more and 13000 or less from the viewpoint of low temperature fixability and hot offset resistance. Further, the acid value of the binder resin of the present invention is preferably 10 mgKOH / g or less from the viewpoint of charge stability in a high temperature and high humidity environment.

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

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

The number average molecular weight of the low molecular weight binder resin B is preferably 1500 or more and 3500 or less from the viewpoint of low temperature fixability. Further, the acid value of the low molecular weight binder resin is preferably 10 mgKOH / g or less from the viewpoint of charge stability in a high temperature and high humidity environment.

<Wax (release agent)>
In the present invention, the toner particles contain ester wax from the viewpoint of improving low temperature fixability. Examples of the ester wax include the following.
Waxes containing fatty acid esters as the main component, such as carnauba wax, and deoxidized fatty acid esters such as carnauba wax, which are partially or wholly deoxidized.

In addition, saturated linear fatty acids such as stearic acid, behenic acid, tetracosanoic acid and montanic acid, unsaturated fatty acids such as braszic acid, eleostearic acid and valinalic acid, and stearyl alcohols, aralkyl alcohols and behenyl alcohols. , Carnauvir alcohol, ceryl alcohol, lignoceryl alcohol (1-tetracosanol) and ester compounds with saturated alcohols such as melisyl alcohol and polyhydric alcohols such as sorbitol. Partial esterification of fatty acids and polyhydric alcohols such as behenic acid monoglyceride. A methyl ester compound having a hydroxy group obtained by hydrogenating a vegetable oil.

In the present invention, the wax content is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

The peak temperature of the maximum endothermic peak measured using a differential scanning calorimeter (DSC) of wax is preferably 45 ° C. or higher and 140 ° C. or lower, and more preferably 70 ° C. or higher and 100 ° C. or lower. When the peak temperature of the maximum endothermic peak of the wax is within the above range, it is more preferable from the viewpoint of achieving both blocking resistance and hot offset resistance of the toner.

<Wax dispersant>
The wax dispersant of the present invention is a polymer in which a styrene acrylic polymer is graft-polymerized on polyolefin, and the styrene acrylic polymer contains a unit having a saturated alicyclic group .

In the wax dispersant of the present invention, the styrene acrylic polymer moiety has an affinity with the resin constituting the toner particles, and the polyolefin moiety has an affinity with the wax contained in the toner particles. Therefore, the wax can be finely dispersed in the toner particles.

Further, when the styrene acrylic polymer has a unit having a saturated alicyclic group , the wax is finely dispersed in the toner particles, and at the same time, the chargeability is maintained even if the toner is left under high temperature and high humidity. It becomes possible to do.

As a result of the examination by the present inventors, the following mechanism is presumed.

When the toner is left at high temperature and high humidity, the wax is usually transferred to the surface of the toner particles. On the other hand, when the toner particles contain the wax dispersant of the present invention, it is presumed that when the wax is transferred to the surface of the toner particles, the wax dispersant is also transferred to the surface of the toner particles together with the wax. Toner.

Compared with the conventional wax dispersant, the wax dispersant of the present invention has a structural portion having a bulky saturated alicyclic group, so that even if the wax dispersant is transferred to the surface of the toner particles, the wax is waxed. Elution is suppressed. As a result, it is considered that the fluidity of the toner does not decrease even if the toner is left under high temperature and high humidity, the blocking resistance is improved, and the chargeability is not deteriorated.

Further, when the wax dispersant is transferred to the surface of the toner particles, the structural portion having a saturated alicyclic group exhibits hydrophobicity, so that the hydrophobicity of the toner particles is improved and the toner particles are charged even when left in a high temperature and high humidity. It is considered that the sex does not deteriorate.

The wax dispersant of the present invention contains a styrene acrylic polymer graft-modified with poreolefin, and the styrene acrylic polymer has a structural site having a saturated alicyclic group .

The poreolefin is not particularly limited, but may be selected from the wax (release agent) used for the toner of the present invention described above from the viewpoint of affinity with the wax in the toner particles.

In the present invention, it can be preferably exemplified that the poreolefin is a wax such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, microcrystalline wax, ester wax, paraffin wax, and Fishertropch wax.

Further, from the viewpoint of reactivity of the wax dispersant during production, it is preferable to have a branched structure like polypropylene.

In the present invention, the method for graft-modifying a styrene acrylic resin with a hydrocarbon compound is not particularly limited, and a conventionally known method can be used.

In the wax dispersant of the present invention, the styrene acrylic polymer is not particularly limited as long as it has a structural site having a saturated alicyclic group . For example, an embodiment in which the styrene acrylic polymer has a monomer unit represented by the following formula (4) can be mentioned.

（式（４）中、Ｒ³は、水素原子又はメチル基を示し、Ｒ⁴は、飽和脂環式基を示す。）

(In formula (4), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a saturated alicyclic group.)

As the saturated alicyclic group in R ⁴ , a saturated alicyclic hydrocarbon group is preferable, a saturated alicyclic hydrocarbon group having 3 or more and 18 or less carbon atoms is more preferable, and a saturated alicyclic hydrocarbon group having 4 or more and 12 or less carbon atoms is more preferable. It is a saturated alicyclic hydrocarbon group. Saturated alicyclic hydrocarbon groups include cycloalkyl groups, condensed polycyclic hydrocarbon groups, bridging ring hydrocarbon groups, spirohydrocarbon groups and the like.

Examples of such a saturated alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecanyl group, and a decahydro-2-naphthyl group. , Tricyclo [5.2.1.02,6] decane-8-yl group, pentacyclopentadecanyl group, isobornyl group, adamantyl group, dicyclopentanyl group, tricyclopentanyl group and the like. ..

Further, the saturated alicyclic group may also have an alkyl group, a halogen atom, a carboxy group, a carbonyl group, a hydroxy group or the like as a substituent. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable.

Among these saturated alicyclic groups, a cycloalkyl group, a condensed polycyclic hydrocarbon group, and a bridged ring hydrocarbon group are preferable, a cycloalkyl group having 3 to 18 carbon atoms, and a substituted or unsubstituted dicyclopentanyl. A group, substituted or unsubstituted tricyclopentanyl group is more preferable, a cycloalkyl group having 4 or more and 12 or less carbon atoms is further preferable, and a cycloalkyl group having 6 or more and 10 or less carbon atoms is particularly preferable.

The position and number of the substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different.

The styrene acrylic resin may be a homopolymer of a vinyl-based monomer (a) having a structural moiety having a saturated alicyclic group , or may be a copolymer with another monomer (b).

Examples of the vinyl-based monomer (a) include cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, and cycloheptyl methacrylate. Examples thereof include monomers such as cyclooctyl methacrylate, dihydrocyclopentadiethyl acrylate, dicyclopentanyl acrylate, and dicyclopentanyl methacrylate, and a combination thereof.

Among these, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, and cyclooctyl methacrylate are preferable from the viewpoint of hydrophobicity.

Examples of the other monomer (b) include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, and phenylstyrene. , Styrene-based monomers such as benzyl styrene; alkyl esters of unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate (carbon of the alkyl). Number is 1 or more and 18 or less); Vinyl ester-based monomers such as vinyl acetate; Vinyl ether-based monomers such as vinyl methyl ether; Halogen element-containing vinyl-based monomers such as vinyl chloride; Diene-based monomers such as butadiene and isobutylene and theirs. Combined use can be mentioned.

The styrene content of the styrene acrylic polymer of the wax dispersant of the present invention is preferably 20% by mass or more and 90% by mass or less, and more preferably 40% by mass or more and 75% by mass or less. When the styrene content of the styrene acrylic polymer in the wax dispersant of the present invention is within the above range, the hydrophobicity of the toner particles is improved, and the chargeability does not deteriorate even when left in a high temperature and high humidity. It is considered that this is because the styrene portion in the wax dispersant exhibiting hydrophobicity improves the hydrophobicity of the toner particles. If it exceeds 90% by mass, the amount of poreolefin, which is a wax-affinitive component in the wax dispersant, becomes small, so that the wax cannot be dispersed in the toner, which is not preferable. If the wax is not dispersed, the wax dispersant is not dispersed, so that the hydrophobicity cannot be sufficiently exhibited in the toner and the chargeability is not improved, which is not preferable. On the other hand, if it is less than 20% by mass, the styrene content is reduced, so that the hydrophobicity cannot be sufficiently exhibited and the chargeability may not be improved, which is not preferable.

<Colorant>
Examples of the colorant that can be contained in the toner include the following.

Examples of the black colorant include carbon black; a color toned black using a yellow colorant, a magenta colorant, and a cyan colorant. A pigment may be used alone as the colorant, but it is more preferable to use a dye and a pigment in combination to improve the sharpness from the viewpoint of the image quality of a full-color image.

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

Examples of the cyan toner pigment include the following. C. I. Pigment Blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalocyanine methyl groups are substituted in the phthalocyanine skeleton.

Examples of dyes for cyan toner include C.I. I. There is Solvent Blue 70.

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

Examples of the dye for yellow toner include C.I. I. There is Solvent Yellow 162.

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

<Charge control agent>
If necessary, the toner may contain a charge control agent. As the charge control agent contained in the toner, known ones can be used, but in particular, a metal compound of an aromatic carboxylic acid which is colorless, has a high charge speed of the toner, and can stably maintain a constant charge amount is preferable.

The negative charge control agent has a metal salicylate compound, a metal naphthoate compound, a metal dicarboxylic acid compound, a polymer compound having a sulfonic acid or a carboxylic acid in the side chain, a sulfonate or a sulfonic acid esterified product in the side chain. Examples thereof include a high molecular weight compound, a high molecular weight compound having a carboxylate or a carboxylic acid esterified product in a side chain, a boron compound, a urea compound, a silicon compound, and a calix array. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound. The charge control agent may be added internally or externally to the toner particles. The amount of the charge control agent added 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.

<Inorganic particles>
If necessary, the toner of the present invention may contain inorganic fine particles. The inorganic fine particles may be internally added to the toner particles or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine powder such as silica, titanium oxide, and aluminum oxide is preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

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

The external additive is preferably used in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. A known mixer such as a Henschel mixer can be used for mixing the toner particles and the external additive.

<Developer>
Although the toner of the present invention can be used as a one-component developer, it is preferably mixed with a magnetic carrier and used as a two-component developer in order to further improve dot reproducibility. It is also preferable in that a stable image can be obtained for a long period of time.

Examples of the magnetic carrier include iron powder whose surface has been oxidized, unoxidized iron powder, and metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth. A magnetic material such as alloy particles, oxide particles, ferrite, etc., or a magnetic material-dispersed resin carrier (so-called resin carrier) containing the magnetic material and a binder resin that holds the magnetic material in a dispersed state is generally known. You can use things.

When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio at that time is preferably 2% by mass or more and 15% by mass or less as the toner concentration in the two-component developer. When the value is 4% by mass or more and 13% by mass or less, good results are usually obtained.

<Manufacturing method>
Next, the procedure for producing toner in the present invention will be described.

First, in the raw material mixing step, a predetermined amount of a crystalline polyester resin, an amorphous polyester resin, a hydrocarbon wax or the like is weighed and mixed as a toner raw material, and then mixed. As an example of a mixing device, Henschel mixer (manufactured by Nippon Coke Co., Ltd.); Super mixer (manufactured by Kawata Co., Ltd.); Ribocorn (manufactured by Okawara Seisakusho); Nowter mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin Mixer (manufactured by Pacific Kiko Co., Ltd.); Ladyge mixer (manufactured by Matsubo Co., Ltd.), etc.

Further, the mixed toner raw materials are melt-kneaded in a melt-kneading step to melt the resins and disperse the colorants and the like in the resins. As an example of the kneading machine, TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Japan Steel Works); PCM kneader (manufactured by Ikekai Iron Works); Kneedex (manufactured by Mitsui Mining Co., Ltd.) However, a continuous kneader such as a single-screw or twin-screw extruder is preferable to a batch kneader because of its superiority such as continuous production.

Further, the colored resin composition obtained by melt-kneading the toner raw material is melt-kneaded, rolled by two rolls or the like, and cooled through a cooling step of cooling by water cooling or the like.

The cooled product of the colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the crushing process, first, it is roughly crushed by a crusher, a hammer mill, a feather mill, etc., and then finely crushed by a Cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), etc. to obtain toner fine particles. ..

The obtained toner fine particles are classified into toner powder particles having a desired particle size in a classification step. Classifiers include turboplex, faculty, TSP, TTSP (manufactured by Hosokawa Micron); elbow jet (manufactured by Nittetsu Mining Co., Ltd.) and the like.

Subsequently, the obtained powder particles for toner are sphericalized in a heat treatment step using a heat treatment apparatus as shown in FIG.

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 the conical protruding member 4 provided in the central portion of the raw material supply means, and is guided to the supply pipe 5 in eight directions that spread radially to perform heat treatment. Guided to.

At this time, the flow of the mixture supplied to the treatment chamber is regulated by the regulating means 9 for regulating the flow of the mixture provided in the treatment chamber. Therefore, the mixture supplied to the treatment chamber is heat-treated while swirling in the treatment 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 by spirally swirling the hot air into the processing chamber by the swirling member 13 for swirling the hot air. Will be done. As its configuration, the swirling member 13 for swirling the hot air has a plurality of blades, and the swirling of the hot air can be controlled by the number and angles thereof. The temperature of the hot air supplied to the processing chamber at the outlet of the hot air supply means 7 is preferably 100 ° C. or higher and 300 ° C. or lower, and more preferably 130 ° C. or higher and 170 ° C. or lower. 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 fusion and coalescence of the toner particles due to overheating of the mixture. Become. Hot air is supplied from the hot air supply means outlet 11.

Further, the heat-treated heat-treated toner particles 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. When 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 are prevented from being fused or coalesced without impeding the uniform spherical treatment of the mixture. be able to. The absolute water 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. A blower (not shown) is provided at the tip of the collecting means, and the suction is conveyed by the blower.

Further, 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 in the same direction, and the recovery means 10 of the surface treatment apparatus is a swirling powder particle. It is provided on the outer peripheral portion of the processing chamber so as to maintain the turning direction. Further, the cold air supplied from the cold air supply means 8 is configured to be supplied horizontally and tangentially from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber. The swirling direction of the toner particles before heat treatment supplied from the powder supply port, the swirling direction of the cold air supplied from the cold air supply means, and the swirling direction of the hot air supplied from the hot air supply means are all in 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 that the number of coalesced particles is small. , Heat-treated toner particles having a uniform shape can be obtained.

In the method for producing a toner of the present invention, inorganic fine particles or the like may be added to the obtained powder particles for toner before the heat treatment step, if necessary. As a method of adding inorganic fine particles or the like to toner powder particles, a predetermined amount of toner powder particles and various known external additives are mixed, and Henshell mixer, mechano hybrid (manufactured by Nippon Coke Co., Ltd.), super mixer, novirta. A high-speed stirrer (manufactured by Hosokawa Micron) or the like that applies shearing force to the powder is used as an external mixer to stir and mix.

In the method for producing a toner of the present invention, if coarse particles are present after heat treatment, a step of removing the coarse particles by classification may be provided, if necessary. Examples of the classifier for removing coarse particles include turboplex, TSP, TTSP (manufactured by Hosokawa Micron Co., Ltd.), elbow jet (manufactured by Nittetsu Mining Co., Ltd.), and the like.

Further, after the heat treatment, in order to sieve coarse particles and the like as necessary, for example, Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); ); A sieving machine such as a high bolter (manufactured by Toyo Hi-Tech) may be used.

The heat treatment step of the present invention may be performed after the above-mentioned fine pulverization or after classification.

The average circularity of the toner of the present invention is preferably 0.960 or more, and more preferably 0.965 or more. When the average circularity of the toner is in the above range, the transfer efficiency of the toner is improved.

Methods for measuring various physical properties of toner and raw materials will be described below.

<Measurement of alcohol release rate of ester compounds>
The alcohol liberation rate of the ester compound was calculated by measuring under the following conditions using a nuclear magnetic resonance analyzer "JNM-ECA FT-NMR" (manufactured by JOEL).
Solvent: CDCl ₃ 8mg / ml, ^{measured: 1 H, 13 C, HMQC} , HMBC
Alcohol release rate:
(3.6 ppm integral value derived from OH end) / (4.1 ppm integral value derived from OH ester bond + 3.6 ppm integral value derived from OH end)

<Measurement of resin glass transition temperature (Tg)>
The glass transition temperature of the resin is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments).

The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.

Specifically, about 5 mg of resin is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rise rate is 10 ° C./min in the measurement range of 30 to 200 ° C. Measure with. The temperature is once raised to 180 ° C. and held for 10 minutes, then lowered to 30 ° C., and then the temperature is raised again. In this second heating process, a change in specific heat is obtained in the temperature range of 30 to 100 ° C. The intersection of the line at the midpoint of the baseline before and after the specific heat change at this time and the differential thermal curve is defined as the glass transition temperature (Tg) of the resin.

<Measurement of DSC heat absorption (ΔH) of wax and CPES>
The peak temperature (Tp) of the maximum endothermic peak of toner or the like in the present invention is measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.
Heating rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C

The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.

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

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

The maximum endothermic peak means a peak having the maximum endothermic amount when there are a plurality of peaks. The endothermic amount (ΔH) of the maximum endothermic peak is calculated from the area of the peak using the analysis software attached to the device.

<Weight average molecular weight of crystalline resin>
The weight average molecular weight of the crystalline resin is measured by gel permeation chromatography (GPC) as follows.

First, 0.03 g of a crystalline resin is dispersed in 10 ml of o-dichlorobenzene to dissolve it, and then left at 135 ° C. for 24 hours to dissolve it. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Maeshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. This sample solution is used for measurement under the following conditions.

[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) x 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene Mobile phase flow rate: 1.0 ml / min.
Sample concentration: Approximately 0.3%
Injection volume: 300 μl
Detector: Differential Refractometer Detector Shodex RI-71
In calculating the molecular weight of the sample, standard polystyrene resin (TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- 10. The molecular weight calibration curve prepared by F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500) is used.

<Measuring method of softening point of resin>
The softening point of the resin is measured by using a constant load extrusion type thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) and following the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the amount of piston drop at this time. A flow curve showing the relationship between and temperature can be obtained.

In the present invention, the softening point is the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation device flow tester CFT-500D". The melting temperature in the 1/2 method is calculated as follows. First, 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time when the outflow starts is obtained (this is defined as X. X = (Smax-Smin) / 2). Then, the temperature of the flow curve when the amount of descent of the piston becomes X in the flow curve is the melting temperature in the 1/2 method.

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

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rise method Start temperature: 50 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Heating 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: 1.0 mm

<Measuring method of weight average particle size (D4) of toner particles>
The weight average particle size (D4) of the toner particles is measured with a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter) equipped with an aperture tube of 100 μm by the pore electric resistance method. Using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting conditions and analyzing measurement data, measurement is performed with 25,000 effective measurement channels, and the measurement data Is analyzed and calculated.

As the electrolytic aqueous solution used for the measurement, one in which special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

Before performing measurement and analysis, the dedicated software is set as follows.

In the "Standard measurement method (SOM) change screen" of the dedicated software, the total count number in the control mode is set to 50,000 particles, the number of measurements is once, and the Kd value is "Standard particle 10.0 μm" (Beckman Coulter). Set the value obtained using (manufactured by the company). By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flush of the aperture tube after measurement.

In the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution is placed in a glass 250 ml round bottom beaker dedicated to Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the analysis software.
(2) Approximately 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat-bottomed beaker made of glass, and "Contaminone N" (nonionic surfactant, anionic surfactant, and organic builder) as a dispersant is used as a dispersant for precise measurement of pH 7. Add about 0.3 ml of a diluted solution obtained by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning a vessel, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and are installed in the water tank of the ultrasonic disperser "Ultrasonic Dispension System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is added, and about 2 ml of the Contaminone N is added into 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. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the aqueous electrolyte solution of (5) in which toner is dispersed is dropped onto the round-bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to about 5%. .. Then, the measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the analysis / volume statistical value (arithmetic mean) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measuring method of average circularity>
The average circularity of the toner particles is measured by the flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex) under the measurement and analysis conditions at the time of calibration work.

The specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids and the like have been removed in advance is placed in a glass container. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument at pH 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted about 3 times by mass with ion-exchanged water, and about 0.2 ml of the diluted solution is added. Further, about 0.02 g of the measurement sample is added, and the dispersion treatment is performed for 2 minutes using an ultrasonic disperser to prepare a dispersion liquid for measurement. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion is 10 ° C. or higher and 40 ° C. or lower. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervocreer)) with an oscillation frequency of 50 kHz and an electrical output of 150 W is used, and a predetermined amount of ions are contained in the water tank. Exchange water is added, and about 2 ml of the Contaminone N is added into the water tank.

The flow-type particle image analyzer equipped with a standard objective lens (10 times) was used for the measurement, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion liquid adjusted according to the above 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, the binarization threshold value at the time of particle analysis is set to 85%, the diameter of the analyzed particle is limited to 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

In the measurement, automatic focus adjustment is performed using standard latex particles (“RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before the start of the measurement. After that, it is preferable to perform focus adjustment every 2 hours from the start of measurement.

In the embodiment of the present application, a flow-type particle image analyzer for which a calibration work was performed by Sysmex Corporation and a calibration certificate issued by Sysmex Corporation was issued was used. The measurement was performed under the measurement and analysis conditions at the time of receiving the calibration certificate, except that the diameter of the analysis particle was limited to 1.985 μm or more and less than 39.69 μm in equivalent circle diameter.

<Production example of amorphous polyester resin A>
After replacing a 5 L four-necked flask equipped with a nitrogen introduction tube, a cooling tube, a stirrer and a thermocouple with nitrogen, the raw material monomer and tin octylate (II) shown in Table 1 were added and raised at 180 ° C. After warming, it was reacted for 10 hours. After further reacting at 15 mmHg for 5 hours, as a second reaction step, trimellitic anhydride was added according to Table 1 and reacted at 180 ° C. for 3 hours to obtain an amorphous polyester resin A. The physical characteristics of the resin are shown in Table 1.

<Production example of amorphous polyester resin B>
In the production example of the amorphous polyester resin A, using the raw materials shown in Table 1, it was confirmed that the softening point measured according to ASTM D36-86 reached the desired temperature shown in Table 1 in the second reaction step. Then, the resin B was synthesized in almost the same manner as in the production example of the resin A except that the reaction was stopped. The physical characteristics of the resin are shown in Table 1.

<Production example of crystalline polyester resin 1>
In a nitrogen atmosphere, a pressure reactor equipped with a dropping funnel, a Liebig condenser and a stirrer contains 118 g of 1,6-hexanediol, 230 g of dodecanedioic acid, 36.2 g of styrene, 2.5 g of acrylic acid, and dicumyl peroxide 3. 0.0 g was added, the temperature was raised to 170 ° C., and the mixture was reacted for 10 hours. The pressure at this time was 8.3 kPa.

Then, 2.0 g of tin octylate was added, the temperature was raised to 200 ° C., the reaction was carried out for 8 hours, and the temperature was further raised to 210 ° C. over 8 hours.

Then, the pressure inside the reaction vessel was reduced to 5 kPa or less again to obtain a crystalline polyester resin 1.

<Production examples of crystalline polyester resins 2 and 3>
In the production example of the crystalline polyester resin 1, the same operation as in the production example of the crystalline polyester resin 1 was performed except that the acid component and the alcohol component were changed so as to be shown in Table 2, and the crystalline polyester resin 2 to the crystallinity was performed. A polyester resin 3 was obtained.

<Production example of polypropylene 1>
4000 ml of n-heptane was placed in a heat-dried 10-liter autoclave, degassed, hydrogen 0.2 MPa was introduced, and propylene was further introduced, and the polymerization temperature was raised to 90 ° C. and the total pressure was increased to 0.8 MPa. .. Triisobutylaluminum 5 mmol, dimethylanilinium tetrakispentafluorophenylborate 5 micromol, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride 1 micromol Was added and polymerized for 50 minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain polypropylene 1 as a propylene-based polymer. The physical characteristics of polypropylene 1 are shown in Table 3.

<Production example of polypropylene 2 to 5>
Polypropylenes 2 to 5 were produced in the same manner as in the production example of polypropylene 1, except that the amount of catalyst, the polymerization temperature, and the reaction time were adjusted and controlled so as to have predetermined physical properties.

<Production example of wax dispersant 1>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 300 parts by mass of xylene and 10 parts by mass of polypropylene 1 were put and sufficiently dissolved, and after nitrogen substitution, 42.0 parts by mass of styrene and 40.0 parts by mass of cyclohexyl methacrylate, A mixed solution of 8.0 parts by mass of butyl acrylate and 250 parts by mass of xylene is added dropwise at 180 ° C. for 3 hours for polymerization. Further, the mixture was kept at this temperature for 30 minutes to remove the solvent to obtain a wax dispersant 1. The composition of the obtained wax dispersant 1 is shown in Table 4.

<Production example of wax dispersants 2 to 7>
In the production example of the wax dispersant 1, the same operation as in the production example of the wax dispersant 1 except that the conditions are appropriately changed so that the type and number of parts of the poreolefin and the composition and number of parts of the styrene acrylic polymer are shown in Table 4. Was carried out to obtain wax dispersants 2 to 7. The composition of the obtained wax dispersant is shown in Table 4.

<Production Examples of Ester Compounds 1 to 5>
A four-necked flask reactor equipped with a Dimroth condenser and a Dean-Stark water separator contains 1740 parts by mass of benzene, 1300 parts by mass of a long-chain alkylcarboxylic acid component, 1200 parts by mass of a long-chain alkylalcohol component, and p-toluenesulfonic acid. After adding 120 parts by mass, stirring well and dissolving, and refluxing for 5 hours, the valve of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the mixture was sufficiently washed with sodium hydrogen carbonate, dried, and benzene was distilled off. The obtained product was recrystallized, washed and purified to obtain an ester wax. Each ester wax was prepared by changing the type and amount of the long-chain alkylcarboxylic acid and the type and amount of the long-chain alkylalcohol. The composition of the obtained ester compound is shown in Table 5.

<Manufacturing example of toner 1>
・ Amorphous polyester resin A 70 parts by mass ・ Amorphous polyester resin B 30 parts by mass ・ Crystalline polyester resin 1 7.5 parts by mass ・ Wax dispersant 18 parts by mass ・ Wax (ester compound 1) 5 parts by mass ・C. I. Pigment Blue 15:37 parts by mass, 3,5-di-t-butylsalicylate aluminum compound (Bontron E101, manufactured by Orient Chemical Industry Co., Ltd.) 0.3 parts by mass Henshell mixer (FM-75 type, Mitsui Mine Co., Ltd.) ) Was mixed at a rotation speed of 20 s ^-1 and a rotation time of 5 min, and then kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 150 ° C. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed product. The obtained pyroclastic material was finely pulverized with a mechanical crusher (T-250, manufactured by Turbo Industries, Ltd.). Further, using Faculti F-300 (manufactured by Hosokawa Micron Co., Ltd.), classification was performed to obtain toner particles 1. The operating conditions were a classification rotor rotation speed of 130 s ^-1 and a distributed rotor rotation speed of 120 s ^-1 .

Using the obtained toner particles 1, heat treatment was performed by the surface treatment apparatus shown in FIG. 1 to obtain heat-treated toner particles. The operating conditions are feed amount = 5 kg / hr, hot air temperature = 160 ° C., hot air flow rate = 6 m ³ / min. , Cold air temperature = -5 ° C, cold air flow rate = 4 m ³ / min. , Blower air volume = 20 m ³ / min. , Injection air flow rate = 1 m ³ / min. And said.

The heat treatment the toner particles of 100 parts by weight of hydrophobic silica (BET: 200m ² /g)1.0 parts by mass of titanium oxide fine particles (BET surface-treated with isobutyl trimethoxysilane: 80m ² / g) 1.0 mass Toner 1 was obtained by mixing with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Machinery Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min. The weight average particle size (D4) of the toner 1 was 6.5 μm, and the average circularity was 0.970.

<Manufacturing example of toner 2>
In the production example of the toner 1, the same operation as in the production example of the toner 1 was performed except that the obtained toner particles 1 were not heat-treated to obtain the toner 2.

<Manufacturing example of toners 3 to 20>
In the production example of the toner 2, the toner 2 is produced except that the conditions are appropriately changed so that the type and content of the crystalline polyester resin, the type and content of the wax, and the type and content of the wax dispersant are shown in Table 6. The same operation as in the example was carried out to obtain toner 3 to toner 20. The Fischer-Tropsch wax used in the toner 20 had a peak temperature of a maximum endothermic peak of 78 ° C.

<Production example of magnetic core particle 1>
・ Process 1 (weighing / mixing process):
Fe ₂ O ₃ 62.7 parts by mass MnCO ₃ 29.5 parts by mass Mg (OH) ₂ 6.8 parts by mass SrCO ₃ 1.0 part by mass The ferrite raw material was weighed so as to have the above composition ratio. Then, it was pulverized and mixed for 5 hours with a dry vibration mill using stainless beads having a diameter of 1/8 inch.

-Step 2 (temporary firing step):
The obtained pulverized product was made into pellets of about 1 mm square by a roller compactor. Coarse powder is removed from the pellets with a vibrating sieve having a mesh opening of 3 mm, and then fine powder is removed with a vibrating sieve having a mesh opening of 0.5 mm. It was calcined at a temperature of 1000 ° C. for 4 hours at 01% by volume) to prepare a calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393

-Step 3 (crushing step):
After crushing to about 0.3 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and the mixture was crushed with a wet ball mill for 1 hour. The slurry was pulverized for 4 hours with a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

・ Process 4 (granulation process):
To 100 parts by mass of calcined ferrite, 1.0 part by mass of ammonium polycarboxylic acid as a dispersant and 2.0 parts by mass of polyvinyl alcohol as a binder were added to the ferrite slurry, and a spray dryer (manufacturer: Okawara Kakoki) was used. It was granulated into spherical particles. After adjusting the particle size of the obtained particles, the particles were heated at 650 ° C. for 2 hours using a rotary kiln to remove organic components of the dispersant and the binder.

-Step 5 (firing step):
In order to control the firing atmosphere, the temperature was raised from room temperature to a temperature of 1300 ° C. in 2 hours under a nitrogen atmosphere (oxygen concentration 1.00% by volume) in an electric furnace, and then firing was performed at a temperature of 1150 ° C. for 4 hours. Then, over 4 hours, the temperature was lowered to 60 ° C., the nitrogen atmosphere was returned to the atmosphere, and the temperature was taken out at 40 ° C. or lower.

・ Process 6 (sorting process):
After crushing the agglomerated particles, the low magnetic force product is cut by magnetic force beneficiation, sieved with a sieve having a mesh size of 250 μm to remove coarse particles, and 50% particle size (D50) of 37.0 μm based on the volume distribution. Magnetic core particles 1 were obtained.

<Preparation of coating resin 1>
Cyclohexyl methacrylate monomer 26.8% by mass
Methyl methacrylate monomer 0.2% by mass
Methyl methacrylate macromonomer 8.4% by mass
(Macromonomer having a methacryloyl group at one end and having a weight average molecular weight of 5000)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3% by mass
Azobisisobutyronitrile 2.0% by mass
Of the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone are added to a four-port separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirrer, and nitrogen gas is added. Was introduced to give a sufficient nitrogen atmosphere, the mixture was heated to 80 ° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was separated by filtration and then vacuum dried to obtain a coating resin 1. The obtained coating resin 1 was dissolved in 30 parts by mass, 40 parts by mass of toluene, and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content: 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid content concentration 30%) 33.3% by mass
Toluene 66.4% by mass
Carbon black (Regal330; manufactured by Cabot) 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption 75 ml / 100 g)
Was dispersed in a paint shaker for 1 hour using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Manufacturing example of magnetic carrier 1>
(Resin coating process):
The coating resin solution 1 was added to a vacuum degassing type kneader maintained at room temperature so as to be 2.5 parts by mass as a resin component with respect to 100 parts by mass of the packed core particles 1. After the addition, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes, the solvent was volatilized above a certain level (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, toluene was distilled off over 2 hours, and then the mixture was cooled. The obtained magnetic carrier is separated into low magnetic force products by magnetic force beneficiation, passed through a sieve having an opening of 70 μm, and then classified by a wind power classifier, and the magnetic carrier having a 50% particle size (D50) of 38.2 μm based on the volume distribution. I got 1.

<Production examples of two-component developing agents 1 to 20>
Add 8.0 parts by mass of toners 1 to 20 to 92.0 parts by mass of magnetic carrier 1 and mix them with a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to add two-component developer 1 to 20. Obtained.

[Example 1]
As an image forming apparatus, a Canon digital commercial printing printer imageRUNNER ADVANCE C9075 PRO remodeling machine was used, and a two-component developer 1 was put into a developer at the cyan position to form an image in which the amount of toner on paper was desired. , The evaluation described later was performed. As a modification point, the fixing temperature and process speed were changed so that they could be set freely. At the time of image output evaluation, the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power were such that the amount of toner on the paper of the FFh image (solid image) was 0.35 mg. It was adjusted to / cm ² . FFh is a value obtained by displaying 256 gradations in hexadecimal, 00h is the first gradation of 256 gradations (white background portion), and FFh is the 256th gradation of 256 gradations (solid portion). ..

Evaluation is based on the following evaluation methods, and the results are shown in Table 7.

[Low temperature fixability]
Paper: CS-680 (68.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 1.20 mg / cm ²
Evaluation image: An image of 10 cm ² is placed in the center of the above A4 paper. Fixing test environment: Low temperature and low humidity environment: Temperature 15 ° C / Humidity 10% RH (hereinafter “L / L”)

After adjusting the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power so that the amount of toner loaded on the paper is as described above, the process speed is 450 mm / sec. The fixing temperature was set to 130 ° C. and the low temperature fixing property was evaluated. The value of the image density reduction rate was used as an evaluation index of low temperature fixability. The image density reduction rate is determined by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g / cm ² ) is applied to the portion where the image density is measured, and the fixed image is rubbed (5 reciprocations) with Sylbon paper, and the image density is measured again. Then, the rate of decrease in image density (%) before and after rubbing was measured.

(Evaluation criteria)
A: Concentration reduction rate less than 1.0% (very excellent)
B: Concentration reduction rate 1.0% or more and less than 5.0% (good)
C: Concentration reduction rate 5.0% or more and less than 10.0% (level that does not cause any problem in the present invention)
D: Concentration reduction rate 10.0% or more (a level unacceptable in the present invention)

[Chargeability]
The triboelectric charge amount and the toner loading amount of the toner were calculated by suction-collecting the toner on the electrostatic latent image carrier using a metal cylindrical tube and a cylindrical filter. Specifically, the triboelectric charge amount and the toner loading amount of the toner on the electrostatic latent image carrier were measured by a Faraday-Cage.

A Faraday cage is a coaxial double cylinder, and the inner cylinder and outer cylinder are insulated. If a charged body having an electric charge Q is placed in this inner cylinder, it is as if a metal cylinder having an electric charge Q exists due to electrostatic induction. This induced charge amount is measured with an electrometer (Kesley 6517A, manufactured by Kessley Co., Ltd.), and the toner mass (kg) in the inner cylinder divided by the charge amount Q (mC) (Q / M) is the triboelectric charge of the toner. The amount was taken.

Further, by measuring the sucked area S, the toner mass M was divided by the sucked area S (cm ² ) to obtain the amount of toner loaded per unit area.

The toner stops the rotation of the electrostatic latent image carrier before the toner layer formed on the electrostatic latent image carrier is transferred to the intermediate transfer body, and directly airs the toner image on the electrostatic latent image carrier. It was measured by suction.
Toner loading amount (mg / cm ² ) = M / S
Triboelectric charge of toner (mC / kg) = Q / M

In the image forming apparatus, the amount of toner loaded on the electrostatic latent image carrier is adjusted to 0.35 mg / cm ² in a high temperature and high humidity environment (30 ° C., 80% RH), and the metal cylindrical tube is adjusted. And collected by suction with a cylindrical filter. At that time, the amount of charge Q stored in the condenser and the mass M of the collected toner are measured through a metal cylindrical tube, the amount of charge Q / M (mC / kg) per unit mass is calculated, and the electrostatic latent image is carried. The amount of charge per unit mass on the body was Q / M (mC / kg) (initial evaluation).

After performing the above evaluation (initial evaluation), the developing device was removed from the machine and left in a high temperature and high humidity environment (32.5 ° C., 80% RH) for 48 hours. After being left unattended, the developer was mounted in the machine again, and the amount of charge Q / M per unit mass on the electrostatic latent image carrier was measured at the same DC voltage _VDC as the initial evaluation (evaluation after being left unattended).

The Q / M per unit mass on the electrostatic latent image carrier in the above initial evaluation is set to 100%, and the amount of charge Q per unit mass on the electrostatic latent image carrier after being left for 48 hours (evaluation after leaving). The maintenance rate of / M (evaluation after leaving / initial evaluation × 100) was calculated and judged according to the following criteria.

(Evaluation criteria)
A: Maintenance rate is 80% or more (very excellent)
B: Maintenance rate is 70% or more and less than 80% (good)
C: Maintenance rate is 60% or more and less than 70% (allowable level in the present invention)
D: Maintenance rate is less than 60% (a level unacceptable in the present invention)

[Preservation]
5 g of toner was placed in a 100 cc polycup and left in a constant temperature bath (55 ° C., 41%) with variable temperature and humidity for 48 hours, and the cohesiveness of the toner was evaluated after leaving. For the cohesiveness, the residual ratio of the remaining toner was used as an evaluation index when shaken with a powder tester PT-X manufactured by Hosokawa Micron Co., Ltd. at an amplitude of 0.5 mm for 10 seconds with a mesh having a mesh size of 20 μm.

(Evaluation criteria)
A: Residual rate less than 2.0% (very excellent)
B: Residual rate 2.0% or more and less than 10.0% (good)
C: Residual rate 10.0% or more and less than 15.0% (level that does not cause any problem in the present invention)
D: Residual rate of 15.0% or more (a level unacceptable in the present invention)

[Wax dispersibility (F / M)]
The wax DSC heat absorption (ΔH) in the toner was measured using the toner particles classified in the classification step of the toner production example and the fine particle side particles separated and recovered from the toner particles.

The wax dispersibility was evaluated by a value (F / M) obtained by dividing F by M, where ΔH of the toner particles was M and ΔH of the particles on the fine particle side was F. When the wax is not finely dispersed and exists as a large domain in the kneaded product, the domain becomes a pulverization interface during the pulverization process, and the wax domain is released from the resin. Since the liberated wax is recovered as fine powder side particles in the classification step, if the dispersibility of the wax is poor, the wax forming the domain is recovered on the fine powder side. Therefore, it was decided to simply evaluate the wax dispersibility by comparing the DSC heat absorption amount (ΔH) of the toner particles and the fine powder side particles.

(Evaluation criteria)
A: F / M is 1.00 or more and less than 1.10 (very excellent)
B: F / M is 1.10 or more and less than 1.20 (good)
C: F / M is 1.20 or more and less than 1.30 (level that does not cause any problem in the present invention)
D: F / M is 1.30 or more (a level unacceptable in the present invention)

[Examples 2 to 17 and Comparative Examples 1 to 3]
Evaluation was carried out in the same manner as in Example 1 except that the two-component developing agents 2 to 20 were used. The evaluation results are shown in Table 7.

1. 1. Raw material quantitative supply means, 2. Compressed gas flow rate adjusting means, 3. Introductory tube, 4. Protruding member, 5. Supply pipe, 6. Processing room, 7. Hot air supply means, 8. Cold air supply means, 9. Regulatory means, 10. Recovery means, 11. Hot air supply means outlet, 12. Distributor, 13. Swivel member, 14. Powder particle supply port

Claims (7)

A toner having toner particles containing an amorphous polyester resin, a crystalline polyester resin, a wax, and a wax dispersant.
The wax dispersant is a polymer having a styrene acrylic polymer moiety having a unit represented by the following formula (4) and a polyolefin moiety.
A toner characterized in that the wax is an ester compound represented by the following formula (1) or behenyl stearate .
R ^1- CO-O-R ² (1)
(In the formula (1), R ¹ and R ² each independently represent an alkyl group having 18 or more and 24 or less carbon atoms.)

(In formula (4), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a saturated alicyclic group.) The toner according to claim 1, wherein the unit represented by the formula (4) is a unit derived from cyclohexyl acrylate or a unit derived from cyclohexyl methacrylate. The toner according to claim 1 or 2, wherein the proportion of the unreacted alcohol component in the ester compound is 1.5% or less. The polyolefin moiety contains polypropylene and
The toner according to any one of claims 1 to 3, wherein the polypropylene has a melting point Mp (p) that satisfies the following formula (2).
70 ≤ Mp (p) ≤ 90 (2) The crystalline polyester resin is a polycondensation polymer of an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid compound having 6 to 12 carbon atoms.
Any of claims 1 to 4, wherein the content of the crystalline polyester resin in the toner particles is 3 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the amorphous polyester resin in the toner particles. The toner according to item 1. The toner according to any one of claims 1 to 5, wherein the content B (parts by mass) of the wax dispersant and the content W (parts by mass) of the wax satisfy the following formula (3).
B ≧ 1.5 × W (3) The toner according to any one of claims 1 to 6, wherein the wax is behenic behenate or behenic stearate.

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