JP6794137B2 - Toner and toner manufacturing method - Google Patents

Description

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

In recent years, as electrophotographic full-color copiers have become widespread, further speeding up, high image quality, energy saving, and the like are required. As a specific energy saving measure, in order to reduce the power consumption in the fixing process, a toner that can be fixed at a lower fixing temperature is required. In order to achieve high image quality, it is required to improve the transfer efficiency of the toner image on the electrostatic latent image carrier to the intermediate transfer body and the transfer efficiency of the toner image on the intermediate transfer body to paper.

Therefore, in order to achieve low-temperature fixing, a toner using a crystalline polyester resin as a toner softener has been proposed (see Patent Document 1). By using the crystalline polyester resin, a certain effect was obtained on the low temperature fixability. However, it is difficult to finely disperse the crystalline polyester resin in the toner, and the crystalline polyester resin exists as a crystalline domain without being compatible with the binder resin as a softening agent, and the effect as a softening agent is fully utilized. There was an aspect that it was not cut.

On the other hand, in order to improve the transfer efficiency, it has been proposed that inorganic fine particles having a large particle size serving as spacers are fixed to the toner surface (see Patent Document 2). At the interface between the toner and the electrostatic latent image carrier and the interface between the toner and the intermediate transfer body, the inorganic fine particles act as spacers, so that the contact area of the toner with respect to the latent image carrier and the intermediate transfer body becomes smaller. Since the adhesive force can be reduced, the transfer efficiency can be improved.

Japanese Unexamined Patent Publication No. 2012-98719 Japanese Unexamined Patent Publication No. 2013-47754

However, if image output is performed for a long period of time in a high temperature and high humidity environment, the temperature inside the copier body may rise. At that time, when the above-mentioned crystalline polyester resin is used and a toner to which inorganic fine particles having a large particle size are fixed is used, the crystalline polysell resin existing as a domain in the vicinity of the toner surface becomes soft. As a result, the inorganic fine particles having a large particle size, which were spacers, may be embedded inside the toner, and the transfer efficiency may be reduced.

Further, in recent years, there has been a demand for multimedia compatibility that can be applied not only to plain paper but also to various media such as thick paper and thin paper. As the thick paper, not only thick paper having a flat surface but also paper having relatively low surface smoothness such as embossed paper and rough paper having irregularities on the front surface and both front and back surfaces are used. Since sufficient transfer pressure is not applied to these papers, a part of the toner image on the intermediate transfer body is not transferred, and image quality defects called white spots may occur. Therefore, there is a demand for toners with even higher transfer efficiency.
From the above, there is an urgent need to develop a toner that has further low-temperature fixing performance and can satisfy high transferability even in long-term image output.

An object of the present invention is to provide a toner that solves the above problems. Specifically, it is an object of the present invention to provide a toner that can satisfy high transferability even in a long-term image output because it has further low-temperature fixing performance and is excellent in durability and storage stability.

In order to achieve the above object, the toner according to the present invention is
A toner containing a binder resin, a colorant, a mold release agent, a crystalline polyester resin, and a resin composition.
The resin composition is a styrene acrylic resin graft-modified with an aliphatic hydrocarbon compound.
The weight average molecular weight Mw of the crystalline polyester resin is not more 1.0 × 10 ⁵ or less 5.0 × 10 ⁴ or more,
The slope Sv of melt viscosity-temperature characteristics measured by the toner flow tester heating method is 1. The present invention relates to a toner characterized by having a temperature of 3 × 10 ⁵ Pa · s / ° C or higher and 2.0 × 10 ⁵ Pa · s / ° C or lower .

By using the toner of the present invention, it is possible to provide a toner which has further low temperature fixing performance and is excellent in durability and storage stability, so that high transferability can be satisfied even in long-term image output. Can be done.

It is the schematic of the thermosphere processing apparatus applicable to the manufacture of the toner of this invention.

The toner of the present invention is a toner containing a binder resin, a colorant, a mold release agent, a crystalline polyester resin, and a resin composition.
The resin composition is a styrene acrylic resin graft-modified with an aliphatic hydrocarbon compound.
The weight average molecular weight Mw of the crystalline polyester resin is not more 1.0 × 10 ⁵ or less 5.0 × 10 ⁴ or more,
The slope Sv of melt viscosity-temperature characteristics measured by the toner flow tester heating method is 1. It is characterized in that it is 3 × 10 ⁵ Pa · s / ° C or higher and 2.0 × 10 ⁵ Pa · s / ° C or lower .

As described above, when image output is performed for a long period of time in a high temperature and high humidity environment, the temperature inside the copier main body may rise. At that time, the crystalline polyester resin that existed as the domain near the surface of the toner became soft, and the inorganic fine particles having a large particle size that were spacers were embedded inside the toner, which may reduce the transfer efficiency.
Therefore, in order to improve the transferability after repeated diligent studies, it is important for the present inventors to sufficiently finely disperse the crystalline polyester resin in the toner so that it does not exist as a domain while increasing the molecular weight of the crystalline polyester resin. And came to the present invention.

By increasing the molecular weight of the crystalline polyester resin, even if the temperature inside the copying machine body rises, the crystallinity of the crystalline polyester resin does not easily collapse and it becomes difficult to soften. For this reason, it becomes difficult for large particle size inorganic fine particles serving as spacers to be embedded inside the toner. The reason why the crystallinity of the crystalline polyester resin is less likely to collapse is that by increasing the molecular weight of the crystalline polyester resin, the number of low molecular weight components that easily undergo molecular motion with increasing temperature is reduced. This is supported by the fact that the half-value width is smaller in the DSC measurement.
On the other hand, if the molecular weight of the crystalline polyester resin is simply increased, it becomes more difficult to finely disperse the crystalline polyester resin, and since it is incompatible with the binder resin as a softening agent, the plasticizing effect is reduced and the original The target low temperature fixability cannot be improved.

Therefore, the present inventors have paid attention to a styrene-based resin in which a crystalline polyester resin is finely dispersed. The present inventors have made extensive studies, and since crystalline polyester is an ester compound of a long-chain hydrocarbon diol and a dicarboxylic acid, among the constituent substances of the toner, among the release agents and the binder resin. It was found that it is located in the polarity of the order. Furthermore, since it is composed of a long-chain hydrocarbon diol and a dicarboxylic acid, it tends to have an affinity with an aliphatic hydrocarbon compound. Taking these into consideration, the present inventors can finely disperse a high-molecular-weight crystalline polyester resin by using a styrene-acrylic resin graft-modified with an aliphatic hydrocarbon compound as a resin composition. I found out what I could do.

Further, in the resin composition, the monomer unit having a functional group containing a nitrogen atom is 10.0 mol% or more and 50.0 mol% or less with respect to the total number of moles of all the monomer units constituting the resin composition. It is preferable from the viewpoint of obtaining excellent transfer efficiency and low-temperature fixability. When the total number of moles of the monomer unit having a functional group containing a nitrogen atom is within the above range, the polarity of the resin composition can be controlled to a medium polarity between the binder resin and the crystalline polyester resin, so that the crystalline polyester The resin can be finely dispersed as much as possible. As a result, the maximum plasticizing effect is brought out, the low temperature fixability is improved, and the amount of crystalline polyester resin existing as a domain is reduced, so that large particle size inorganic fine particles serving as spacers are not embedded. Transfer efficiency is improved.

By finely dispersing a high-molecular-weight crystalline polyester resin in the toner using the above-mentioned resin composition, the hardness is maintained in the in-machine temperature rise region in the copying machine main body, and the temperature at which the fixing viscosity region is reached is lowered. Can be compatible. The physical properties can be expressed by the gradient Sv of melt viscosity-temperature characteristics measured by the flow tester heating method, and the larger the gradient Sv, the more the hardness and low viscosity of the toner can be achieved. There is. Furthermore, the present inventors have studying could both transfer efficiency and low-temperature fixing toner is melt viscosity - found that tilting Sv temperature characteristic becomes more 1.0 × 10 5 ^Pa · s. If the gradient Sv of melt viscosity-temperature characteristics is less than 1.0 × 10 ⁵ Pa · s, the viscosity of the toner decreases quickly, and the hardness in the in-machine temperature rise region inside the copying machine cannot be satisfied. This means that the temperature at which the fixing viscosity region is reached is high, and low-temperature fixing property cannot be realized.

As a result of diligent studies, the present inventors have a weight average molecular weight Mw of 5.0 × 10 as a molecular weight at which the crystallinity of the crystalline polyester resin does not easily collapse even when the temperature inside the copying machine is expected to rise. ⁴ was found to be more than is 1.0 × 10 ⁵ or less. When the weight average molecular weight of the crystalline polyester resin is in the above range, both crystallinity and fine dispersibility with respect to the temperature of the crystalline polyester resin can be achieved.

If the weight average molecular weight Mw of the crystalline polyester resin is less than 5.0 × 10 ^4, it reduces the molecular mobility and easy low molecular weight component, and reduction of the half-width is not sufficient in the DSC measurement. Therefore, due to long-term image output, large particle size inorganic fine particles that have become spacers may be embedded inside the toner. Further, if the weight average molecular weight Mw of greater than 1.0 × 10 ⁵ of the crystalline polyester resin, it is difficult to finely disperse the crystalline polyester resin. Therefore, the plasticizing effect as a softener is reduced, and it may not be possible to improve the low temperature fixability, which is the original purpose.

Further, it is preferable that the crystalline polyester resin of the present invention has an isocyanate unit from the viewpoint that excellent transfer efficiency and low temperature fixability can be obtained. After forming an ester compound of a long-chain hydrocarbon diol and a dicarboxylic acid, which form the framework of the crystalline polyester resin, an isocyanate monomer is used as a cross-linking agent. By doing so, the molecular weight of the crystalline polyester resin itself can be increased while keeping the molecular weight of the skeleton of the crystalline polyester resin small. Then, the present inventors have found that the dispersibility of the crystalline polyester resin is largely derived from the molecular weight of the skeleton of the crystalline polyester. On the other hand, it was also found that the crystallinity of the crystalline polyester resin is derived from the molecular weight of the crystalline polyester resin itself. As a result, it is preferable to use an isocyanate monomer as a cross-linking agent and suppress the molecular weight of the skeleton of the crystalline polyester resin because both the crystallinity and the fine dispersibility of the crystalline polyester resin can be achieved.

The crystalline polyester resin has a polyvalent carboxylic acid unit, a polyhydric alcohol unit, and an isocyanate unit, and the content of the isocyanate unit is 1.0 mol% or more and 10.0 mol% or less with respect to the total number of moles of the units. This is preferable from the viewpoint that excellent transfer efficiency and low-temperature fixability can be obtained. When the isocyanate units falls within the range mentioned above, be designed weight-average molecular weight Mw of the backbone of the crystalline polyester resin 1.0 × 10 ⁴ back and forth, the weight average molecular weight Mw of the crystalline polyester resin itself is 5.0 × 10 ⁴ is because it controls the 1.0 × 10 ⁵ or less.

Further, the isocyanate unit of the crystalline polyester resin of the present invention is preferably derived from a linear aliphatic diisocyanate monomer having 4 to 8 carbon atoms from the viewpoint of obtaining excellent low-temperature fixability and storage stability. .. In the case of a linear aliphatic diisocyanate monomer having 4 or more and 8 or less carbon atoms, the chain length is close to that of the polyvalent carboxylic acid unit and the polyhydric alcohol unit, which are the skeletons of the crystalline polyester resin, so that the crystalline polyester resin has a regular folding structure. Is realized.

Further, the plasticizing effect of the crystalline polyester resin is realized by the following 1) and 2).
1) The polar group (ester bond portion) of the crystalline polyester resin is oriented to the polar group of the binder resin,
2) The non-polar groups of the crystalline polyester resin (hydrocarbons of the polyvalent carboxylic acid unit and the polyhydric alcohol unit) widen the molecular spacing of the binder resin, so that the crystallinity easily enters between the molecular chains of the binder resin. Polyester resin is preferred. From this point of view, the crystalline polyester resin is preferable because it can be folded regularly and does not cause steric hindrance and can bring out the maximum plasticizing effect.

Further, the crystalline polyester resin of the present invention is a crystalline polyester resin having 6 to 18 carbon atoms obtained by polycondensation of a polyvalent carboxylic acid unit and a polyhydric alcohol unit, which has excellent transfer efficiency and It is preferable from the viewpoint that low-temperature fixability can be obtained. As described above, since the plastic effect of the crystalline polyester resin is exhibited by entering between the molecular chains of the binder resin, the crystalline polyester resin having a small number of carbon atoms in terms of three-dimensional structure is preferable. Further, a small number of carbon atoms means a high concentration of ester groups, and the polarity is close to that of the non-binding resin. Therefore, it becomes easier to be compatible with each other, and the amount of crystalline polyester resin existing as a domain is reduced. Therefore, inorganic fine particles having a large particle size serving as spacers are not embedded, so that excellent transfer efficiency can be obtained. It is also preferable from.

Further, it is preferable that the toner of the present invention is surface-treated with hot air using, for example, the surface treatment apparatus shown in FIG. 1 from the viewpoint of obtaining excellent transfer efficiency and low-temperature fixability. The hot air from the surface treatment apparatus shown in FIG. 1 causes the toner to instantly melt and then quench. As a result, the crystalline polyester resin can be maintained in a state of being compatible with the binder resin without recrystallizing, so that the maximum plastic effect can be brought out and the low temperature fixability can be improved, and as a domain. The existing crystalline polyester resin can be eliminated. Therefore, it is possible to reduce the possibility that the large particle size inorganic fine particles that have become spacers are embedded inside the toner.

Further, it is preferable to use the toner of the present invention as a binder resin by mixing a low molecular weight binder resin and a high molecular weight binder resin from the viewpoint of obtaining excellent low temperature fixability. By using the low molecular weight binder resin and the high molecular weight binder resin, the functions can be separated from the low temperature fixability and the high temperature offset property, and the maximum low temperature fixability can be realized. As a result, it becomes possible to steep the slope Sv of the melt viscosity-temperature characteristics measured by the flow tester heating method.

<Bundling resin>
The binder resin used in the toner of the present invention needs to contain a 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 the binder resin in the molecule, 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 trivalent or higher value, an acid anhydride thereof or a lower alkyl ester thereof, and / or an alcohol having a trivalent or higher value.
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; diols represented by the formula (B); Can be mentioned.

（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。）

(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.)

Examples of the trihydric or higher alcohol component include the following. Sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol , 2-Methylpropantriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene. 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 the following. Maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid , N-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids and lower alkyl esters thereof. 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 the following. 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalentricarboxylic acid, 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 acids, their acid anhydrides or their lower alkyl esters. 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.

The method for producing the polyester unit of the present invention is not particularly limited, and a known method can be used. For example, the above-mentioned alcohol monomer and carboxylic acid monomer are simultaneously mixed and polymerized through an esterification reaction, a transesterification reaction, and a condensation reaction to produce a polyester resin. The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C. or higher and 290 ° C. or lower. When polymerizing the polyester unit, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used. In particular, the binder resin of the present invention is more preferably a polyester unit polymerized using a tin catalyst.

The binder resin used for the toner of the present invention may be a hybrid resin containing a polyester resin as a main component and other resin components. For example, a hybrid resin of a polyester resin and a vinyl resin can be mentioned. The following method is preferable as a method for obtaining a reaction product of a vinyl-based resin or a vinyl-based copolymer unit and a polyester resin, such as a hybrid resin.
-A method in which one or both resins are polymerized in the presence of a polymer containing a monomer component capable of reacting with each of a vinyl resin, a vinyl copolymer unit, and a polyester resin.

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 acid 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 a resin compound include the following. Phenolic 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, epoxy resin, xylene resin, polyvinyl butyral, terpen Resin, kumaroinden resin, petroleum resin, etc.

Further, it is preferable that the peak molecular weight of the binder resin of the present invention is 5,000 or more and 13,000 or less from the viewpoint that excellent low temperature fixability and hot offset resistance can be obtained. Further, it is preferable that the acid value of the binder resin of the present invention is 15 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint that excellent charge stability can be obtained in a high temperature and high humidity environment. Further, the hydroxyl value of the binder resin of the present invention is preferably 2 mgKOH / g or more and 20 mgKOH / g or less from the viewpoint of obtaining excellent low-temperature fixability and storage stability.

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 should be 10/90 or more and 60/40 or less on a mass basis for excellent low temperature fixability and hot offset resistance. It is preferable from the viewpoint that

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 that excellent hot offset resistance can be obtained. Further, it is preferable that the acid value of the high molecular weight binder resin is 15 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint that excellent charge stability can be obtained in a high temperature and high humidity environment.
The peak molecular weight of the low molecular weight binder resin B is preferably 4000 or more and 6000 or less from the viewpoint of obtaining excellent low-temperature fixability. Further, it is preferable that the acid value of the low molecular weight binder resin is 10 mgKOH / g or less from the viewpoint that excellent charge stability can be obtained in a high temperature and high humidity environment.

<Crystalline polyester resin>
The crystalline polyester resin of the present invention is preferably a crystalline polyester resin having 6 to 18 carbon atoms obtained by polycondensation of a polyvalent carboxylic acid unit and a polyhydric alcohol unit. At that time, it is obtained by polycondensation reaction of a monomer composition containing an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms as main components.

The aliphatic diol having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but is preferably a chain-like (more preferably linear) aliphatic diol, for example, ethylene. Glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene Examples thereof include glycol, 1,6-hexanediol, octamethylene glycol, nonamethylene glycol, decamethylene glycol and neopentyl glycol. Among these, linear aliphatics such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, α, ω-diol are preferably exemplified.

Of the alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more is an alcohol selected from an aliphatic diol having 2 to 22 carbon atoms.
In the present invention, a polyhydric alcohol monomer other than the above aliphatic diol can also be used. Examples of the dihydric alcohol monomer among the polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylene bisphenol A and polyoxypropylene bisphenol A; 1,4-cyclohexanedimethanol and the like. Among the polyhydric alcohol monomers, the trihydric or higher polyhydric alcohol monomer includes aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, and tripentaerythritol. , 1,2,4-Butantriol, 1,2,5-Pentantriol, Glycerin, 2-Methylpropantriol, 2-Methyl-1,2,4-Butantriol, Trimethylolethane, Trimethylolpropane and other fats Examples include triol alcohol.

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

On the other hand, the aliphatic dicarboxylic acid having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. .. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, undecandicarboxylic acid, dodecandicarboxylic acid, Examples thereof include maleic acid, fumaric acid, mesaconic acid, citraconic acid and itaconic acid, and those obtained by hydrolyzing these acid anhydrides or lower alkyl esters are also included.

In the present invention, preferably 50% by mass or more, more preferably 70% by mass or more of the carboxylic acid components are carboxylic acids selected from aliphatic dicarboxylic acids having 2 to 22 carbon atoms.
In the present invention, a polyvalent carboxylic acid other than the above-mentioned aliphatic dicarboxylic acid having 2 to 22 carbon atoms can also be used. Among other polyvalent carboxylic acid monomers, the divalent carboxylic acid includes aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids of n-dodecylsuccinic acid and n-dodecenylsuccinic acid; cyclohexanedicarboxylic acids. Examples thereof include alicyclic carboxylic acids such as acids, and these acid anhydrides or lower alkyl esters are also included. Among other carboxylic acid monomers, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1, Aromatic carboxylic acids such as 2,4-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 the like, 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 contained so as not to impair the characteristics of the crystalline polyester. Examples of the monovalent carboxylic acid include monocarboxylic acids such as 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. Acid is mentioned.

Further, the crystalline polyester resin of the present invention is preferably a urethane-modified crystalline polyester resin having an isocyanate unit from the viewpoint of obtaining excellent transfer efficiency and low-temperature fixability. Among them, it is preferable to bond the crystalline polyester resins obtained by polycondensing an aliphatic dicarboxylic acid and an aliphatic diol with a diisocyanate monomer from the viewpoint of obtaining excellent transfer efficiency and low-temperature fixability.

Examples of the diisocyanate monomer include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and carbon atoms. 8 to 15 aromatic aliphatic diisocyanates and modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product, etc.) and Examples include a mixture of two or more of these. Further, if necessary, a polyisocyanate having a valence of 3 or more may be used in combination.

Specific examples of the above aromatic diisocyanates (including trivalent or higher valent polyisocyanates) include 1,3- and / or 1,4-phenylenediocyanates, 2,4- and / or 2,6-tolylene diisocyanates (TDI). ), Crude TDI, 2,4'-and / or 4,4'-diphenylmethane diisocyanate (MDI), Crude MDI [Crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; diamino A mixture of diphenylmethane and a small amount (for example, 5 to 20% by mass) of trifunctional or higher polyamine] phosgenated product: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4', 4 "- Examples thereof include triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate.

Specific examples of the above aliphatic diisocyanate (including trivalent or higher valent polyisocyanate) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecantryisocyanate, 2, 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2 , 6-Diisocyanatohexanoate and the like.

Specific examples of the above alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrophilic TDI), and bis (2-). Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornan diisocyanate and the like.

Specific examples of the aromatic aliphatic diisocyanate include m- and / or p-xylene diisocyanate (XDI), α, α, α', α'-tetramethylxylene diisocyanate (TMXDI) and the like.
Examples of the modified product of the diisocyanate include a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, a uretdione group, a uretoimine group, an isocyanurate group, and a modified product containing an oxazolidone group.

Specifically, modified products of diisocyanates such as modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI ( Combined use with isocyanate-containing prepolymer)] is included.
Of these, aliphatic diisocyanates having 4 to 6 carbon atoms are preferable.

The crystalline polyester resin used in the present invention can be produced, for example, by the following method. After the above-mentioned aliphatic dicarboxylic acid and the aliphatic dialcohol are subjected to an esterification reaction or a transesterification reaction, the unmodified crystalline polyester resin is subjected to a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. Can be obtained.
Then, after returning the reaction system to the upper pressure, the urethane-modified crystalline polyester resin can be obtained by adding the above-mentioned isocyanate monomer and reacting.
The esterification or transesterification reaction can be carried out using a usual esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate and magnesium acetate, if necessary.

Further, the polycondensation reaction can be carried out using a usual polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. .. 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 may be mixed together in order to increase the strength of the obtained crystalline polyester resin. Further, in order to reduce the low molecular weight component, a method such as first reacting a divalent monomer and then adding a trivalent or higher valent monomer to react may be used.
The urethane-modified crystalline polyester resin is not limited to the above-mentioned production method, and may be produced by a conventionally known production method.

<Styrene-based resin graft-modified with an aliphatic hydrocarbon compound>
It is important that the toner in the present invention contains a styrene resin graft-modified with an aliphatic hydrocarbon compound.

The content of the styrene resin graft-modified with the aliphatic hydrocarbon compound is preferably 1.0 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the binder resin. When the content is in this range, it is considered that the fine dispersion of the crystalline polyester in the binder resin by the styrene resin graft-modified with the aliphatic hydrocarbon compound is efficiently performed.

Further, as the constituent monomer unit of the styrene resin, it is preferable to contain a monomer unit having a functional group containing a nitrogen atom, such as acrylonitrile or metaacrylonitrile. It is considered that the inclusion of the monomer unit having a functional group containing a nitrogen atom as the constituent monomer unit increases the affinity with the crystalline polyester resin and enhances the fine dispersion effect of the crystalline polyester resin.

Regarding the styrene resin graft-modified with an aliphatic hydrocarbon compound, the polyolefin is not particularly limited as long as it is a polymer or copolymer of an unsaturated hydrocarbon having one double bond, and various polyolefins may be used. Can be done. In particular, polyethylene-based and polypropylene-based are preferably used.

Examples of the monomer having a vinyl-based group include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, and the like. p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn -Styrene-based units such as styrene such as decylstyrene and pn-dodecylstyrene and derivatives thereof.

Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl-based units containing N atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, metaacrylonitrile and acrylamide.

Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; unsaturated dibasic acids such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride, etc. Dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl shaving Half esters of unsaturated dibasic acids such as acid methyl half ester, methyl fumaric acid half ester, and methyl mesaconic acid half ester; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; acrylic acid, methacrylic acid, croton Α, β-unsaturated acids such as acids and citraconic acids; α, β-unsaturated acid anhydrides such as crotonic acid anhydrides and citraconic acid anhydrides, and anhydrides of the α, β-unsaturated acids and lower fatty acids. A vinyl-based unit containing carboxyl groups such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, their acid anhydrides, and their monoesters.

Acrylic acids or methacrylate esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) Hexyl) A vinyl-based unit containing a hydroxy group such as styrene.

Methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, propyl acrylate, -n-octyl acrylate, dodecyl acrylate, -2-ethylhexyl acrylate, stearyl acrylate, -2- acrylate An ester unit composed of acrylic acid esters such as acrylic acid esters such as chlorethyl and phenyl acrylate.

Methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-octyl methacrylate, dodecyl methacrylate, -2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic Examples thereof include ester units composed of methacrylic acid esters such as α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid acid and diethylaminoethyl methacrylate.
The graft polymer in which a vinyl-based monomer is graft-polymerized to the polyolefin used in the present invention can be obtained by a known method such as a reaction between these polymers described above or a reaction between a monomer of one polymer and a polymer of the other. Obtainable.

<Release agent>
Examples of the wax used for the toner of the present invention include the following. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystallin wax, paraffin wax, Fishertropch wax; oxides of hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof; Waxes containing fatty acid esters such as carnauba wax as the main component; deoxidized fatty acid esters such as carnauba wax partially or wholly deoxidized. In addition, the following can be mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brushzic acid, eleostearic acid, and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, and meli Saturated alcohols such as syl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, and meli Esters with alcohols such as silalic acid; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid Saturated fatty acid bisamides such as acid amides; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N'diorail adipic acid amide, N, N'diorail sebasic acid amide; m -Aromatic bisamides such as xylene bisstearate amide, N, N'distearyl isophthalic acid amide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally with metal soap) (It is said); Waxes obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid; a partial esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; A methyl ester compound having a hydroxyl group obtained by hydrogenation of.

Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, and fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low temperature fixability and hot offset resistance. In the present invention, a hydrocarbon wax is more preferable in that the hot offset resistance is further improved.
In the present invention, the wax is preferably used in an amount of 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the binder resin.

Further, in the endothermic curve at the time of temperature rise measured by the differential scanning calorimetry (DSC) device, the peak temperature of the maximum endothermic peak of the wax is preferably 45 ° C. or higher and 140 ° C. or lower. It is preferable that the peak temperature of the maximum endothermic peak of the wax is within the above range because both toner storage stability and hot offset resistance can be achieved.

<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 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.

Examples of the negative charge control agent include the following. Metallic salicylate compound, metal naphthoate compound, metal dicarboxylic acid compound, polymer compound having sulfonic acid or carboxylic acid in the side chain, polymer compound having sulfonate or sulfonic acid esterified product in the side chain, carboxylate Alternatively, a polymer compound having a carboxylic acid esterified product in the side chain, a boron compound, a urea compound, a silicon compound, or 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 fine 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 powders such as silica, titanium oxide, and aluminum oxide are preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As 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 in order to stabilize durability, a specific surface area of 10 m ² / g or more is preferable. It is preferably an inorganic fine powder of 50 m 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 part 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>
The toner of the present invention can also be used as a one-component developer, but in order to further improve dot reproducibility, it is possible to mix it with a magnetic carrier and use it as a two-component developer, and an image that is stable for a long period of time. Is preferable in that

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. Known as a magnetic material-dispersed resin carrier (so-called resin carrier) containing a magnetic material such as alloy particles, oxide particles, ferrite, etc., and a binder resin that holds the magnetic material in a dispersed state. 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 it is 4% by mass or more and 13% by mass or less, good results are usually obtained.

<Manufacturing method>
As a method for producing toner particles, it is necessary to melt-knead a binder resin, a mold release agent, a colorant, and a crystalline polyester. Therefore, the above materials are melt-kneaded, the kneaded product is cooled, and then pulverized and classified. The pulverization method is preferable.
Hereinafter, the toner manufacturing procedure by the pulverization method will be described.

In the raw material mixing step, other components such as a binder resin, a mold release agent, a colorant, a crystalline polyester, and if necessary, a charge control agent are weighed and blended as materials constituting the toner particles. , Mix. As an example of a mixing device, a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henchel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industries Co., Ltd. (formerly manufactured by Mitsui Miike Machinery Co., Ltd.)), etc. Can be mentioned.

Next, the mixed materials are melt-kneaded to disperse wax and the like in the binder resin. In the melt-kneading process, a batch-type kneader such as a pressure kneader or a Bambary mixer or a continuous-type kneader can be used, and a single-screw or twin-screw extruder has become the mainstream because of the advantage of continuous production. ing. For example, KTK type twin-screw extruder (manufactured by Kobe Steel), TEM type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Co., Ltd.), twin-screw extruder (KTC).・ Ktk Inc.), Co-Kneader (Bus), Kneedex (Nippon Coke Industries Co., Ltd.), etc. Further, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

The cooled product of the resin composition is then pulverized to a desired particle size in the pulverization step. In the crushing process, for example, after coarse crushing with a crusher such as a crusher, a hammer mill, or a feather mill, further, for example, a cryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo mill. (Made by Freund Turbo Co., Ltd.) or an air jet type crusher to pulverize.

After that, if necessary, inertial classification type elbow jet (manufactured by Nittetsu Mining Co., Ltd.), centrifugal force classification type turboplex (manufactured by Hosokawa Micron Co., Ltd.), TSP separator (manufactured by Hosokawa Micron Co., Ltd.), faculty (manufactured by Hosokawa Micron Co., Ltd.) Classify using a classifier such as (manufactured by Co., Ltd.) or a sieving machine.
After that, it is preferable to perform the surface treatment with hot air using the surface treatment apparatus shown in FIG. 1 from the viewpoint that excellent transfer efficiency and low temperature fixability can be obtained.

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 the 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 hot air for heat-treating the supplied mixture is supplied from the hot air supply means 7, and is introduced by spirally swirling the hot air into the processing chamber by the swirling member 13 for swirling the hot air. 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. to 300 ° C. 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 suppressing the fusion and coalescence of the toner particles due to overheating of the mixture. Become.

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 fusion and coalescence of the heat-treated toner particles are suppressed without hindering the uniform spheroidizing 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 device 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 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 device is strengthened, a strong centrifugal force is applied to the toner, and the dispersibility of the toner is further improved, so that the toner has a small number of coalesced particles and has a uniform shape. Can be obtained.
When the average circularity of the toner is 0.950 or more and 0.980 or less, transferability is improved and cleanability can be achieved at the same time, which is preferable.

Further, if necessary, an external additive is added to the surface of the toner particles. As a method of externally adding an external additive, a predetermined amount of classified toner and various known external additives are mixed, and a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano are used. A method of stirring and mixing using a mixing device such as a hybrid (manufactured by Nippon Coke Industries Co., Ltd. (formerly manufactured by Mitsui Miike Machinery Co., Ltd.)) and Nobilta (manufactured by Hosokawa Micron Co., Ltd.) as an external attachment is mentioned. Be done.

Methods for measuring various physical properties of toner and raw materials will be described below.
<Measurement of molecular weight of crystalline polyester resin by GPC>
First, the crystalline polyester resin is dissolved in o-dichlorobenzene at room temperature for 24 hours. 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. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.

Equipment: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Column: TSKgel GMHHR-H HT 7.8 cm I. D x 30 cm ² stations (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Temperature: 135 ° C
Solvent: o-dichlorobenzene (with 0.05% ionol added)
Flow velocity: 1.0 mL / min Sample: 0.4 mL injection of 0.1% sample Measured under the above conditions, and use the molecular weight calibration curve prepared from the monodisperse polystyrene standard sample to calculate the molecular weight of the sample. Further, it is calculated by converting to polyethylene by a conversion formula derived from the Mark-Houwink viscosity formula.

<Measurement of molecular weight of resin composition by GPC>
The molecular weight distribution of the THF-soluble component of the composition resin is measured by gel permeation chromatography (GPC) as follows.
First, the toner is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. 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. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.

Equipment: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation)
Column: 7 series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0 mL / min Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-" 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Toso Co., Ltd.) is used for the molecular weight calibration curve.

<Measuring method of softening point of binder resin, crystalline polyester resin, resin composition, toner>
The softening point of the resin is measured using a constant load extrusion type thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with 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: Hot compress Start temperature: 50 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature rise 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

<Calculation of melt viscosity of toner-slope Sv of temperature characteristics>
Toner melt viscosity-Temperature characteristic gradient Sv is calculated using a constant load extrusion type thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. .. In this device, while applying a constant load from the top of the measurement sample with a piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the amount of piston drop at this time. The measurement sample capable of obtaining a flow curve showing the relationship between the temperature and the temperature is a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) in an environment of 25 ° C. with about 1.0 g of toner. Is used by compression molding at about 10 MPa for about 60 seconds to form a cylinder having a diameter of about 8 mm.
The measurement conditions of CFT-500D are as follows.

Test mode: Hot compress Start temperature: 50 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature rise 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

From the obtained melt viscosity-temperature characteristic data, the melt viscosity is calculated in 1 ° C increments. Then, the melt viscosity v1 and the temperature T1 immediately before the viscosity decrease of 10.0% or more with respect to the immediately preceding viscosity are calculated. Further, as the fixing viscosity region, the temperature T2 immediately before the melt viscosity v2 becomes 5 × 10 ⁴ Pa · s or less is calculated.
From these values, the slope Sv of the melt viscosity-temperature characteristic can be calculated by using the following formula.

<Measurement of glass transition temperature (Tg) of amorphous resin and toner>
The glass transition temperature of the resin is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q2000" (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. Further, the amount of heat obtained from the area of the maximum endothermic peak of the temperature-endothermic amount curve in the temperature range of 60 to 90 ° C. is defined as the endothermic amount.

<Measuring method of weight average particle size (D4) of toner particles>
The weight average particle size (D4) of the toner particles is the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter Co., Ltd.) equipped with an aperture tube of 100 μm by the pore electric resistance method. , Measurement with 25,000 effective measurement channels using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter Co., Ltd.) for setting measurement conditions and analyzing measurement data. Then, the measurement data is analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, 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, Inc.) 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). -Set the value obtained using Coulter Co., Ltd. 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 flash 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) Put about 200 mL of the electrolytic aqueous solution in a glass 250 mL round bottom beaker dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod 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) About 30 mL of the electrolytic aqueous solution is placed in a 100 mL flat-bottomed beaker made of glass, and about 0.3 mL of the following diluent is added as a dispersant.
-Diluted solution: "Contaminone N" (10% by mass aqueous solution of neutral detergent for cleaning pH 7 precision measuring instruments consisting of nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Diluted 3 times by mass with ion-exchanged water

(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and the water tank of the ultrasonic disperser "Ultrasonic Dispension System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put therein, and about 2 mL of the contaminanton 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 particles to be measured 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 of toner>
The average circularity of the toner is measured by the flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions at the time of calibration work.
The measurement principle of the flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) is to image the flowing particles as a still image and perform image analysis. The sample added to the sample chamber is sent to the flat sheath flow cell by the sample suction syringe. The sample sent into the flat sheath flow is sandwiched between the sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Moreover, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is image-processed at an image processing resolution of 512 × 512 pixels (0.37 × 0.37 μm per pixel), the contour of each particle image is extracted, and the particle image is obtained. The projected area S, the peripheral length L, and the like are measured.
Next, the equivalent circle diameter and circularity are obtained using the area S and the peripheral length L. The circle equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is the value obtained by dividing the circumference length of the circle obtained from the circle equivalent diameter by the circumference length of the particle projection image. It is defined as and calculated by the following formula.
Circularity C = 2 × (π × S) 1/2 / L

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

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 with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, Wako Pure Chemical Industries, Ltd. ) Is diluted with ion-exchanged water about 3 times by mass, 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 having an oscillation frequency of 50 kHz and an electrical output of 150 W (for example, "VS-150" (manufactured by Vervocreer Co., Ltd.)) is used. A predetermined amount of ion-exchanged water is placed in the water tank, and about 2 mL of the contaminanton N is added into the water tank.

For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10 times) was used, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the total count mode in the HPF measurement mode. Then, by setting the binarization threshold value at the time of particle analysis to 85% and specifying the analysis particle diameter, the number ratio (%) of particles in that range and the average circularity can be calculated. The average circularity of the toner was set to a circle equivalent diameter of 1.98 μm or more and 39.96 μm or less, and the average circularity of the toner was determined.

In the measurement, automatic focus adjustment is performed using standard latex particles (for example, "RESAARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific) diluted with ion-exchanged water before the start of 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 that has been calibrated by Sysmex Corporation and has received a calibration certificate issued by Sysmex Corporation 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 the equivalent circle diameter of 1.98 μm or more and less than 39.69 μm.

<Production example of high molecular weight binder resin A1>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 72.0 parts by mass (0.20 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)
·Terephthalic acid:
21.0 parts by mass (0.13 mol; 75.0 mol% based on the total number of moles of polyvalent carboxylic acid)
・ Adipic acid:
3.7 parts by mass (0.03 mol; 15.0 mol% based on the total number of moles of polyvalent carboxylic acid)
-Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass

The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure (first reaction step).
・ Trimellitic anhydride:
3.3 parts by mass (0.02 mol; 10.0 mol% with respect to the total number of moles of polyvalent carboxylic acid)
-Tert-Butylcatechol (polymerization inhibitor): 0.1 parts by mass

Then, the above-mentioned material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160 ° C. After confirming that the softening point measured according to ASTM D36-86 reached a temperature of 140 ° C., the temperature was lowered to stop the reaction (second reaction step), and a binder resin A1 was obtained. The obtained binder resin A1 had a peak molecular weight of Mp of 10,000, a softening point of Tm of 140 ° C., and a glass transition temperature of Tg of 60 ° C.

<Production example of low molecular weight binder resin B1>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 71.9 parts by mass (0.20 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)
·Terephthalic acid:
26.8 parts by mass (0.16 mol; 96.0 mol% based on the total number of moles of polyvalent carboxylic acid)
-Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass

The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure (first reaction step).

・ Trimellitic anhydride:
3 parts by mass (0.01 mol; 4.0 mol% based on the total number of moles of polyvalent carboxylic acid)
-Tert-Butylcatechol (polymerization inhibitor): 0.1 part by mass Then, the above material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 1 hour while maintaining the temperature at 180 ° C. After confirming that the softening point measured according to ASTM D36-86 reached the temperature of 90 ° C., the temperature was lowered to stop the reaction (second reaction step), and the binder resin B1 was obtained. The obtained binder resin B1 had a peak molecular weight of Mp 6,000, a softening point of Tm 90 ° C., and a glass transition temperature of Tg 55 ° C.

<Production example of medium molecular weight binder resin C1>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 72.1 parts by mass (0.20 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)
·Terephthalic acid:
22.4 parts by mass (0.14 mol; 80.0 mol% based on the total number of moles of polyvalent carboxylic acid)
・ Adipic acid:
3.5 parts by mass (0.02 mol; 14.0 mol% based on the total number of moles of polyvalent carboxylic acid)
-Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass

The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure (first reaction step).
・ Trimellitic anhydride:
2.0 parts by mass (0.01 mol; 6.0 mol% based on the total number of moles of polyvalent carboxylic acid)
-Tert-Butylcatechol (polymerization inhibitor): 0.1 parts by mass

Then, the above-mentioned material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160 ° C. After confirming that the softening point measured according to ASTM D36-86 reached a temperature of 120 ° C., the temperature was lowered to stop the reaction (second reaction step), and a binder resin C1 was obtained. The obtained binder resin C1 had a peak molecular weight of Mp 9,000, a softening point of Tm of 120 ° C., and a glass transition temperature of Tg of 58 ° C.

<Production example of crystalline polyester resin D1>
·ethylene glycol:
23.9 parts by mass (0.32 mol; 100.0 mol% with respect to the total number of moles of polyhydric alcohol)
・ Sebacic acid:
76.1 parts by mass (0.31 mol; 100.0 mol% based on the total number of moles of polyvalent carboxylic acid)

The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140 ° C.
-Tin 2-ethylhexanoate: 0.5 parts by mass Then, the above material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200 ° C. (first reaction). Process).
・ Hexamethylene diisocyanate:
5.3 parts by mass (0.03 mol; 4.0 mol% based on the total number of moles of polyvalent carboxylic acid, polyhydric alcohol and isocyanate)

Then, the pressure in the reaction vessel was gradually released to return to normal pressure, and then the above materials were added and reacted at 100 ° C. for 3 hours under normal pressure to obtain a crystalline polyester resin D1 (second reaction). Process). Table 1 shows the weight average molecular weight Mw and the melting peak temperature Tm of the obtained crystalline polyester polyester resin D1.

<Production example of crystalline polyester resins D2 to D15>
In the production example of the crystalline polyester resin C1, the type and mass number of each monomer of the polyhydric alcohol component and the polyvalent carboxylic acid component in the first reaction step, the reaction time, and the type and mass number of monomers in the second reaction step. Was changed as shown in Table 1. Except for these changes, the reaction was carried out in the same manner as in the production example of the crystalline polyester resin C1 to obtain crystalline polyester resins D2 to D15. Table 1 shows the physical properties of the crystalline polyester resins D2 to D15.

<Production example of resin composition E1>
-Low molecular weight polypropylene (Viscol 660P manufactured by Sanyo Chemical Industries, Ltd.):
51.6 parts by mass (0.11 mol; 15.0 mol% based on the total number of moles of the resin composition monomer)
-Xylene: 25.0 parts by mass The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, the inside of the flask was replaced with nitrogen gas, and then the temperature was gradually raised to 175 ° C. with stirring.
·styrene:
30.7 parts by mass (0.29 mol; 42.0 mol% with respect to the total number of moles of the resin composition monomer)
・ Acrylonitrile:
14.5 parts by mass (0.27 mol; 39.0 mol% with respect to the total number of moles of the resin composition monomer)
・ Acrylic acid:
0.5 parts by mass (0.01 mol; 1.0 mol% with respect to the total number of moles of the resin composition monomer)
・ Butyl acrylate:
2.7 parts by mass (0.02 mol; 3.0 mol% with respect to the total number of moles of the resin composition monomer)
-Xylene: 10.0 parts by mass-Di-t-butylperoxyhexahydroterephthalate: 0.5 parts by mass Then, the above material was added dropwise over 3 hours and stirred for another 30 minutes. Then, the solvent was distilled off to obtain a resin composition E1. Table 2 shows the peak molecular weight and softening point of the obtained resin composition E1. In ΔH (calorific value of melting) measured by the DSC apparatus, ΔH of the resin composition E1 is smaller than ΔH of the amount of the added hydrocarbon compound, so that it is clear that the resin composition is graft-modified.

<Production example of resin compositions E2 to E9>
In the example of producing the resin composition E1, the reaction was carried out in the same manner except that the constituent monomers and the number of parts by mass were changed to obtain the resin compositions E2 to E9. Table 2 shows the physical properties of the resin compositions E2 to E9. It was confirmed that the resin compositions E2 to E8 were graft-modified by the same method as the resin composition E1.

<Toner 1 manufacturing example>
・ 40 parts by mass of binder resin A1 ・ 50 parts by mass of binder resin B1 ・ 10 parts by mass of crystalline polyester resin C1 ・ 5 parts by mass of resin composition D1 ・ Fisher tropschwax (peak temperature of maximum heat absorption peak 90 ° C) 5 parts by mass・ C. I. Pigment Blue 15:37 parts by mass ・ 3,5-di-t-Aluminum salicylate compound (Bontron E88 Orient Chemical Industry Co., Ltd.) 0.3 parts by mass

A twin-screw kneader set to a temperature of 130 ° C. after mixing the above materials using a Mitsui Henschel mixer (FM-75 type, manufactured by Mitsui Miike Machinery Co., Ltd.) at a rotation speed of 20s- ¹ and a rotation time of 5 minutes. It was kneaded with (PCM-30 type, manufactured by Ikekai Co., Ltd.). 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 Freund Turbo Co., Ltd.). Further, using Faculti F-300 (manufactured by Hosokawa Micron Co., Ltd.), classification was performed to obtain toner particles. The operating conditions were a classification rotor rotation speed of 130s-1 and a distributed rotor rotation speed of 120s-1.

Using the obtained toner particles, heat treatment was performed by the surface treatment apparatus shown in FIG. 1 to obtain heat-treated toner particles. The operating conditions and the feed amount = 5 kg / hr, The hot air temperature C = 160 ° C., hot air flow rate = 6 m ³ / min, the cold air temperature E = -5 ° C., the cold air flow rate = 4m ³ / min, the blower air volume = ^{20 m} 3 / Minutes, injection air flow rate = 1 m ³ / min.

To 100 parts by mass of a heat treatment the toner particles obtained, hydrophobic silica (BET: 200m ² /g)1.0 parts by mass of titanium oxide fine particles surface-treated with isobutyl trimethoxysilane (BET: a 80m ² / g) 1 Toner 1 was obtained by mixing 0.0 parts by mass with a Mitsui Henchel 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 minutes. The weight average particle size (D4) of the toner 1 was 6.5 μm, and the average circularity was 0.970. Table 3 shows the physical properties of the toner 1.

<Manufacturing example of toners 2-29>
In the production example of the toner 1, the binder resin, the crystalline polyester resin, and the resin composition were changed as shown in Table 3, and the same operation was performed except that the step of the surface treatment device was omitted. I got 29. Table 3 shows the physical properties of the toners 2 to 29.

<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 parts by mass The ferrite raw materials were 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 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 with a wet ball mill using alumina beads having a diameter of 1/16 inch for 4 hours 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 mixture was taken out at a temperature of 40 ° C. or lower.

・ Process 6 (sorting process):
After crushing the agglomerated particles, low magnetic force products are cut by magnetic force beneficiation, sieved with a sieve having a mesh size of 250 μm to remove coarse particles, and have a volume distribution-based 50% particle size (D50) of 37.0 μm. 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 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 amount 75 mL / 100 g) were dispersed for 1 hour with a paint shaker 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 example of two-component developer 1>
8.0 parts by mass of toner 1 was added to 92.0 parts by mass of magnetic carrier 1 and mixed with a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain a two-component developer 1.

<Production example of two-component developer 2-29>
In the production example of the two-component developer 1, the same operation was carried out except for the changes as shown in Table 4, to obtain the two-component developer 2-29.

<Example 1>
As an image forming apparatus, a modified machine of a digital commercial printing printer imageRUNNER ADVANCE C9075 PRO manufactured by Canon Inc. was used. Then, the two-component developer 1 was placed in the developer at the cyan position and / and the magenta position to form an image in which the amount of toner loaded on the paper was desired, and the evaluation described later was performed. As the modification points, the fixing temperature, process speed, DC voltage V _DC of the developer carrier, charging voltage V _D of the electrostatic latent image carrier, and laser power were changed so that they could be set freely. For the image output evaluation, an FFh image (solid image) having a desired image ratio was output. 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 5.

[durability]
Paper: CS-680 (68.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 0.35 mg / cm ² (FFh image)
(Adjusted by DC voltage V _DC of developer carrier, charging voltage V _D of electrostatic latent image carrier, and laser power)
Evaluation image: Chart with 100% image ratio of the above A4 paper Fixing test environment: High temperature and high humidity environment: Temperature 30 ° C / Relative humidity 85% (hereinafter "H / H")
Fixing temperature: 170 ℃
Process speed: 450 mm / sec As a durable image output test, 10,000 sheets were output on A4 paper using a band chart with an FFh output with an image ratio of 0.1%. Then, the evaluation image was output, and the number of white spots in the image was visually confirmed. If it is D rank or higher, it is set to the level at which the effect of the present invention is obtained.

(Evaluation criteria)
A: Less than 5 white spots B: 5 or more and less than 10 white spots C: 10 or more and less than 15 white spots D: 15 or more and less than 20 white spots E: 20 white spots More than one

[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
(Adjusted by DC voltage V _DC of developer carrier, charging voltage V _D of electrostatic latent image carrier, and laser power)
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 / Relative humidity 10% (hereinafter “L / L”)
Fixing temperature: 170 ℃
Process speed: 450 mm / sec

The above evaluation image was output and the low temperature fixability 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. If it is D rank or higher, it is set to the level at which the effect of the present invention is obtained.

(Evaluation criteria)
A: Concentration reduction rate less than 2.0% B: Concentration reduction rate 2.0% or more and less than 5.0% C: Concentration reduction rate 5.0% or more and less than 10.0% D: Concentration reduction rate 10.0 % Or more and less than 15.0% E: Concentration reduction rate 15.0% or more

[Preservation]
5 g of toner was placed in a 100 cc resin cup and allowed to stand in a constant temperature bath (55 ° C. 41%) with variable temperature and humidity for 48 hours, and after standing, the cohesiveness of the toner was evaluated. The cohesiveness was evaluated by using the residual rate of the remaining toner when shaken with a powder tester PT-X manufactured by Hosokawa Micron Co., Ltd. with a mesh having a mesh size of 20 μm for 10 seconds at an amplitude of 0.5 mm. If it is D rank or higher, it is set to the level at which the effect of the present invention is obtained.

(Evaluation criteria)
A: Residual rate less than 2.0% B: Residual rate 2.0% or more and less than 5.0% C: Residual rate 5.0% or more and less than 10.0% D: Residual rate 10.0% or more, 15 Less than 0.0% E: Residual rate 15.0% or more

<Examples 2 to 24 and Comparative Examples 1 to 5>
The evaluation was carried out in the same manner as in Example 1 except that the two-component developer 2 to 24 was used. The evaluation results are shown in Table 5.
Since the surface modification step is eliminated in Example 2, the low temperature fixability is inferior to that of Example 1.
In Example 3, since the binder resin is only a binder resin having a medium molecular weight, the low temperature fixability is inferior to that of Example 2.
In Example 4, since the compatibility of the crystalline polyester resin is slightly lowered, the low temperature fixability and white spots are inferior to those of Example 3.

In Example 5, since the compatibility of the crystalline polyester resin is slightly lowered, the low temperature fixability and white spots are inferior to those of Example 4.
In Example 6, since the compatibility of the crystalline polyester resin is slightly lowered, the low temperature fixability and white spots are inferior to those of Example 5.
In Example 7, since the compatibility of the crystalline polyester resin is high, the storage stability is inferior to that of Example 6.
In Example 8, since the plasticizing effect of the crystalline polyester resin is reduced, the low-temperature fixability is inferior to that of Example 7. Further, since the crystallinity of the crystalline polyester resin is lowered, the storage stability is inferior to that of Example 7.
In Example 9, since the fine dispersibility of the crystalline polyester resin is lowered, the low temperature fixability and white spots are inferior to those of Example 8.
In Example 10, since the fine dispersibility of the crystalline polyester resin is lowered, the low temperature fixability and white spots are inferior to those of Example 8.

In Example 11, since the fine dispersibility of the crystalline polyester resin is lowered, the low temperature fixability and the white spots are inferior to those of Example 9.
In Example 12, since the fine dispersibility of the crystalline polyester resin is lowered, the low temperature fixability and the white spots are inferior to those of Example 10.
In Example 13, since the molecular weight of the crystalline polyester resin is high, the low temperature fixability is inferior to that of Example 12.
In Example 14, since the molecular weight of the skeleton of the crystalline polyester resin is high, the low temperature fixability is inferior to that of Example 12.
In addition, Examples 11 to 24 are described as reference examples.

In Example 15, since the molecular weight of the skeleton of the crystalline polyester resin is high, the low temperature fixability is inferior to that of Example 13.
In Example 16, since the molecular weight of the skeleton of the crystalline polyester resin is high, the low temperature fixability is inferior to that of Example 14.
In Example 17, since the molecular weight of the skeleton of the crystalline polyester resin is high, the low temperature fixability is inferior to that of Example 16.
In Example 18, since the fine dispersibility of the crystalline polyester resin is lowered, the low temperature fixability and white spots are inferior to those of Example 17.
In Example 19, since the fine dispersibility of the crystalline polyester resin is lowered, the low temperature fixability and the white spots are inferior to those of Example 17.

In Example 20, since the molecular weight of the crystalline polyester resin is large, the low temperature fixability and white spots are inferior to those of Example 17.
In Example 21, since the molecular weight of the crystalline polyester resin is small, white spots and storage stability are inferior to those of Example 17.
In Example 22, since the number of copies of the crystalline polyester resin added is large, white spots and storage stability are inferior to those of Example 17.
In Example 23, since the number of copies of the crystalline polyester resin added is small, the low temperature fixability is inferior to that of Example 17.
In Example 24, since the resin composition does not have a “monomer unit having a functional group containing a nitrogen atom”, the concentration reduction rate, which is an evaluation standard for low temperature fixability, is inferior to that of Example 23.

In Comparative Example 1, since the number of copies of the crystalline polyester resin added is small, the low temperature fixability is inferior to that of Example 23.
In Comparative Example 2, since the fine dispersibility of the crystalline polyester resin is lowered, the low temperature fixability and the white spots are inferior to those of Example 17.
In Comparative Example 3, since the fine dispersibility of the crystalline polyester resin is lowered, the low temperature fixability and the white spots are inferior to those of Example 17.
In Comparative Example 4, since the molecular weight of the crystalline polyester resin is large, the low temperature fixability and the white spots are inferior to those of Example 20.
In Comparative Example 5, since the molecular weight of the crystalline polyester resin is small, white spots and storage stability are inferior to those of Example 21.

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

Claims (9)

A toner containing a binder resin, a colorant, a mold release agent, a crystalline polyester resin, and a resin composition.
The resin composition is a styrene acrylic resin graft-modified with an aliphatic hydrocarbon compound.
The weight average molecular weight Mw of the crystalline polyester resin is not more 1.0 × 10 ⁵ or less 5.0 × 10 ⁴ or more,
The slope Sv of melt viscosity-temperature characteristics measured by the toner flow tester heating method is 1. A toner characterized by having a temperature of 3 × 10 ⁵ Pa · s / ° C or higher and 2.0 × 10 ⁵ Pa · s / ° C or lower . The crystalline polyester resin has a polyvalent carboxylic acid unit, a polyhydric alcohol unit, and an isocyanate unit.
The toner according to claim 1, wherein the content of the isocyanate unit is 1.0 mol% or more and 10.0 mol% or less with respect to the total number of moles of the units. The toner according to claim 2, wherein the isocyanate unit is derived from a linear aliphatic diisocyanate monomer having 4 or more and 8 or less carbon atoms. The resin composition further has a monomer unit having a functional group containing a nitrogen atom.
Claims 1 to 3 that the content of the monomer unit having a functional group containing a nitrogen atom is 10.0 mol% or more and 50.0 mol% or less with respect to the total number of moles of all the monomer units constituting the resin composition. The toner according to any one item. The inclination Sv is 1.5 × 10 ⁵ The toner according to claim 1, which is Pa · s / ° C. or higher. The toner according to any one of claims 1 to 5, wherein the melting peak temperature Tm of the crystalline polyester resin is 66 ° C. or higher and 89 ° C. or lower. A method for producing a toner, which comprises a step of melt-kneading a binder resin, a colorant, a mold release agent, a crystalline polyester resin, and a resin composition, and a step of finely pulverizing the obtained kneaded product to obtain toner particles. There,
The resin composition is a styrene acrylic resin graft-modified with an aliphatic hydrocarbon compound.
The weight average molecular weight Mw of the crystalline polyester resin is 5.0 × 10. ⁴ More than 1.0 × 10 ⁵ Is below
The slope Sv of melt viscosity-temperature characteristics measured by the flow tester heating method of the obtained toner is 1.3 × 10. ⁵ Pa · s / ° C or higher 2.0 × 10 ⁵ A method for producing a toner, which comprises Pa · s / ° C. or lower. The inclination Sv is 1.5 × 10 ⁵ The method for producing a toner according to claim 7, wherein the toner is Pa · s / ° C. or higher. The method for producing a toner according to claim 7 or 8, wherein the melting peak temperature Tm of the crystalline polyester resin is 66 ° C. or higher and 89 ° C. or lower.

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