JP6700779B2 - toner - Google Patents

Description

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

In recent years, electrophotographic full-color copying machines have become widespread, and their application to the printing market has begun. In the printing market, high speed, high image quality, and high productivity are required while supporting a wide range of media (paper types). For example, even if the paper type is changed from thick paper to thin paper, it is required to have constant velocity of the medium, which allows printing to continue without changing the process speed or changing the heating temperature of the fixing device according to the paper type. From the viewpoint of constant velocity of the medium, the toner is required to properly complete the fixing in a wide fixing temperature range from low temperature to high temperature.
In order to fix the toner at a wide range of fixable temperatures, there is a method of adding wax to the toner to give the toner releasability. In this case, the dispersed state of the wax in the toner has a great influence on the properties of the toner, and therefore it is desired that the wax be fine and uniform.
Therefore, as disclosed in Japanese Patent Laid-Open No. 2004-242242, a technique has been proposed in which a toner contains a wax dispersant in order to control the dispersed state of the wax in the toner. Further, as in Patent Document 2, it has been proposed to improve the dispersibility of the wax and suppress image deterioration by using a toner binder composed of a high-viscosity resin, a low-viscosity resin, and a dispersant.
However, even if the dispersion state of the wax in the toner is controlled, if the toner is left under high temperature and high humidity, the wax will dissolve on the surface of the toner and the fluidity of the toner will be deteriorated, so that the chargeability may be poor. ..
Further, as in Patent Document 3, various toners in which a crystalline resin having a sharp melt property is added to the toner to improve the low-temperature fixing performance in order to fix at a wide range of fixable temperatures have been proposed. Further, as in Patent Document 4, it has been proposed to use a crystalline resin as a fixing auxiliary component and a wax dispersant in combination to maintain good low-temperature fixability and fluidity while maintaining chargeability.
However, in order to further increase the speed and save energy, the low-temperature fixability required in recent years has not been achieved. Further, in a toner containing a crystalline resin, the resin strength is lowered, so that the external additive on the surface is likely to be liberated or embedded, so that the chargeability may be deteriorated under high temperature and high humidity. Further, since the toner shape is not controlled, the transfer efficiency may be insufficient.
On the other hand, in Patent Document 5, in order to improve transfer efficiency, it is proposed that the shape of the toner is controlled by hot air treatment to reduce the adhesive force of the toner.
It is known that the toner treated with hot air has the shape of the toner controlled, while the highly adherent wax elutes in the vicinity of the toner surface. For this reason, the fluidity of the toner may be deteriorated due to the influence of the wax eluted near the surface of the toner, and the chargeability may be deteriorated.
As described above, there is still room for study in order to control the dispersion state of the wax in the toner and satisfy the charging property, the fixing property, and the blocking resistance.

JP, 2011-13548, A JP, 2007-264349, A JP, 2011-123352, A JP, 2011-59604, A JP, 2013-15830, A

  An object of the present invention is to provide a toner that solves the above problems. Specifically, by controlling the dispersion state of the wax in the toner and exposing the toner surface with a highly hydrophobic wax dispersant while satisfying the low temperature fixing property, hot offset resistance and blocking resistance, An object of the present invention is to provide a toner capable of exhibiting a sufficient chargeability under humidity.

The present invention provides a toner particle containing a binder resin, a crystalline polyester resin, a wax, and a styrene acrylic resin composition,
The binder resin contains an amorphous polyester resin,
The styrene acrylic resin composition contains a styrene acrylic resin graft-modified with an aliphatic hydrocarbon resin, and the styrene acrylic resin composition graft modified with the aliphatic hydrocarbon resin is The content of the styrene-acrylic resin composition containing a unit derived from the compound represented by the following formula (1) and graft-modified with the aliphatic hydrocarbon resin is 100 parts by mass of the toner particles. The present invention relates to a toner having a content of 1.0 part by mass or more and 10 parts by mass or less.
_{CH 2 = C-R-CO} -O-C n H 2n + 1 (1)
[ 12 ≤ n ≤ 18 , R is H or CH ₃ ]

  According to the present invention, there is provided a toner capable of exhibiting sufficient chargeability under high temperature and high humidity while controlling the dispersion state of wax in the toner and satisfying the low temperature fixability, hot offset resistance and blocking resistance. be able to.

It is a figure of the thermo-sphericalization processing apparatus used for this invention.

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

［１０≦ｎ≦２０、ＲはＨまたはＣＨ₃］ The toner of the present invention is a toner particle containing an amorphous polyester resin as a binder resin, a crystalline polyester resin as a softening agent, a wax, and a styrene acrylic resin composition as a wax dispersant, The styrene acrylic resin composition contains a styrene acrylic resin graft-modified with an aliphatic hydrocarbon resin, and the styrene acrylic resin composition graft modified with the aliphatic hydrocarbon resin is as follows. The content of the styrene acrylic resin composition containing a unit derived from the compound represented by the formula (1) and graft-modified with the aliphatic hydrocarbon resin is 1 with respect to 100 parts by mass of the toner particles. It is characterized in that it is 0.0 part by mass or more and 10 parts by mass or less.

[10≦n≦20, R is H or CH ₃ ]

  In the wax dispersant of the present invention, the styrene acrylic resin has an affinity with the polyester binder resin in the toner, and the graft-modified aliphatic hydrocarbon compound has an affinity with the wax in the toner. Therefore, the domains of the wax and the wax dispersant are formed in the toner, and the wax can be finely dispersed. This makes it possible to satisfy low-temperature fixability, hot offset resistance, and blocking resistance.

  Further, in the present invention, since the wax dispersant has a unit derived from the compound represented by the formula (1), the wax in the toner is finely dispersed as in the conventional wax dispersant, and at the same time, the toner has high temperature and high humidity. It was found that the chargeability was maintained even when left underneath.

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

  When the toner is left under high temperature and high humidity, wax migrates to the toner surface. In the present invention, since the toner contains the wax dispersant, it is presumed that when the wax migrates to the toner surface, the wax dispersant also migrates to the toner surface together with the wax. In the present invention, the wax dispersant contains a unit derived from the compound represented by the formula (1) which is bulky as compared with the conventional wax dispersant. Therefore, it is considered that even if the wax dispersant migrates to the surface of the toner, the elution of the wax is suppressed and the chargeability does not deteriorate even if the wax dispersant is left under high temperature and high humidity. In addition, since the compound containing the long-chain monomer represented by the formula (1) has hydrophobicity, when it is transferred to the toner surface, the hydrophobicity of the toner is improved and the chargeability is not deteriorated even if the toner is left under high temperature and high humidity. Thought to be a thing.

  From the above results, it was found that there is an optimum wax dispersant and toner so that the chargeability is not deteriorated even when the toner is left under high temperature and high humidity, and the present invention has been completed.

  In the present invention, n of the compound represented by the formula (1) is 10≦n≦20. When n is in the above range, the hydrophobicity of the wax dispersant is improved, the chargeability and the blocking resistance are improved, and at the same time, the wax dispersibility is improved and the hot offset resistance is also improved.

  When n is less than 10, the bulkiness of the wax dispersant is insufficient and the hydrophobicity is insufficient, so that the fluidity of the toner is deteriorated under high temperature and high humidity, and the blocking resistance and chargeability are deteriorated. There is a case. When n is more than 20, low temperature fixability may be impaired.

  In the present invention, the content of the wax dispersant contained in the toner particles is 1.0 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the toner particles. When the content of the wax dispersant of the present invention is within the above range, the dispersibility of the wax is improved, the blocking resistance and the hot offset resistance are improved, and at the same time, the low temperature fixability is not impaired.

  When the content of the wax dispersant is less than 1.0 part by mass, the wax is likely to be insufficiently dispersed in the toner. Therefore, the releasability at the time of fixing is deteriorated, and high temperature offset is likely to occur, which is not preferable in some cases. If the content of the wax dispersant exceeds 10 parts by mass, the low temperature fixability may be impaired.

  The toner of the present invention is preferably manufactured through a step of cooling a kneaded product obtained by melt-kneading and crushing the obtained cooled product to subject the resulting toner particles to hot air treatment. Since the toner of the present invention is manufactured through the air treatment step, the charging property and blocking resistance are improved as compared with the case where the conventional wax dispersant is used.

  Usually, in a toner treated with hot air, wax having high adhesiveness elutes in the vicinity of the surface of the toner, so that the blocking resistance of the toner may decrease, or charging failure due to the decrease in fluidity may occur. .. However, when the toner using the wax dispersant of the present invention is treated with hot air, the hydrophobic wax dispersant migrates to the toner surface at the same time as the wax, so that the fluidity of the toner does not deteriorate even under high temperature and high humidity, and the toner is not charged. Sex does not deteriorate. Further, since the wax dispersant of the present invention contains the compound represented by the formula (1) containing a bulky long-chain monomer, the wax at the time of hot air treatment is compared with the case of using the conventional wax dispersant. Spilling out is suppressed. Therefore, it is possible to prevent the blocking resistance of the toner from decreasing.

  In the present invention, the solubility parameter (SP value) of the styrene-acrylic resin composition as the wax dispersant is preferably 10.3 or more and 10.7 or less. The SP value used in the present invention is the Fedors method [Poly. Eng. Sci. , 14(2) 147 (1974)].

  When the SP value is within the above range, the hydrophobicity of the wax is improved, the charging property and the blocking resistance are improved, the dispersibility of the wax is improved, and the hot offset resistance is also improved.

  If the SP value is less than 10.3, the affinity between the binder resin and the wax dispersant becomes low, so that the wax may be domainized in the toner particles and may not be sufficiently dispersed. As a result, blocking resistance and hot offset resistance may deteriorate. When the SP value is more than 10.7, the hydrophobicity of the wax dispersant unevenly distributed on the toner surface is not sufficient, so that the fluidity of the toner is deteriorated under high temperature and high humidity, and the blocking resistance and the charging property are deteriorated. There are cases.

  The toner of the present invention is preferably produced through a step of melt-kneading a mixture containing a binder resin, a crystalline polyester resin, a colorant, a wax, and the resin composition as a wax dispersant.

  Since the toner manufacturing method of the present invention is manufactured through the melt-kneading step, the dispersibility of the wax is improved. This is because the toner manufactured by the melt-kneading method mixes the toner raw materials (particularly the binder resin, the wax dispersant, and the wax) firmly due to the heat and shear during the kneading, and when the toner becomes the toner, It is presumed that this is because the dispersibility of the wax is improved. As a result, the wax in the toner is finely dispersed and the hot offset resistance is improved. In addition, the elution of the wax to the toner surface due to being left at high temperature and high humidity is reduced, and the blocking resistance of the toner is improved.

  In the wax dispersant of the present invention, the aliphatic hydrocarbon resin grafted with the styrene acrylic resin composition is preferably polyethylene and/or polypropylene.

  Hereinafter, the constitutions of the wax dispersant and toner preferable in the present invention will be described in detail.

<Wax dispersant>
The wax dispersant used in the toner of the present invention contains a styrene acrylic resin graft-modified with a hydrocarbon compound, and the styrene acrylic resin contains a unit derived from a compound represented by the following formula (1). is doing.
_{CH 2 = C-R-CO} -O-C n H 2n + 1 (1)

  The hydrocarbon compound used in the wax dispersant of the present invention is not particularly limited, but is preferably polyethylene or polypropylene from the viewpoint of affinity with the wax in the toner.

  The styrene acrylic resin graft-modified with the hydrocarbon compound used in the wax dispersant of the present invention is not particularly limited as long as it contains a unit derived from the compound represented by the formula (1). ..

  The styrene acrylic resin graft-modified with the hydrocarbon compound used in the wax dispersant of the present invention may be a homopolymer of the vinyl monomer (a), but a copolymer with the monomer (b). Is more preferable.

  Examples of the vinyl-based monomer (a) include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, dodecanyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate. , N-butyl methacrylate, isobutyl methacrylate, octyl methacrylate, dodecanyl methacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, and the like, and combinations thereof. Of these, stearyl methacrylate is particularly preferable.

  As the monomer (b), styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, benzylstyrene. Styrene-based monomers such as vinyl acetate; vinyl ester-based monomers such as vinyl acetate; vinyl ether-based monomers such as vinyl methyl ether; halogen element-containing vinyl-based monomers such as vinyl chloride; diene-based monomers such as butadiene and isobutylene; and combinations thereof. Be done.

  When a toner is produced using the wax dispersant of the present invention, the binder resin for toner is not particularly limited, but the wax dispersant of the present invention is sufficiently effective as a binder resin. This is the case when a polyester resin is used.

  When a polyester resin is used as the binder resin in the present invention, the compatibility between the polyester resin and the hydrocarbon wax is originally poorer. Therefore, when the wax is added as it is to form a toner, the wax is segregated and present in the toner, and free wax and the like are also generated, resulting in problems such as charging failure. It may not be preferable.

<Crystalline polyester resin>
The toner of the present invention contains a crystalline polyester resin as a softening agent. The crystalline polyester resin in the present invention is a resin whose endothermic peak is observed in differential scanning calorimetry (DSC).

  In the toner of the present invention, the crystalline polyester resin contained in the toner particles is 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. It is obtained by subjecting the product to a polycondensation reaction.

  Among these, as a result of intensive studies by the present inventors, an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms are preferable from the viewpoint of low-temperature fixability and storability. The reason why the low-temperature fixability of the toner containing the crystalline polyester resin is improved is that the binder resin and the crystalline polyester resin are compatible with each other and the distance between the molecular chains of the binder resin is widened to weaken the intermolecular force. The reason is that the glass transition temperature (Tg) is significantly lowered and the melt viscosity of the binder resin is lowered. Therefore, the low-temperature fixability tends to be improved by increasing the compatibility between the binder resin and the crystalline polyester resin. Then, in order to improve the compatibility between the binder resin and the crystalline polyester resin, the carbon number of the aliphatic diol and/or the aliphatic dicarboxylic acid of the monomer constituting the crystalline polyester resin is shortened and the ester group concentration is reduced. It will be higher and the polarity will be higher. On the other hand, it is necessary to secure storability in use and transportation in a high-temperature and high-humidity environment even for a toner having a significantly lowered Tg. To this end, when the toner is exposed to such an environment, it is necessary to recrystallize the compatible crystalline polyester resin in the toner and return the Tg of the toner to near the Tg of the binder resin. There is. Here, when the ester group concentration of the crystalline polyester resin is high and the compatibility between the binder resin and the crystalline polyester resin is too high, it becomes difficult to recrystallize the crystalline polyester resin, and the storage stability of the toner becomes low. It will get worse. From the above, it is preferable to use an aliphatic diol having 6 or more and 12 or less carbon atoms and an aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms as the monomer composition of the crystalline polyester resin that can achieve both low temperature fixability and storage stability. I found it preferable.

  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 (more preferably straight chain) 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, Examples include pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, and neopentyl glycol. Among these, particularly preferred are straight chain aliphatic such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and α,ω-diol.

  Of the above alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more is an alcohol selected from aliphatic diols having 2 to 22 carbon atoms.

  In the present invention, a polyhydric alcohol monomer other than the above aliphatic diol may be used. Among the polyhydric alcohol monomers, examples of the dihydric alcohol monomer include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropyleneated bisphenol A; 1,4-cyclohexanedimethanol and the like. Among the polyhydric alcohol monomers, trivalent or higher polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol. Fats such as 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane Group alcohols and the like can be mentioned.

  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 a chain (more preferably linear) aliphatic dicarboxylic acid. Is preferred. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, Examples thereof include maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and also include those obtained by hydrolyzing these acid anhydrides or lower alkyl esters.

  In the present invention, preferably 50% by mass or more, more preferably 70% by mass or more of the above 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 aliphatic dicarboxylic acid having 2 to 22 carbon atoms may be used. Among other polyvalent carboxylic acid monomers, divalent carboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid; cyclohexanedicarboxylic acid. Examples thereof include alicyclic carboxylic acids such as acids, and also include acid anhydrides or lower alkyl esters thereof. Among the other carboxylic acid monomers, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1, Aromatic carboxylic acids such as 2,4-naphthalene tricarboxylic acid and pyromellitic acid, 1,2,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, 1,3-dicarboxyl-2-methyl-2 And aliphatic carboxylic acids such as methylene carboxypropane, etc., and derivatives thereof such as acid anhydrides or lower alkyl esters thereof are also included.

  The weight average molecular weight (Mw) of the crystalline polyester resin that can be used in the present invention is preferably 7,000 or more and 13,000 or less.

  If the weight average molecular weight is less than 7,000, heat resistant storage stability and hot offset resistance may be deteriorated, and if it exceeds 13,000, low temperature fixability may be deteriorated. Further, 7,000 or more and 13,000 or less are more preferable from the viewpoints of low temperature fixability, heat resistant storage stability and hot offset resistance.

  In the present invention, the content of the crystalline polyester resin is preferably 1.0 part by mass or more and 15 parts by mass or less per 100 parts by mass of the amorphous polyester resin as the binder resin.

  When the content is less than 1.0 part by mass, the low temperature fixability may be deteriorated, and when the content is more than 15 parts by mass, the charging stability and the heat resistant storage stability in a high temperature and high humidity environment may be deteriorated. May be

  The crystalline polyester resin of the present invention is derived from one or more aliphatic compounds selected from the group consisting of aliphatic monocarboxylic acids having 11 to 21 carbon atoms and aliphatic monoalcohols having 10 to 20 carbon atoms. It is preferable to contain the part to do.

  When the aliphatic compound is added in the process of synthesizing a crystalline polyester resin having a small molecular weight, it reacts with the end of the molecular chain constituting the crystalline polyester resin and plays a role like an end cap, so that the molecular chain is long. It is hard to become too much. Therefore, in synthesizing the crystalline polyester resin having the required molecular weight, most of the unreacted free monomer reacts, so that the low molecular weight component derived from the unreacted monomer is reduced, and a structure having a sharp molecular weight distribution can be realized.

  In the aliphatic compound, when the aliphatic monocarboxylic acid has less than 11 carbon atoms or the aliphatic monoalcohol has less than 10 carbon atoms, storage stability may be deteriorated. If the aliphatic monocarboxylic acid has 22 or more carbon atoms or the aliphatic monoalcohol has 21 or more carbon atoms, the compatibility of the crystalline polyester resin and the amorphous polyester resin decreases, and thus the low temperature fixability is improved. May worsen.

  Furthermore, when the number of carbon atoms is within the above range, it is easy to condense at the terminal of the molecular chain, and it does not exist as a free monomer, which is preferable from the viewpoint of storage stability.

  Examples of the aliphatic monocarboxylic acid having 11 to 21 carbon atoms include capric acid (decanoic acid), undecyl acid, lauric acid (dodecanoic acid), tridecyl acid, myristylic acid (tetradecanoic acid), pentadecyl acid, palmitic acid (hexadecanoic acid). ), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadecyl acid, and arachidic acid (icosanoic acid).

  Examples of the aliphatic monoalcohol having 10 to 20 carbon atoms include capryl alcohol (decanol), undecanol, lauryl alcohol (dodecanol), tridecanol, myristyl alcohol (tetradecanol), pentadecanol, palmityl alcohol (hexadecanol). , Margaryl alcohol (heptadecanol), stearyl alcohol (octadecanol), nonadecanol, and arachidyl alcohol (icosanol).

  The crystalline polyester resin in the present invention can be manufactured according to a usual polyester synthesis method. For example, the carboxylic acid monomer and the alcohol monomer are esterified or transesterified, and then polycondensation reaction is carried out under a reduced pressure or by introducing a nitrogen gas according to a conventional method to obtain a crystallinity. A polyester resin can be obtained. Thereafter, the above-mentioned aliphatic compound is further added to carry out an esterification reaction, whereby a desired crystalline polyester resin can be obtained.

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

  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. .. The polymerization temperature and the amount of catalyst are not particularly limited and may be appropriately determined.

  In the esterification or transesterification reaction or polycondensation reaction, all the monomers are charged at one time to increase the strength of the crystalline polyester obtained, or a divalent monomer is first reacted to reduce the low molecular weight components. After that, a method of adding a monomer having a valence of 3 or more and reacting it may be used.

<Binder resin>
The binder resin used in the toner of the present invention needs to have an amorphous polyester resin as a main component. Monomers used for the polyester unit of the amorphous polyester resin include polyhydric alcohols (dihydric or trihydric or higher alcohols), polyhydric carboxylic acids (dihydric or trihydric or higher carboxylic acids), and acid anhydrides thereof. Alternatively, a lower alkyl ester thereof is used. Here, in the case of producing a branched polymer, it is effective to partially crosslink in the molecule of the binder resin, and for that purpose, it is preferable to use a polyfunctional compound having a valence of 3 or more. Therefore, it is preferable that the raw material monomer of the polyester unit contains a trivalent or higher carboxylic acid, an acid anhydride thereof or a lower alkyl ester thereof, and/or a trivalent or higher alcohol.

  As the polyhydric alcohol monomer used for the polyester unit of the amorphous polyester resin, the following polyhydric alcohol monomers can be used.

  Examples of the dihydric alcohol component include 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, hydrogenated bisphenol A, bisphenol represented by formula (A) and derivatives thereof;

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

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

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

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

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

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

  The binder resin used in the toner of the present invention may be a hybrid resin containing an amorphous polyester resin as a main component and other resin components. For example, a hybrid resin of an amorphous polyester resin and a vinyl resin may be mentioned. As a method for obtaining a reaction product of a vinyl-based resin or a vinyl-based copolymerization unit and an amorphous polyester resin such as a hybrid resin, a monomer that can react with each of the vinyl-based resin, the vinyl-based copolymerization unit and the polyester resin is used. A method of carrying out a polymerization reaction of one or both of the resins in the presence of the polymer containing the components is preferable.

  For example, among the monomers constituting the amorphous polyester resin component, those capable of reacting with the vinyl-based copolymer include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid and itaconic acid or anhydrides thereof. Etc. 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, and acrylic acid or methacrylic acid esters.

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

  The peak molecular weight of the binder resin of the present invention is preferably 8,000 or more and 13,000 or less from the viewpoint of low-temperature fixability and hot offset resistance. Further, the acid value of the binder resin of the present invention is preferably 15 mgKOH/g or more and 30 mgKOH/g or less from the viewpoint of charging stability in a high temperature and high humidity environment. 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 low-temperature fixability and storability.

  Further, the binder resin of the present invention may be used by mixing a low molecular weight binder resin C and a high molecular weight binder resin B. The content ratio (B/C) of the binder resin B having a high molecular weight and the binder resin C having a low molecular weight is 10/90 or more and 60/40 or less on a mass basis. Is preferred.

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

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

<Wax>
Examples of the wax used in the toner of the present invention include the following. Hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymers thereof; Waxes containing a fatty acid ester such as carnauba wax as a main component; deoxidized fatty acid esters such as carnauba wax, which are partially or entirely deoxidized. Further, the following may be mentioned. Saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol, melyl alcohol Saturated alcohols such as sil alcohol; Polyhydric alcohols such as sorbitol; Fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, and melyl alcohol. Esters with alcohols such as sil alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearin Saturated fatty acid bisamides such as acid amides; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'dioleyl adipamide, N,N'dioleyl sebacic acid amide; m -Aromatic bisamides such as xylene bisstearic acid amide and N,N' distearylisophthalic acid amide; Aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metallic soap) Waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; partial esterification products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; hydrogen of vegetable oils and fats A methyl ester compound having a hydroxyl group obtained by addition.

  Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax or fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low-temperature fixability and hot offset resistance. In the present invention, a hydrocarbon wax is more preferable because 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, and when it is 3 parts by mass or more and 10 parts by mass or less, the storage stability and the hot offset resistance are improved. It is more preferable from the viewpoint of compatibility.

  In addition, the peak temperature of the maximum endothermic peak of the wax in the endothermic curve at the time of heating measured by a differential scanning calorimetry (DSC) device is preferably 45°C or higher and 140°C or lower. When the temperature is 60° C. or higher and 100° C. or lower, the storage stability of the toner and the hot offset resistance can both be achieved, which is more preferable.

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

  Examples of the black colorant include carbon black; those obtained by toning black with a yellow colorant, a magenta colorant and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment together 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. Butt 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 Red 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; C.I. 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 having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

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

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

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

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

<Inorganic fine particles (mainly external additives)>
The toner of the present invention may contain inorganic fine particles, if necessary. 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 a specific surface area of 10 m ² /g or more and 50 m or more for stabilizing durability. It is preferably an inorganic fine powder of ² /g or less. In order to achieve both improvement of fluidity and stabilization of durability, inorganic fine powder having a specific surface area in the above range may be used together.

  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 based on 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 be used also as a one-component developer, but in order to further improve dot reproducibility, it can be mixed with a magnetic carrier and used as a two-component developer, and a stable image can be obtained for a long time. Is preferred in that

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

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

<Manufacturing method>
The method for producing the toner of the present invention is not particularly limited, but the melt-kneading production method is preferable from the viewpoint of wax dispersibility so that the effect of the wax dispersant of the present invention can be sufficiently exhibited.

  The procedure for producing the toner in the present invention will be described.

  First, in the raw material mixing step, as a toner raw material, a crystalline polyester resin, an amorphous polyester resin, a hydrocarbon wax, a wax dispersant, and the like are weighed in predetermined amounts, mixed, and mixed. As an example of a mixing device, a Henschel mixer (manufactured by Nippon Coke Co., Ltd.); a super mixer (manufactured by Kawata Co., Ltd.); a ribocon (manufactured by Okawara Seisakusho); a Nauta mixer, a turbulizer, a cyclomix (manufactured by Hosokawa Micron); a spiral pin Mixers (manufactured by Taiheiyo Kiko Co., Ltd.); Reedige mixers (manufactured by Matsubo Co., Ltd.) and the like.

  Further, the mixed toner raw materials are melt-kneaded in a melt-kneading step to melt the resins and disperse the colorant and the like therein. As an example of the kneading device, a TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); a TEX twin-screw kneader (manufactured by Japan Steel Works Ltd.); a PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.); However, continuous kneaders such as single-screw or twin-screw extruders are preferable to batch-type kneaders because of their superiority such as continuous production.

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

  The cooled product of the colored resin composition obtained above is then ground to a desired particle size in a grinding process. In the pulverizing process, first, coarse pulverization is performed with a crusher, a hammer mill, a feather mill, etc., and further fine pulverization is performed with a Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.) and a super rotor (manufactured by Nisshin Engineering Co., Ltd.) to obtain toner fine particles. .

  The obtained toner fine particles are classified into toner powder particles having a desired particle diameter in a classification step. Examples of classifiers include Turboplex, Faculty, TSP, TTSP (manufactured by Hosokawa Micron); Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.).

  In the present invention, it is preferable that the toner particles are subjected to a surface treatment by hot air using a surface modification device by hot air treatment as shown in FIG.

  The toner particles quantitatively supplied by the raw material quantitative supply means 1 are guided by the compressed gas adjusted by the compressed gas adjusting means 2 to the introduction pipe 3 installed on the vertical line of the raw material supply means. The toner particles that have passed through the introduction tube are uniformly dispersed by the conical protruding member 4 provided at the center of the raw material supply means, and are guided to the radially extending eight-direction supply tube 5 to be subjected to hot air treatment. Guided to chamber 6.

  At this time, the flow of the toner particles supplied to the processing chamber is regulated by the regulation unit 9 provided in the processing chamber for regulating the flow of the toner particles. Therefore, the toner particles supplied to the processing chamber are subjected to wind treatment while swirling in the processing chamber and then cooled.

  The hot air for treating the supplied toner particles with hot air is supplied from the hot air supply means 7, and is swirled 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 angle of the blades. The temperature of the hot air supplied into the processing chamber at the outlet of the hot air supply means 7 is preferably 100°C to 300°C. When the temperature at the outlet of the hot air supply means is within the above range, it is possible to uniformly sphericalize the toner particles while preventing fusion or coalescence of the toner particles due to overheating of the toner particles. Becomes

Further, the hot air-treated toner particles that have been subjected to hot air treatment are cooled by the cold air supplied from the cold air supply means 8, and the temperature supplied from the cold air supply means 8 is preferably −20° C. to 30° C. If the temperature of the cold air is within the above range, the hot air-treated toner particles can be efficiently cooled, and fusion or coalescence of the hot air-treated toner particles can be performed without disturbing the uniform spheroidizing treatment of the toner particles. Can be prevented. Further, the cold air is preferably dehumidified cold air. Specifically, it is preferable that the absolute water content of the cold air is 5 g/m ³ or less. More preferably, it is 3 g/m ³ or less. If the absolute water content of the cold air exceeds 5 g/m ³ , the hydrophilicity of the cold air increases, and as a result, the elution rate of the wax may be slow.

  Next, the cooled hot air-treated toner particles are collected by the collecting means 10 at the lower end of the processing chamber. A blower (not shown) is provided at the tip of the collecting means, and suction and conveyance are performed by the blower.

  Further, the powder particle supply port 14 is provided so that the swirling direction of the supplied toner particles and the swirling direction of the hot air are the same direction, and the collecting means 10 of the surface treatment apparatus is the swirling powder particle. Is provided on the outer peripheral portion of the processing chamber so as to maintain the swirling direction. Further, the cold air supplied from the cold air supply means 8 is configured to be horizontally and tangentially supplied from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber. Turbulence in the processing chamber occurs because the swirling direction of the toner supplied from the powder supply port, the swirling direction of the cool air supplied from the cold air supply unit, and the swirling direction of the hot air supplied from the hot air supply unit are all in the same direction. Does not occur, the swirling flow in the apparatus is strengthened, a strong centrifugal force is applied to the toner, and the dispersibility of the toner is further improved. Therefore, it is possible to obtain a uniform toner having few coalescing particles.

  In addition, in the production method of the present invention, inorganic fine particles and the like may be added to the obtained powder particles for toner, if necessary. As a method of adding inorganic fine particles and the like to the toner powder particles, a predetermined amount of the toner powder particles and various known external additives are blended, and a Henschel mixer, mechano hybrid (manufactured by Nippon Coke Co., Ltd.), super mixer, and novirta are added. (Hosokawa Micron Co., Ltd.) and the like are stirred and mixed by using a high-speed stirrer that gives a shearing force to the powder as an external additive.

  Further, for sieving coarse particles, etc., if necessary, for example, Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resonator Sieve, Gyro Shifter (Tokuju Kosakusho Co., Ltd.); Turbo Screener (Turbo Kogyo Co., Ltd.); High Volter A sieving machine such as (manufactured by Toyo High-Tech Co., Ltd.) may be used.

  The methods for measuring various physical properties of the toner and raw materials will be described below.

<Measurement of glass transition temperature (Tg) of resin>
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 point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat.

  Specifically, about 5 mg of resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature raising 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 raised again. In the second heating process, a specific heat change is obtained in the temperature range of 30 to 100°C. The glass transition temperature (Tg) of the resin is defined as the intersection between the line at the midpoint of the baseline and the differential heat curve before and after the change in specific heat. Further, the amount of heat obtained from the area of the maximum endothermic peak of the temperature-endotherm curve in the temperature range of 60 to 90° C. is taken as the endothermic amount.

<Measurement of DSC endothermic amount (ΔH) of wax and crystalline resin>
The peak temperature (Tp) of the maximum endothermic peak of the wax and crystalline resin in the present invention is measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.
Temperature rising rate: 10°C/min
Measurement start temperature: 20°C
Measurement end temperature: 180°C

  The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat.

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

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

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

<Measurement of weight average molecular weight by GPC>
The column is stabilized in a heat chamber at 40° C., THF as a solvent is caused to flow through the column at a flow rate of 1 ml/min, and a THF sample solution of about 100 μl is injected for measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count value of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh or Showa Denko is used, and it is suitable to use a standard polystyrene sample of at least about 10 points. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, a combination of Shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK, or manufactured by Tosoh Corporation. The combination of TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), and TSKgurd column is listed. be able to.

  The sample is manufactured as follows.

  The sample is placed in THF, left to stand at 25° C. for several hours, shaken well, mixed well with THF (until the coalescence of the sample disappears), and left still for 12 hours or more. At that time, the leaving time in THF is set to be 24 hours. After that, a sample that has passed through a sample processing filter (pore size 0.2 μm or more and 0.5 μm or less, for example, Mysholydisk H-25-2 (manufactured by Tosoh Corporation) can be used) is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 mg/ml or more and 5.0 mg/ml or less.

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

  The electrolytic aqueous solution used for the measurement may be prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).

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

  On the "Change standard measurement method (SOM) screen" of the dedicated software, set the total count number in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). (Manufactured by the company) is used to set the value obtained. The threshold and noise level are automatically set by pressing the threshold/noise level measurement button. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the flash of the aperture tube after the measurement is checked.

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

The specific measuring method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker for Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution was put into a 100 ml flat-bottom beaker made of glass, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder, pH7 precise measurement as a dispersant was put therein) Approximately 0.3 ml of a diluting solution prepared by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning vessels with Wako Pure Chemical Industries, Ltd. with ion-exchanged water 3 times by mass is added.
(3) Two oscillators with an oscillating frequency of 50 kHz are built in with the phases shifted by 180 degrees, and are placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electric output of 120 W. A predetermined amount of ion-exchanged water is added, and about 2 ml of the Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. 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 becomes maximum.
(5) About 10 mg of toner is added little by little to the electrolytic aqueous solution in a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the 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, drop the aqueous solution of the electrolyte (5) in which the toner is dispersed into the round-bottom beaker (1) installed in the sample stand, and adjust so that the measured concentration is about 5%. .. Then, the measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis/volume statistical value (arithmetic mean) screen when the graph/volume% is set with the dedicated software is the weight average particle diameter (D4).

  The basic configuration and features of the present invention have been described above. The present invention will be specifically described below based on Examples. However, the present invention is not limited to this.

<Production Example of Styrene Acrylic Resin Composition A1>
In an autoclave reaction tank equipped with a thermometer and a stirrer, 300 parts by mass of xylene and 10 parts by mass of polyethylene were sufficiently dissolved and, after nitrogen substitution, 68 parts by mass of styrene, 2 parts by mass of stearyl methacrylate, 30 parts by mass of acrylonitrile and xylene. 250 parts by mass of the mixed solution was added dropwise at 180° C. for 3 hours for polymerization, and the mixture was kept at this temperature for 30 minutes. Next, the solvent was removed to obtain a styrene acrylic resin composition A1 as a wax dispersant.

  Table 1 shows the composition and SP value of the obtained wax dispersant. The SP value used in the present invention is a value calculated by the Fedors method.

<Production Example of Styrene Acrylic Resin Compositions A2 and A3>
In the production examples of the styrene acrylic resin composition A1, except that the aliphatic hydrocarbon resin is determined as appropriate conditions such that the Table 1, the same operation as in Production Example of Styrene acrylic resin composition A 1 , Styrene acrylic resin compositions A2 and A3 were obtained. Table 1 shows the composition and SP value of the obtained wax dispersant.

<Production Example of Styrene Acrylic Resin Composition A4>
In the production examples of the styrene acrylic resin composition A1, except that the aliphatic hydrocarbon resin and the SP value is changed as appropriate conditions and monomer ratios such that the Table 1, preparation examples of the styrene acrylic resin composition A 1 The same operation as above was performed to obtain a styrene-acrylic resin composition A4. Table 1 shows the composition and SP value of the obtained wax dispersant.

<Production Example of Styrene Acrylic Resin Compositions A5 and A6>
In the production examples of the styrene acrylic resin composition A1, except that the compound of the aliphatic hydrocarbon resin and (1) changes the appropriate conditions such that the Table 1, the production of styrene acrylic resin composition A 1 The same operation as in the example was performed to obtain styrene acrylic resin compositions A5 and A6. Table 1 shows the composition and SP value of the obtained wax dispersant.

<Production Example of Styrene Acrylic Resin Composition A7>
In the production examples of the styrene acrylic resin composition A1, aliphatic hydrocarbon resins, compounds of formula (1), and except that the SP value is changed as appropriate conditions and monomer ratios such that the Table 1, styrene-acrylic The same operation as in the production example of the resin composition A 1 was performed to obtain a styrene-acrylic resin composition A7. Table 1 shows the composition and SP value of the obtained wax dispersant.

<Production Example of Styrene Acrylic Resin Compositions A8 to A10>
In the production examples of the styrene acrylic resin composition A1, aliphatic hydrocarbon resins, except that compound and other compounds of formula (1) changes the appropriate conditions and monomer ratios such that the Table 1, styrene-acrylic The same operation as in the production example of the resin composition A 1 was performed to obtain styrene-acrylic resin compositions A8 to A10. Table 1 shows the composition and SP value of the obtained wax dispersant.

<Production Example of Crystalline Polyester Resin B1>
*1,6-hexanediol:
34.5 parts by mass (0.29 mol; 100.0 mol% based on the total number of polyhydric alcohols)
・Dodecanedioic acid:
65.5 parts by mass (0.28 mol; 100.0 mol% based on the total number of polyvalent carboxylic acids)
-Tin 2-ethylhexanoate: 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introducing tube, and a thermocouple. After replacing the inside of the flask with nitrogen gas, the temperature was gradually raised with stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140°C.

  Next, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was performed for 4 hours while maintaining the temperature at 200°C.

  Further, the pressure in the reaction vessel was gradually released to return to normal pressure, 10.0 parts by mass of lauric acid was added to 100 parts by mass of the raw material monomer, and the mixture was reacted at 200° C. for 2 hours under normal pressure.

  Then, the pressure in the reaction tank was reduced to 5 kPa or less again and the reaction was carried out at 200° C. for 3 hours to obtain a crystalline polyester resin B1. Table 1 shows the weight average molecular weight (Mw) of the obtained crystalline polyester resin B1.

<Production Example of Crystalline Polyester Resins B2 to B8>
Production Example of Crystalline Polyester Resin B1, except that the conditions were appropriately changed so that the weight average molecular weight (Mw) of dicarboxylic acid, diol, and crystalline polyester resin was as shown in Table 2. By performing the same operation as above, crystalline polyester resins B2 to B8 were obtained. Table 2 shows the weight average molecular weight (Mw) of the obtained crystalline polyester resin B.

<Production Example of Binder Resin C with High Molecular Weight>
-Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 72.3 parts by mass (0.20 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)
·Terephthalic acid:
18.3 parts by mass (0.11 mol; 65.0 mol% based on the total number of polycarboxylic acid mols)
・Fumaric acid:
2.9 parts by mass (0.03 mol; 15.0 mol% based on the total number of polyvalent carboxylic acids)
Tin 2-ethylhexanoate (esterification catalyst): 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask 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.

  Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa and maintained for 1 hour, then cooled to 180° C. and returned to atmospheric pressure (first reaction step).

・Trimellitic anhydride:
6.5 parts by mass (0.03 mol; 20.0 mol% based on the total number of polycarboxylic acid mols)
Tert-Butylcatechol (polymerization inhibitor): 0.1 parts by mass After that, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160° C., ASTM D36 After confirming that the softening point measured according to -86 reached the desired temperature, the temperature was lowered to stop the reaction (second reaction step), and a binder resin C was obtained. The binder resin C thus obtained had a softening point of 141° C. and a glass transition temperature of 63° C.

<Example of producing low molecular weight binder resin D>
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 polyhydric alcohols)
·Terephthalic acid:
28.0 parts by mass (0.17 mol; 100.0 mol% based on the total number of polyvalent carboxylic acids)
Tin 2-ethylhexanoate (esterification catalyst): 0.5 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask 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.

  Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa and maintained for 1 hour, then cooled to 180° C. 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 polyvalent carboxylic acids)
Tert-Butylcatechol (polymerization inhibitor): 0.1 parts by mass After that, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 1 hour while maintaining the temperature at 180° C., ASTM D36 After confirming that the softening point measured according to -86 reached the desired temperature, the temperature was lowered to stop the reaction (second reaction step), and a binder resin D was obtained. The binder resin D thus obtained had a softening point of 94°C and a glass transition temperature of 57°C.

<Production Example of Toner 1: Melt-kneading production method including hot air treatment step>
Binder resin C 35 parts by mass Binder resin D 65 parts by mass Crystalline polyester resin B1 7.5 parts by mass Fischer-Tropsch wax (hydrocarbon wax, peak temperature of maximum endothermic peak 90° C.) 5 parts by mass Styrene Acrylic resin composition A1 5 parts by mass C.I. I. Pigment Blue 15:3 7 parts by mass 3,5-di-t-butylsalicylic acid aluminum compound (Bontron E88 manufactured by Orient Chemical Industry Co., Ltd.) 0.3 parts by mass The above materials are used as a Henschel mixer (FM-75 type, Mitsui Mining Co., Ltd. ) Was used for mixing at a rotation speed of 20 s ⁻¹ and a rotation time of 5 min, and then kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 130° C. The obtained kneaded product was cooled and coarsely pulverized with a hammer mill to 1 mm or less to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized by a mechanical pulverizer (T-250, manufactured by Turbo Industry Co., Ltd.). Further, using a Faculty F-300 (manufactured by Hosokawa Micron Co., Ltd.), classification was performed to obtain toner particles 1. The operating conditions were a classification rotor rotation speed of 130 s ⁻¹ and a dispersion rotor rotation speed of 120 s ⁻¹ .

The obtained toner particles 1 were subjected to hot air treatment by the surface treatment device shown in FIG. 1 to obtain hot air treated particles of toner. The operating conditions were a feed rate of 5 kg/hr, a hot air temperature C of 150° C., and a hot air flow rate of 6 m ³ /min. , Cold air temperature E=−5° C., cold air flow rate=4 m ³ /min. , Blower air volume=20 m ³ /min. , Injection air flow rate=1 m ³ /min. And

To 100 parts by mass of hot air treatment the particles of the obtained toner, of hydrophobic silica (BET: a ^{80m 2 / g): 200m 2} /g)1.0 parts by mass of titanium oxide fine particles surface-treated with isobutyl trimethoxysilane (BET 1.0 part by mass, Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.), rotation speed 30 s ⁻¹ , rotation time 10 min. And mixed to obtain Toner 1.

  The toner 1 thus obtained was left at 55° C./41% RH for 48 hours and subjected to DSC measurement. As a result, an endothermic peak derived from the crystalline resin and an endothermic peak derived from the wax were observed.

<Production Example of Toners 2 to 12, Toners 14 to 26, and Toner 28>
Toner 1 was prepared in the same manner as in Toner 1 except that the type and content of styrene-acrylic resin composition A and the type and content of crystalline polyester resin B were changed as shown in Table 3. Toner 12, Toner 14 to Toner 26, and Toner 28 were obtained.

  The toners 2 to 12, the toners 14 to 26, and the toner 28 thus obtained were allowed to stand at 55° C./41% RH for 48 hours and then subjected to DSC measurement. As a result, an endothermic peak derived from the crystalline resin and a wax were derived. Endothermic peaks were observed.

<Production Example of Toner 13: Emulsion Aggregation Production Method>
(Amorphous polyester resin dispersion)
The composition of the amorphous polyester resin is 80% ion-exchanged water, the concentration of the amorphous polyester resin is 20%, the pH is adjusted to 8.5 with ammonia, and the cavitron is operated under the condition of heating 150° C., An amorphous polyester resin dispersion liquid (solid content: 20%) was obtained.

(Crystalline polyester dispersion)
80 parts by mass of crystalline polyester resin B1 and 720 parts by mass of ion-exchanged water were placed in a stainless beaker and heated to 99°C. When the crystalline polyester resin C1 was melted, it was stirred using a homogenizer. Next, while anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, solid content: 20%) 2.0 parts by mass was added dropwise, emulsification and dispersion were performed to obtain crystalline polyester resin B1 dispersion (solid content). : 10%) was obtained.

(Colorant dispersion)
C. I. Pigment Blue 15:3 1000 parts by mass/anionic surfactant 150 parts by mass/ion-exchanged water 9000 parts by mass The above components were mixed and dissolved, and then dispersed using a high-pressure impact disperser. The volume average particle diameter D50 of the colorant particles in the obtained colorant dispersion was 0.16 μm, and the colorant concentration was 23%.

(Wax dispersion)
-Fischer-Tropsch wax (hydrocarbon wax, peak temperature of maximum endothermic peak 90°C) 45 parts by mass- Styrene acrylic resin composition A1 45 parts by mass-Anionic surfactant 5 parts by mass-Ion-exchanged water 150 parts by mass or more After being heated to 95° C. and dispersed using a homogenizer, a pressure-release type Gohlin homogenizer is subjected to a dispersion treatment to disperse a releasing agent having a volume average particle diameter of 210 nm (wax concentration: wax concentration: 20%) was prepared.
-Amorphous polyester resin dispersion liquid 500 parts by mass-Crystalline polyester resin B1 dispersion liquid 75 parts by mass The above components were mixed and dispersed by a homogenizer in a round stainless steel flask. To this, 0.15 parts of polyaluminum chloride was added, and the dispersion operation was continued with Ultra Turrax. afterwards,
Colorant dispersion liquid 30.5 parts by mass Release agent dispersion liquid 25 parts by mass The above components were added, and further polyaluminum chloride 0.05 parts by mass was added, and the dispersion operation was continued with Ultra Turrax.

  A stirrer and a mantle heater are installed, and while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred, the temperature is raised to 60°C and kept at 60°C for 15 minutes, and then at 0.05°C/minute. The particle size was measured with a Coulter Multisizer II (aperture diameter: 50 μm, manufactured by Beckman-Coulter, Inc.) every 10 minutes while the temperature was raised. When the volume average particle size was 5.0 μm, the amorphous polyester was used. 75 parts by mass of the resin dispersion (additional resin) was added over 3 minutes. After being charged for 30 minutes, the pH was adjusted to 9.0 using a 5% aqueous sodium hydroxide solution. Then, while adjusting the pH to 9.0 at every 5° C., the temperature was raised to 96° C. at a temperature rising rate of 1° C./min and maintained at 96° C. Observation of the particle shape and surface property with an optical microscope and a scanning electron microscope (FE-SEM) every 30 minutes revealed that the particles became spherical in the 5th hour, so the temperature was lowered to 20°C at 1°C/minute to solidify the particles. Let

  After that, the reaction product was filtered, thoroughly washed with ion-exchanged water, and then dried using a vacuum dryer to obtain toner particles 13.

The toner particles 13 of 100 parts by weight of 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. 0 parts by mass, using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.), a rotation speed of 30 s ⁻¹ and a rotation time of 10 min. And mixed to obtain Toner 13.

  The toner 13 thus obtained was allowed to stand at 55° C./41% RH for 48 hours and subjected to DSC measurement. As a result, an endothermic peak derived from the crystalline resin and an endothermic peak derived from the wax were observed.

<Production Example of Toner 27: Melt Kneading Manufacturing Method>
In the production example of Toner 1, except that the type and content of the styrene-acrylic resin composition A and the crystalline polyester resin B were changed as shown in Table 2 and the toner particles 1 were not treated with hot air, Toner 27 was obtained by the same manufacturing method as Toner 1. The toner 27 thus obtained was allowed to stand at 55° C./41% RH for 48 hours and subjected to DSC measurement. As a result, an endothermic peak derived from the crystalline resin and an endothermic peak derived from the wax were observed.

<Production Example of Toner 29 and Toner 30>
In the production example of Toner 1, the same operation was performed except that the crystalline polyester resin was not used, and the kind and content of the styrene-acrylic resin composition A were changed as shown in Table 2, and the same operation was performed. Got The toners 29 and 30 thus obtained were allowed to stand at 55° C./41% RH for 48 hours, and DSC measurement was carried out. As a result, an endothermic peak derived from wax was observed.

<Production Example of Magnetic Core Particle 1>
・Process 1 (weighing/mixing process):
Fe ₂ O ₃ 62.7 parts by mass MnCO ₃ 29.5 parts by mass Mg(OH) ₂ 6.8 parts by mass SrCO ₃ 1.0 part by mass The ferrite raw material was weighed so that the above material had 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.

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

・Process 3 (crushing process):
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 for 1 hour with a wet ball mill. The slurry was pulverized for 4 hours by a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

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

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

・Process 6 (selection process):
After disintegrating the agglomerated particles, a low magnetic force product is cut by magnetic separation, coarse particles are removed by sieving with a sieve having an opening of 250 μm, and 50% particle size (D50) of 37.0 μm based on volume distribution. Magnetic core particles 1 were obtained.

<Preparation of coating resin 1>
Cyclohexyl methacrylate monomer 26.8 mass%
Methyl methacrylate monomer 0.2 mass%
Methyl methacrylate macromonomer 8.4 mass%
(Macromonomer having 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 mass%
Of the above materials, cyclohexylmethacrylate, methylmethacrylate, methylmethacrylate macromonomer, toluene, methylethylketone were added to a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stirring device, and nitrogen gas was added. Was introduced into the autoclave to make it sufficiently nitrogen atmosphere, then 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 filtered off and dried in vacuum to obtain a coating resin 1. The obtained coating resin 1 was dissolved in 30 parts by mass, toluene 40 parts by mass, and methyl ethyl ketone 30 parts by mass 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 mass%
Toluene 66.4% by mass
Carbon black (Regal 330; 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)
Was dispersed with a paint shaker for 1 hour using zirconia beads having a diameter of 0.5 mm. The obtained dispersion liquid was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Production 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 such that the resin component was 2.5 parts by mass with respect to 100 parts by mass of the filled core particles 1. After charging, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes, the solvent was volatilized at 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 magnetic carrier thus obtained is separated into low magnetic force products by magnetic separation, passed through a sieve having an opening of 70 μm, and then classified by an air classifier, and a magnetic carrier having a volume distribution-based 50% particle diameter (D50) of 38.2 μm. Got 1.

<Production Example of Two-Component Developer 1>
To 92.0 parts by mass of the magnetic carrier 1, 8.0 parts by mass of the toner 1 were added and mixed by a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain a two-component developer 1.

<Production Examples of Two-Component Developers 2 to 30>
In the production example of the two-component developer 1, the same operation was performed except that the toner was changed as shown in Table 4, and two-component developers 2 to 30 were obtained.

[Example 1]
Evaluation was performed using the obtained two-component developer 1.

As an image forming apparatus, a Canon digital commercial printer printer imageRUNNER ADVANCE C9075 PRO remodeling machine is used, and the two-component developer 1 is put in the developing device at the cyan position so that the amount of toner deposited on the electrostatic latent image carrier or paper is The DC voltage V _DC of the developer carrying member, the charging voltage V _D of the electrostatic latent image carrying member, and the laser power were adjusted as desired, and the evaluations described below were performed. As a modification point, it was changed so that the fixing temperature and the process speed could be freely set.

  Evaluation was carried out based on the following evaluation methods, and the results are shown in Table 5.

<Evaluation 1> Charging property, Q/M (mC/kg) maintenance rate after being left under a high temperature and high humidity environment (32.5° C., 80% RH), the applied amount of the electrostatic latent image carrier is 0.35 mg/cm 3. ^It was adjusted to ² and collected by suction with a metal cylindrical tube and a cylindrical filter. At that time, the amount of electric charge Q accumulated in the condenser through the metal cylindrical tube and the mass M of collected toner are measured, and the amount of electric charge Q/M (mC/kg) per unit mass is calculated to carry an electrostatic latent image. Body Q/M (mC/kg) was used.

After performing the above evaluation, the developing device was removed from the machine, left in an environment of 32.5° C. and 80% RH for 72 hours, and then the developing device was mounted again in the machine, and the same DC voltage V _DC as in the initial evaluation was applied. Then, the amount of charge Q/M per unit mass on the electrostatic latent image carrier was measured.

  The above-mentioned initial Q/M on the electrostatic latent image bearing member was set to 100%, and the maintenance ratio of the Q/M on the photosensitive member after being left for 72 hours was calculated and judged according to the following criteria.

(Evaluation criteria)
A: Q/M maintenance ratio on the electrostatic latent image carrier is 80% or more: very good.
B: Q/M maintenance ratio on the electrostatic latent image bearing member is 70% or more and less than 80%: Good.
C: Q/M maintenance ratio on the electrostatic latent image carrier is 60% or more and less than 70%: acceptable level in the present invention.
D: Q/M maintenance ratio on the electrostatic latent image bearing member is less than 60%: Not at a level in the present invention.

<Evaluation 2> Low temperature fixing paper: CS-680 (68.0 g/m ² ).
(Sold by Canon Marketing Japan Inc.)
Amount of applied toner: 1.20 mg/cm ²
Evaluation image: An image of 10 cm ² is placed in the center of the A4 paper. Fixing test environment: low temperature and low humidity environment: temperature 15°C/humidity 10% RH (hereinafter “L/L”)
After the unfixed image was prepared, the process speed was set to 450 mm/sec and the fixing temperature was set to 130° C. to evaluate the low temperature fixability. The value of the image density reduction rate was used as an evaluation index of low temperature fixability. The image density reduction rate is obtained by first measuring the image density of the central portion 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 sillbon paper, and the image density is measured again. Then, the reduction rate (%) of the image density before and after the rubbing was measured.

(Evaluation criteria)
A: Density reduction rate of less than 2.0% (very excellent)
B: Density reduction rate 2.0% or more and less than 5.0% (good)
C: Concentration decrease rate 5.0% or more and less than 10.0% (at a level that does not cause a problem in the present invention)
D: Density reduction rate 10.0% or more (not acceptable in the present invention)

<Evaluation 3> Blocking resistance (storability)
5 g of the toner was put in a 100 cc poly cup and left in a temperature and humidity variable type constant temperature bath (55° C., 41%) for 48 hours, and the cohesiveness of the toner was evaluated after the standing. The cohesiveness was determined by using the powder tester PT-X manufactured by Hosokawa Micron Co., Ltd., and sieving with a mesh having a mesh size of 20 μm for 10 seconds at an amplitude of 0.5 mm as an evaluation index.

(Evaluation criteria)
A: Residual rate is less than 2.0% (very excellent)
B: Residual rate 2.0% or more and less than 10.0% (good)
C: Residual rate 10.0% or more and less than 15.0% (at a level where there is no problem in the present invention)
D: Residual rate 15.0% or more (not acceptable in the present invention)

<Evaluation 4> Hot offset resistant paper: CS-680 (68.0 g/m ² ).
(Sold by Canon Marketing Japan Inc.)
Amount of applied toner: 0.08 mg/cm ²
Evaluation image: Images of 10 cm ² are arranged at both ends of the A4 paper. Fixing test environment: normal temperature and low humidity environment: temperature 23° C./humidity 5% RH (hereinafter “N/L”)

After the unfixed image was prepared, the process speed was set to 450 mm/sec, the fixing temperature was increased from 150° C. by 5° C. at a time, and the hot offset resistance was evaluated. As a procedure, first, 10 sheets of plain postcards were passed through the central position of the fixing belt, and then the unfixed image was passed through. The fog value was used as an evaluation index for hot offset. Fog is caused by a reflectometer (“REFLECTOMETER MODEL TC-6DS” manufactured by Tokyo Denshoku Co., Ltd.), which is the average reflectance Dr (%) of the evaluation paper before image formation and the reflectance Ds (%) of the white area after the fixing test. ) Was measured and calculated using the following formula. The fog thus obtained was evaluated according to the following evaluation criteria.
Fog (%) = Dr (%)-Ds (%)

(Evaluation criteria)
A: less than 0.2% (very excellent)
B: 0.2% or more and less than 0.5% (good)
C: 0.5% or more and less than 1.0% (at a level where there is no problem in the present invention)
D: 1.0% or more (not acceptable in the present invention)

[Examples 2 to 24]
Evaluations were made in the same manner as in Example 1 except that the two-component developers 2 to 24 shown in Table 4 were used. The results are shown in Table 5.

[Comparative Examples 1 to 6]
Evaluation was performed in the same manner as in Example 1 except that the two-component type developers 25 to 30 shown in Table 4 were used. The results are shown in Table 5.

  Toner 1 used in Example 1 had good charge stability, low-temperature fixability, storability, and hot offset resistance.

  The toner 25 used in Comparative Example 1 is a toner in which the compound of the formula (1) is butyl methacrylate of n=4 in the composition of the styrene acrylic resin in the wax dispersant and does not contain stearyl methacrylate. Since the SP value of the wax dispersant is low and the mixing with the binder resin is deteriorated, the dispersibility of the wax is deteriorated and the wax is domainized, so that the charge stability and the storage stability under high temperature and high humidity are deteriorated. Conceivable.

  The toner 26 used in Comparative Example 2 is a toner in which the compound of formula (1) is behenyl methacrylate of n=22 in the composition of the styrene acrylic resin in the wax dispersant and does not contain stearyl methacrylate. It is considered that the SP value of the wax dispersant was low and the mixing with the binder resin was aggravated, so that the wax was domainized and the charge stability and storage stability under high temperature and high humidity were deteriorated. Further, since it contains a long-chain behenyl methacrylate as the compound of the formula (1), it is considered that the low temperature fixability is also deteriorated.

  The toner 27 used in Comparative Example 3 is a toner in which the compound of the formula (1) is the same behenyl methacrylate as that of the toner 26 in Comparative Example 2, and further, the hot air treatment is not performed in the manufacturing process of the toner particles. Since the migration of the wax and the wax dispersant to the toner surface is reduced by not performing the hot air treatment, it is presumed that the hydrophobicity is not sufficient and the storage stability is deteriorated.

  The toner 28 used in Comparative Example 4 is a toner in which the compound of formula (1) is the same behenyl methacrylate as the toner 26 of Comparative Example 2 and further contains 12.0 parts by mass of a wax dispersant. It is presumed that, since the amount of the wax dispersant was too much with respect to the wax, the low-temperature fixability was deteriorated, the releasing effect of the wax could not be sufficiently exhibited, and the hot offset resistance was deteriorated.

  The toner 29 used in Comparative Example 5 is a toner in which the compound of the formula (1) is the same behenyl methacrylate as the toner 26 in Comparative Example 2 and does not further contain a crystalline polyester resin. As a result, the preservability and charge stability were improved, but it is speculated that the low temperature fixability was significantly deteriorated.

  The toner 30 used in Comparative Example 6 is a toner containing neither a crystalline polyester resin nor a wax dispersant. As a result, the dispersibility of the wax was significantly deteriorated, and it is speculated that the present invention achieved unacceptable levels of charge stability, low-temperature fixability, storage stability, and hot offset resistance.

  As shown by the above results, according to the present invention, it is possible to control the dispersion state of the wax in the toner, satisfy the low temperature fixing property, the hot offset resistance, and the storage property, and even in a situation where the charging property is severe. Thus, it is possible to obtain a toner that can exhibit sufficient chargeability.

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

Claims (7)

A toner particle containing a binder resin, a crystalline polyester resin, a wax, and a styrene acrylic resin composition,
The binder resin contains an amorphous polyester resin,
The styrene acrylic resin composition contains a styrene acrylic resin graft-modified with an aliphatic hydrocarbon resin, and the styrene acrylic resin composition graft modified with the aliphatic hydrocarbon resin is The content of the styrene-acrylic resin composition containing a unit derived from the compound represented by the following formula (1) and graft-modified with the aliphatic hydrocarbon resin is 100 parts by mass of the toner particles. A toner having a content of 1.0 part by mass or more and 10 parts by mass or less.

[ 12 ≤ n ≤ 18 , R is H or CH ₃ ] The toner according to claim 1, wherein the solubility parameter (SP value) of the styrene acrylic resin is 10.3 or more and 10.7 or less. The crystalline polyester resin, the toner according to claim 1 or 2 weight-average molecular weight (Mw) in the range of 7000 or more 13000 or less. The toner was obtained in a step of melt-kneading a mixture containing the binder resin, the crystalline polyester resin, the wax, and the styrene acrylic resin composition obtained by graft-modifying the aliphatic hydrocarbon resin. the toner according to any one of claims 1 to 3 having the toner particles. The toner according to any one of claims 1 to 4 , wherein the aliphatic hydrocarbon resin is polyethylene and/or polypropylene. The crystalline polyester resin is a crystalline polyester resin obtained by polycondensing an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms,
The content of the crystalline polyester resin, the toner according to any one of claims 1 to 5 100 parts by weight non-crystalline polyester resin to which 15 parts by mass or less than 1.0 part by weight. The toner particles, the toner according to any one of claims 1 to 6 surface treatment with hot air is applied.

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