JP2020106748A - toner - Google Patents

Abstract

To provide a toner which can improve scratch resistance while improving low temperature fixability.SOLUTION: A toner contains an amorphous polyester resin, a hydrocarbon-based wax, and toner particles containing a crystalline polyester resin A, a polymer B and a polymer C, in which the polymer B is a polymer in which a vinyl-based polymer unit D is bonded to a hydrocarbon unit, the polymer C is a polymer in which a crystalline polyester unit F is bonded to a terminal of a vinyl-based polymer unit E and a liner alkyl group having 6 or more and 30 or less carbon atoms is boned to the terminal of the crystalline polyester unit F, a ratio of a styrene-derived structural unit in the vinyl-based polymer unit D to the total structural unit in the vinyl-based polymer unit D is 80 mass% or more and 100 mass% or less, and a ratio of a styrene-derived structural unit in the vinyl-based polymer unit E is 80 mass% or more and 100 mass% or less to the total structural unit in the vinyl-based polymer unit E.SELECTED DRAWING: None

Description

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

In recent years, 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 type of paper 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 type of paper. From the viewpoint of constant velocity of the medium, the toner is required to properly complete fixing in a wide fixing temperature range from low temperature to high temperature. Various toners have been proposed in which a crystalline resin having a sharp melt property is added to the toner to fix the toner at a wide range of fixable temperatures to improve the low-temperature fixing performance (Patent Document 1).

JP, 2012-063559, A

However, even if the toner is fixed in the state where the image density is 100% with the toner as described above, toner transfer may occur due to rubbing when the image density is low (hereinafter, scratching), and simple low-temperature fixability is sufficient. There are cases where it cannot be realized. From the viewpoint of high image quality, there is room for consideration regarding this scratching property.
An object of the present invention is to solve the above problems and to provide a toner capable of improving scratch resistance while improving low-temperature fixability.

The present invention relates to a toner containing toner particles containing an amorphous polyester resin, a hydrocarbon wax, a crystalline polyester resin A, a polymer B, and a polymer C,
The polymer B is a polymer in which a vinyl polymer unit D is bonded to a hydrocarbon unit,
In the polymer C, the crystalline polyester unit F is bonded to the end of the vinyl-based polymer unit E, and the linear alkyl group having 6 to 30 carbon atoms is bonded to the end of the crystalline polyester unit F. Is a polymer
The proportion of structural units derived from styrene in the vinyl polymer unit D is 80% by mass or more and 100% by mass or less based on the vinyl polymer unit D,
The present invention relates to a toner and a hydrocarbon unit alkyl group, wherein the ratio of structural units derived from styrene in the vinyl polymer unit E is 80% by mass or more and 100% by mass or less based on the vinyl polymer unit E.

According to the present invention, it is possible to provide a toner capable of improving rubbing of a printed matter on paper while improving low-temperature fixability.

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.

The toner of the present invention is a toner containing toner particles containing an amorphous polyester resin, a hydrocarbon wax, a crystalline polyester resin A, a polymer B, and a polymer C,
The polymer B is a polymer in which a vinyl polymer unit D is bonded to a hydrocarbon unit,
In the polymer C, the crystalline polyester unit F is bonded to the end of the vinyl-based polymer unit E, and the linear alkyl group having 6 to 30 carbon atoms is bonded to the end of the crystalline polyester unit F. Is a polymer
The proportion of structural units derived from styrene in the vinyl polymer unit D is 80% by mass or more and 100% by mass or less based on the vinyl polymer unit D,
The ratio of structural units derived from styrene in the vinyl-based polymer unit E is 80% by mass or more and 100% by mass or less based on the vinyl-based polymer unit E, and the hydrocarbon-based wax hydrocarbon unit is an alkyl group. ..

The present inventors consider the abradability and its improvement mechanism as follows.

As a result of the study by the present inventors, it was found that the abrasion resistance is related to the slipperiness of the toner on the image, and that the wax on the image surface is highly effective in improving the abrasion resistance. It is presumed that the wax exuded on the surface of the image after fixing and crystallized, so that the slidability with respect to the image and paper was improved and the toner became difficult to peel off. Upon further investigation, it was found that a crystalline material exerts a similar effect. However, it was not possible to satisfy the process speed and the goal of high image quality, which are improving day by day, only by adding these at the same time.

The present inventors have reached the constitution of the present invention by adding the polymer B and the polymer C in addition to the wax and the crystalline material as a further study. Although a specific mechanism has not been established, it is estimated as follows.

The polymer B has a structure in which a vinyl polymer unit D is bonded to a hydrocarbon unit. The hydrocarbon unit easily interacts with the hydrocarbon wax in the toner, and the vinyl polymer unit D easily interacts with the amorphous polyester resin which is the binder resin.

The polymer C has a structure in which the crystalline polyester unit F is bonded to the end of the vinyl polymer unit E. The vinyl-based polymer unit E easily interacts with the amorphous polyester resin, but more easily interacts with the vinyl-based polymer unit D of the polymer B. The vinyl-based polymer unit D and the vinyl-based polymer unit E have a ratio of structural units derived from styrene to structural units of 80% by mass or more and 100% by mass or less, and are configured to further strengthen the interaction between them. This is because It is presumed that the crystalline polyester unit F at the terminal is likely to interact with the crystalline polyester resin A added to the toner.

It is considered that the hydrocarbon wax in the toner and the crystalline polyester A can be bound by the action of the polymer B and the polymer C. Further, a linear alkyl group having 6 to 30 carbon atoms is bonded to the end of the crystalline polyester unit F of the polymer C. It is presumed that the linear alkyl group has a function of easily crystallizing the crystalline polyester A deposited on the surface, and it is considered that the scratch resistance can be further improved.

As a result, a large amount of crystalline material can be deposited on the image surface by the interaction of the hydrocarbon wax, the polymer B, the polymer C, and the crystalline polyester resin A, and the recrystallization of the crystalline polyester A is promoted. As a result, it is estimated that scratch resistance satisfied the target.

The constitution of preferable materials will be described below.

<Amorphous polyester resin (binder resin)>
The amorphous polyester resin used in the toner of the present invention needs to contain a polyester resin as a main component. Monomers used in the polyester unit of the polyester resin include polyhydric alcohols (dihydric or trihydric or higher alcohols), polyhydric carboxylic acids (dihydric or trihydric or higher carboxylic acids), acid anhydrides or lower thereof. Alkyl esters are 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 carboxylic acid having a valence of 3 or more, an acid anhydride thereof or a lower alkyl ester thereof, and/or an alcohol having a valence of 3 or more.

The following polyhydric alcohol monomers can be used as the polyhydric alcohol monomer used in the polyester unit of the polyester resin.

As the dihydric alcohol component, 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。）

(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);

が挙げられる。

Are listed.

Examples of the trihydric or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 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 in the polyester unit of the polyester resin, the following polyvalent carboxylic acid monomers can be used.

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

A hybrid resin containing other resin components may be used as long as it contains a polyester resin as a main component. For example, a hybrid resin of polyester resin and vinyl resin may be mentioned. A method for obtaining a reaction product of a vinyl resin or a vinyl copolymer unit and a polyester resin, such as a hybrid resin, includes a monomer component capable of reacting with each of the vinyl resin, the vinyl copolymer unit and the polyester resin. Where the polymer is present, a method of carrying out a polymerization reaction of one or both resins is preferable.

For example, among the monomers constituting the polyester resin component, examples of monomers capable of reacting with the vinyl copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. To be 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 a polyester resin is a main component as the binder resin, various resin compounds conventionally known as the binder resin can be used in combination with the above vinyl-based resin. 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 20 mgKOH/g or less from the viewpoint of charging stability in a high temperature and high humidity environment.

Further, the binder resin of the present invention may be used as a mixture of a low molecular weight binder resin L and a high molecular weight binder resin H. The content ratio (H/L) of the high molecular weight binder resin H and the low molecular weight binder resin L is 10/90 or more and 60/40 or less on a mass basis, which is low-temperature fixability and hot offset resistance. Is preferred.

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

It is preferable that the low molecular weight binder resin L has a peak molecular weight of 4,000 or more and 6,000 or less from the viewpoint of low temperature fixability. Further, the acid value of the low molecular weight binder resin L is preferably 10 mgKOH/g or less from the viewpoint of charge stability in a high temperature and high humidity environment.

<Wax (release agent)>
It is important that the wax used in the toner of the present invention is a hydrocarbon wax from the viewpoint of improving low-temperature fixability and hot offset resistance.

Examples of hydrocarbon waxes include paraffin wax and Fischer-Tropsch wax.

In the present invention, the wax is preferably used in an amount of 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the binder resin.

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

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

Examples of the black colorant include carbon black; 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 dye for magenta toner 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 based on 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 the side chain, and a sulfonate or a sulfonate ester compound in the side chain Examples thereof include a polymer type compound, a polymer type compound having a carboxylic acid salt or a carboxylic ester 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.

<Crystalline polyester resin A>
The toner of the present invention contains a crystalline polyester resin, and the low-temperature fixability is improved by containing the crystalline polyester resin. Further, it can be deposited on the image surface after fixing to reduce friction and improve rubbing property.

The low-temperature fixability of the crystalline polyester resin is improved by the glass transition temperature because the binder resin and the crystalline polyester resin are compatible with each other, the molecular chains of the binder resin are widened, and the intermolecular force is weakened. This is because (Tg) is significantly lowered and the melt viscosity 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 increase 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 is better to increase the polarity and increase the polarity. On the other hand, it is necessary to secure storability for use and transportation in a high temperature and high humidity environment even for a toner having a glass transition temperature (Tg) significantly lowered. For that purpose, when the toner is exposed to such an environment, it is necessary to recrystallize the crystalline polyester in the compatible toner and return the Tg of the toner to the Tg of the binder resin. .. 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, and the storage stability of the toner deteriorates. Will be done. 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 that can achieve both low temperature fixability and storage stability. ..

In the toner of the present invention, the crystalline polyester resin contained in the toner particles is obtained by subjecting a monomer composition containing an aliphatic diol and an aliphatic dicarboxylic acid as main components to a polycondensation reaction. The aliphatic diol and the aliphatic dicarboxylic acid preferably have 6 or more and 12 or less carbon atoms.

The aliphatic diol is not particularly limited, but is preferably a chain (more preferably linear) aliphatic diol, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, and 1 ,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene Examples include glycol neopentyl glycol. Among these, particularly preferred are linear aliphatic α-ω-diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol. Of the above alcohol components, preferably 50 mass% or more, more preferably 70 mass% or more is an alcohol selected from aliphatic diols having 6 to 12 carbon atoms. In addition, the chain-like structure increases the interaction with the crystalline polyester portion of the polymer C and enhances the effect.

In the present invention, a polyhydric alcohol monomer other than the above aliphatic diol can also be used. Examples of the dihydric alcohol monomer among the polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropyleneated bisphenol A; 1,4-cyclohexanedimethanol and the like. Further, 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 Examples include group alcohols.

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

On the other hand, the aliphatic dicarboxylic acid is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, 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 6 to 12 carbon atoms.

In the present invention, a polycarboxylic acid other than the aliphatic dicarboxylic acid can be used. Among the 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.

Further, in the present invention, a monovalent carboxylic acid may be contained to the extent that the characteristics of the crystalline polyester resin are not impaired. Examples of the monovalent carboxylic acid include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, Examples include monocarboxylic acids such as dodecanoic acid and stearic acid.

The crystalline polyester resin in the present invention can be manufactured according to a usual polyester synthesis method. For example, after the esterification reaction or the transesterification reaction of the above-mentioned carboxylic acid monomer and alcohol monomer is carried out, a polycondensation reaction is carried out under a reduced pressure or by introducing nitrogen gas according to a conventional method to obtain a desired polycondensation reaction. A crystalline polyester 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 may be charged at once in order to increase the strength of the crystalline polyester obtained. In order to reduce the amount of low molecular weight components, a method in which a divalent monomer is first reacted and then a monomer having a valence of 3 or more is added and reacted, may be used.

The crystalline polyester resin is preferably contained in an amount of 1.0 part by mass or more and 15 parts by mass or less based on 100 parts by mass of the amorphous resin. When the amount of the crystalline resin is small, a sufficient plasticizing effect cannot be obtained and the low temperature fixing property cannot be improved. On the other hand, if too much is added, water tends to be adsorbed, and the tint stability is impaired.

From the viewpoint of suppressing moisture adsorption, the acid value is preferably 2 mgKOH/g or more and 20 mgKOH/g or less.

<Polymer B>
In the present invention, the polymer in which the vinyl polymer unit D is bonded to the hydrocarbon unit is added. The hydrocarbon unit easily interacts with the hydrocarbon wax in the toner, and the vinyl polymer unit D easily interacts with the amorphous polyester resin and the styrene acrylic resin E in the polymer C. By this action, the wax can be dispersed in the toner, and the polymer B and the polymer C can be easily bound together.

Further, the ratio of the structural unit derived from styrene in the vinyl-based polymer unit D is 80% by mass or more and 100% by mass or less based on the vinyl-based polymer unit D, and the above interaction is strengthened. There is.

Further, the mass ratio of the hydrocarbon unit and the vinyl polymer unit D is preferably 5/95 or more and 20/80 or less.

The polymer B of the present invention preferably has a weight average molecular weight (Mw) of 5,000 or more and 70,000 or less in the molecular weight distribution of styrene acrylic resin by GPC. When the polymer B of the present invention is in the above range, the dispersibility of the wax is improved, and at the same time, the blocking resistance and the hot offset resistance are improved.

When the weight average molecular weight (Mw) is less than 5,000, the polymer B easily moves in the toner. As a result, the wax is more likely to be eluted on the surface of the toner due to being left at high temperature and high humidity, and the blocking resistance of the toner may be deteriorated, which is not preferable in some cases.

If the weight average molecular weight (Mw) exceeds 70,000, the wax finely dispersed in the toner cannot be rapidly transferred to the surface of the molten toner during fixing and melting. Therefore, the releasability at the time of fixing is deteriorated, and high-temperature offset is likely to occur, which is not preferable.

In the present invention, the hydrocarbon unit is preferably a unit derived from a hydrocarbon compound such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax. Is.

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

The hydrocarbon compound serving as the hydrocarbon unit preferably has a peak temperature of a maximum endothermic peak measured using a differential scanning calorimeter (DSC) of 70°C or higher and 90°C or lower.

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

In the polymer B of the present invention, the styrene acrylic polymer may have a unit derived from cycloalkyl acrylate or cycloalkyl methacrylate.

The unit derived from cycloalkyl acrylate or cycloalkyl methacrylate is preferably a saturated alicyclic hydrocarbon group, more preferably a saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms, and further preferably 4 to 12 carbon atoms. Is a saturated alicyclic hydrocarbon group. The saturated alicyclic hydrocarbon group includes a cycloalkyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group and the like.

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

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

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

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

The styrene acrylic polymer may be a homopolymer of the vinyl monomer (a) having a structural portion derived from a saturated alicyclic compound, or may be a copolymer with another monomer (b).

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

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

Examples of the other monomer (b) include styrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene and benzylstyrene. Styrene-based monomers; alkyl esters of unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate (wherein the alkyl has 1 to 18 carbon atoms). The following); 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.

Further, a monomer for adding an acid group or a hydroxyl group may be added to adjust the polarity. Examples of the monomer that adds an acid group or a hydroxyl group include acrylic acid, methacrylic acid, maleic anhydride, maleic acid half ester, and 2-ethylhexyl acrylate.

In the present invention, it is preferable that the styrene acrylic resin has a monomer unit represented by the following formula (2) from the viewpoint of low temperature fixability of the toner.

When the styrene acrylic resin has a monomer unit represented by the formula (2), the glass transition temperature (Tg) of the polymer tends to decrease. As a result, when the wax dispersant is contained in the toner particles, the chargeability does not decrease even when the toner is left under high temperature and high humidity, and the low temperature fixability is further improved.

［前記式（２）中、Ｒ₃は水素原子又はメチル基を表し、ｎは１以上１８以下の整数を表す。］

[In the formula (2), R ₃ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more and 18 or less. ]

It is preferable that n is an integer of 2 or more and 7 or less. Within this range, the glass transition temperature (Tg) can be lowered efficiently. When it is less than 2, it is difficult to obtain the effect of lowering the glass transition temperature (Tg), and when it is more than 7, the glass transition temperature (Tg) is too low with respect to the joint, and adjustment may not be possible.

The polymer is preferably contained in an amount of 1.0 part by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the binder resin.

<Polymer C>
The polymer C used in the present invention has a crystalline polyester unit F bonded to the end of a vinyl polymer unit E, and a linear alkyl group having 6 to 30 carbon atoms at the end of the crystalline polyester unit F. Is a polymer in which is bonded. The vinyl polymer unit E interacts with the vinyl polymer unit D of the polymer B, and the crystalline polyester unit F interacts with the crystalline polyester resin A. By this action, the hydrocarbon wax and the crystalline polyester resin A can be made to act as domains, and the rubbing property can be improved.

Further, the ratio of structural units derived from styrene in the vinyl-based polymer unit E is characterized by being 80% by mass or more and 100% by mass or less based on the vinyl-based polymer unit E. The action can be strengthened.

Furthermore, it is preferable that the mass ratio (F/E) of the vinyl polymer unit E which is an amorphous site and the crystalline polyester unit F which is a crystalline site is 35/65 or more and 65/35 or less. When the ratio difference between the crystalline polyester portion and the amorphous vinyl portion becomes large, the interaction between the polymer B and the crystalline polyester resin A is biased, and it becomes difficult to exert the effect.

Next, the crystalline polyester as the crystalline polyester unit F in the polymer C according to the present invention can be obtained by the reaction of a divalent or higher polyvalent carboxylic acid and a diol. Among them, polyester having an aliphatic diol and an aliphatic dicarboxylic acid as main components is preferable because of high crystallinity. The crystalline polyester may be used alone or in combination of two or more kinds.

The crystalline polyester is obtained by polycondensing 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. To be 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.

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 linear aliphatic α-ω-diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

Of the above alcohol components, 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 can also be used. Examples of the dihydric alcohol monomer among the polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropyleneated bisphenol A; 1,4-cyclohexanedimethanol and the like. Further, 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 Examples include group alcohols.

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

On the other hand, the aliphatic dicarboxylic acid having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but is 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 the 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 -Aliphatic carboxylic acids such as methylene carboxypropane and the like, and their derivatives such as acid anhydrides or lower alkyl esters are also included.

In the present invention, the method for producing the polymer C includes a method in which a polymerization reaction is allowed to proceed in a pressurized environment when producing an amorphous vinyl moiety. Specifically, the transesterification reaction between the hydroxyl group contained in the polyester and the acrylic ester or methacrylic acid ester contained in the amorphous vinyl-based polymer, the hydroxyl group contained in the polyester and the amorphous vinyl-based polymer The esterification reaction with the contained carboxyl group, the esterification reaction between the carboxyl group contained in the polyester and the hydroxyl group contained in the amorphous vinyl-based polymer, the hydrogen abstraction reaction to generate radicals in the polyester Examples include a method of adding a system monomer and polymerizing under a pressure environment.

As the vinyl-based polymerizable monomer used when producing the amorphous vinyl moiety in the polymer C, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Examples of the monofunctional polymerizable monomer include styrene; styrene derivatives such as α-methylstyrene, o-methylstyrene, m-methylstyrene and p-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso- Acrylics such as propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate. Polymerizable Monomer: Methacrylic polymerizable monomer in which the acrylic polymerizable monomer is changed to methacrylate.

Examples of polyfunctional polymerizable monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol. Acrylic polyfunctional polymerizable monomers such as diacrylate, polypropylene glycol diacrylate, 2,2′-bis(4-(acryloxydiethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate; Examples of the methacrylic polyfunctional polymerizable monomer in which the acrylic polyfunctional polymerizable monomer is replaced with methacrylate include divinylbenzene, divinylnaphthalene, and divinyl ether.

As the polymerization initiator used for polymerizing the vinyl-based polymerizable monomer described above when producing the polymer C, other than those used in the present invention, as long as the effects of the present invention are not impaired. An oil-soluble initiator and/or a water-soluble initiator can be appropriately used. For example, as the oil-soluble initiator, an azo compound such as 2,2′-azobisisobutyronitrile; t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, lauroyl peroxide, t-butyl Peroxides such as peroxy 2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyisophthalate, di-t-butylperoxide are mentioned.

As the water-soluble initiator, ammonium persulfate, potassium persulfate, 2,2′-azobis(N,N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis(2-aminodinopropane) hydrochloric acid Salt, azobis(isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2 -Hydroxyethyl]propionamide}, 2,2'-azobis{2-methyl-N-[2-(1-hydroxybutyl)]-propionamide}, hydrochloride ferrous sulfate or hydrogen peroxide.

In particular, a peroxide is preferable, and when a polyester resin is vinyl-modified by a hydrogen abstraction reaction, a 10-hour half-life temperature is preferably 70° C. or higher and 170° C. or lower, and when 75° C. or higher and 130° C. or lower is used, It is more preferable because it has an appropriate reactivity.

Further, in the present invention, it is important that a linear alkyl group having 6 to 30 carbon atoms is bonded to the terminal of the crystalline polyester unit F. Since the linear alkyl group is bonded, recrystallization of the crystalline polyester resin A can be promoted. It is presumed that the straight-chain alkyl group is likely to become the nucleus of the crystalline polyester after fixing and promotes recrystallization.

In order to introduce the linear alkyl group into the terminal of the polyester unit F, for example, the terminal of the polyester unit may be used as a hydroxy group and reacted with a monovalent saturated aliphatic carboxylic acid. Examples of the monovalent saturated aliphatic carboxylic acid include monocarboxylic acids such as lauric acid and stearic acid.

Whether or not the linear alkyl group is bonded to the polyester part is determined by the following analysis. A sample solution is prepared by precisely weighing 2 mg of the sample and adding 2 ml of chloroform to dissolve it. A crystalline polyester resin is used as the resin sample, but if the crystalline polyester resin is difficult to obtain, a toner containing the crystalline polyester resin can be used as a sample instead. Next, 20 mg of 2,5-dihydroxybenzoic acid (DHBA) is precisely weighed, and 1 ml of chloroform is added and dissolved to prepare a matrix solution. Further, after accurately weighing 3 mg of Na trifluoroacetate (NaTFA), 1 ml of acetone is added and dissolved to prepare an ionization aid solution. 25 μl of the sample solution thus prepared, 50 μl of the matrix solution, and 5 μl of the ionization aid solution were mixed, dropped on a sample plate for MALDI analysis, and dried to obtain a measurement sample. A mass spectrum is obtained using MALDI-TOFMS (Reflex III manufactured by Bruker Daltonics) as an analytical instrument. In the obtained mass spectrum, each peak in the oligomer region (m/Z is 2000 or less) is assigned and it is confirmed whether or not there is a peak corresponding to the composition in which the aliphatic compound is bonded to the molecular end.

<Inorganic fine particles>
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 an external additive for improving fluidity, an inorganic fine powder having a specific surface area of 50 m ² /g or more and 400 m ² /g or less is preferable, 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. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.

<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 is preferably mixed with a magnetic carrier and used as a two-component developer. It is also preferable in that a stable image can be obtained for a long period of time.

Examples of the magnetic carrier include iron powder whose surface is oxidized, or unoxidized iron powder, and iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, metal particles such as rare earths, 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 in that case is 2% by mass or more and 15% by mass or less, preferably 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>
Next, the procedure for producing the toner in the present invention will be described. The method for producing a toner of the present invention comprises a melt-kneading step of melt-kneading a toner composition to obtain a melt-kneaded product, a crushing step of cooling and solidifying the melt-kneaded product and crushing a cooled solidified product to obtain a crushed product, a crushed product A heat-treating step of heat-treating the pre-thermospherical toner particles to obtain toner particles, and an external addition step of adding and mixing inorganic fine particles to the toner particles to obtain a toner. ing.

First, in the raw material mixing step, as a toner raw material, a crystalline polyester resin, an amorphous polyester resin, a hydrocarbon wax, and the like are weighed in predetermined amounts, mixed, and mixed.

As an example of the 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 extruder (manufactured by Toshiba Machine Co., Ltd.); a TEX twin-screw kneader (manufactured by Japan Steel Works); a PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.); Kneedex (manufactured by Mitsui Mining 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 crushing process, first, coarse crushing is performed with a crusher, a hammer mill, a feather mill, etc., and further finely crushed with a Kryptron system (Kawasaki Heavy Industry Co., Ltd.), a super rotor (Nisshin Engineering Co., Ltd.), etc. to obtain toner fine particles. ..

The obtained toner fine particles are classified into toner powder particles having a desired particle 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.).

Then, the obtained powder particles for toner are subjected to a spheroidizing treatment in a heat treatment step using a heat treatment apparatus as shown in FIG.

The mixture quantitatively supplied by the raw material quantitative supply means 1 is guided 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 mixture that has passed through the introduction pipe is uniformly dispersed by the conical projection-shaped member 4 provided in the central portion of the raw material supply means, and is guided to the radially extending 8-direction supply pipe 5 to be subjected to heat treatment. Be led to.

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

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

Further, the heat-treated toner particles which have been further heat-treated are cooled by the cold air supplied from the cold air supply means 8, and the temperature supplied from the cold air supply means 8 is preferably −20° C. to 30° C. When the temperature of the cold air is within the above range, the heat-treated toner particles can be efficiently cooled, and fusion and coalescence of the heat-treated toner particles are prevented without disturbing the uniform spheroidizing treatment of the mixture. be able to. The absolute water content of the cold air is preferably 0.5 g/m ³ or more and 15.0 g/m ³ or less.

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

Further, the powder particle supply port 14 is provided such that the swirling direction of the supplied mixture and the swirling direction of the hot air are in the same direction, and the collecting means 10 of the surface treatment device is arranged to collect the swirled powder particles. It is provided on the outer peripheral portion of the processing chamber so as to maintain the turning direction. Further, the cold air supplied from the cold air supply means 8 is configured to be horizontally and tangentially supplied from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber. The swirl direction of the pre-heat treatment toner particles supplied from the powder supply port, the swirl direction of the cold air supplied from the cold air supply unit, and the swirl direction of the hot air supplied from the hot air supply unit are all in the same direction. Therefore, turbulent flow does not occur in the processing chamber, the swirling flow in the apparatus is strengthened, a strong centrifugal force is applied to the toner particles before heat treatment, and the dispersibility of the toner particles before heat treatment is further improved. Thus, heat-treated toner particles having a uniform shape can be obtained.

In the toner manufacturing method of the present invention, inorganic fine particles and the like may be added to the obtained toner powder particles before the heat treatment step, if necessary. As a method for adding the 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.), a super mixer, and novirta (Hosokawa Micron Co., Ltd.) and the like are stirred and mixed using a high-speed stirrer that gives a shearing force to the powder as an external additive.

The method for producing a toner of the present invention may include a step of removing coarse particles by classification, if necessary, when the coarse particles are present after the heat treatment. Examples of the classifier that removes coarse particles include Turboplex, TSP, TTSP (manufactured by Hosokawa Micron), and Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.).

Further, after heat treatment, for example, to screen coarse particles, if necessary, for example, Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona Sieve, Gyro Shifter (Tokuju Kosakusho Co., Ltd.); Turbo Screener (Turbo Sangyo Co., Ltd.) ); A sieving machine such as Hibolter (manufactured by Toyo High-Tech Co., Ltd.) may be used.

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

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

The methods for measuring various physical properties of 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 "Q1000" (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 rising rate is 10° C./min at a measurement range of 30 to 200° C. Measure with. The temperature is once raised to 180° C. and kept 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.

<Measurement of DSC endothermic amount (ΔH) of wax and CPES>
The peak temperature (Tp) of the maximum endothermic peak of the toner and the like in the present invention is measured under the following conditions using DSC Q1000 (manufactured by TA Instruments).
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 directly treated 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, if the endothermic peak of the resin other than the wax and the binder resin overlaps with the maximum endothermic peak of the binder resin, the endothermic amount derived from the resin other than the wax and the binder resin is , It is necessary to subtract from the obtained endothermic amount of the maximum endothermic peak.

The maximum endothermic peak means a 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.

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

First, 0.03 g of the crystalline resin is dispersed in 10 ml of o-dichlorobenzene and dissolved, and then left at 135° C. for 24 hours to be dissolved. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Maeshoridisc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Using this sample solution, measurement is performed under the following conditions.

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

<Measurement of Weight Average Molecular Weight of Amorphous Vinyl Part in Polymer C and Mass Ratio of Crystalline Polyester Part to Amorphous Vinyl Part in Polymer C>
The measurement of the molecular weight of the amorphous vinyl part in the crystalline resin, and the mass ratio of the crystalline polyester part and the amorphous vinyl part in the crystalline resin are carried out by hydrolyzing the polyester part of the crystalline resin with water. Take a measurement. Specifically, 50 ml of dioxane and 10 ml of a 10 mass% potassium hydroxide aqueous solution were added to 300 mg of the crystalline resin, and a commercially available horizontal shaker was used at a temperature of 70° C. at a rate of about 2 reciprocations per second for 6 seconds. The polyester part is hydrolyzed by shaking for a time. Then, the solvent is distilled off under reduced pressure, and further dried in a 90° C. atmosphere under reduced pressure for 24 hours to prepare a sample for measuring the molecular weight of the vinyl part. The mass of the obtained measurement sample is A (mg). Then, the mass ratio (mass %) of the amorphous vinyl moiety in the crystalline resin is calculated by the following formula.
Mass ratio (% by mass) of amorphous vinyl moieties in the crystalline resin=A/300×100

Next, 0.03 g of the measurement sample is dispersed in 10 ml of o-dichlorobenzene and dissolved, and then left at 135° C. for 24 hours to be dissolved. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Maeshoridisc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Using this sample solution, analysis is performed under the same conditions as the weight average molecular weight of the crystalline resin.

<Measurement of molecular weight of resin by GPC>
The molecular weight distribution of the THF-soluble component of the resin is measured by gel permeation chromatography (GPC) as follows.

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

<Measuring method of softening point of resin>
The softening point of the resin is measured using a constant-load extrusion type thin tube rheometer "Flow characteristic evaluation device Flow tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. With this device, while applying a constant load from the top of the measurement sample by the piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the melted measurement sample is extruded from the die at the bottom of the cylinder. It is possible to obtain a flow curve showing the relationship between temperature and temperature.

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

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

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

<Method of measuring 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 to a concentration of 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 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). Set the value obtained by using the product. 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 measurement is checked.

In the dedicated software “pulse to particle size conversion setting screen”, 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 into 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 placed in a glass 100 ml flat-bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder, pH7 precision measurement as a dispersant was added to this). Approximately 0.3 ml of a diluting solution prepared by diluting a 10% by weight aqueous solution of a neutral detergent for cleaning vessels with Wako Pure Chemical Industries, Ltd. with ion-exchanged water 3 times by weight is added.

(3) Two oscillators with an oscillating frequency of 50 kHz are built in with their phases shifted by 180 degrees, and are placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetra 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, 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 the above (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 toner-dispersed aqueous electrolyte solution of (5) into the round-bottom beaker of (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 to calculate the weight average particle diameter (D4). The “average diameter” on the analysis/volume statistical value (arithmetic mean) screen when the graph/volume% is set by the dedicated software is the weight average particle diameter (D4).

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

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

The flow type particle image analyzer equipped with a standard objective lens (10 times) was used for the measurement, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and the total count mode. Then, the binarization threshold value at the time of particle analysis is set to 85%, the analyzed particle size is limited to the equivalent circle diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

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

In the examples of the present application, a flow-type particle image analyzer which has been calibrated by Sysmex Co. and has received a calibration certificate issued by Sysmex Co. was used. The measurement was performed under the conditions and the analysis conditions when the calibration certificate was received, except that the analysis particle size was limited to the equivalent circle diameter of 1.985 μm or more and less than 39.69 μm.

In the following examples, the number of parts is based on parts by mass.

<Production Example of Amorphous Polyester Resin L>
-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 tube, a stirrer, a nitrogen introducing tube, 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.

・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 90°C, the temperature was lowered to stop the reaction, and an amorphous polyester resin L was obtained.

<Production Example of Amorphous Polyester Resin H>
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 polyhydric alcohols)
·Terephthalic acid:
18.3 parts by mass (0.11 mol; 65.0 mol% based on the total number of polyvalent carboxylic acids)
・Fumaric acid:
2.9 parts by mass (0.03 mol; 15.0 mol% with respect to 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 tube, a stirrer, a nitrogen introducing tube, 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 and returned to atmospheric pressure.

・Trimellitic anhydride:
6.5 parts by mass (0.03 mol; 20.0 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 15 hours while maintaining the temperature at 160° C., and ASTM D36 After confirming that the softening point measured according to -86 reached 137[deg.] C., the temperature was lowered to stop the reaction, and an amorphous polyester resin H was obtained.

<Crystalline polyester resin A-1>
*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.

Furthermore, after gradually releasing the pressure in the reaction tank to return it to normal pressure, one or more aliphatic compounds selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols shown in Table 1. Was added to 100.0 mol% of the raw material monomer and reacted at 200° C. for 2 hours under normal pressure.

Then, the pressure inside 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 A-1.

<Production Example of Crystalline Polyester Resin A-2>
Under a nitrogen atmosphere, a pressure-resistant reactor equipped with a dropping funnel, a Liebig cooling tube and a stirrer 118 g of 1,6-hexanediol, 230 g of dodecanedioic acid, 36.2 g of styrene, 2.5 g of acrylic acid, and 3 of dicumyl peroxide. 0.0 g was added, the temperature was raised to 170° C., and the reaction was performed for 10 hours. The pressure at this time was 8.3 kPa.

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

Furthermore, after gradually releasing the pressure in the reaction tank to return it to normal pressure, one or more aliphatic compounds selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols shown in Table 1. (Stearic acid) was added in an amount of 7.0 mol% to 100.0 mol% of the raw material monomer, and the mixture was reacted at 200° C. for 2 hours under normal pressure.

Then, the pressure inside the reaction tank was reduced to 5 kPa or lower again and the reaction was carried out at 200° C. for 3 hours to obtain a crystalline polyester resin A-2.

<Production Example of Crystalline Polyester Resins A-3 and A-4>
In the production example of the crystalline polyester resin A-1, the same operation as in the production example of the crystalline polyester resin A-1 was performed except that the conditions were changed as shown in Table 1 to obtain the crystalline polyester resin A-3. , A-4 was obtained.

<Production Example of Polymer B-1>
1. In an autoclave reaction tank equipped with a thermometer and a stirrer, 300 parts by mass of xylene and 10 parts by mass of polypropylene (melting point 81° C.) were put and sufficiently dissolved, and after nitrogen substitution, 42.0 parts by mass of styrene and cyclohexyl methacrylate 2. A mixed solution of 0 parts by mass, 2.0 parts by mass of butyl acrylate, and 250 parts by mass of xylene is added dropwise at 180° C. for 3 hours for polymerization. Further, the mixture was kept at this temperature for 30 minutes to remove the solvent to obtain a polymer B-1. The proportion of structural units derived from styrene is 91%.

<Production Example of Polymer B-2>
Polymer B-2 was prepared in the same manner as in Polymer B-1, except that 42.0 parts by mass of styrene, 4.0 parts by mass of cyclohexyl methacrylate, and 4.0 parts by mass of butyl acrylate were used. Obtained. The proportion of structural units derived from styrene is 84%.

<Production Example of Polymer B-3>
Polymer B-3 was prepared in the same manner as in Polymer B-1 except that 42.0 parts by mass of styrene, 10.0 parts by mass of cyclohexyl methacrylate and 8.0 parts by mass of butyl acrylate were used. Obtained. The proportion of structural units derived from styrene is 53%.

<Production Example of Polymer C-1>
Under a nitrogen atmosphere, 100 parts by mass of styrene, 50 parts by mass of xylene, and 2 parts by mass of an azo polymerization initiator (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) were added to a pressure resistant reactor equipped with a stirrer equipped with a thermocouple. The temperature was raised to 100° C. and the reaction was carried out for 5 hours to synthesize polystyrene having methoxycarbonyl groups at both ends. Next, 3 parts by mass of 1,6-hexanediol was added to obtain polystyrene having hexanol units bonded to both ends.

Next, in the pressure resistant reactor described above,
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 polycarboxylic acid mols)
-Tin 2-ethylhexanoate: 0.5 parts by mass was added, the pressure inside the reactor was lowered to 8.3 kPa, and the reaction was performed for 4 hours while maintaining the temperature at 200°C, and the crystalline polyester unit was added to the end of polystyrene. A polymer in which was bonded was obtained.

Furthermore, the pressure in the reactor was gradually released to return to normal pressure, 7.0 parts by mass of stearic acid was added, and the mixture was reacted at 200° C. for 2 hours under normal pressure. Then, the pressure inside the reactor was reduced to 5 kPa or lower again and the reaction was carried out at 200° C. for 3 hours to obtain a polymer C-1.
It shows in Table 2.

<Production Example of Polymers C-2 to C-10>
The same operations as those for the polymer C-1 were carried out except that the configuration of the polymer C1 was changed as shown in Table 2 to obtain polymers C2 to C-10.

<Production Example of Toner 1>
-Amorphous polyester resin L 60 parts by mass-Amorphous polyester resin H 40 parts by mass-Crystalline polyester resin A-1 5 parts by mass-Polymer B-1 5 parts by mass-Polymer C-1 5 parts by mass- Fischer-Tropsch wax (hydrocarbon wax, peak temperature of maximum endothermic peak 90°C) 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 Henschel mixer (FM-75 type, Mitsui Mining Co., Ltd.) )) was mixed at a rotation speed of 20 s ⁻¹ and a rotation time of 5 min, and then kneaded with a biaxial kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.). The barrel temperature during kneading was set so that the outlet temperature of the kneaded product was 120°C. The outlet temperature of the kneaded product was directly measured using a handy type thermometer HA-200E manufactured by Anritsu Keiki Co., Ltd.

The obtained kneaded product was cooled and roughly pulverized to 1 mm or less by a hammer mill 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 heat-treated by the surface treatment apparatus shown in FIG. 1 to obtain heat-treated particles of toner. The operating conditions were a feed rate of 5 kg/hr, a hot air temperature of 150° C., and a hot air flow rate of 6 m ³ /min. , Cold air temperature=−5° C., cold air flow rate=4 m ³ /min. , Blower air volume=20 m ³ /min. , Injection air flow rate = 1 m ³ /min. And

The heat treatment the particles 100 parts by weight of the resulting toner, the 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 0.0 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 1.

<Production Examples of Toners 2 to 19>
In the production example of Toner 1, the same operations as in the production example of Toner 1 were performed except that the crystalline polyester resin A, the polymer B, the polymer C, and the heat treatment method were changed as appropriate as shown in Table 3. 2 to 19 were obtained. Table 3 shows the manufacturing conditions and toner physical properties.

<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 materials were weighed so that the above material had the above composition ratio. Then, the mixture was pulverized and mixed for 5 hours by a dry vibration mill using stainless beads having a diameter of 1/8 inch.

・Step 2 (temporary firing step):
The obtained pulverized product was made into pellets of about 1 mm square 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. Then, using a burner type firing furnace, under a nitrogen atmosphere (oxygen concentration: (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 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 (finely calcinated ferrite product).

・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 Kakoki) 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 1300° C. in 2 hours in a nitrogen atmosphere (oxygen concentration 1.00% by volume) in an electric furnace, and then firing was performed at 1150° C. for 4 hours. Then, 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 diameter (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 a methacryloyl group at one end and having a weight average molecular weight of 5000)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3% by mass
Azobisisobutyronitrile 2.0 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 introducing 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 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 so as to be 2.5 parts by mass as a resin component with respect to 100 parts by mass of the magnetic 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 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 19>
Two-component developers 2 to 19 were obtained by changing the toner in the production example of the two-component developer 1. It shows in Table 4.

[Example 1]
As the image forming apparatus, a Canon digital commercial printing printer image RUNNER ADVANCE C9075 PRO remodeling machine is used, and the two-component developer 1 is put in the developing device at the cyan position to form an image having a desired toner amount on the paper. The below-mentioned evaluation was performed. As a modification point, it was changed so that the fixing temperature and the process speed could be set freely. At the time of image output evaluation, 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 are 0.35 mg when the amount of toner of the FFh image (solid image) on the paper is 0.35 mg. It was adjusted to be /cm ² . FFh is a value in which 256 gradations are displayed in hexadecimal notation, 00h is the first gradation of 256 gradations (white background portion), and FFh is the 256th gradation of 256 gradations (solid portion). ..

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

<Evaluation 1: Low temperature fixability>
As an image forming apparatus, a Canon digital commercial printing printer image RUNNER ADVANCE C5051 was used and modified so that the fixing temperature and the process speed could be freely set. A two-component developer is put in the developing device at the cyan position of this modified machine, and the DC voltage V _{DC of} the electrostatic latent image carrier or the electrostatic latent image carrier or the electrostatic capacity of the developer carrier is adjusted so that the toner amount on the paper becomes desired. The charging voltage V _D of the latent image carrier and the laser power were adjusted, and the evaluation described below was performed. The results are shown in Table 5.

Paper: CS-680 (68.0 g/m ² ).
(Sold by Canon Marketing Japan Inc.)
Amount of applied toner on paper: 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
After adjusting 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 so that the amount of toner deposited on the paper is as described above, the process speed is 450 mm/sec, The fixing temperature was set to 130° C. and the low temperature fixing property was evaluated. The value of the image density reduction rate was used as an evaluation index of low temperature fixability. The image density reduction rate is 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 ) was applied to the portion where the image density was measured, and the fixed image was rubbed (5 reciprocations) with the sillbon paper, and the image density was 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 1.5% (very excellent)
B: Density reduction rate of 1.5% or more and less than 2.0% (good)
C: Density reduction rate of 2.0% or more and less than 3.0% (a level that does not cause a problem in the present invention)
D: Density reduction rate of 3.0% or more (not acceptable in the present invention)

<Evaluation 2: Scratch resistance>
By using the two-component developer 1 and the two-component developer C, a secondary color blue image was formed. At this time, an image from 00H (solid white) to FFH image (solid portion) was formed with 16 gradations. In the image formation of the secondary color, the application amount of the FFH image (solid portion) of the two-component developer 1 is set to the application amount at which the image density of a single color is 1.40.
Paper: 270 g (270.0 g/m ² ) of Oce Top Coated Plus Silk
Fixing test environment: normal temperature and normal humidity environment: temperature 23°C/humidity 50%RH

The process speed was set to 450 mm/sec, the fixing temperature was set to 140° C., and the scratch evaluation image was output.

Regarding the resulting 16-gradation secondary color (blue) image, the fourth lightest image including solid white is cut into strips and set in the following device in an upward direction. Only paper is set in the damper part, and a rubbing test is performed under the above conditions.
Rub tester: Gakushin-type friction fastness tester (AB-301)
Weight: 500g (0.5kgf)
Stroke: 10 round trips

Toner was transferred to the rubbed paper (rubbed paper), and the rubbed paper and the white paper were subjected to spectroscan transmission (manufactured by GretagMacbeth) (measurement condition: D ₅₀ viewing angle 2°). ^* , a ^* , and b ^* were measured.
ΔE=(rubbing paper) {(L ^* ) ² +(a ^* ) ² +(b ^* ) ² } ^0.5- (blank paper) {(L ^* ) ² +(a ^* ) ² +(b ^* ) ² } ^0.5 ΔE was compared and used as an index for scratch evaluation.

(Evaluation criteria)
A: less than 3.0% (very excellent)
B: 3.0% or more and less than 6.0% (good)
C: 6.0% or more and less than 10.0% (at a level where there is no problem in the present invention)
D: 10.0% or more (not acceptable in the present invention)

[Examples 2 to 13 and Comparative Examples 1 to 6]
Evaluation was performed in the same manner as in Example 1 except that the two-component developers 2 to 19 were used. The evaluation results are shown in Table 5.

In Comparative Example 1, the ratio of structural units derived from styrene in the vinyl-based polymer unit E in the polymer C was 70% by mass with respect to all structural units in the vinyl-based polymer unit E, and 80% by mass or more. It does not satisfy 100 mass% or less. The interaction of the polymer B with the vinyl polymer unit D is weakened, and the hydrocarbon wax in the toner and the crystalline polyester A are less likely to appear on the image surface. As a result, it is considered that the scratchability evaluation became unacceptable.

In Comparative Example 2, the ratio of the structural unit derived from styrene in the vinyl polymer unit D in the polymer B was 70% by mass with respect to all the structural units in the vinyl polymer unit D, and 80% by mass or more. It does not satisfy 100 mass% or less. The interaction of the polymer C with the vinyl polymer unit E is weakened, and the hydrocarbon wax in the toner and the crystalline polyester A are less likely to appear on the image surface. As a result, it is considered that the scratchability evaluation became unacceptable.

Comparative Example 3 uses a polymer in which a linear alkyl group is not bonded to the terminal of the crystalline polyester unit F of the polymer C. Since the alkyl group promotes recrystallization of the crystalline polyester A in the image surface layer and has an effect of improving scratch resistance, it is considered that the effect was not obtained without the alkyl group.

Comparative Example 4 is a case where the polymer C was not added. The interaction of the polymer B with the vinyl polymer unit D is eliminated, and the hydrocarbon wax and the crystalline polyester A in the toner are less likely to appear on the image surface. As a result, it is considered that the scratchability evaluation became unacceptable.

Comparative Example 5 is a case where neither polymer B nor polymer B was added. The hydrocarbon wax and the crystalline polyester resin A in the toner are less likely to appear on the image surface. As a result, it is considered that the scratchability evaluation became unacceptable.

Comparative Example 6 is a case where the crystalline polyester A and the polymer C were not added. Since the crystalline polyester resin also has an effect on rubbing, it is considered that the rubbing evaluation cannot be accepted only with wax.

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 (4)

A toner containing toner particles containing an amorphous polyester resin, a hydrocarbon wax, a crystalline polyester resin A, a polymer B, and a polymer C,
The polymer B is a polymer in which a vinyl polymer unit D is bonded to a hydrocarbon unit,
In the polymer C, the crystalline polyester unit F is bonded to the end of the vinyl-based polymer unit E, and the linear alkyl group having 6 to 30 carbon atoms is bonded to the end of the crystalline polyester unit F. Is a polymer
The proportion of structural units derived from styrene in the vinyl polymer unit D is 80% by mass or more and 100% by mass or less based on the vinyl polymer unit D,
A toner characterized in that the proportion of structural units derived from styrene in the vinyl polymer unit E is 80% by mass or more and 100% by mass or less based on the vinyl polymer unit E. The toner according to claim 1, wherein the crystalline polyester resin A is a crystalline polyester containing no vinyl polymer unit. 3. The toner according to claim 1, wherein the polymer C has a mass ratio of the vinyl polymer unit E and the crystalline polyester unit F of 35/65 or more and 65/35 or less. The method for producing a toner according to claim 1, wherein the toner composition contains an amorphous polyester resin, a hydrocarbon wax, a crystalline polyester resin A, a polymer B, and a polymer C. Melt-kneading to obtain a melt-kneaded product Melt-kneading process, cooling and solidification of the melt-kneaded product to obtain a pulverized product by pulverizing the cooled solidified product, classification of the pulverized product to obtain toner particles before thermal spheronization A method for producing a toner, comprising a step, a heat treatment step of heat-treating the toner particles before thermal sphering to obtain toner particles, and an external addition step of adding and mixing inorganic fine particles to the toner particles to obtain a toner.

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