JP2017125977A - Toner and production method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that can exhibit high transfer property even in an image output for a long period of time.SOLUTION: The toner is obtained by heat-treating toner particles comprising a polyester resin composition, a colorant and a crystalline polyester resin. The polyester resin composition comprises (i) a polyester resin having a unit at a terminal derived from at least one of an alkyl monoalcohol having 25 or more and 102 or less carbon atoms in average and an alkyl monocarboxylic acid having 25 or more and 102 or less carbon atoms in average, and an aliphatic hydrocarbon having 25 or more and 102 or less carbon atoms in average; and has (ii) a content percentage of the hydrocarbon and the above unit in total of 6.0 mass% or more and 16.0 mass% or less based on the mass of the polyester resin composition.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, and a method for producing the toner.

  In recent years, with the widespread use of electrophotographic full-color image forming apparatuses, higher image quality has been demanded. In order to achieve high image quality, it is required to increase the transfer efficiency of the toner on the electrostatic latent image carrier to the intermediate transfer member and the transfer efficiency of the toner on the intermediate transfer member to the paper.

  Therefore, in order to improve the transfer efficiency of the toner, a proposal has been made to increase the circularity of the toner by heat-treating the toner (see Patent Document 1). By increasing the circularity of the toner, the contact area of the toner with respect to the surface of the electrostatic latent image carrier and the surface of the intermediate transfer member can be reduced, and the adhesive force can be reduced. Transfer efficiency to paper can be increased. Furthermore, in the transfer step, the electric field formed is more likely to be closer to a true sphere, and the electric field acts more uniformly on the toner, so that the transfer efficiency of the toner is increased, and by increasing the circularity of the toner, A certain effect was obtained.

  However, the heat-treated toner increases the circularity of the toner, while the highly adhesive wax is eluted near the surface of the toner particles. For this reason, the elution of wax becomes a factor that reduces the effect of improving the transfer efficiency of the heat-treated toner, and there is an aspect in which the effect of improving the transfer efficiency of the heat-treated toner is not fully utilized. Furthermore, in recent years, there is also a demand for multimedia compatibility that can support various media such as thick paper and thin paper as well as plain paper. As the thick paper, not only a thick paper having a flat surface but also a paper having a relatively low surface smoothness such as an embossed paper or a rough paper having irregularities on the front surface and both front and back surfaces is used. Since it is difficult to apply a sufficient transfer pressure to these papers, a part of the toner on the intermediate transfer member is not transferred, and image quality defects called white spots may occur. Therefore, there is a need for a toner with further improved transfer efficiency.

  In order to further improve transfer efficiency, a proposal has been made in which inorganic fine particles having a large particle size serving as a spacer are fixed to the surface of toner particles (see Patent Document 2). By using inorganic fine particles as spacers at the interface between the toner and the electrostatic latent image carrier and between the toner and the intermediate transfer member, it is difficult to be affected by the wax that has eluted near the surface of the toner particles. As a result, the transfer efficiency can be increased.

  However, when an image is output for a long period of time in a high temperature and high humidity environment, the temperature in the image forming apparatus main body rises, so that the wax near the surface of the toner particles tends to be soft. As a result, the inorganic fine particles having a large particle size that have become spacers are embedded in the toner particles, and transfer efficiency may be reduced.

  In view of the above, there is a need for a toner that can satisfy high transferability even in long-term image output.

JP 2013-15830 A JP 2013-47754 A

  An object of the present invention is to provide a toner that solves the above problems. Specifically, an object of the present invention is to provide a toner that can exhibit high transferability even in long-term image output.

  As a result of intensive studies, the present inventors have found a toner that can exhibit high transferability even during long-term image output.

The present invention is a toner obtained by heat-treating toner particles containing an amorphous polyester resin, a wax, a colorant, and a crystalline polyester resin,
The toner has inorganic fine particles on the surface of the toner particles;
The amorphous polyester resin is
An alkyl monoalcohol having a peak carbon number of 25 to 102, and
Having a unit derived from at least one of alkyl monocarboxylic acids having a peak carbon number of 25 or more and 102 or less at the end of the molecular chain;
The wax has an aliphatic hydrocarbon having a peak carbon number of 25 to 102,
An aliphatic hydrocarbon having a peak carbon number of 25 to 102 in the toner particles;
A unit derived from an alkyl monoalcohol having a peak carbon number of 25 or more and 102 or less present at the terminal of the amorphous polyester resin; and
The total content of units derived from the alkyl monocarboxylic acid having a peak carbon number of 25 or more and 102 or less present at the terminal of the amorphous polyester resin is based on the total mass of the amorphous polyester resin and the wax. 6.0 mass% or more and 16.0 mass% or less,
The crystalline polyester resin has an ester unit derived from an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms.
This invention relates to a toner.

Furthermore, the present invention includes a step of melt-kneading a toner composition containing an amorphous polyester resin, a wax, a colorant, and a crystalline polyester resin to obtain a melt-kneaded product, and pulverizing and classifying the melt-kneaded product. In the toner production method, the amorphous polyester resin has an alkyl monoalcohol having a peak carbon number of 25 or more and 102 or less, and a peak carbon number of 25. A unit derived from at least one of alkyl monocarboxylic acids of 102 or less at the end of the molecular chain, and the wax has an aliphatic hydrocarbon having a peak carbon number of 25 or more and 102 or less, and the peak carbon number is 25 or more and 102 or less aliphatic hydrocarbons, and the peak carbon number existing at the terminal of the amorphous polyester resin is 25 or more and 102 or less. The total content of the units derived from the rumonoalcohol and the units derived from the alkyl monocarboxylic acid having a peak carbon number of 25 or more and 102 or less present at the terminal of the amorphous polyester resin is such that the amorphous polyester resin and The crystalline polyester resin is an aliphatic diol having 2 to 22 carbon atoms and an aliphatic diol having 2 to 22 carbon atoms, based on the total mass of the wax. A resin having an ester unit derived from an aliphatic dicarboxylic acid,
The present invention relates to a toner manufacturing method, wherein a hot air temperature in the heat treatment step is 100 ° C. or higher and 300 ° C. or lower.

  By using the toner of the present invention, high transferability can be ensured even during long-term image output.

It is a figure of the thermal spheronization processing apparatus used for this invention.

  Hereinafter, embodiments of the invention will be described in detail.

  As described above, when image output is performed for a long time in a high-temperature and high-humidity environment, the wax in the vicinity of the surface of the toner particles becomes soft, and the large-sized inorganic fine particles that have been spacers are embedded inside the toner particles. In some cases, the transfer efficiency is reduced.

  In order to improve the transferability, the inventors of the present invention need to suppress the wax that elutes near the surface of the toner particles while increasing the circularity of the toner. And found the present invention.

  The present inventors paid attention to a crystalline polyester resin used as a toner softening agent. The inventors of the present invention have made extensive studies and the crystalline polyester resin is an ester compound of an aliphatic hydrocarbon diol and an aliphatic dicarboxylic acid, and has a relatively low polarity, and therefore has high affinity with wax. And found that the wax can be trapped. Further, the present inventors have found that the crystalline polyester resin has a high molecular weight relative to the wax even though the polarity is low, so that it is difficult to elute near the surface of the toner particles even when heat treatment is performed. In other words, by utilizing the affinity between the crystalline polyester resin and the wax, it is difficult to quantify the degree of elution suppression even after heat treatment, but it is possible to suppress the elution of wax near the surface of the toner particles. I found it.

  However, as described above, the crystalline polyester resin tends to exist as a domain in the toner particle because of its high molecular weight. Accordingly, since there are few contacts with the wax, elution of the wax in contact with the crystalline polyester resin to the vicinity of the surface of the toner particles can be suppressed by heat treatment. However, there is a problem that the elution of the wax that is not in contact with the crystalline polyester resin to the vicinity of the surface of the toner particles cannot be suppressed.

  Therefore, the present inventors have made further studies, and at the end of the polyester resin as the binder resin, a unit derived from an alkyl monoalcohol having a peak carbon number of 25 or more and 102 or less, and a peak carbon number of 25 or more and 102. It has been found that the crystalline polyester resin can be finely dispersed in the toner particles by containing a unit derived from the following alkyl monocarboxylic acid. This is because the alkyl monoalcohol and alkyl monocarboxylic acid incorporated in the amorphous polyester resin become the nucleus when the crystalline polyester resin is crystallized, so that it can inevitably be finely dispersed and crystallized. Because. The crystalline polyester resin finely dispersed in the toner particles can form contacts with all the wax domains, and the elution of the wax to the vicinity of the surface of the toner particles due to heat treatment can be suppressed.

[Amorphous polyester resin]
The amorphous polyester resin used in the toner of the present invention is a resin having an irregular molecular chain and a glass transition temperature but no melting point. Monomers used in the ester unit of the amorphous polyester resin include polyhydric alcohols (divalent or trivalent or higher alcohols), polyvalent carboxylic acids (divalent or trivalent or higher carboxylic acids), and acid anhydrides thereof. Alternatively, lower alkyl esters thereof are used. Here, when preparing a branched polymer, it is effective to partially crosslink in the molecule | numerator of binder resin, and it is preferable to use the polyfunctional compound more than trivalence for that purpose. Therefore, it is preferable to include a trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester, and / or a trivalent or higher alcohol as a raw material monomer for the ester unit.

  Furthermore, the amorphous polyester resin is composed of an alkyl monoalcohol having a peak carbon number (the carbon number of most molecules in the carbon number distribution of the compound molecule) of 25 to 102, and an alkyl monocarboxylic acid having a peak carbon number of 25 to 102. It has a unit derived from at least one of the above at the end of the molecular chain.

  As the alkyl monoalcohol having a peak carbon number of 25 or more and 102 or less, any of primary, secondary, tertiary, saturated and unsaturated can be used. Among these, primary saturated alcohols are preferable from the viewpoint of promoting crystallization of the crystalline polyester resin. Examples thereof include saturated alcohols such as pentacosanol, seryl alcohol (hexacosanol), heptacosanol, octacosanol, nonacosanol, melicyl alcohol (triacontanol), and gedyl alcohol (tetratriacontanol).

  As the alkyl monocarboxylic acid having a peak carbon number of 25 or more and 102 or less, any of primary, secondary, tertiary, saturated and unsaturated can be used. Among these, primary saturated fatty acids are preferable from the viewpoint of promoting crystallization of the crystalline polyester resin. Examples thereof include saturated fatty acids such as pentacosanoic acid, serotic acid (hexacosanoic acid), heptacosanoic acid, montanic acid (octacosanoic acid), nonancosanoic acid, melicic acid (triacontanoic acid), and tetratriacontanoic acid.

  Examples of the alkyl monoalcohol having a peak carbon number of 25 to 102 and the alkyl monocarboxylic acid having a peak carbon number of 25 to 102 in the present invention include the following. For example, a modified wax produced through a modification step for producing a wax having a hydroxy group or a carboxyl group from an aliphatic hydrocarbon wax can also be used. The step of modifying the aliphatic hydrocarbon wax is not particularly limited, and examples thereof include a method of hydrolyzing a boric acid ester of the wax from an aliphatic hydrocarbon wax to generate a wax having a hydroxy group. . In this case, the modified wax may be a mixture in which alcohols having a valence of 0 and a polyvalent component are mixed, but a monovalent modified wax is more preferable from the viewpoint of promoting crystallization of the crystalline polyester resin.

  The hydroxyl value of the alcohol-modified wax is preferably from 100 to 150 mgKOH / g, more preferably from 120 to 140 mgKOH / g.

  The acid value of the acid-modified wax is preferably 30 to 50 mgKOH / g, more preferably 40 to 45 mgKOH / g.

  The preferable peak carbon number of the alkyl monoalcohol having a peak carbon number of 25 to 102 and the alkyl monocarboxylic acid having a peak carbon number of 25 to 102 in the present invention is preferably 30 to 80, more preferably 35 to 50. It is as follows. When the peak carbon number is in the above range, the amorphous polyester resin can be satisfactorily reacted, and the modification rate of the hydroxy group or carboxyl group is improved. Furthermore, since the molecular chain serving as a nucleus when the crystalline polyester resin is crystallized has a sufficient length, an effect of improving the fine dispersibility of the crystalline polyester resin can be obtained. As a result, the elution of the wax to the vicinity of the toner surface due to the heat treatment of the toner particles can be suppressed, so that high transferability can be satisfied even during long-term image output.

  When the peak carbon number is 103 or more, it becomes difficult to react with the amorphous polyester resin, the modification rate of the hydroxy group or carboxyl group decreases, and it tends to exist as a free monomer. Therefore, the effect of improving the fine dispersibility of the crystalline polyester resin in the toner particles cannot be obtained. As a result, the elution of the wax to the vicinity of the surface of the toner particles due to the heat treatment of the toner particles cannot be suppressed. Further, since the amount of free monomer that is a low molecule increases, the storage stability of the toner also deteriorates.

  When the peak carbon number is 24 or less, it is easy to react with the amorphous polyester resin, but since the straight chain length of the molecule is short, it becomes difficult to become the nucleus of the crystalline polyester resin. Therefore, the effect of improving the fine dispersibility of the crystalline polyester resin in the toner particles cannot be obtained. As a result, the elution of the wax to the vicinity of the surface of the toner particles due to the heat treatment of the toner particles cannot be suppressed.

  The aliphatic hydrocarbon is an aliphatic hydrocarbon having a peak carbon number of 25 or more and 102 or less. In the present invention, the aliphatic hydrocarbon is derived from wax. The aliphatic hydrocarbon is present in a dispersed state in the amorphous polyester resin.

  Here, in the present invention, a peak derived from an aliphatic hydrocarbon having a peak carbon number of 25 or more and 102 or less, a unit derived from an alkyl monoalcohol having a peak carbon number of 25 or more and 102 or less at the terminal of the polyester resin, and a terminal of the polyester resin. The total content ratio of units derived from alkyl monocarboxylic acids having a peak carbon number of 25 to 102 is 6.0% by mass to 16.0% by mass based on the mass of the amorphous polyester resin and wax. The following is preferable. More preferably, it is the case of 9.0 mass% or more and 13.0 mass% or less. When the content is in the above range, it means that an appropriate amount of wax is contained, so that hot offset resistance and low temperature fixability can be satisfied. Furthermore, since it also means that a unit derived from a proper alkyl monoalcohol and / or a unit derived from a proper alkyl monocarboxylic acid is contained, the effect of improving the fine dispersibility of the crystalline polyester resin is improved. can get. As a result, the elution of the wax to the vicinity of the surface of the toner particles due to the heat treatment of the toner particles can be suppressed, so that high transferability can be satisfied even during long-term image output.

  When the content exceeds 16.0% by mass due to an increase in wax, all the wax cannot be trapped because the wax contains more wax than the crystalline polyester resin can trap. As a result, when the toner particles are heat-treated, the elution of the wax to the vicinity of the surface of the toner particles due to the heat treatment cannot be suppressed.

  All alkyl monoalcohols and / or alkylmonocarboxylic acids when the content exceeds 16.0% by weight due to an increase in units derived from the proper alkyl monoalcohol and / or units derived from the proper alkyl monocarboxylic acid It becomes difficult to react with the binder resin. As a result, the amount of free monomer, which is a low molecule, increases, and the storage stability of the toner also deteriorates.

  When the content is less than 6.0% by mass due to the reduction of the wax, the resistance to hot offset deteriorates and the fixing property cannot be satisfied.

  When the content is less than 5.0% by mass due to a decrease in units derived from alkyl monoalcohol having an appropriate molecular chain and / or units derived from alkyl monocarboxylic acid having an appropriate molecular chain, Since there are few long chain parts used as the nucleus of a polyester resin, the effect which improves the fine dispersibility of crystalline polyester resin is not acquired. As a result, the elution of the wax to the vicinity of the toner surface due to the heat treatment of the toner particles cannot be suppressed.

  The toner of the present invention has an endothermic peak having a peak top of 60 ° C. or more and 90 ° C. or less in a temperature-endotherm curve obtained by a differential scanning calorimeter (DSC). Furthermore, the endothermic amount calculated from the peak area of the endothermic peak is preferably 10.0 J / g or less. If the endothermic amount is in the above range, it means that an excessive amount of wax is not contained. Further, since the alkyl monoalcohol and / or alkyl monocarboxylic acid according to the present invention surely reacts with the amorphous polyester resin and does not exist as a free component, the fixing property and the high transfer property are satisfied. be able to.

  When the endothermic amount is 10.0 J / g or more, it means that an excessive amount of wax is contained or that there are many free monomers of alkyl monoalcohol and / or alkyl monocarboxylic acid. Therefore, the elution of the wax to the vicinity of the surface of the toner particles due to the heat treatment of the toner particles cannot be suppressed, and the storage stability of the toner is deteriorated.

  The alkyl monoalcohol having a peak carbon number of 25 to 102 and the alkyl monocarboxylic acid having a peak carbon number of 25 to 102 of the present invention are added simultaneously with other monomers used in the unit constituting the amorphous polyester resin. However, it is preferable to perform condensation polymerization. Thereby, it can introduce | transduce into the unit of an amorphous polyester resin reliably.

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

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

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

  Examples of the trivalent 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 divalent 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 amorphous polyester resin, the following polyvalent carboxylic acid monomers can be used.

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

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

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

  The amorphous polyester resin used in the toner of the present invention may be a hybrid resin containing other resin components excluding the crystalline resin component as long as the amorphous polyester resin is a main component. For example, a hybrid resin of an amorphous polyester resin and a vinyl resin can be given. As a method of obtaining a reaction product of a vinyl resin or vinyl copolymer unit and an amorphous polyester resin, such as a hybrid resin, a monomer capable of reacting with each of the vinyl resin, vinyl copolymer unit and polyester resin Where a polymer containing a component is present, a method of conducting a polymerization reaction of one or both of the resins is preferred.

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

  In the present invention, if a non-crystalline polyester resin is a main component as a binder resin, in addition to the above vinyl resins, various resin compounds conventionally known as binder resins may be used in combination. Can do. Examples of such resin compounds include phenol resin, natural resin-modified phenol resin, natural resin-modified male resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene. Examples thereof include resins, polyvinyl butyral, terpene resins, coumaroindene resins, and petroleum resins.

  The peak molecular weight of the amorphous polyester resin is preferably 3500 or more and 20000 or less from the viewpoint of low-temperature fixability and hot offset resistance. The acid value of the amorphous polyester resin is preferably 15 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment. Furthermore, the hydroxyl value of the amorphous polyester resin of the present invention is preferably 2 mgKOH / g or more and 20 mgKOH / g or less from the viewpoint of low-temperature fixability and storage stability.

  The amorphous polyester resin may be used by mixing the low molecular weight binder resin B and the high molecular weight binder resin A together. The content ratio (A / B) of the high molecular weight binder resin A and the low molecular weight binder resin B is 10/90 or more and 60/40 or less in terms of mass, from the viewpoint of low temperature fixability and hot offset resistance. To preferred.

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

  The peak molecular weight of the low molecular weight binder resin B is preferably 3500 or more and 7000 or less from the viewpoint of low-temperature fixability. The acid value of the low molecular weight binder resin is preferably 10 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment.

[Crystalline polyester resin]
The toner of the present invention contains a crystalline polyester resin as a softening agent.

  A crystalline resin is a resin in which molecular chains are regularly arranged and have a glass transition temperature and a melting point. In the toner of the present invention, the crystalline polyester resin contained in the toner particles is a resin having an ester unit derived from an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms. . In production, it is obtained by polycondensation reaction between an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid monomer composition having 2 to 22 carbon atoms.

  Among these, as a result of intensive studies by the present inventors, a crystalline polyester resin comprising an ester unit derived from an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms as a constituent element is obtained. From the viewpoint of low-temperature fixability and storage stability, it is preferable. The reason why the low-temperature fixability of the toner is improved by using the crystalline polyester resin is that the amorphous polyester resin and the crystalline polyester resin are compatible with each other, and the interval between the molecular chains of the amorphous polyester resin is increased. This is because the intermolecular force can be weakened. As a result, the glass transition temperature (Tg) is drastically lowered and the melt viscosity is lowered. Therefore, the low temperature fixability tends to be improved by increasing the compatibility between the amorphous polyester resin and the crystalline polyester resin. In order to increase the compatibility between the amorphous polyester resin and the crystalline polyester resin, the number of carbon atoms of the aliphatic diol and / or aliphatic dicarboxylic acid as a monomer constituting the crystalline polyester resin is shortened, The concentration will increase and the polarity will increase. On the other hand, it is necessary to ensure storage stability in use and transportation in a high-temperature and high-humidity environment even for a toner whose Tg is significantly reduced. For that purpose, when the toner is exposed to such an environment, it is necessary to recrystallize the crystalline polyester resin in the compatible toner particles and return the Tg of the toner to the Tg of the binder resin. There is. Here, if the ester group concentration of the crystalline polyester resin is high and the compatibility between the amorphous polyester resin and the crystalline polyester resin is too high, it becomes difficult to recrystallize the crystalline polyester resin, and the toner is stored. Sexuality will deteriorate. From the above, it is preferable to use an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms as the monomer structure of the crystalline polyester resin capable of achieving both low temperature fixability and storage stability. I found.

  The aliphatic diol having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but is preferably a linear (more preferably linear) aliphatic diol, , Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, Pentamethylene glycol, hexamethylene glycol (hexanediol), octamethylene glycol, nonamethylene glycol, decamethylene glycol (decane diol), neopentyl glycol, dodecamethylene glycol (dodecane diol) Is lower. Among these, ethylene glycol, diethylene glycol, linear aliphatic, such as 1,4-butanediol, and 1,6-hexanediol, alpha, .omega.-diol is preferably exemplified.

  Among the alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more is an alcohol selected from aliphatic diols having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms).

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

  Furthermore, in this invention, you may use a monovalent alcohol to such an extent that the characteristic of crystalline polyester resin is not impaired. Examples of the monovalent 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 (hexanedioic acid), pimelic acid, peric acid, glutaconic acid, nonanedicarboxylic acid, decanedicarboxylic acid (decanedioic acid), undecanedicarboxylic acid, Examples include dodecanedicarboxylic acid (dodecanedioic acid), maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, and hydrolyzed acid anhydrides or lower alkyl esters thereof.

  Of these, hexanedioic acid, decanedioic acid, and dodecanedioic acid are particularly preferred.

  In the present invention, among the carboxylic acid components, preferably 50% by mass or more, more preferably 70% by mass or more is an aliphatic dicarboxylic acid having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms). The carboxylic acid chosen.

  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; n-dodecyl succinic acid, n-dodecenyl succinic aliphatic carboxylic acid; cyclohexane dicarboxylic acid Examples thereof include alicyclic carboxylic acids such as acids, and these acid anhydrides or lower alkyl esters are also included. Among the other carboxylic acid monomers, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, Aromatic carboxylic acids such as 2,4-naphthalenetricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2 -Aliphatic carboxylic acids of methylenecarboxypropane, including derivatives of these acid anhydrides or lower alkyl esters.

  Furthermore, in this invention, you may contain monovalent carboxylic acid to such an extent that the characteristic of crystalline polyester resin is not impaired. Examples of monovalent carboxylic acids include monocarboxylic acids such as benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, and octanoic acid. Is mentioned.

  The crystalline polyester resin according to the present invention has a unit derived from at least one of an aliphatic monocarboxylic acid having 10 to 20 carbon atoms and an aliphatic monoalcohol having 10 to 20 carbon atoms at the end of the molecular chain. The case is preferred. In production, these monomer compositions are obtained by a condensation reaction. Use of such a crystalline polyester resin is preferable from the viewpoints of low-temperature fixability and storage stability. Generally, in the recrystallization of a crystalline polyester resin, a crystal grows starting from a crystal nucleus. Therefore, by adding at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 10 to 20 carbon atoms and an aliphatic monoalcohol having 10 to 20 carbon atoms to the end of the molecular chain, That is the crystal nucleus. Accordingly, recrystallization of the crystalline polyester resin can be promoted, so that the storage stability is improved. Furthermore, when the carbon number is in the above range, it is easy to condense at the end of the molecular chain, and it is not present as a free monomer, which is preferable from the viewpoint of storage stability. Furthermore, when the carbon number is in the above range, the compatibility between the crystalline polyester resin and the amorphous polyester binder resin is not impaired, and this is preferable from the viewpoint of low-temperature fixability.

  Further, one or more aliphatic compounds selected from the group consisting of the aliphatic monocarboxylic acid and the aliphatic monoalcohol are 1.0 mol% or more and 10.0 mol% based on the raw material monomer of the crystalline polyester resin. % Or less is preferable. More preferably, it is 4.0 mol% or more and 8.0 mol% or less. It is preferable for the amount of the aliphatic compound to be in the above range since an appropriate amount of crystal nuclei can be present without inhibiting the low-temperature fixability.

  Examples of the aliphatic monocarboxylic acid having 10 to 20 carbon atoms include capric acid (decanoic acid), undecyl acid, lauric acid (dodecanoic acid), tridecyl acid, myristic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid). ), Margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadecylic acid, arachidic acid (icosanoic acid).

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

  In the present invention, the crystalline polyester resin is preferably used in an amount of 3 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the binder resin from the viewpoint of low temperature fixability and chargeability in a high temperature and high humidity environment.

  The crystalline polyester resin in the present invention can be produced according to a normal polyester synthesis method. For example, the carboxylic acid monomer and the alcohol monomer are esterified or transesterified, and then subjected to a polycondensation reaction under reduced pressure or by introducing nitrogen gas in accordance with a conventional method. A polyester resin can be obtained. Thereafter, the desired crystalline polyester resin can be obtained by further adding the aliphatic compound and performing an esterification reaction.

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

  The polycondensation reaction can be carried out using a conventional polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide. . The polymerization temperature and the catalyst amount are not particularly limited, and may be determined appropriately.

  In the esterification or transesterification reaction or polycondensation reaction, all monomers are charged together to increase the strength of the resulting crystalline polyester, or divalent monomers are first reacted to reduce low molecular weight components. Then, a method of adding a trivalent or higher monomer and reacting the monomer may be used.

[wax]
Examples of the wax used in the toner of the present invention include the following. Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof Products; waxes mainly composed of fatty acid esters such as carnauba wax; fatty acid esters such as deoxidized carnauba wax partially or fully deoxidized. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol , Saturated alcohols such as merisyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, and carnauvir alcohol , Esters with alcohols such as ceryl alcohol, melyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylenebisstearic acid amide, ethylene Saturated fatty acid bisamides such as scapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N 'Unsaturated fatty acid amides such as dioleyl sebacic acid amide; m-xylene bis stearic acid amide, N, N' aromatic bisamides such as distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate , Aliphatic metal salts such as magnesium stearate (generally referred to as metal soap); waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; behenine Acid monoglyceride Una fatty acids with polyhydric alcohols of the partial ester; methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable fats and oils.

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

  In the present invention, the wax is preferably used in an amount of 1 to 20 parts by mass per 100 parts by mass of the binder resin.

  Moreover, in the endothermic curve at the time of temperature rise measured with a differential scanning calorimetry (DSC) apparatus, 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 of the toner and the hot offset resistance can be achieved.

[Colorant]
Examples of the colorant that can be contained in the toner include the following.

  Examples of the black colorant include carbon black; those prepared by using a yellow colorant, a magenta colorant, and a cyan colorant and adjusting the color to black. As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.

  Examples of the magenta toner pigment include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.

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

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

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

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

[Charge control agent]
The toner may contain a charge control agent as necessary. As the charge control agent contained in the toner, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.

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

[Inorganic particles]
The toner of the present invention has inorganic fine particles on the surface of the toner particles. The inorganic fine particles are of course externally added to the surface of the toner particles, but may be internally added. As the external additive, inorganic fine particles such as silica, titanium oxide, and aluminum oxide are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof. As an external additive for improving fluidity, inorganic fine particles having a specific surface area of 50 m 2 / g or more and 400 m 2 / g or less are preferable. For stabilization of durability, the specific surface area is 10 m 2 / g or more and 50 m 2 / g or less. Inorganic fine particles are preferable. In order to achieve both improvement in fluidity and stabilization of durability, inorganic fine particles having a specific surface area in the above range may be used in combination.

  The external additive is preferably used in an amount of 0.1 to 10.0 parts by mass with respect to 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 also be used as a one-component developer, but in order to further improve dot reproducibility, it can be mixed with a magnetic carrier and used as a two-component developer. Is preferable in that it is obtained.

  As the magnetic carrier, for example, iron powder whose surface is oxidized or unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth, Magnetic materials dispersed resin carriers (so-called resin carriers) containing magnetic materials such as alloy particles, oxide particles, and ferrite, and magnetic materials and binder resins that hold the magnetic materials in a dispersed state are generally known. Can be used.

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

[Production method]
As a method for producing toner particles, a pulverization method in which a toner composition containing an amorphous polyester resin, a wax, a colorant, and a crystalline polyester resin is melt-kneaded, the melt-kneaded product is cooled, and pulverized and classified is preferable.

  Hereinafter, a toner manufacturing procedure using the pulverization method will be described.

  In the raw material mixing step, for example, amorphous polyester resin, wax, colorant, crystalline polyester resin, and if necessary, charge control agent and other components are weighed and blended as materials constituting the toner particles. , Mix. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano-hybrid (manufactured by Nippon Coke Industries, Ltd.).

  Next, the mixed material is melt-kneaded to disperse the wax and other materials in the binder resin. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. From the advantage of continuous production, a single-screw or twin-screw extruder is the mainstream. It has become. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko), twin screw extruder (manufactured by Kay Sea Kay Co., Ltd.) ), Co-kneader (manufactured by Buss), kneedex (manufactured by Nippon Coke Industries Co., Ltd.), and the like. Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

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

  After that, if necessary, such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification type turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) The toner particles are obtained by classification using a classifier or a sieving machine.

  Thereafter, surface treatment of the toner particles by heating is performed to increase the circularity of the toner. For example, the surface treatment can be performed with hot air using the surface treatment apparatus shown in FIG.

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

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

  Hot air for heat-treating the supplied mixture is supplied from the hot air supply means 7 and is introduced into the processing chamber by swirling the hot air in a spiral manner by the swirling member 13 for swirling the hot air. As the structure, the turning member 13 for turning hot air has a plurality of blades, and the turning of hot air can be controlled by the number and angle of the blades. The hot air supplied into the processing chamber preferably has a temperature at the outlet of the hot air supply means 7 (hereinafter referred to as hot air temperature) of 100 ° C. or higher and 300 ° C. or lower. More preferably, it is the range of 120 degreeC or more and 200 degrees C or less. If the temperature at the outlet of the hot air supply means is within the above range, it is possible to uniformly spheroidize the toner particles while suppressing fusing and coalescence of the toner particles due to overheating of the mixture. Become.

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

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

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

  Further, an external additive is applied to the surface of the toner particles as necessary. As a method of externally adding the external additive, a predetermined amount of classified toner particles and various known external additives are mixed, and a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, Examples thereof include a method of stirring and mixing using a mixing apparatus such as Mechano Hybrid (manufactured by Nippon Coke Industries Co., Ltd.) and Nobilta (manufactured by Hosokawa Micron Corporation) as an external additive.

  When the average circularity of particles having an equivalent circle diameter of 1.985 μm or more and less than 39.69 μm measured by a toner flow-type particle image measuring device is 0.950 or more and 1.000 or less, transferability and cleaning properties are improved. It is preferable because it is compatible.

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

[Measurement of molecular weight of alkyl monoalcohol and alkyl monocarboxylic acid by GPC]
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Column: TSKgel GMHHR-HHT 7.8 cmI. D x 30cm2 (Tosoh Corporation)
Detector: RI for high temperature
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.05% ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml injection of 0.1% sample A molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Furthermore, it calculates by carrying out polyethylene conversion with the conversion formula derived | led-out from the Mark-Houwink viscosity formula.

[Measurement of acid value of alkyl monoalcohol and alkyl monocarboxylic acid]
Apparatus and instrument: Erlenmeyer flask (300 ml), burette (25 ml), water bath or hot plate Reagent: 0.1 kmol / m ³ hydrochloric acid, 0.1 kmol / m ³ potassium hydroxide ethanol solution (standard is 0.1 kmol / Take 25 ml of m ³ hydrochloric acid in an Erlenmeyer flask using a whole pipette, add a phenolphthalein solution, titrate with 0.1 kmol / m ³ potassium hydroxide ethanol solution, and determine the factor from the amount required for neutralization). Phenolphthalein solution, solvent (diethyl ether and ethanol (99.5) mixed at a volume ratio of 1: 1 or 2: 1. These were added just a few drops of phenolphthalein solution as an indicator just before use. Neutralize with 1 kmol / m ³ potassium hydroxide ethanol solution.)

・ Measurement method:
(A) 1-20 g of hydrocarbon wax (a) is precisely weighed into an Erlenmeyer flask.
(B) Add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well on a water bath until the hydrocarbon wax is completely dissolved.
(C) Titrate with a 0.1 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the light red color of the indicator lasts for 30 seconds.

・ Calculation:
A = 5.611 × B × f / S where A: acid value (mgKOH / g)
B: Amount of 0.1 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml)
f: Factor of 0.1 kmol / m ³ potassium hydroxide ethanol solution S: Mass (g) of hydrocarbon wax (a)
5.611: Formula weight of potassium hydroxide 56.11 × 1/10

[Measurement of hydroxyl value of alkyl monoalcohol and alkyl monocarboxylic acid]
・ Apparatus and instruments: graduated cylinder (100 ml), total pipette (5 ml), flat bottom flask (200 ml), glycerin bath ・ Reagent: acetylating reagent (25 g of acetic anhydride is added to 100 ml flask and pyridine is added to make 100 ml in total. Shake well)), phenolphthalein solution, 0.5 kmol / m ³ potassium hydroxide ethanol solution

Measurement method (a) A hydrocarbon-based wax is precisely weighed into a 0.5 to 6.0 g flat bottom flask, and 5 ml of an acetylating reagent is added to the whole using a pipette.
(B) Place a small funnel on the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at a temperature of 95-100 ° C. and heat. In order to prevent the temperature of the neck of the flask from rising due to the heat of the glycerin bath, a cardboard disc with a round hole in it is put on the base of the neck of the flask.
(C) After 1 hour, the flask is removed from the glycerin bath, allowed to cool, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride.
(D) Further, in order to complete the decomposition, the flask is heated again in the glycerin bath for 10 minutes, and after cooling, the funnel and the wall of the flask are washed with 5 ml of ethanol (95).
(E) A few drops of phenolphthalein solution is added as an indicator, and titrated with 0.5 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the indicator is light red for about 30 seconds.
(F) In the blank test, (a) to (e) are performed without adding the hydrocarbon wax (a).
(G) If the sample is difficult to dissolve, add a small amount of pyridine, or add xylene or toluene to dissolve.

Calculation A = [{(BC) × 28.05 × f} / S] + D where A: hydroxyl value (mgKOH / g)
B: Amount (ml) of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for the blank test
C: Amount of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml)
f: Factor of 0.5 kmol / m ³ potassium hydroxide ethanol solution S: Mass of hydrocarbon wax (g)
D: Acid value 28.05: Formula weight of potassium hydroxide 56.11 × 1/2

[Measurement of ester value of alkyl monoalcohol and alkyl monocarboxylic acid]
Calculated by the following formula.
(Ester value) = (Saponification value)-(Acid value)
Measurement of saponification value ・ Apparatus and instruments: Erlenmeyer flask (200 to 300 ml), air cooler (outer diameter 6 to 8 mm, length 100 cm glass tube or recirculating cooler, all connected to the mouth of the Erlenmeyer flask Possible), water bath, sand bath or hot plate (can be adjusted to a temperature of about 80 ° C.), burette (50 ml), total pipette (25 ml)
Reagent: 0.5 kmol / m ³ hydrochloric acid, 0.5 kmol / m ³ potassium hydroxide ethanol solution phenolphthalein solution

Measurement method (a) 1.5 to 3.0 g of hydrocarbon wax (a) is precisely weighed to an order of 1 mg in an Erlenmeyer flask.
(B) Add 25 ml of 0.5 kmol / m ³ potassium hydroxide ethanol solution using a pipette.
(C) Attach an air cooler to the Erlenmeyer flask and allow it to react by gently heating on a water bath, sand bath or hot plate for 30 minutes with occasional shaking. When heating, the heating temperature is adjusted so that the circulating ethanol ring does not reach the top of the air cooler.
(D) Immediately after the reaction is completed, the inner wall is washed by spraying a small amount of water or a mixed solution of xylene: ethanol = 1: 3 from the top of the air cooler before the contents are hardened into agar. After that, remove the air cooler.
(E) Add 1 ml of phenolphthalein solution as an indicator, titrate with 0.5 kmol / m ³ hydrochloric acid, and when the light red color of the indicator does not appear for about 1 minute, the end point is set.
(F) In the blank test, (a) to (e) are performed without adding the hydrocarbon wax (a).
(G) If the sample is difficult to dissolve, dissolve it in advance using xylene or a xylene-ethanol mixed solvent.

Calculation A = {(BC) × 28.05 × f} / S where A: saponification value (mgKOH / g)
B: Amount of 0.5 kmol / m ³ hydrochloric acid used for the blank test (ml)
C: Amount of 0.5 kmol / m ³ hydrochloric acid used for titration (ml)
f: Factor of 0.5 kmol / m ³ hydrochloric acid S: Mass (g) of hydrocarbon wax (a)
28.05: Formula weight of potassium hydroxide 56.11 × 1/2

[Molecular weight measurement of resin by GPC]
The molecular weight distribution of the THF soluble part of the resin is measured by gel permeation chromatography (GPC) as follows.

First, the toner is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by 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, 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 Tosoh Corporation) are used.

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

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

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

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

[Measurement of glass transition temperature (Tg) of resin and endothermic amount of toner]
The glass transition temperature of the resin is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 5 mg of resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the heating rate is 10 ° C. between a measurement range of 30 ° C. and 200 ° C. Measure at / min. The temperature is raised to 180 ° C. and held for 10 minutes, then the temperature is lowered to 30 ° C., and then the temperature is raised again. In the second temperature raising process, a specific heat change is obtained in the temperature range of 30 ° C. or more and 100 ° C. or less. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature (Tg) of the resin. Further, the endothermic amount of the toner is the area of the maximum endothermic peak of the temperature-endothermic curve in the temperature range of 60 ° C. to 90 ° C. in the temperature-endothermic curve obtained in the same manner as the Tg measurement method for the resin. Ask from.

[Method for Measuring Weight Average Particle Size (D4) of Toner Particles]
The weight average particle diameter (D4) of the toner particles is measured with a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. Measured data with 25,000 effective measurement channels using the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (Beckman Coulter, Inc.) for condition setting and measurement data analysis Analyze and calculate.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

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

  In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

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

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion exchange water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkiki Bios Co., Ltd.) having an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned 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. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

[Measurement method of average circularity of toner]
The average circularity of the toner is measured with a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.

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

Next, the equivalent circle diameter and the circularity are obtained using the area S and the peripheral length L. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. And is calculated by the following formula.
Circularity C = 2 × (π × S) 1/2 / L
When the particle image is circular, the circularity is 1.000, and the greater the degree of unevenness around the particle image, the smaller the circularity. After calculating the circularity of each particle, the range of the circularity of 0.200 or more and 1.000 or less is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity.

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is put in, and about 2 ml of the contamination N is added to the water tank.

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

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

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.98 μm or more and less than 39.69 μm.

[Production Example of Alkyl Monoalcohol A1]
Paraffin wax: 100.0 parts by mass (number average molecular weight (Mn = 399), average carbon number 35)
Boric acid / boric anhydride = 1.44 (molar ratio) (mixed catalyst): 2.6 parts by mass (0.04 mol)
The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after raising the temperature to 140 ° C., the reaction was carried out at 180 ° C. for 2 hours while blowing air and nitrogen. After completion of the reaction, an equal amount of warm water (95 ° C.) was added to the reaction mixture, the reaction mixture was hydrolyzed, and the reaction mixture separated by standing and separated was separated and washed with water to obtain an alkyl monoalcohol A1. . Table 1 shows the number average molecular weight, average carbon number, hydroxyl value, ester value, and acid value of the resulting alkyl monoalcohol A1.

(Production example of alkyl monocarboxylic acid B1)
In the production example of alkyl monoalcohol A1, the reaction was carried out in the same manner except that the amount of catalyst and the synthesis conditions were changed so that the physical properties shown in Table 1 were obtained, to obtain long-chain alkyl monocarboxylic acid B1. Table 1 shows the physical properties of the alkyl monocarboxylic acid B1.

(Production example of alkyl monoalcohols A2 to A5)
In the production example of alkyl monoalcohol A1, the reaction was carried out in the same manner except that the raw materials, the amount of catalyst and the synthesis conditions were changed so that the physical properties shown in Table 1 were obtained, and alkyl monoalcohols A2 to A5 were obtained. Table 1 shows the physical properties of the alkyl monoalcohols A2 to A5.

[Production Example of Polyester Resin C1]
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 67.9 parts by mass (0.19 mol; 93.0 mol% based on the total number of polyhydric alcohols)
Alkyl monoalcohol A1: 5.1 parts by mass (0.01 mol; 7.0 mol% based on the total number of polyhydric alcohols)
-Terephthalic acid: 20.8 parts by mass (0.13 mol; 75.0 mol% with respect to the total number of polyvalent carboxylic acids)
・ Fumaric acid: 2.9 parts by mass (0.03 mol; 15.0 mol% based on the total number of polyvalent carboxylic acids)
Titanium tetrabutoxide (esterification catalyst): 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C.

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

Trimellitic anhydride: 3.2 parts by mass (0.03 mol; 15.0 mol% with respect to the total number of polyvalent carboxylic acids)
-Tert-butylcatechol (polymerization inhibitor): 0.1 mass part Then, the said material was added, and it was made to react for 15 hours, keeping the pressure in a reaction tank to 8.3 kPa, and maintaining the temperature at 160 degreeC. After confirming that the softening point measured according to ASTM D36-86 reached the desired temperature shown in Table 2, the reaction was stopped by lowering the temperature (second reaction step) to obtain a polyester resin C1. Table 2 shows the peak molecular weight, softening point, and glass transition temperature of the obtained polyester resin C1.

[Production Example of Polyester Resin C2-10]
In the polyester resin C1 production example, the number of parts by mass of each monomer was changed so that the molar ratio of the polyhydric alcohol component and / or the polycarboxylic acid component was as shown in Table 1.

  The reaction was performed in the same manner except that the time of the second reaction was changed so that the softening point was as shown in Table 1, and polyester resins C2 to A10 were obtained. Table 2 shows the physical properties of the polyester resins C2 to C10.

[Production Example of Crystalline Polyester Resin D1]
Hexanediol: 34.5 parts by mass (0.29 mol; 100.0 mol% with respect to the total number of polyhydric alcohols)
-Dodecanedioic acid: 65.5 parts by mass (0.28 mol; 100.0 mol% with respect to the total number of polyvalent carboxylic acids)
The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140 ° C.

-Tin 2-ethylhexanoate: 0.5 part by mass Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was continued for 4 hours while maintaining the temperature at 200 ° C (first reaction step) ).

Octadecanoic acid: 11.5 parts by mass (0.04 mol; 7.0 mol% based on the total number of moles of polycarboxylic acid and polyhydric alcohol)
Thereafter, the pressure in the reaction vessel was gradually released and returned to normal pressure, and then the above materials were added and reacted at 200 ° C. for 2 hours under normal pressure. Thereafter, the inside of the reaction vessel was again decompressed to 5 kPa or less and reacted at 200 ° C. for 3 hours to obtain a crystalline polyester resin D1 (second reaction step). Table 3 shows the peak molecular weight and softening point of the obtained polyester resin D1.

[Production Example of Crystalline Polyester Resin D2-11]
The reaction was carried out in the same manner as in the production of D1 except that the number of parts by mass of each monomer of the polyhydric alcohol component and / or the polycarboxylic acid component in the first reaction step was changed from the case of the production of D1 as shown in Table 3. Further, the reaction is carried out in the same manner as in the production of D1 except that the monomer mass part of alcohol or carboxylic acid in the second reaction step is changed from the production of D1, as shown in Table 3, to obtain crystalline polyester resins D2 to D11. It was. Table 3 shows the physical properties of the crystalline polyester resins D2 to D11.

[Toner 1 production example]
Polyester resin C1: 90 parts by mass Crystalline polyester resin D1: 10 parts by mass Fischer-Tropsch wax (peak temperature of maximum endothermic peak 78 ° C): 5 parts by mass I. Pigment Blue 15: 3: 7 parts by mass ・ Aluminum 3,5-di-t-butylsalicylate compound (Bontron E88 manufactured by Orient Chemical Industries): 0.3 parts by mass

The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, and then a twin-screw kneader (PCM-30) set at a temperature of 130 ° C. Kneading with a mold, manufactured by Ikegai Co., Ltd.). The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions were a classification rotor rotational speed of 130 s ⁻¹ and a distributed rotor rotational speed of 120 s ⁻¹ .

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

To 100 parts by mass of a heat treatment the toner particles obtained, hydrophobic silica ^(BET: 200m 2 /g)1.0 parts by mass of titanium oxide fine particles surface-treated with isobutyl trimethoxysilane (BET: a ^80m 2 / g) 1 Toner 1 was obtained by mixing at 0.030 parts by mass with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min. Toner 1 had a weight average particle diameter (D4) of 6.5 μm and an average circularity of 0.970. Table 4 shows the physical properties of Toner 1. The content ratio in Table 4 is derived from aliphatic hydrocarbons, units derived from alkyl monoalcohol present at the terminal of amorphous polyester resin, and alkyl monocarboxylic acid with respect to the total mass of amorphous polyester resin and wax. It is the ratio of the total mass of the unit.

[Production Example of Toners 2 to 22]
In the toner 1 production example, the same operation was performed except that the polyester resin C and the crystalline polyester resin D were changed as shown in Table 4 and the hot air temperature of the surface treatment apparatus was changed as appropriate so that the average circularity became as shown in Table 4. And toner 2 to toner 22 were obtained.

[Production Example of Magnetic Core Particle 1]
-Process 1 (weighing / mixing process):
Fe ₂ O ₃ : 62.7 parts by mass MnCO ₃ : 29.5 parts by mass Mg (OH) ₂ : 6.8 parts by mass SrCO ₃ : 1.0 parts by mass Weighed. Thereafter, the mixture was pulverized and mixed for 5 hours in a dry vibration mill using 1/8 inch diameter stainless steel beads.

-Process 2 (temporary baking process):
The obtained pulverized product was formed into pellets of about 1 mm square using a roller compactor. After removing the coarse powder from the pellets with a vibrating sieve having a mesh opening of 3 mm, and then removing the fine powders with a vibrating sieve having a mesh opening of 0.5 mm, using a burner-type firing furnace, under a nitrogen atmosphere (oxygen concentration of 0.1. And calcined at a temperature of 1000 ° C. for 4 hours to prepare calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393

-Step 3 (grinding step):
After pulverizing 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 pulverized with a wet ball mill for 1 hour. The slurry was pulverized for 4 hours by a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

-Process 4 (granulation process):
To the ferrite slurry, 1.0 part by mass of ammonium polycarboxylate as a dispersant and 100 parts by mass of polyvinyl alcohol as a binder are added to 100 parts by mass of the calcined ferrite, and a spray dryer (manufacturer: Okawara Kako) is used. Granulated into spherical particles. After adjusting the particle size of the obtained particles, using a rotary kiln, it was heated at 650 ° C. for 2 hours 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 a nitrogen atmosphere (oxygen concentration: 1.00 vol%) in an electric furnace in 2 hours, and then fired at a temperature of 1150 ° C. for 4 hours. Thereafter, the temperature was lowered to 60 ° C. over 4 hours, returned from the nitrogen atmosphere to the atmosphere, and taken out at a temperature of 40 ° C. or lower.

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

<Adjustment of coating resin 1>
Cyclohexyl methacrylate monomer 26.8% by mass
Methyl methacrylate monomer 0.2% by mass
Methyl methacrylate macromonomer 8.4% by mass
(Macromonomer having a weight average molecular weight of 5000 having a methacryloyl group at one end)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3 mass%
Azobisisobutyronitrile 2.0% by mass
Of the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, methyl ethyl ketone are added to a four-necked separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirring device, and nitrogen gas is added. Then, the mixture was sufficiently brought to a nitrogen atmosphere, 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 under vacuum to obtain coating resin 1. The obtained coating resin 1 was dissolved in 30 parts by mass, 40 parts by mass of toluene, and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid content concentration 30%): 33.3% by mass
Toluene: 66.4% by mass
Carbon black (Regal 330; manufactured by Cabot): 0.3% by mass
(Primary particle size 25nm, nitrogen adsorption specific surface area 94m2 / g, DBP oil absorption 75ml / 100g)
Was dispersed with a paint shaker for 1 hour using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

[Example of manufacturing magnetic carrier 1]
(Resin coating process):
The coating resin solution 1 was added to a vacuum degassing kneader maintained at room temperature so that the resin component was 2.5 parts by mass with respect to 100 parts by mass of the filled core particles 1. After the addition, the mixture was stirred for 15 minutes at a rotation speed of 30 rpm, and after the solvent was volatilized above a certain level (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, and toluene was distilled off over 2 hours, followed by cooling. The obtained magnetic carrier is separated by low-magnetization 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 50% particle size (D50) of 38.2 μm based on volume distribution. 1 was obtained.

[Production Example of Two-Component Developer 1]
To 92.0 parts by mass of magnetic carrier 1, 8.0 parts by mass of toner 1 was added and mixed with a V-type mixer (V-20, manufactured by Seishin Enterprise) to obtain two-component developer 1.

[Production Examples of Two-Component Developers 2 to 22]
In the production example of the two-component developer 1, the same operation was performed except that the changes were made as shown in Table 5 to obtain two-component developers 2 to 22.

[Example 1]
The obtained two-component developer 1 was used for evaluation.

As an image forming apparatus, a digital commercial printing printer “imageRUNNER ADVANCE C9075 PRO” modified from Canon was used. The two-component developer 1 was placed in the developing device at the cyan position to form an image with the desired toner loading on the paper, and the evaluation described below was performed. The modification point was changed so that the fixing temperature and process speed could be set freely. At the time of image output evaluation, the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power are such that the amount of toner on the paper of the FFh image (solid image) is 0.35 mg. It adjusted so that it might become / cm < ² >. FFh is a value in which 256 gradations are displayed in hexadecimal, 00h is the first gradation (white background part) of 256 gradations, and FFh is the 256th gradation (solid part) of 256 gradations. .

  Evaluation is based on the following evaluation methods, and the results are shown in Table 6.

[durability]
Paper: CS-680 (68.0 g / m ² )
(Sold from Canon Marketing Japan Inc.)
Amount of toner on paper: 0.35 mg / cm ² (FFh image)
Evaluation image: Chart of A4 paper image ratio 100% Fixing test environment: High temperature and high humidity environment: Temperature 30 ° C./Humidity 85% RH (hereinafter “H / H”)
As a durable image output test, 10,000 sheets were output on A4 paper using a band chart of FFh output with an image ratio of 0.1%. Thereafter, the evaluation image was output, and the number of white spots in the image was visually confirmed.

(Evaluation criteria)
A: Less than 5 vitiligo spots (very good)
B: White spots are 5 or more and less than 10 (good)
C: 10 or more and less than 20 vitiligo spots (at a level that is not a problem in the present invention)
D: 20 or more white spots (not acceptable in the present invention)

[Low temperature fixability]
Paper: CS-680 (68.0 g / m ² )
(Sold from Canon Marketing Japan Inc.)
Amount of toner on paper: 1.20 mg / cm ²
Evaluation image: An image of 10 cm ² is placed in the center of the A4 paper. Fixing test environment: low temperature and low humidity environment: temperature 15 ° C./humidity 10% RH (hereinafter “L / L”)
After adjusting the direct current voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power so that the toner loading amount on the paper becomes the 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 for low-temperature fixability. The image density reduction rate is determined by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g / cm 2) is applied to the portion where the image density has been measured, and the fixed image is rubbed (reciprocated five times) with sylbon paper, and the image density is measured again. Then, the reduction rate (%) of the image density before and after rubbing was measured.

(Evaluation criteria)
A: Density reduction rate is less than 1.0% (very good)
B: Density reduction rate of 1.0% or more and less than 5.0% (good)
C: Density reduction rate of 5.0% or more and less than 10.0% (at a level that is not a problem in the present invention)
D: Density reduction rate of 10.0% or more (not acceptable in the present invention)

[Preservation]
5 g of toner was placed in a 100 cc polycup and allowed to stand for 48 hours in a temperature and humidity variable type thermostatic chamber (55 ° C., 41%). For the cohesiveness, when the powder tester PT-X manufactured by Hosokawa Micron Co., Ltd. was shaken with a mesh having an opening of 20 μm at an amplitude of 0.5 mm for 10 seconds, the residual rate of toner was used as an evaluation index.

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

[Transfer efficiency]
Paper: CS-680 (68.0 g / m ² )
(Sold from Canon Marketing Japan Inc.)
Amount of toner on the latent image carrier: 0.35 mg / cm ²
Evaluation image: Chart of A4 paper image ratio 100% Fixing test environment: High temperature and high humidity environment: Temperature 30 ° C./Humidity 85% RH (hereinafter “H / H”)
When outputting the image, the image was stopped during development, and the transfer residual toner on the latent image carrier at the time of image formation was removed by taping with a transparent polyester adhesive tape. Each density difference was calculated by subtracting the density of the adhesive tape only on the paper from the density of the adhesive tape peeled off on the paper. Evaluation was performed based on the following evaluation criteria. The residual transfer density was measured with an X-Rite color reflection densitometer (500 series).
A: Concentration difference is less than 0.10 (very good)
B: Concentration difference is 0.10 or more and less than 0.15 (good)
C: Concentration difference is 0.15 or more and less than 0.25 (at a level that is not a problem in the present invention)
D: Concentration difference is 0.25 or more (not acceptable in the present invention)

[Examples 2 to 19 and Comparative Examples 1 to 3]
Evaluation was performed in the same manner as in Example 1 except that two-component developers 2 to 22 were used. The evaluation results are shown in Table 6.

  In Example 2, since the circularity of the toner is small, the transfer efficiency is inferior to that in Example 1.

  In Example 3, since the circularity of the toner is further reduced, the transfer efficiency is inferior to that in Example 2.

  In Example 4, since the compatibility of the crystalline polyester resin is slightly lowered, the low-temperature fixability is inferior to that in Example 3.

  In Example 5, since the compatibility of the crystalline polyester resin is slightly lowered, the low-temperature fixability is inferior to that in Example 4.

  Example 6 is inferior in storage stability to Example 5 because the compatibility of the crystalline polyester resin is too high.

  Example 7 is inferior in storage stability to Example 6 because the compatibility of the crystalline polyester resin is too high.

  Example 8 was changed to an aliphatic monoalcohol, and the dialcohol-side crystal nucleus in which a lamella structure was difficult to be formed disappeared. Therefore, the recrystallization rate was reduced and storage stability was inferior to Example 7.

  In Example 9, since the number of carbon atoms of the aliphatic monocarboxylic acid was shortened, it became difficult to form a crystal nucleus, so that the recrystallization rate was lowered and storage stability was inferior to Example 8.

  In Example 10, since the carbon number of the aliphatic monocarboxylic acid was increased, the compatibility was lowered, and the low-temperature fixability was inferior to Example 8.

  In Example 11, since the number of carbon atoms of the aliphatic monocarboxylic acid was shortened, it became difficult to form crystal nuclei, so that the recrystallization rate was reduced and storage stability was inferior to Example 9.

  In Example 12, since the carbon number of the aliphatic monocarboxylic acid was increased, the compatibility was lowered and the low-temperature fixability was inferior to Example 10.

  In Example 13, since the crystal nucleus disappeared, the recrystallization rate decreased, and the storage stability was inferior to Example 11.

  Since Example 14 became an alkyl monocarboxylic acid, the reactivity with the binder resin was slightly lowered, and the storage stability was inferior to Example 13.

  Since Example 15 has a large endotherm and a large amount of free alkyl monoalcohol, durability and storage stability are inferior to Example 14.

  In Example 16, since the amount of alkyl monoalcohol added is large and the endothermic amount is further increased, the amount of free alkyl monoalcohol increases, and durability and storage stability are inferior to Example 15.

  In Example 17, the addition amount of the alkyl monoalcohol is small, and the fine dispersibility of the crystalline polyester resin is deteriorated. Therefore, the durability is inferior to that in Example 15.

  In Example 18, since the alkyl monoalcohol has a long carbon number, the amount of free alkyl monoalcohol increases, and durability and storage stability are inferior to Example 15.

  In Example 19, since the carbon number of the alkyl monoalcohol is short, the fine dispersibility of the crystalline polyester resin is deteriorated, and therefore, the durability is inferior to that of Example 15.

  In Comparative Example 1, since the carbon number of the alkyl monoalcohol is short, the fine dispersibility of the crystalline polyester resin is deteriorated, so that the durability is inferior to that of Example 14.

  In Comparative Example 2, the amount of alkyl monoalcohol added was small, and the fine dispersibility of the crystalline polyester resin was deteriorated.

  Since Comparative Example 3 has a large endothermic amount and a large amount of free alkyl monoalcohol, durability and storage stability are inferior to Example 14.

DESCRIPTION OF SYMBOLS 1 Raw material fixed supply means 2 Compressed gas flow rate adjustment means 3 Introducing pipe 4 Protruding member 5 Supply pipe 6 Processing chamber 7 Hot air supply means 8 Cold air supply means 9 Control means 10 Recovery means 11 Hot air supply means outlet 12 Distribution member 13 Turning member 14 Powder particle supply port

Claims (7)

A toner obtained by heat-treating toner particles containing an amorphous polyester resin, a wax, a colorant, and a crystalline polyester resin,
The toner has inorganic fine particles on the surface of the toner particles;
The amorphous polyester resin is
An alkyl monoalcohol having a peak carbon number of 25 to 102, and
Having a unit derived from at least one of alkyl monocarboxylic acids having a peak carbon number of 25 or more and 102 or less at the end of the molecular chain;
The wax has an aliphatic hydrocarbon having a peak carbon number of 25 to 102,
An aliphatic hydrocarbon having a peak carbon number of 25 to 102 in the toner particles;
A unit derived from an alkyl monoalcohol having a peak carbon number of 25 or more and 102 or less present at the terminal of the amorphous polyester resin; and
The total content of the units derived from the alkyl monocarboxylic acid having a peak carbon number of 25 or more and 102 or less present at the terminal of the amorphous polyester resin is 6 based on the total mass of the amorphous polyester resin and wax. 0.0 mass% or more and 16.0 mass% or less,
A toner, wherein the crystalline polyester resin has an ester unit derived from an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms.   The crystalline polyester resin has at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 10 to 20 carbon atoms and an aliphatic monoalcohol having 10 to 20 carbon atoms at the end of the molecular chain. The toner according to claim 1, which is a condensed resin.   The toner according to claim 1, wherein the crystalline polyester resin is a resin obtained by polycondensation of an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. .   4. The average circularity of particles having an equivalent circle diameter of 1.985 μm or more and less than 39.69 μm measured by the toner flow type particle image measuring device is 0.950 or more and 1.000 or less. The toner according to item 1. A step of melt-kneading a toner composition containing an amorphous polyester resin, a wax, a colorant, and a crystalline polyester resin to obtain a melt-kneaded product;
Pulverizing and classifying the melt-kneaded product to obtain toner particles;
Heat treating the toner particles;
In a method for producing a toner having
The amorphous polyester resin is
An alkyl monoalcohol having a peak carbon number of 25 to 102, and
Having a unit derived from at least one of alkyl monocarboxylic acids having a peak carbon number of 25 to 102 at the end of the molecular chain;
The wax has an aliphatic hydrocarbon having an average carbon number of 25 or more and 102 or less,
An aliphatic hydrocarbon having an average value of the carbon number of 25 to 102,
A unit derived from an alkyl monoalcohol having an average value of 25 to 102 carbon atoms present at the terminal of the polyester resin; and
The total content of units derived from alkyl monocarboxylic acids having an average value of 25 to 102 carbon atoms present at the terminal of the polyester resin is 6 based on the total mass of the polyester resin and the wax. 0.0 mass% or more and 16.0 mass% or less,
The crystalline polyester resin is a resin having an ester unit derived from an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms,
A method for producing a toner, wherein a hot air temperature in the heat treatment step is 100 ° C. or higher and 300 ° C. or lower.   The crystalline polyester resin has at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 10 to 20 carbon atoms and an aliphatic monoalcohol having 10 to 20 carbon atoms at the end of the molecular chain. The method for producing a toner according to claim 5, wherein the toner is a condensed resin.   The toner according to claim 5 or 6, wherein the crystalline polyester resin is a resin obtained by polycondensation of an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. Manufacturing method.