JP2015118341A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To achieve both the promotion of crystallization and the promotion of plasticization during fixation and fusion of a crystalline polyester resin at high level, so as to provide a toner having high durable stability and excellent low-temperature fixability.SOLUTION: There is provided a toner that has toner particles containing a crystalline polyester resin A, an amorphous polyester resin B, hexagonal system boron nitride, and colorant, where the crystalline polyester resin A has a crystal nucleus agent part on the terminal of a polyester molecular chain, and the boron nitride includes primary particles having a number average particle diameter of 0.050 μm or more and 3.0 μm or less and a crystallinity GI value determined by the powder X-ray diffraction method of 1.60 or more and 35.0 or less.

Description

  The present invention relates to an electrophotographic method, an image forming method for developing an electrostatic charge image, and a toner used in a toner jet method.

  In recent years, toners used in electrophotography and toner jet methods have been required to have low-temperature fixability for energy saving in order to save power in the apparatus and shorten wait time. In addition, with the recent increase in printing speed, the time for media such as toner and paper to pass through the nip of the fixing device has become shorter year by year. Therefore, a toner having further low-temperature fixability that achieves both energy saving and high speed is widely desired.

Furthermore, there are increasing opportunities for users to output images with a low printing ratio for office use to graphic images with a high printing ratio using an image forming apparatus such as a copying machine or a laser printer (LBP). A graphic image with a high printing ratio is image data or a poster captured by a digital camera, a portable terminal, or the like. Accordingly, there is a need for a toner that achieves both durability stability capable of outputting an image with a low printing ratio over a long period of time and low-temperature fixability capable of printing out an image with a high printing ratio in a short time.
Against this background, many toners using a crystalline resin as a binder resin have been proposed in order to achieve excellent low-temperature fixability. In recent years, as a toner for improving the low-temperature fixability, a crystalline resin has been widely used as an improvement of the binder resin.

Patent Document 1 discloses that the low-temperature fixability of the toner is improved by rapidly melting the crystalline resin near the glass transition temperature and increasing the compatibility between the crystalline resin and the amorphous resin. Has been. However, if the compatibility between the two is too high, the durability stability of the toner is significantly reduced.
Conversely, if the compatibility between the amorphous resin and the crystalline resin is lowered, crystals of the crystalline resin tend to be easily formed, but both of them are difficult to be compatible even at the melting point or higher, so the printing ratio is particularly high. When printing out an image in a short time, it is difficult to improve the low-temperature fixability.

Patent Document 2 discloses that a heat treatment process at a specific temperature is added to the toner manufacturing process to promote recrystallization of the crystalline resin. According to the method described in Patent Document 2, a toner containing crystalline resin crystals can be obtained. However, if the toner is once melted in the fixing step, the crystalline resin and the amorphous resin become compatible and do not return to the original crystalline state. In some cases, the toner images adhere to each other.
Therefore, a method has been proposed in which crystallization of a crystalline resin is promoted by adding a crystal nucleating agent to the toner. Patent Document 3 describes using an organic crystal nucleating agent such as a metal salt of benzoic acid or a fatty acid amide as a nucleating agent. Patent Document 4 describes that a fine inorganic crystal nucleating agent such as silica is used as the nucleating agent. However, organic nucleating agents are often low molecular weight compounds such as benzoic acid metal salts and fatty acid metal salts, and these nucleating agents segregate on the toner surface, resulting in insufficient effects as crystal nucleating agents. The durability stability of the toner may deteriorate.
On the other hand, an inorganic crystal nucleating agent such as silica exhibits a filler effect when the amount is large, and may increase the melt viscosity of the toner, thereby inhibiting the low-temperature fixability. In addition, inorganic crystal nucleating agents affect charging characteristics and often make it difficult to control the chargeability of the toner. Patent Document 5 also describes inorganic crystal nucleating agents as crystal nucleating agents for crystalline resins, but these also cannot be said to have sufficient effects as low-temperature fixability, charging properties, and crystal nucleating agents.
On the other hand, in recent years, in order to achieve excellent low-temperature fixability, inorganic fine particles having excellent thermal conductivity have been added to promote plasticization at the time of fixing and melting the toner and to improve low-temperature fixability. Yes.
Patent Document 6 proposes a toner having improved low-temperature fixability by adding a nitride having high thermal conductivity to the toner. However, although the thermal conductivity is high, if the added amount is large, a filler effect is exhibited, and in order to increase the melt viscosity of the toner, the effect of promoting plasticization at the time of fixing and melting is offset, and sufficient low-temperature fixing property is achieved. It may not be obtained.
Thus, there is room for further improvement in order to achieve both high durability stability and excellent low-temperature fixability.

JP 2010-102058 A JP 2010-152102 A JP 2007-033773 A JP 2006-113473 A Japanese Patent No. 3360527 JP 2012-103535 A

  An object of the present invention is to provide a toner having high durability stability and excellent low-temperature fixability by achieving both high-dimensional promotion of crystallization of a crystalline polyester resin and plasticization at the time of fixing and melting. is there.

The present invention is a toner having toner particles containing crystalline polyester resin A, amorphous polyester resin B, hexagonal boron nitride, and colorant,
The crystalline polyester resin A has a crystal nucleating agent site at the end of the polyester molecular chain,
The boron nitride is
The number average particle size of the primary particles is 0.050 μm or more and 3.0 μm or less,
The present invention relates to a toner having a crystallinity GI value obtained by a powder X-ray diffraction method of 1.60 or more and 35.0 or less.
Further, in the present invention, the crystal nucleating agent site is a site derived from an aliphatic monocarboxylic acid having 10 to 30 carbon atoms and / or an aliphatic monoalcohol having 11 to 31 carbon atoms. It relates to a characteristic toner.
In the present invention, the crystalline polyester resin A has an SP value Sa ((cal / cm ³ ) ^1/2 ) of 9.00 or more and 11.50 or less, and the Sa and the amorphous polyester resin are used. The present invention relates to a toner wherein the SP value Sb ((cal / cm ³ ) ^1/2 ) of B satisfies the following formula (1).
-1.50 <= Sb-Sa <= 0.80 ... Formula (1)

  According to the present invention, crystallization is achieved by using a toner containing a crystalline polyester resin A having a nucleating agent moiety at the end of a molecular chain, an amorphous polyester resin B, and a specific hexagonal boron nitride. It is possible to provide a toner that achieves both high-dimensional acceleration of crystallization of the polyester resin and promotion of plasticization of the binder resin during fixing and melting. That is, it is possible to provide a toner that has both high durability stability capable of outputting an image with a low printing ratio over a long period of time and excellent low-temperature fixability for printing out an image with a high printing ratio in a short time.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
First, the toner of the present invention is a toner having toner particles containing a crystalline polyester resin A, an amorphous polyester resin B, hexagonal boron nitride, and a colorant. The crystalline polyester resin A has a crystal nucleating agent site at the end of the polyester molecular chain. The boron nitride has a number average particle size of primary particles of 0.050 μm or more and 3.0 μm or less, and a crystallinity GI value obtained by a powder X-ray diffraction method of 1.60 or more and 35.0 or less.

The toner of the present invention has a synergistic effect of having a crystal nucleating agent site at the end of the molecular chain of the crystalline polyester resin and using a specific hexagonal boron nitride in combination to promote crystallization and plasticization of the toner. It was found that both can be achieved at a high level. The present inventors consider the reason as follows.
Conventionally, crystalline polyester resin and amorphous polyester resin have improved compatibility and improved low-temperature fixing. However, when a crystalline polyester resin and an amorphous polyester resin are simply mixed, for example, by a melt-kneading process, they are compatible, and the crystalline polyester does not crystallize, and the toner has a low glass transition point (Tg). End up.

  Therefore, the present inventors first have a crystal nucleating agent site at the end of the molecular chain of the crystalline polyester resin, so that the crystalline polyester resin in a compatible state is crystallized, in particular, a nucleating action that forms a crystal nucleus. Has been found to increase. It has also been found that by using a specific hexagonal boron nitride in combination with the crystal nucleating agent site, crystallization of the crystalline polyester resin, particularly a crystal growth action for growing a crystal nucleus can be promoted.

Further, even if inorganic particles having high thermal conductivity are added to the binder resin to promote the plasticization of the toner as in the past, the increase in toner viscosity due to the filler effect inhibits the plasticization of the toner. However, in the present invention, by using a specific crystalline polyester resin together with a specific hexagonal boron nitride, the thermal conductivity due to the lattice vibration unique to the hexagonal network structure of boron nitride is crystallized in the toner. It has been found that the plasticization of the obtained resin component can be promoted.
Although this reason is not certain, the present inventors consider the reason as follows.

By making the crystallinity of the hexagonal network structure of boron nitride within a specific range, the crystallization rate of the crystalline nucleating agent site itself at the end of the crystalline polyester molecular chain is increased, and the crystallization of the crystalline polyester resin, especially the crystal I think that the nucleation action that forms the nuclei may be further improved. Also, during plasticization at the time of fixing and melting, the heat conduction due to the lattice vibration unique to the hexagonal network structure of boron nitride first promotes plasticization of the crystal nucleus part itself, making it easier to induce plasticization of the crystalline polyester resin. I think that it is.
Therefore, the combination of the specific crystalline polyester resin and the specific hexagonal boron nitride at the end of the molecular chain of the present invention can achieve both high crystallization promotion and plasticization promotion at a high level. The present inventors have found that durability stability and excellent low-temperature fixability can be achieved, and have reached the present invention.

The hexagonal boron nitride used in the present invention has a primary particle number average particle size of 0.050 μm or more and 3.0 μm or less. By being in this range, the crystal growth action for growing crystal nuclei in the toner can be effectively promoted, and at the time of fixing and melting, the plasticization of the resin component crystallized in the toner can be effectively promoted. Can do.
If it is less than 0.050 μm, the degree of crystallinity of the boron nitride itself becomes low, and the desired crystallization promoting effect cannot be obtained, and the boron nitride itself tends to aggregate in the toner, and the desired heat conduction. Sexuality may not be obtained. On the other hand, if it exceeds 3.0 μm, although the degree of crystallization of boron nitride itself is high, it becomes difficult to be taken into the toner, so that the effect of promoting the crystallization and plasticization of the toner cannot be sufficiently obtained.

In addition, the hexagonal boron nitride used in the present invention has a crystallinity G by a powder X-ray diffraction method.
The I (Graphization Index) value is 1.60 or more and 35.0 or less. This value is determined by J. Thomas et al. Am.
Chem. Soc. , 24, 4619 (1962), and can be obtained by calculating the integrated intensity ratio, that is, the area ratio, of the (100), (101), and (102) lines of the X-ray diffraction diagram by the following equation. The smaller this value, the higher the crystallinity.
GI value = [area {(100) + (101)}] / [area (102)]
The area {(100) + (101)} is the sum of the peak area related to the (100) plane and the peak area related to the (101) plane, and the area (102) is the peak area related to the (102) plane.
As described above, the GI value is an index of the crystallinity of hexagonal boron nitride. The higher the crystallinity, the smaller this value. In the case of complete crystallization (graphitization), the GI value = 1.60. It is supposed to be.

When the GI value is 1.60 or more and 35.0 or less, the crystal growth action for growing crystal nuclei in the toner can be effectively promoted, and the resin crystallized in the toner at the time of fixing and melting. The plasticization of the components can be effectively promoted.
When it exceeds 35.0, the degree of crystallinity of boron nitride itself becomes low, and a desired crystallization promoting effect cannot be obtained. If it is less than 1.60, the degree of crystallinity of boron nitride itself is high, and the particles also have a crystal-grown particle size, which makes it difficult to be incorporated into the toner. It becomes difficult to obtain a sufficient promotion effect.

  Further, since hexagonal boron nitride used in the present invention has high lubricity and high chargeability as conventionally used, it goes without saying that it functions as a transfer improver and a charge imparting agent. In view of the fact that various properties as a toner can be improved, a toner that achieves a high level of crystallization and plasticization promoting effects found in the present invention can be said to be a toner that does not adversely affect other properties. .

The addition amount of hexagonal boron nitride used in the present invention is preferably 0.2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the toner particles. Furthermore, it is more preferable that it is added at 0.2 to 10 parts by mass.
When the amount is 0.2 parts by mass or more, the above effect is easily obtained, and when the amount is 20 parts by mass or less, the toner is easily taken into the toner, and the liberated boron nitride adheres to the developing member and causes image defects. There are few cases.

<Crystal nucleator site bonded to the end of the molecular chain of crystalline polyester A>
In general, the crystalline component of the crystalline polyester in the toner can be formed by the crystal growing after the crystal nucleus is formed. In the present invention, by having a crystal nucleating agent at the end of the crystalline polyester molecular chain, crystallization can be induced at a site where a crystal structure can be formed, and crystallization of the crystalline polyester resin A, particularly formation of a crystal nucleus is formed. The nucleating action can be promoted.
When the polyester molecular chain does not have a crystal nucleating agent, crystallization cannot be induced, and thus the crystallization of the crystalline polyester resin does not occur sufficiently. In addition, the crystal nucleating agent site is often a low molecular weight substance. If such a low molecular weight substance is present in the toner in a free state, the free crystal nucleating agent is likely to be deposited on the surface of the toner. The durability stability may deteriorate.

The crystal nucleating agent site is not particularly limited as long as it is a compound having a crystallization rate faster than that of the crystalline polyester resin A. In view of the high crystallization speed, the main chain preferably contains a hydrocarbon-based moiety and has a monovalent or higher functional group capable of reacting with the end of the resin molecule of the polyester resin A.
From the viewpoint of easily increasing the crystallization rate, the crystal nucleating agent portion is preferably a compound in which the hydrocarbon portion is linear and the functional group is monovalent. In addition, the molecular weight of the crystal nucleating agent site is preferably 100 to 10,000, more preferably 150 to 5,000 in terms of increasing the reactivity between the crystal nucleating agent site and the resin terminal of the crystalline polyester resin A. preferable.

  The crystal nucleating agent site is not particularly limited as long as it is bonded to the polyester molecule terminal of the crystalline polyester resin A. It is preferably a site derived from an aliphatic monocarboxylic acid having 10 to 30 carbon atoms and / or an aliphatic monoalcohol having 11 to 31 carbon atoms. Since the crystal nucleating agent portion has a specific number of carbon atoms, the crystal nucleating agent has a higher degree of crystallinity, and further has higher molecular mobility than the crystalline polyester resin A. Can be increased.

From the viewpoint of increasing the crystallization rate, the crystal nucleating agent portion is contained in the polyester resin A in an amount of 0.1 mol or more and 7.0 mol or less with respect to 100 mol of the raw material monomer of the polyester molecular chain of the polyester resin A. It is preferable. More preferably, the content is 0.2 mol or more and 5.0 mol or less.
In the case of 0.1 mol or more, the crystallization rate is not lowered, the polyester resin A and the polyester resin B are hardly compatible, the glass transition point (Tg) of the toner is not lowered, and the durability stability of the toner is improved. Less likely to get worse. On the other hand, in the case of 7.0 mol or less, the degree of crystallinity does not become too high, and the polyester resin A and the polyester resin B do not easily become compatible at the time of fixing, and sufficient fixability is obtained. There are few cases.

Whether or not the crystal nucleating agent site is bonded to the molecular chain of the crystalline polyester resin is determined by the following analysis.
A sample solution is prepared by accurately weighing 2 mg of a sample and adding 2 mL of chloroform to dissolve the sample. The polyester resin A is used as the resin sample. However, when it is difficult to obtain the polyester resin A, a toner containing the polyester resin A can be used as a sample.
Next, 20 mg of 2,5-dihydroxybenzoic acid (DHBA) is precisely weighed, and 1 mL of chloroform is added and dissolved to prepare a matrix solution. Further, after precisely weighing 3 mg of Na trifluoroacetate (NaTFA), 1 mL of acetone is added and dissolved to prepare an ionization aid solution.

  25 μL of the sample solution thus prepared, 50 μL of the matrix solution, and 5 μL of the ionization aid solution are mixed, dropped onto a sample plate for MALDI analysis, and dried to obtain a measurement sample. A mass spectrum is obtained using MALDI-TOFMS (Reflex III manufactured by Bruker Daltonics) as an analytical instrument. In the obtained mass spectrum, assignment of each peak in the oligomer region (m / Z is 2000 or less) is performed, and it is confirmed whether or not there is a peak corresponding to the composition in which the crystal nucleating agent is bonded to the molecular end.

  In the present invention, polyester resin A having a crystal nucleating agent site at the end of a polyester molecular chain capable of taking a crystal structure and polyester resin B having no site capable of taking a crystal structure are used. In the present invention, having a portion that can take a crystal structure means that there is an endothermic peak at the time of temperature increase in the differential scanning calorimeter (DSC) measurement and an exothermic peak at the time of temperature decrease, and the measurement is “ASTM D3418-82. "Perform according to the measurement method."

<Crystalline polyester resin A and amorphous polyester resin B>
By controlling the SP value (solubility parameter) and SP value difference between the crystalline polyester resin A and the amorphous polyester resin B, the present inventors have used a combination of a crystal nucleating agent site and a specific hexagonal boron nitride. It is considered that the effect of promoting crystallization and plasticization can be easily obtained.

Note that the SP value used in the present invention is the Fedors method [Poly. Eng. Sci. , 14 (2) 147 (1974)], from the types and ratios of the monomers constituting the resin. The SP value of the polyester resin A represents the SP value of the polyester molecular chain excluding the crystal nucleating agent.
The SP value Sa ((cal / cm ³ ) ^1/2 ) of the crystalline polyester resin A is preferably 9.00 or more and 11.50 or less because the degree of crystallinity is high. In the crystalline polyester resin A, a low SP value indicates that the aliphatic carboxylic acid and / or the aliphatic alcohol constituting the crystalline polyester resin A has a large number of carbon atoms. From the viewpoint of increasing the crystallinity of the crystalline polyester resin A, the larger the number of carbon atoms, that is, the lower the SP value, the better. Further, from the viewpoint of increasing the compatibility of the crystallized polyester resin A, the smaller the number of carbon atoms, that is, the higher the SP value, the better.

The state of compatibility between the crystalline polyester resin A and the amorphous polyester resin B in the toner is controlled by the SP value Sb ((cal / cm ³ ) ^1/2 ) of the amorphous polyester resin B and the Sa. Is the difference. In order to effectively exhibit crystallization promotion and plasticization promotion by the combined use of a crystal nucleating agent site and a specific hexagonal boron nitride, the SP value Sa of the polyester resin A and the SP value Sb of the polyester resin B Preferably satisfies the following relational expression (1).
−1.5 ≦ Sb−Sa ≦ 0.80 (1)

When the value of Sb-Sa is decreased, the crystalline polyester resin A is easily compatible and has excellent low-temperature fixability. However, since the glass transition point (Tg) of the toner is decreased, high durability stability is achieved. It becomes difficult.
When the value of Sb-Sa increases, the crystalline polyester resin A is easily crystallized and the toner has a high glass transition point (Tg), so that it has high durability stability, but it is difficult to achieve excellent low-temperature fixability. Become.

  As an alcohol component used as a raw material monomer of the crystalline polyester resin A, an aliphatic diol having 6 to 18 carbon atoms is preferably used from the viewpoint of enhancing the crystallinity of the polyester resin A. Among these, an aliphatic diol having 6 to 12 carbon atoms is preferable from the viewpoint of fixability and heat stability. Examples of the aliphatic diol include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1, Examples thereof include 12-dodecanediol. From the viewpoint of further improving the crystallinity of the polyester resin A, the content of the aliphatic diol is preferably 80 to 100 mol% in the alcohol component.

  As an alcohol component for obtaining crystalline polyester resin A, you may contain polyhydric alcohol components other than said aliphatic diol. For example, the polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane and the polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane are represented by the following formula (I). Aromatic diols such as alkylene oxide adducts of bisphenol A; trivalent or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane.

（式中、Ｒは、炭素数２または３のアルキレン基を示す。ｘおよびｙは、正の数を示し、ｘとｙの和は、１〜１６、好ましくは１．５〜５である。）

(In the formula, R represents an alkylene group having 2 or 3 carbon atoms. X and y represent a positive number, and the sum of x and y is 1 to 16, preferably 1.5 to 5. )

As the carboxylic acid component used for the raw material monomer of the crystalline polyester resin A, an aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms is preferably used from the viewpoint of enhancing the crystallinity of the polyester resin A. Among these, an aliphatic dicarboxylic acid compound having 6 to 12 carbon atoms is preferable from the viewpoint of toner fixing properties and heat stability.
Examples of the aliphatic dicarboxylic acid compound include 1,8-octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, and the like. It is done. The content of the aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms is preferably 80 to 100 mol% in the carboxylic acid component.

As the carboxylic acid component for obtaining the crystalline polyester resin A, a carboxylic acid component other than the aliphatic dicarboxylic acid compound may be contained. For example, an aromatic dicarboxylic acid compound, a trivalent or higher valent aromatic polycarboxylic acid compound and the like can be mentioned, but the invention is not particularly limited thereto. The aromatic dicarboxylic acid compound also includes an aromatic dicarboxylic acid derivative.
Preferable examples of the aromatic dicarboxylic acid compound include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, anhydrides of these acids, and alkyl (C1 to C3) esters thereof. Examples of the alkyl group in the alkyl ester include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the trivalent or higher polyvalent carboxylic acid compounds include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, and the like. Derivatives such as acid anhydrides and alkyl (C1-3) esters are mentioned.

  The crystalline polyester resin A that can be used in the present invention has a heat of fusion (ΔH) of 80 J / g or more, 140 J / g determined from the area of the endothermic peak observed at the time of temperature rise in differential scanning calorimetry (DSC) measurement. The following is preferable. In addition, the melting point of the polyester resin A is preferably 60 ° C. or higher and 120 ° C. or lower, and more preferably 70 ° C. or higher and 90 ° C. or lower, from the viewpoint of low-temperature fixability of the toner.

The acid value of the crystalline polyester resin A is preferably 2 mgKOH / g or more and 40 mgKOH / g or less from the viewpoint of good charging characteristics of the toner. The hydroxyl value of the polyester resin A is preferably 2 mgKOH / g or more and 40 mgKOH / g or less from the viewpoints of fixability and storage stability.
Examples of the alcohol component for obtaining the amorphous polyester resin B include the following. Examples of the divalent alcohol component include 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene adduct, 2,2-bis (4-hydroxyphenyl) propane polyoxyethylene adduct, etc. Examples include alkylene oxide adducts of bisphenol A represented by (I), ethylene glycol, 1,3-propylene glycol, neopentyl glycol, and the like. Examples of the trihydric or higher alcohol component include sorbitol, pentaerythritol, dipentaerythritol and the like.
The divalent alcohol component and the trihydric or higher polyhydric alcohol component can be used alone or in combination of a plurality of compounds.

  Examples of the carboxylic acid component for obtaining the amorphous polyester resin B include the following. Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, n-dodecenyl succinic acid, and anhydrides or lower alkyl esters of these acids. It is done. Examples of the trivalent or higher polyvalent carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, emporic trimer acid and acid anhydrides thereof, Examples thereof include alkyl esters.

The amorphous polyester resin B can be produced by an esterification reaction or a transesterification reaction using the above alcohol component and carboxylic acid component. In the condensation polymerization, a known esterification catalyst such as dibutyltin oxide may be appropriately used to promote the reaction.
The glass transition temperature (Tg) of the amorphous polyester resin B is preferably 45 ° C. or higher and 70 ° C. or lower from the viewpoints of fixability and durability stability. The softening point of the amorphous polyester resin B is preferably 80 ° C. or higher and 130 ° C. or lower, and more preferably 90 ° C. or higher and 120 ° C. or lower, from the viewpoint of low-temperature fixability of the toner. When the amorphous polyester resin B is used in combination of a low molecular weight resin and a high molecular weight resin, the softening point of the low molecular weight resin is from 80 ° C. to 110 ° C. The softening point of is preferably 120 ° C. or higher and 150 ° C. or lower.

The acid value of the amorphous polyester resin B is preferably 2 mgKOH / g or more and 40 mgKOH / g or less from the viewpoint of good charging characteristics of the toner. The hydroxyl value of the polyester resin B is preferably 2 mgKOH / g or more and 40 mgKOH / g or less from the viewpoint of fixability and storage stability.
The mass ratio of the polyester resin A and the polyester resin B contained in the toner of the present invention is preferably 5:95 to 40:60 from the viewpoint of low-temperature fixability and durability stability.

<Physical properties of toner>
The softening point of the toner is preferably 80 ° C. or higher and 120 ° C. or lower from the viewpoint of low temperature fixability of the toner. The weight average molecular weight of the toner is preferably 3000 or more and 100,000 or less from the viewpoint of fixability and suppression of high temperature offset.
In order to improve the releasability of the toner, wax may be used for the toner as necessary. As the wax, hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax are preferable from the viewpoint of easy dispersion in the toner and high releasability. If necessary, two or more kinds of waxes may be used in combination.

  Specific examples of the wax include the following. Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industry Co., Ltd.), High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemical Co., Ltd.), Sazol H1, H2, C80, C105, C77 (Schumann Sazol), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiki) Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark), Unicid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite Co., Ltd.), wood wax, beeswax , Rice wax, candelilla wax, carnauba wax (available from Celerica NODA).

When the toner is produced by a pulverization method, the wax is preferably added at the time of melt kneading. Further, a wax may be added during the production of the amorphous polyester resin B.
The toner preferably contains 1 part by mass or more and 20 parts by mass or less of wax with respect to 100 parts by mass of the binder resin.
The toner of the present invention may be a magnetic toner or a non-magnetic toner. When used as a magnetic toner, it is preferable to use magnetic iron oxide as the magnetic material. As the magnetic iron oxide, iron oxides such as magnetite, maghematite, and ferrite are used. The amount of magnetic iron oxide contained in the toner is preferably 25 parts by mass or more and 45 parts by mass or less, more preferably 30 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the polyester resins A and B. is there.

  When the toner of the present invention is used as a nonmagnetic toner, carbon black or other known pigments or dyes can be used as a colorant. Further, only one kind of pigment or dye may be used, or two or more kinds may be used in combination. The colorant contained in the toner is preferably 0.1 parts by mass or more and 60.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the polyester resins A and B. 0.0 parts by mass or less.

  For the toner, a fluidity improver such as an inorganic fine powder can be used. Examples of the fluidity improver include the following. Fluorine resin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder; fine powder silica such as wet process silica, dry process silica, silica with silane coupling agent, titanium coupling agent, or silicone oil Treated silica with surface treatment. A preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is dry process silica or fumed silica.

Among these, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is preferably used. The treated silica fine powder preferably has a degree of hydrophobicity of 30 or more and 98 or less titrated by a methanol titration test.
Examples of the method for hydrophobizing silica fine powder include a method of chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. A preferred method is a method in which silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound. Examples of organosilicon compounds include the following. Hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α- Chlorethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1 -Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyl Ludisiloxane and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and containing hydroxyl groups (hydroxy groups) bonded to Si per unit in the terminal unit. These are used alone or in a mixture of two or more.

The silica fine powder may be treated with silicone oil, or may be treated with a combination of silicone oil and the organosilicon compound. As the silicone oil, those having a viscosity at a temperature of 25 ° C. of 30 mm ² / s or more and 1000 mm ² / s or less are preferable. Examples thereof include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.

  Examples of the method for hydrophobizing the silica fine powder with silicone oil include the following methods. A method in which silica fine powder treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer; a method in which silicone oil is sprayed onto a silica fine powder as a base. Alternatively, after dissolving or dispersing silicone oil in an appropriate solvent, silica fine powder is added and mixed to remove the solvent. The silicone oil-treated silica is more preferably obtained by heating the silica in an inert gas at a temperature of 200 ° C. or higher (more preferably 250 ° C. or higher) to stabilize the surface coating after the silicone oil treatment.

The inorganic fine powder is preferably used in an amount of 0.01 to 8.0 parts by weight, more preferably 0.10 to 4.0 parts by weight, based on 100 parts by weight of the toner particles.
If necessary, other external additives may be added to the toner. For example, charging aids, conductivity imparting agents, anti-caking agents, release agents at the time of heat roller fixing, lubricants, resin fine particles and inorganic fine particles that function as abrasives.
Examples of the lubricant include polyfluorinated ethylene powder, zinc stearate powder, and polyvinylidene fluoride powder. Of these, polyvinylidene fluoride powder is preferred. Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder.

  The toner of the present invention can be used as a one-component developer, but can also be mixed with a magnetic carrier and used as a two-component developer. As the magnetic carrier, a known carrier such as a ferrite carrier or a magnetic material-dispersed resin carrier (so-called resin carrier) in which a magnetic material is dispersed in a binder resin such as a polyester resin can be used. When the toner is mixed with a magnetic carrier and used as a two-component developer, the toner concentration in the developer is preferably 2% by mass or more and 15% by mass or less.

  The method for producing the toner of the present invention is not particularly limited, but a pulverization method is preferable from the viewpoint of obtaining a toner having better low-temperature fixability. In the pulverization method, the molecular chain of the crystalline polyester resin A is likely to enter the amorphous polyester resin B by mixing the material by applying shear in the melt-kneading step. For this reason, at the time of fixing, the crystalline polyester resin A and the amorphous polyester resin B can be satisfactorily compatibilized, and the low-temperature fixability of the toner can be improved.

  Conventionally, when a toner is produced by a pulverization method, it has been difficult to maintain the crystallinity of the polyester resin. Therefore, it has been difficult to form a crystal part in the toner once it is compatibilized in the melt-kneading step. However, even when the polyester resin A is produced by a pulverization method by controlling the crystal nucleating agent at the molecular end of the polyester resin A or the difference in SP value between the polyester resin A and the polyester resin B, the crystalline portion is good in the toner. Can be obtained.

<Method of obtaining toner by pulverization method>
In the raw material mixing step, a predetermined amount of crystalline polyester resin A, amorphous polyester resin B, colorant, and other additives are weighed and mixed as materials constituting the toner particles and mixed. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a nauter mixer, and a mechano hybrid (manufactured by Nihon Coke Industries Co., Ltd.).

  Next, the mixed material is melt-kneaded to disperse the colorant and the like in the polyester resin. In the melt-kneading step, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Due to the advantage of continuous production, single-screw or twin-screw extruders are the mainstream. For example, KTK type twin screw extruder (manufactured by Kobe Steel, Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko Co., Ltd.), twin screw extruder ( And Kneader (manufactured by NIPPON Coke Industries Co., Ltd.). 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 a pulverization step. In the pulverization step, for example, after coarsely pulverizing with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.) Finely pulverize with a turbo mill (made by Turbo Kogyo) or an air jet type fine pulverizer. Then, if necessary, inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classifier turboplex (manufactured by Hosokawa Micron Corporation), TSP separator (manufactured by Hosokawa Micron Corporation), Faculty (Hosokawa Micron) The toner particles are obtained by classification using a classifier or a sieving machine.

If necessary, after pulverization, hybridization system (manufactured by Nara Machinery Co., Ltd.), mechano-fusion system (manufactured by Hosokawa Micron Co., Ltd.), Faculty (manufactured by Hosokawa Micron Co., Ltd.), Meteorinbo MR Type (Nippon Pneumatic) The surface treatment of toner particles such as spheronization treatment can also be performed using Kogyo Co., Ltd.
Furthermore, if necessary, desired additives can be sufficiently mixed by a mixer such as a Henschel mixer.
The methods for measuring the physical properties of the binder resin, boron nitride and toner are as follows. Also in the examples described later, the physical property values are measured based on these methods.

<Measurement of number average particle diameter (D1) of primary particles of boron nitride>
The number average particle diameter (D1) of the primary particles of boron nitride used in the present invention is measured according to JIS Z8825-2 (2001), and is specifically as follows.
As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. The dedicated software “HORIBA LA-920 for Windows (registered trademark) WET (LA-920) Ver. 2.02” attached to LA-920 is used for setting measurement conditions and analyzing measurement data. As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used.
The measurement procedure is as follows.

(1) A batch type cell holder is attached to LA-920.
(2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.
(3) The inside of the batch cell is stirred using a dedicated stirrer chip.
(4) Press the “refractive index” button on the “display condition setting” screen and select the file “110A000I” (relative refractive index 1.10).
(5) In the “display condition setting” screen, the particle diameter standard is the number standard.

(6) After performing warm-up operation for 1 hour or more, the optical axis is adjusted, the optical axis is finely adjusted, and blank measurement is performed.
(7) About 60 mL of ion exchange water is put into a glass 100 mL flat bottom beaker. Among them, as a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 mL of a diluted solution obtained by diluting the product (made by manufacture) with ion-exchanged water about 3 times by mass.
(8) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora150” (manufactured by Nikki Bios Co., Ltd.) with an electrical output of 120 W is prepared. To do. About 3.3 L of ion exchange water is placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminone N is added to the water tank.

(9) The beaker of (7) 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 aqueous solution in a beaker may become the maximum.
(10) In a state where the aqueous solution in the beaker of (9) is irradiated with ultrasonic waves, about 1 mg of boron nitride is added to the aqueous solution in the beaker little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In this case, boron nitride may become a solid and float on the liquid surface. In this case, ultrasonic dispersion is performed for 60 seconds after the mass is submerged by shaking the beaker. Moreover, in ultrasonic dispersion, it adjusts suitably so that the water temperature of a water tank may become 10 to 40 degreeC.
(11) The aqueous solution in which boron nitride prepared in (10) is dispersed is immediately added little by little to the batch type cell while taking care not to enter bubbles, and the transmittance of the tungsten lamp is 90% to 95%. Adjust so that Then, the particle size distribution is measured. Based on the obtained particle size distribution data based on the number, the number average particle size of the primary particles is calculated.

<Measurement of Crystallinity Index (GI) Value of Boron Nitride>
The crystallinity GI value of boron nitride is obtained from the X-ray diffraction spectrum of boron nitride by the powder X-ray diffractometer “RINT TTRII” system manufactured by Rigaku Corporation (100) plane, (101) plane, (102) plane The peak area intensity ratio was determined from the following formula.
GI value = [area {(100) + (101)}] / [area (102)]
X-rays are CuKα as an X-ray source, and CuKβ rays are removed by a nickel filter. High purity silicon is used as the standard substance, and the main measurement conditions are as shown in Table 1 below.

<Measurement of weight average molecular weight by GPC>
The column is stabilized in a heat chamber at a temperature of 40 ° C., THF (tetrahydrofuran) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 mL / min, and about 100 μL of a THF sample solution is injected for measurement. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value.
As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko Co., Ltd. is used. Is appropriate. The detector uses an RI (refractive index) detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko K.K. (Ltd.) of _{TSKgel G1000H (H XL), G2000H} (H XL), G3000H (H XL), G4000H (H XL), G5000H (H XL), G6000H (H XL), G7000H (H XL), TSKgurd column Can be mentioned.

<Preparation of sample>
The sample is put in THF and allowed to stand at a temperature of 25 ° C. for several hours, and then shaken sufficiently, mixed well with THF (until the sample is completely united), and further left to stand for 12 hours or more. At that time, the standing time in THF is set to 24 hours. Then, GPC (gel permeation chromatography) was passed through a sample processing filter (pore size 0.2 μm or more and 0.5 μm or less, for example, Myshor Disc H-25-2 (manufactured by Tosoh Corporation)). This sample. The sample concentration is adjusted so that the resin component is 0.5 mg / mL or more and 5.0 mg / mL or less.

<Measurement of melting point and heat of fusion of polyester resin and wax>
The melting point of the polyester resin and the wax is the peak temperature of the maximum endothermic peak in the DSC curve measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments). The amount of heat obtained from the peak area is defined as the amount of heat of fusion.
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 2 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measure at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak temperature of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the melting point and the amount of heat determined from the peak area as the heat of fusion.

<Measurement of glass transition temperature Tg of polyester resin>
The Tg of the polyester resin and the toner is measured according to 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 2 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measure at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again.
A specific heat change is obtained in the temperature range of 40 ° C. to 100 ° C. in the second temperature raising process. 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 polyester resin.

<Measurement of softening point of polyester resin and toner>
The softening point of the polyester resin and the toner is measured using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the apparatus. 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.

The “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation device Flow Tester CFT-500D” is defined as the softening point. The melting temperature in the 1/2 method is calculated as follows. First, 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). And the temperature of the flow curve when the amount of piston descent in the flow curve is the sum of X and Smin is the melting temperature in the 1/2 method.
About 1.0 g of the measurement sample is compressed at about 10 MPa at a temperature of 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NP System Co., Ltd.) for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.
The measurement conditions of CFT-500D are as shown in Table 2 below.

<Measurement of acid value of polyester resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the polyester resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion exchanged water is added to make 100 mL to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 mL of water, and ethyl alcohol (95% by volume) is added to make 1 L. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. As the factor of the potassium hydroxide solution, take 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, add a few drops of the phenolphthalein solution, titrate with the potassium hydroxide solution, and the hydroxylation required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 2.0 g of the pulverized polyester resin sample is precisely weighed into a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Solution factor, S: sample (g).

<Measurement of hydroxyl value of polyester resin>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value of the polyester resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
(1) Preparation of reagent 25 g of special grade acetic anhydride is placed in a 100 mL volumetric flask, pyridine is added to make a total volume of 100 mL, and shaken sufficiently to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.
Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add ion-exchanged water to make 100 mL, and obtain a phenolphthalein solution.
Dissolve 35 g of special grade potassium hydroxide in 20 mL of water and add ethyl alcohol (95% by volume) to 1 L. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container.
The factor of the potassium hydroxide solution is as follows. 25 mL of 0.5 mol / L hydrochloric acid is placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution is added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization. Determined from the amount of potassium solution. As the 0.5 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 1.0 g of a crushed polyester resin sample is precisely weighed into a 200 mL round bottom flask, and 5.0 mL of the acetylating reagent is accurately added to the sample using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.
Place a small funnel in the mouth of the flask and immerse the bottom of the flask about 1 cm in a glycerin bath at a temperature of about 97 ° C. and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.
After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1 mL of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further hydrolysis. After cooling, wash the funnel and flask walls with 5 mL of ethyl alcohol.
Add several drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration similar to the above operation is performed except that a polyester resin sample is not used.

(3) Substituting the obtained results into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D
Here, A: hydroxyl value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Factor of solution, S: sample (g), D: acid value (mgKOH / g) of polyester resin.

<Method for Measuring Toner Weight Average Particle Size (D4)>
The weight average particle diameter (D4) of the toner was calculated by measuring the number of effective measurement channels with 25,000 channels using the following apparatus and software, and analyzing the measurement data.
・ Precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube by the pore electrical resistance method
・ Beckman Coulter Multisizer 3 Version3.51 (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data
As the electrolytic aqueous solution used for the measurement, a 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, dedicated software was set up as follows.
In the “Change Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and the Kd value is “standard particles 10.0 μm” (Beckman Coulter ( The value obtained by using the product) is set. 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 to 60 μm.
The specific measurement method is as follows.

1. About 200 mL of the electrolytic aqueous solution is put 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 about 0.3 mL of a diluted solution obtained by diluting “Contaminone N” with ion-exchanged water 3 times as a dispersant is added thereto. “Contaminone N” is a 10% by weight aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) of a neutral detergent for cleaning precision measuring instruments with a pH of 7 comprising a nonionic surfactant, an anionic surfactant and an organic builder. .

3. Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and a predetermined amount of ion-exchanged water is placed in the water tank of the following ultrasonic disperser having an electrical output of 120 W, and the contamination water is contained in the water tank. Add about 2 mL of N.
Ultrasonic disperser: “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios Co., Ltd.)
4). 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. 4. above. In the state where the electrolytic aqueous solution in the beaker 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 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). The above 1. installed in the sample stand. The toner was dispersed in a round bottom beaker using a pipette. The aqueous electrolyte solution is dropped to adjust the measured concentration to about 5%. The measurement is performed until the number of measured particles reaches 50,000.
7). The fixed 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).

<Method for measuring thermal conductivity of toner>
Regarding the sample, 3.0 g of toner was weighed and set on a pellet making jig having a diameter of 25 mm, and then pressed with a Newton press under a pressure of 20 MPa for 1 minute to produce a pellet having a thickness of about 5 mm. The obtained pellet was allowed to stand for 24 hours or more in a normal temperature and normal humidity (temperature 23 ° C., relative humidity 50% RH) environment, and then used as a measurement sample.
The thermal conductivity measurement is performed using Hot Disk TPS2500 manufactured by Hot Disk Co., Ltd. at 60 mW for 40 seconds, the measurement point is 200 points, and analysis is performed from the measured value of 50 to 200 points, and the thermal conductivity (W / mK) is calculated. Asked. The average value of three measurements was taken as the thermal conductivity of the toner.

In the following examples, the number of parts is based on parts by mass.
<Manufacture of polyester resin A1>
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,10-decanediol as an alcohol monomer and 1,10 decanedioic acid as a carboxylic acid monomer were charged in the amounts shown in Table 3. . Then, 1 part by mass of tin dioctylate as a catalyst was added with respect to 100 parts by mass of the total amount of monomers, and the reaction was carried out for 6 hours while heating to 140 ° C. in a nitrogen atmosphere and distilling off water at normal pressure. Next, the reaction was carried out while increasing the temperature up to 200 ° C. at 10 ° C./hour. After reaching 200 ° C., the reaction was performed for 2 hours, and then the reaction vessel was depressurized to 5 kPa or less and reacted at 200 ° C. for 3 hours.

  Thereafter, the pressure in the reaction vessel was gradually released and returned to normal pressure, then the crystal nucleating agent (n-octadecanoic acid) shown in Table 3 was added, and the reaction was allowed to proceed 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 a temperature of 200 ° C. for 3 hours to obtain a polyester resin A1. In the MALDI-TOFMS mass spectrum of the obtained resin A1, since the peak of the composition in which n-octadecanoic acid was bonded to the molecular end of the resin A was confirmed, the molecular end of the resin A was bonded to the crystal nucleating agent. It was confirmed that Table 4 shows the physical properties of the polyester resin A1.

<Production of polyester resins A2 to A13>
Monomers, crystal nucleating agents, and amounts used were changed as shown in Table 3, and polyester resins A2 to A13 were obtained in the same manner as polyester resin A1 except that. In addition, in the MALDI-TOFMS mass spectrum of the obtained resin A2 to resin A12, a peak of the composition in which the crystal nucleating agent is bonded to the molecular end of the resin A is confirmed, and the molecular end and the crystal nucleating agent are bonded. Was confirmed.
Table 4 shows the physical properties of the polyester resins A2 to A13.

<Manufacture of polyester resin B1>
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the amount of monomer shown in Table 5 was added, and then dibutyltin was used as a catalyst in an amount of 1.5 mass relative to 100 mass parts of the total amount of monomers. Part was added. Next, the temperature was quickly raised to 180 ° C. under normal pressure in a nitrogen atmosphere, and then water was distilled off while heating from 180 ° C. to 210 ° C. at a rate of 10 ° C./hour to perform polycondensation. After reaching a temperature of 210 ° C., the pressure in the reaction vessel was reduced to 5 kPa or less, and polycondensation was performed under conditions of a temperature of 210 ° C. and 5 kPa or less to obtain a polyester resin B1.
At that time, the polymerization time was adjusted so that the softening point of the obtained polyester resin B1 was the value shown in Table 6 (115 ° C.). Table 6 shows the physical properties of the polyester resin B1.

<Production of polyester resins B2 to B4>
Monomers and amounts used were changed as shown in Table 5, and polyester resins B2 to B4 were obtained in the same manner as polyester resin B1 except that. Table 6 shows the physical properties of the polyester resins B2 to B4.

<Example 1>

The materials listed in Table 7 above were mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), and then rotated with a twin-screw kneader (PCM-30 type, manufactured by Ikekai Tekko Co., Ltd.). It knead | mixed on the conditions of several 3.3 s < ^-1 > and the kneading | mixing temperature of 120 degreeC. 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 pulverized product was finely pulverized with a mechanical pulverizer (T-250 manufactured by Turbo Kogyo Co., Ltd.). Further, the obtained finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect, to obtain toner particles having a weight average particle diameter of 7.0 μm.

  To 100 parts by mass of the obtained toner particles, the materials shown in Table 8 below were added and mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain toner 1.

得られたトナーの材料構成と物性に関しては表１３に記載したとおりである。
また、得られたトナーの評価に関しては、下記（１）〜（４）の評価手法と判断基準をもって評価した。

The material composition and physical properties of the obtained toner are as described in Table 13.
The obtained toner was evaluated by the following evaluation methods (1) to (4) and judgment criteria.

(1) Fast fixability (fixable transit time)
A commercially available color laser printer Color Laser Jet CP4525 (manufactured by HP) was used for the evaluation of the fast fixing property of the toner.
The fixing device of the evaluation machine was taken out and used as an external fixing device in which the fixing temperature, fixing nip width and process speed of the fixing device can be arbitrarily set. As the media, color laser copier paper (manufactured by Canon, 80 g / m ² ) was used. The product toner was extracted from a commercially available cyan cartridge, the inside was cleaned by air blow, and 150 g of toner 1 was filled. In each of the magenta, yellow, and black stations, product toner was extracted, and magenta, yellow, and black cartridges with the remaining toner amount detection mechanism disabled were inserted.

The measurement environment was a room temperature and low humidity (temperature 23 ° C., relative humidity 5% RH), and a solid unfixed image was output so that the applied toner amount was 0.8 mg / cm ² .
The fixing temperature of the fixing device is 140 ° C., the fixing nip width is 8 mm and 12 mm, and the process speed is increased every 50 mm / second in the range from 200 mm / second to 500 mm / second. The fixed image was fixed. The obtained solid image was rubbed and rubbed 5 times with a Sylbon paper to which a load of about 100 g was applied, and the point at which the density reduction rate of the image density before and after the rub was 20% or less was defined as the passable time. The shorter the fixing time, the better the fast fixing property, and the toner was evaluated according to the criteria shown in Table 9 below. The evaluation results are shown in Table 14.

(2) Light pressure fixability (separable temperature range)
An evaluation machine was prepared in the same manner as in the evaluation method (1) for evaluating the light pressure fixability of the toner.
The measurement environment was a high-temperature and high-humidity environment (temperature 30 ° C., relative humidity 85% RH), and a solid unfixed image was output so that the applied toner amount was 0.8 mg / cm 2.
The solid unfixed image was fixed while the fixing nip width of the fixing device was 6 mm, the process speed was 400 mm / second, and the fixing temperature was increased by 5 ° C. The solid image thus obtained was rubbed and reciprocated 5 times with a Sylbon paper to which a load of about 100 g was applied, and the point at which the density reduction rate of the image density before and after the rub was 20% or less was determined as the fixable temperature. The temperature at which the received image was wound around the fixing device was determined as the separable temperature. The temperature difference (separable temperature−fixable temperature) was defined as a separable temperature range. The larger the separable temperature range, the better the toner, and the toner was evaluated according to the criteria shown in Table 10 below. The evaluation results are shown in Table 14.

(3) Durability stability evaluation 1 (High-speed, low printing ratio two-component system evaluation)
Toner durability evaluation No. 1 was evaluated using a commercially available copying machine iR-ADVANCE C5051 (manufactured by Canon Inc.).
The cyan developer was taken out and the inside was cleaned by air blow. Then, a two-component developer in which 25 g of toner 1 and 225 g of 50 μm ferrite carrier were mixed was filled in the developer. Further, the cyan bottle was taken out, the inside was cleaned by air blow, and then 500 g of toner 1 was filled.
The measurement environment was high-temperature and high-humidity (temperature 30 ° C., relative humidity 85% RH). Then, the BET values (specific surface area according to the BET method) of the toner before and after the endurance were measured, and the ratio was defined as the BET reduction rate (%) and evaluated according to the judgment criteria described in Table 11 below. The evaluation results are shown in Table 14.

(4) Durability stability evaluation part 2 (High-speed low printing ratio one-component system evaluation)
Toner durability evaluation No. 2 was evaluated in the same manner as in evaluation method (1).
The measurement environment was high temperature and high humidity (temperature 30 ° C., relative humidity 85% RH). The process speed was 400 mm / second and the printing rate was 1%. Then, the BET values of the toners before and after the endurance were measured, and the ratio was defined as a BET reduction rate (%) and evaluated according to the judgment criteria described in Table 12 below. The evaluation results are shown in Table 14.

<Examples 2 to 21>
Toners 2 to 21 were produced in the same manner as in Example 1 except that the material configuration of the toner was changed as shown in Table 13. Table 13 shows the physical properties of Toners 2 to 21. Table 14 shows the results of evaluation performed in the same manner as in Example 1.
In Example 4, AP-170S (manufactured by MARUKA Co., Ltd.) having a primary particle number average particle diameter (D1) of 0.050 μm and a GI value of 33.71 was used as boron nitride. In Example 6, UHP-S1 (manufactured by Showa Denko KK) having a primary particle number average particle size of 1.0 μm and a GI value of 1.97 was used as boron nitride.
In Example 6, AP-10S (manufactured by MARUKA Co., Ltd.) having a primary particle number average particle size of 3.0 μm and a GI value of 1.97 was used as boron nitride.

<Comparative Examples 1-4>
Toners 22 to 25 were produced in the same manner as in Example 1 except that the material configuration of the toner was changed as shown in Table 13. Table 13 shows the physical properties of Toners 22 to 25. Table 14 shows the results of evaluation performed in the same manner as in Example 1.
In Comparative Example 4, AP-10S (manufactured by MARUKA Co., Ltd.) having a primary particle number average particle size of 0.10 μm and a GI value of 95.6 was used as boron nitride.

Incidentally, SP value used in the present invention, more commonly used are that the method is calculated from the type and proportion of monomers constituting the polymer. The SP value of the polyester resin A represents the SP value of the polyester molecular chain excluding the crystal nucleating agent.
The SP value Sa ((cal / cm ³ ) ^1/2 ) of the crystalline polyester resin A is preferably 9.00 or more and 11.50 or less because the degree of crystallinity is high. In the crystalline polyester resin A, a low SP value indicates that the aliphatic carboxylic acid and / or the aliphatic alcohol constituting the crystalline polyester resin A has a large number of carbon atoms. From the viewpoint of increasing the crystallinity of the crystalline polyester resin A, the larger the number of carbon atoms, that is, the lower the SP value, the better. Further, from the viewpoint of increasing the compatibility of the crystallized polyester resin A, the smaller the number of carbon atoms, that is, the higher the SP value, the better.

Claims (3)

A toner having toner particles containing a crystalline polyester resin A, an amorphous polyester resin B, a hexagonal boron nitride, and a colorant,
The crystalline polyester resin A has a crystal nucleating agent site at the end of the polyester molecular chain,
The boron nitride is
The number average particle size of the primary particles is 0.050 μm or more and 3.0 μm or less,
A toner having a crystallinity GI value obtained by a powder X-ray diffraction method of 1.60 or more and 35.0 or less. The crystal nucleant site is
An aliphatic monocarboxylic acid having 10 to 30 carbon atoms and / or
The toner according to claim 1, wherein the toner is a part derived from an aliphatic monoalcohol having 11 to 31 carbon atoms. SP value Sa ((cal / cm ³ ) ^1/2 ) of the crystalline polyester resin A is 9.00 or more and 11.50 or less,
The toner according to claim 1, wherein the Sa and the SP value Sb ((cal / cm ³ ) ^1/2 ) of the amorphous polyester resin B satisfy the following formula (1).
-1.50 <= Sb-Sa <= 0.80 ... Formula (1)