JP6292865B2 - Toner and two-component developer - Google Patents

Description

  The present invention relates to a toner and a two-component developer used in electrophotography and electrostatic recording.

  In full-color image forming apparatuses such as full-color copying machines or full-color printers, further low-temperature fixability is required to support high-speed printing. In order to improve the low-temperature fixability, it is necessary to quickly melt the toner in a short time after passing through the nip of the fixing device. For this reason, in recent years, a toner using a crystalline polyester resin as a binder resin in addition to an amorphous polyester resin has been studied (Patent Document 1). When such a toner is produced, the amorphous polyester resin and the crystalline polyester resin are mixed by melt-kneading. When the melt-kneading process is used, the crystalline polyester resin is compatible with the amorphous polyester resin. In some cases, the heat-resistant storage stability of the toner may be reduced. Therefore, there are a method for controlling the crystallization speed of the toner and a method for performing a heating process (annealing process) on the manufactured toner to crystallize the crystalline polyester resin in the toner, thereby improving the heat resistant storage stability of the toner. Proposals have been made (Patent Documents 2 and 3).

  However, in any of the above methods, there has been a case where a phenomenon (image adhesion) occurs in which images are bonded to each other after fixing.

  Although the mechanism is not clear, the present inventors infer as follows. In a toner containing a crystalline polyester resin and an amorphous polyester resin, the crystalline polyester resin and the amorphous polyester resin are compatible at the time of fixing and are plasticized. As a result, the glass transition point (Tg) of the toner is lowered, and the toner is fixed even at a low temperature. However, after the toner is fixed, the toner has a low glass transition point, and sheet discharge adhesion occurs.

  When the conventionally proposed annealing step is performed, the Tg of the toner immediately after production can be improved, so that the heat resistant storage stability of the toner can be improved. However, after the toner is fixed, similarly to the toner that has not been subjected to the annealing process, the Tg of the toner is lowered, so that it is not possible to prevent the paper discharge adhesion.

  Patent Document 2 describes the crystallization speed, but the crystallization speed is calculated based on the degree of crystallization when held at each temperature for 20 hours. However, the holding time of 20 hours is different in order from the time of several minutes to several tens of minutes when the paper discharge adhesion occurs, and the paper discharge resistance cannot be improved.

  Discharge adhesion is prominent when a large number of papers are ejected in a short period of time as in high-speed printing and double-sided printing is performed to save paper. It has become a challenge. For this reason, there is a need for a toner that has improved sheet discharge adhesion resistance while improving low-temperature fixability and heat-resistant storage stability.

JP 2001-222138 A JP 2009-258234 A JP 2009-063992 A

  An object of the present invention is to provide a toner that has solved the above-described problems, that is, a toner that has improved sheet discharge resistance while improving low-temperature fixability and heat-resistant storage stability.

The above problem can be solved by the toner having the following configuration. The present invention is a toner comprising a binder resin and a wax, wherein the binder resin includes a crystalline polyester resin and an amorphous polyester resin, and the crystalline polyester resin has a crystal nucleating agent site, The crystal nucleating agent site is a site derived from an aliphatic monoalcohol having 10 to 30 carbon atoms and / or an aliphatic monocarboxylic acid having 11 to 31 carbon atoms, and the amorphous resin in the binder resin. The toner is characterized in that the content of the functional polyester resin is 50% by mass or more and the toner satisfies the following mathematical formulas (1) to (4).

TgA-TgB ≧ 10.0 (° C.) (1)
TgC-TgB ≧ 5.0 (° C.) (2)
TgA ≧ 45.0 (° C.) (3)
TgC ≧ 40.0 (° C.) (4).

  In the above formulas (1) to (4), TgA represents the glass transition temperature (° C.) of the toner. TgB is a glass transition temperature obtained by heating the toner to 150 ° C., cooling it with liquid nitrogen within 5 seconds after completion of heating, taking out the liquid nitrogen, and performing differential scanning calorimetry within 1 minute ( ° C). TgC is a glass transition temperature (° C.) obtained by heating the toner to 150 ° C., cooling with liquid nitrogen within 5 seconds after the completion of heating, and holding the toner at 50 ° C. for 20 minutes, and then performing differential scanning calorimetry. ).

  The present invention also provides a two-component developer including the toner and a magnetic carrier.

  According to the present invention, it is possible to provide a toner having improved sheet discharge adhesion resistance while improving low-temperature fixability and heat-resistant storage stability.

  As a result of intensive studies, the present inventors have obtained a toner containing a binder resin and a wax, the binder resin containing a crystalline polyester resin and an amorphous polyester resin, and the amorphous resin in the binder resin. When the content of the polyester resin is 50% by mass or more and the toner satisfies the following mathematical formulas (1) to (4), the toner has three low-temperature fixing properties, heat-resistant storage properties, and paper-proof adhesive properties. I found that it can be improved at the same time.

TgA-TgB ≧ 10.0 (° C.) (1)
TgC-TgB ≧ 5.0 (° C.) (2)
TgA ≧ 45.0 (° C.) (3)
TgC ≧ 40.0 (° C.) (4).

  In the above formulas (1) to (4), TgA represents the glass transition temperature (° C.) of the toner.

  TgB is a glass transition temperature obtained by heating the toner to 150 ° C., cooling it with liquid nitrogen within 5 seconds after completion of heating, taking out the liquid nitrogen, and performing differential scanning calorimetry within 1 minute ( ° C). Specifically, 2 mg of the toner is precisely weighed in a DSC pan and heated on a hot plate heated to 150 ° C. for 5 minutes. Within 5 seconds after the completion of heating, the toner is placed in 100 ml or more of liquid nitrogen liquid, cooled for 1 minute or more, then taken out from the liquid nitrogen and subjected to DSC measurement within 1 minute.

  TgC is a glass transition temperature (° C.) obtained by heating the toner to 150 ° C., cooling with liquid nitrogen within 5 seconds after the completion of heating, and holding the toner at 50 ° C. for 20 minutes, and then performing differential scanning calorimetry. ). Specifically, 2 mg of the toner is precisely weighed in a DSC pan and heated on a hot plate heated to 150 ° C. for 5 minutes. Within 5 seconds after the heating is completed, the toner is placed in 100 ml or more of liquid nitrogen liquid, cooled for 1 minute or more, taken out from the liquid nitrogen, and held at 50 ° C. for 20 minutes within 1 minute, and then DSC measurement is performed. Hereinafter, the constituent features of the present invention will be described in detail.

[Compatibilization speed]
Formula (1) indicates the difference in the glass transition point of the toner before and after fixing.

  The Tg of the toner at the time of fixing cannot be measured. However, as a result of intensive studies, the present inventors have precisely weighed 2 mg of toner in a DSC pan and heated it on a hot plate heated to 150 ° C. for 5 minutes, and within 5 seconds after the heating, 100 ml or more of liquid It was found that the glass transition temperature TgB measured by DSC within 1 minute after taking out from liquid nitrogen was correlated with toner fixability after being immersed in a nitrogen solution and cooled for 1 minute or longer. This TgB is considered to indicate the glass transition temperature at the time of fixing.

  If the difference between the glass transition points of the toner before fixing and at the time of fixing is 10.0 ° C. or higher, the toner Tg before fixing is high, and thus heat-resistant storage stability is good. Fixability is improved. That is, both heat-resistant storage stability and low-temperature fixability of the toner can be achieved. This indicates that the compatibilization speed of the crystalline polyester resin and the amorphous polyester resin is high, and the crystalline polyester quickly dissolves in the amorphous polyester when the toner is fixed, and plasticizes the amorphous polyester. It is shown that. Specifically, the value of “TgA−TgB” needs to be 10.0 ° C. or higher, preferably 12.0 ° C. or higher, more preferably 15.0 ° C. or higher.

  Next, a method for increasing the compatibility rate of the crystalline polyester resin and the amorphous polyester resin will be described.

  The melting point Tc of the crystalline polyester resin is preferably 100 ° C. or less. After the crystalline polyester resin melts, the crystalline polyester resin becomes compatible with the amorphous polyester resin. For this reason, if the melting point of the crystalline polyester resin is 100 ° C. or less, the crystalline polyester resin quickly melts at the time of fixing the toner, and is compatible with the amorphous polyester resin, so that the Tg of the toner is lowered. On the other hand, when the melting point of the crystalline polyester resin is higher than 100 ° C., the melting of the crystalline polyester resin does not start easily when fixing the toner, and the start of the compatibility is delayed. The melting point of the crystalline polyester resin is preferably 50 ° C. or higher from the viewpoint of heat resistant storage stability of the toner.

  In order to increase the compatibility rate between the crystalline polyester resin and the amorphous polyester resin, it is preferable to make the crystalline polyester resin and the amorphous polyester resin easily compatible, that is, the crystalline polyester resin and the amorphous polyester resin. It is preferable to reduce the difference in SP value of the polyester resin. Specifically, it is preferable that the SP value (SPa) of the crystalline polyester resin and the SP value (SPb) of the amorphous polyester resin contained in the toner of the present invention satisfy the following formula (5).

  −1.5 ≦ SPb−SPa ≦ 1.5 (5).

  Conventionally, the SP value (solubility parameter) has been used as an index indicating the ease of mixing between resins and the ease of mixing between resin and wax. The value of “SPb−SPa” is an index indicating the ease of compatibility between the crystalline polyester resin and the amorphous polyester resin during heat melting. By controlling the SP value of each resin within this range, the compatibility rate of the crystalline polyester resin to the amorphous polyester resin is increased, the Tg decrease during toner fixing is increased, and the toner is fixed at low temperature. Improves.

  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 can be controlled by the type and amount of the raw material monomer used during the production of the polyester resin. In order to increase the SP value of the polyester resin, for example, a monomer having a large SP value may be used. On the other hand, in order to reduce the SP value of the polyester resin, for example, a monomer having a small SP value may be used.

  The compatibility rate can also be improved by reducing the dispersion diameter of the crystalline polyester resin phase in the amorphous polyester resin. By reducing the dispersed diameter of the phase of the crystalline polyester resin, the contact area between the crystalline polyester resin and the amorphous polyester resin is increased, and the number of places where the compatibility occurs is increased. As a result, the compatibility rate of both resins is improved.

  In order to finely disperse the crystalline polyester resin phase in the amorphous polyester resin, it is more preferable that the crystalline polyester resin has a crystal nucleating agent site. When the crystalline polyester resin has a crystal nucleating agent site, a large number of small-sized crystals can be generated when the crystalline polyester resin is crystallized. As a result, the interface between the crystalline polyester resin and the amorphous polyester resin is increased, and the crystalline polyester resin can quickly be compatible with the amorphous polyester resin when the toner is fixed.

  By reducing the molecular weight of the crystalline polyester resin, the compatibility rate of the crystalline polyester resin in the amorphous polyester resin can be increased. By reducing the molecular weight of the crystalline polyester, the molecular mobility of the crystalline polyester resin is increased, and the crystalline polyester resin moves quickly into the amorphous polyester resin, so that the compatibility speed is improved.

  As described above, as a method for increasing the compatibility rate between the crystalline polyester resin and the amorphous polyester resin, the melting point, crystal size, and molecular weight of the crystalline polyester resin are controlled, and the crystalline polyester resin There are many, such as control of the difference in SP value from the amorphous polyester resin. The inventors of the present invention satisfy both the above formula (1) regardless of the presence or absence of any of these methods, or some combination of these methods, to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner. Found to be effective.

[Crystallization speed]
Equation (2) shows the difference in the glass transition point of the toner at the time of fixing and after fixing (after paper discharge). As a result of intensive studies, the present inventors have observed that the adhesion of paper discharge occurs mainly within a few minutes to several tens of minutes after paper discharge, so that the crystalline polyester resin is quickly crystallized after fixing the toner. Thus, it has been found that if the Tg of the toner on the fixed image is sufficiently increased, the phenomenon that the images stick to each other at the time of paper discharge does not occur. That is, it is necessary that the crystallization speed of the crystalline polyester resin in the toner is high, and as a result, the toner crystallization on the fixed image proceeds quickly, and as a result, the Tg of the toner on the image increases and the images are separated from each other. I found out that there was no sticking. Specifically, the value of “TgC-TgB” needs to be 5.0 ° C. or higher, preferably 7.0 ° C. or higher, more preferably 10.0 ° C. or higher.

  Next, a method for increasing the crystallization speed of the crystalline polyester resin will be described.

  In order to increase the crystallization speed of the crystalline polyester resin, it is preferable to use a hydrocarbon wax as the wax. Although the mechanism is not clear, the present inventors believe that the wax acts as a nucleating agent. Specifically, when the toner is melted at the time of fixing and cooled after the fixing, first, a wax having high crystallinity is crystallized. It is believed that this crystallized wax acts as a crystal nucleating agent and promotes crystallization of the crystalline polyester. In particular, when the melting point Tw of the wax is higher than the melting point Tc of the crystalline polyester resin, the wax is first crystallized, and then the crystalline polyester resin is crystallized, so that the crystallization rate of the crystalline polyester resin is further increased. Specifically, it is preferable that Tw and Tc satisfy the relationship of the following formula (6).

  Tc <Tw <100.0 (° C.) (6).

  If the difference between Tw and Tc is less than 20 ° C., crystallization of the wax and solidification of the crystalline polyester resin occur at the same time, so that the crystallization of the crystalline polyester resin proceeds more efficiently. Specifically, it is preferable to satisfy the relationship of the following mathematical formula (7). Moreover, it is more preferable to satisfy | fill the relationship of the following numerical formula (8).

Tw−Tc <20.0 (° C.) (7)
Tw−Tc <10.0 (° C.) (8).

  More preferably, the crystalline polyester resin has a crystal nucleating agent site. Since the crystalline polyester resin has a crystal nucleating agent site, the crystalline polyester resin is rapidly crystallized from the crystal nucleating agent site. Furthermore, the crystallization speed of the crystalline polyester resin can be increased by reducing the molecular weight of the crystalline polyester. By reducing the molecular weight of the crystalline polyester, the molecular mobility of the crystalline polyester resin is increased, the molecules are quickly oriented, and the crystallization speed is improved. The weight average molecular weight Mw of the crystalline polyester resin is preferably 100,000 or less, and more preferably 45,000 or less.

  As described above, methods for increasing the crystallization speed of crystalline polyester resin and amorphous polyester resin include the control of the difference in melting point between crystalline polyester and wax, and the presence of a crystalline nucleating agent site in crystalline polyester. , And control of the molecular weight of the crystalline polyester. The inventors of the present invention satisfy the above formula (2) regardless of the presence or absence of any one of these methods or some combination of these methods. It was found to be effective for both.

  Formula (3) indicates that the Tg of the toner needs to be 45 ° C. or higher in order to improve the heat resistant storage stability of the toner. This requirement can be achieved by controlling the difference in SP value between the crystalline polyester resin and the amorphous polyester resin, or by performing an annealing (holding at a high temperature) treatment. TgA is preferably 47 ° C. or higher, more preferably 50 ° C. or higher. Further, TgA is preferably 65 ° C. or less, and more preferably 60 ° C. or less, from the viewpoint of low-temperature fixability.

  Formula (4) indicates that the Tg of the toner after paper discharge needs to be 40 ° C. or higher in order to improve the paper discharge resistance. Since the TgC is high and the crystallization speed represented by the mathematical formula (2) is high, it is possible to improve the discharge resistance of the toner. TgC is preferably 42 ° C. or higher, more preferably 45 ° C. or higher.

  Hereinafter, the configuration of the toner of the present invention will be described in detail.

  The toner of the present invention is a toner containing a binder resin and a wax, and the binder resin contains a crystalline polyester resin and an amorphous polyester resin. The toner of the present invention needs to contain a crystalline polyester resin in order to improve low-temperature fixability. The melting point Tc of the crystalline polyester resin is preferably 100 ° C. or less from the viewpoint of low-temperature fixability of the toner. Moreover, it is preferable that the SP value (SPa) of the crystalline polyester resin and the SP value (SPb) of the amorphous polyester resin satisfy the above formula (5).

  The crystalline polyester resin and the crystalline polyester resin are resins each having a polyhydric alcohol unit and a polycarboxylic acid unit.

[Raw material for crystalline polyester resin]
As an alcohol component used for the raw material monomer of the crystalline polyester resin, an aliphatic diol having 6 to 18 carbon atoms is preferable from the viewpoint of enhancing the crystallinity of the crystalline polyester resin. Among these, aliphatic diols having 6 to 12 carbon atoms are preferable from the viewpoints of toner fixing properties and heat-resistant storage 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 include 12-dodecanediol. The content of the aliphatic diol is preferably 80.0 to 100.0 mol% in the alcohol component from the viewpoint of further improving the crystallinity of the crystalline polyester resin.

  The alcohol component for obtaining the crystalline polyester resin may contain a polyhydric alcohol component other than the above aliphatic diol, and examples thereof include the following. Bisphenol represented by the following chemical formula (I), including polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane, and the like Aromatic diols such as alkylene oxide adducts of A; trihydric or higher alcohols such as glycerin, pentaerythritol, trimethylolpropane.

  In the above chemical formula, R represents an alkylene group having 2 or 3 carbon atoms. x and y represent positive numbers, and the sum of x and y is 1 to 16, preferably 1.5 to 5.

  As a carboxylic acid component used for the raw material monomer of the crystalline polyester resin, an aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms is preferable. Among these, an aliphatic dicarboxylic acid compound having 6 to 12 carbon atoms is preferable from the viewpoint of toner fixing properties and heat-resistant storage 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 80.0 to 100.0 mol% in the carboxylic acid component.

  As a carboxylic acid component for obtaining a crystalline polyester resin, 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 (carbon number 1 to 3) esters of these acids. It is done. 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 trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and other aromatic carboxylic acids, and these acids. And anhydrides of these acids and derivatives of these acids such as alkyl (C1-C3) esters.

  The molar ratio (carboxylic acid component / alcohol component) between the alcohol component and the carboxylic acid component, which are raw material monomers of the crystalline polyester resin, is preferably 0.80 or more and 1.20 or less.

  The weight average molecular weight Mw of the crystalline polyester resin is preferably 8000 or more and 100,000 or less, and 12,000 or more and 45,000 or less in order to improve the compatibility rate, the crystallization rate, and the heat resistant storage stability. More preferably.

[Crystal nucleant site]
Binding-crystalline polyester resin has a crystal nucleating agent sites. Raw material for forming a binding nucleating agent site, having 10 or more carbon atoms, 30 or less aliphatic mono alcohol and / or at least 11 carbon atoms, 31 or less of aliphatic monocarboxylic acids. That is, the crystal nucleating agent portion has a structure in which the aliphatic monoalcohol and / or aliphatic monocarboxylic acid is condensed at the terminal of the crystalline polyester resin in the crystalline polyester resin.

  Examples of the aliphatic monoalcohol include 1-decanol, stearyl alcohol, and behenyl alcohol. Examples of the aliphatic monocarboxylic acid include stearic acid, alkydic acid, and behenic acid.

  In addition, the molecular weight of the crystal nucleating agent moiety is preferably 100 or more and 10,000 or less, more preferably 150 or more and 5,000 or less, from the viewpoint of increasing the reactivity of the molecular chain terminal of the crystalline polyester resin. .

  From the viewpoint of increasing the crystallization rate, the crystal nucleating agent portion is preferably 0.1 mol% or more and 7.0 mol% or less, more preferably 0.5 mol% in the monomer constituting the crystalline polyester resin. The content is 4.0 mol% or less.

  A method for determining whether or not the crystal nucleating agent site is bonded to the crystalline polyester resin will be described later.

[Raw material of amorphous polyester resin]
As an amorphous polyester resin that can be used in the present invention, the SP value with respect to the crystalline polyester resin preferably satisfies the formula (5).

  The following are mentioned as an alcohol component used for the raw material monomer of an amorphous polyester resin. Examples of the divalent alcohol component include the following. 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene adduct, 2,2-bis (4-hydroxyphenyl) propane polyoxyethylene adduct, and the like represented by the above formula (I) A alkylene oxide adduct of A; ethylene glycol, 1,3-propylene glycol, neopentyl glycol and the like. Examples of the trivalent or higher alcohol component include sorbitol, pentaerythritol, dipentaerythritol, and the like. The dihydric alcohol component and the trihydric or higher polyhydric alcohol component can be used alone or in combination of a plurality of compounds.

  Moreover, the following are mentioned as a carboxylic acid component used for the raw material monomer of an amorphous polyester resin. 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. . 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, anhydrides of these acids, And lower alkyl esters of these acids.

  The glass transition temperature (Tg) of the amorphous polyester resin is preferably 45 ° C. or higher and 75 ° C. or lower from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. The softening point of the amorphous polyester resin is preferably 80 ° C. or higher and 150 ° C. or lower from the viewpoint of low-temperature fixability of the toner.

  The mass ratio of the crystalline polyester resin and the amorphous polyester resin contained in the toner is preferably from 3:99 to 50:50 from the viewpoint of low-temperature fixability of the toner and long-term storage stability of the image. 5: 95-40: 60 is more preferable.

〔wax〕
The toner of the present invention needs to use a wax in order to increase the crystallization speed of the crystalline polyester and the releasability of the toner. In order to increase the crystallization speed of the toner, the type of wax is preferably a hydrocarbon wax, and the melting point Tw of the wax is preferably less than 100.0 ° C. The melting point of the wax is preferably 60 ° C. or higher from the viewpoint of heat resistant storage stability of the toner. Furthermore, if the melting point of the wax is higher than the melting point of the crystalline polyester resin and the difference is 20 ° C. or less, the crystallization of the crystalline polyester resin can be further promoted.

  The wax is preferably a hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, or paraffin wax from the viewpoint of ease of dispersion in the toner and high releasability of the toner. If necessary, two or more kinds of waxes may be used in combination.

  Specific examples of the wax include the following. Sazol H1, H2, C80, C77 (Schumann Sazol), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12, HNP-51 (Nippon Seiki Co., Ltd.).

  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. The wax is preferably contained in an amount of 1.0 part by mass or more and 20.0 parts by mass or less based on a total amount of 100.0 parts by mass of the crystalline polyester resin and the amorphous polyester resin.

[Colorant]
The colorant used in the toner of the present invention is not particularly limited, and a known colorant can be used. Specific examples include the following. 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 black colorant include carbon black; a magnetic material; a black colorant using a yellow colorant, a magenta colorant, and a cyan colorant.

  Examples of the color pigment for magenta toner 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: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 185, 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 color pigment for cyan toner include the following. C. I. Pigment blue 2, 3, 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 the coloring dye for cyan include C.I. I. There is Solvent Blue 70.

  Examples of the color pigment for yellow 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 coloring dye for yellow include C.I. I. There is Solvent Yellow 162.

  The amount of the colorant used is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

[Flowability improver]
In the toner of the present invention, 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 and dry process silica; these silicas with silane coupling agent, titanium coupling agent, or silicone oil Treated silica with surface treatment. A preferable 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. As a preferred method, a 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 Rudisiloxane.

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, preferably a viscosity at 25 ° C. is 30 mm ² / s or more, or less 1000 mm ² / s. 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 on a silica fine powder as a base; silicone oil in an appropriate solvent A method in which silica is dissolved or dispersed, then 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 0.1 to 8.0 parts by weight, more preferably 0.1 to 4.0 parts by weight with respect to 100.0 parts by weight of the toner particles. is there.

  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.

[Two-component developer]
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 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.

[Toner Production Method]
The method for producing the toner of the present invention is not particularly limited, but the pulverization method is preferred from the viewpoint of obtaining a toner having better low-temperature fixability. In the pulverization method, in the melt-kneading step, the material is mixed by applying shear so that the molecular chain of the crystalline polyester resin can easily enter the phase of the amorphous polyester resin.

  Hereinafter, a method for obtaining the toner of the present invention by the pulverization method will be described.

  In the raw material mixing step, a predetermined amount of a crystalline polyester resin, an amorphous polyester resin, a wax, a colorant, and other additives as necessary are mixed and mixed as materials constituting the toner particles. To do. 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 nauter mixer, and a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.).

  Next, the mixed material is melt-kneaded to disperse the colorant and the like in the crystalline polyester resin and the amorphous 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 (Kobe Steel Co., Ltd.), TEM type twin screw extruder (Toshiba Machine Co., Ltd.), PCM kneading machine (Ikegai Iron Works Co., Ltd.), twin screw extruder (K-C K Company) Product), 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 step, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill Finely pulverize with a turbomill (made by Turbo Industries) or air jet type fine pulverizer. Then, if necessary, classification such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification 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 machine or a sieving machine.

  If necessary, after pulverization, using a hybridization system (manufactured by Nara Machinery Co., Ltd.), mechano-fusion system (manufactured by Hosokawa Micron), faculty (manufactured by Hosokawa Micron), Meteorenbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) It is also possible to perform surface treatment of toner particles such as spheroidization. Furthermore, if necessary, desired additives can be sufficiently mixed by a mixer such as a Henschel mixer.

〔Evaluation method〕
A method for measuring physical properties of the crystalline polyester resin, the amorphous polyester resin and the toner is as follows. The physical property values are also measured based on these methods in Examples and the like described later.

<1. Measurement of site of crystal nucleating agent>
2 mg of a resin sample is precisely weighed, and 2 ml of chloroform is added and dissolved to prepare a sample solution. A crystalline polyester resin is used as the resin sample, but a toner containing the crystalline polyester resin 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. In addition, after accurately weighing 3 mg of sodium 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. As an analytical instrument, MALDI-TOFMS (Reflex III manufactured by Bruker Daltonics) is used to obtain a mass spectrum. 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 a peak corresponding to a structure in which a crystal nucleating agent is bonded to the molecular end exists.

<2. Measurement of TgA, TgB, and TgC of toner>
The glass transition temperatures TgA, TgB, and TgC of the toner are 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, these glass transition temperatures are measured as follows.

(1) TgA
Weigh accurately 2.0 ± 0.1 mg of toner and place it in an aluminum pan for DSC. Next, Tg is measured by the above method. Let the obtained Tg be TgA.

(2) TgB
Weigh accurately 2.0 ± 0.1 mg of toner and place it in an aluminum pan for DSC. The toner is heated on a hot plate heated to 150 ° C. for 5 minutes. Thereafter, it is placed in a liquid nitrogen solution of 100 ml or more in a container such as a polycup within 5 seconds, cooled for 1 minute or more, then taken out from the liquid nitrogen, and Tg is measured by the above method within 1 minute. The obtained Tg is defined as TgB.

(3) TgC
Weigh accurately 2.0 ± 0.1 mg of toner and place it in an aluminum pan for DSC. The toner is heated on a hot plate heated to 150 ° C. for 5 minutes. Then, put it in a liquid nitrogen liquid of 100 ml or more in a container such as a polycup within 5 seconds, cool it for 1 minute or more, take it out from liquid nitrogen, set it in the DSC apparatus within 1 minute, and set it at 50 ° C. Heat for 20 minutes. Next, Tg is measured by the above method. Let the obtained Tg be TgC.

<3. Measurement of melting point and heat of fusion of crystalline polyester resin and wax>
The melting point of the crystalline polyester resin and wax is the DSC curve measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments), with the peak temperature of the maximum endothermic peak as the melting point, 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. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C. and held for 1 minute, then the temperature is 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 obtained from the peak area is defined as the heat of fusion.

<4. Measurement of Glass Transition Temperature (Tg) of Amorphous Polyester Resin>
The Tg of the amorphous polyester resin is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments). The temperature correction of the apparatus detection unit, the amount of sample used, and the temperature raising condition are the same as those in the case of the “measurement of melting point and heat of fusion”. 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 amorphous polyester resin.

<5. Measurement of weight average molecular weight by gel permeation chromatography (GPC)>
The column is stabilized in a 40 ° C. heat chamber, and tetrahydrofuran (THF) is allowed to flow through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected and measured. 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, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is suitably used, and at least about 10 standard polystyrene samples are used. The detector uses an RI (refractive index) detector. In addition, as a column, it is good to combine several commercially available polystyrene gel columns, for example, the following combinations are mentioned. Showa Denko Co., Ltd. of shodex GPC KF-801,802,803,804,805,806,807,800P of the combination and, Tosoh Corp. of _{TSKgel G1000H (H XL), G2000H} (H XL), G3000H (H XL) , G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), TSKgourd column combination.

  Moreover, a sample is produced as follows.

  Put 0.05 g of the sample in 10 ml of THF, leave it at 25 ° C. for several hours, shake it well, mix well with THF (until the sample is completely united), and let stand for more than 12 hours. Note that the total standing time in THF is 24 hours. Then, a sample processing filter (pore size of 0.2 μm or more and 0.5 μm or less, for example, Myssho Disc H-25-2 (manufactured by Tosoh Corporation)) can be used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 mg / ml or more and 5.0 mg / ml or less.

<6. Measurement of softening point of amorphous polyester resin and toner>
The softening point of the amorphous polyester resin and 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 by the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder, and the piston descends at this time. A flow curve showing the relationship between quantity 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, a value X that is a half of the difference between the piston lowering amount Smax when the outflow is finished and the piston lowering amount Smin when the outflow starts is obtained (X = (Smax−Smin) / 2). In the flow curve, the temperature of the flow curve when the piston lowering amount is “Smin + X” is the melting temperature in the 1/2 method.

  As a measurement sample, a sample of about 1.0 g was compression-molded at about 10 MPa for about 60 seconds at 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NPA System). 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 method.
Temperature increase rate: 4 ° C./min.
Starting temperature: 50 ° C.
Achieving temperature: 200 ° C.
Piston cross-sectional area: 1.000 cm ² .
Test load (piston load): 10.0 kgf (0.9807 MPa).
Preheating time: 300 seconds.
Die hole diameter: 1.0 mm.
Die length: 1.0 mm.

<7. Measuring method of weight average particle diameter (D4) of toner>
The weight average particle diameter (D4) of the toner is determined based on the precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting and analyzing the measurement data, the measurement data is measured with 25,000 effective channels. 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, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) 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 to 60 μm.

Specific measurement methods are as described in the following (1) to (7).
(1) About 200 ml of the electrolytic solution is placed in a 250 ml round bottom beaker made exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. The 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 is used as a dispersant therein. About 0.3 ml of a dilute solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for measuring device washing (manufactured by Wako Pure Chemical Industries, Ltd.) 3 times by weight with ion-exchanged 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 Dispersion System Tetora 150” (manufactured by Nikkiki Bios) with an electrical output of 120 W. A fixed amount of ion-exchanged water is added, 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 aqueous solution of (5) in which the toner is dispersed is dropped using a pipette to prepare a measurement concentration of about 5%. . The 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).

  The present invention will be described below with reference to examples. Prior to Examples, Production Examples 1 to 8 for crystalline polyester resins and Production Examples 11 to 18 for amorphous polyester resins will be described. In the following examples, the number of parts is based on parts by mass.

[Production example]
<Production Example 1>
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 are shown in Table 1 (mol%). ). Then, 1 part by mass of tin dioctylate as a catalyst is added to 100 parts by mass of the total amount of monomers, the inside of the reaction vessel is heated to 140 ° C. under a nitrogen atmosphere, and water is distilled off from the inside of the reaction vessel under normal pressure. The reaction was continued for 6 hours. Next, the monomer was reacted while the temperature in the reaction vessel was raised to 200 ° C. at a rate of temperature increase of 10 ° C./hour, and the reaction was further continued for 2 hours after the temperature in the reaction vessel reached 200 ° C. Then, the inside of 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, and then the amount of crystal nucleating agent (n-octadecanoic acid) shown in Table 1 was added and reacted at 200 ° C. for 2 hours under normal pressure. . Thereafter, the inside of the reaction vessel was again depressurized to 5 kPa or less and reacted at 200 ° C. for 3 hours. 1 was obtained. In the MALDI-TOFMS mass spectrum of the resin, a peak of a structure in which n-octadecanoic acid was bonded to the molecular terminal of the crystalline polyester resin was confirmed, so the molecular terminal of the crystalline polyester resin was bonded to the crystal nucleating agent. It was confirmed that Further, various physical properties of the resin were measured according to the evaluation method. Table 2 shows the evaluation results.

<Production Examples 2 to 8>
The monomer, the crystal nucleating agent and the amount used were changed as shown in Table 1, and the rest was the same as in Production Example 1 except that the crystalline polyester resin No. 2 to No. 8 was obtained. For each of these resins, a mass spectrum of MALDI-TOFMS was obtained in the same manner as in Production Example 1. As a result, a peak of a structure in which a crystal nucleating agent was bonded to the molecular end of each resin was confirmed. It was confirmed that the nucleating agent was bound. Further, various physical properties of each resin were measured in the same manner as in Production Example 1. The evaluation results are shown in Table 2.

<Production Example 11>
Into a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the amount of monomer shown in Table 3 was added, and then dibutyltin was used as a catalyst in an amount of 1.5 mass with respect to 100 mass parts of the total monomer amount 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 210 ° C., the pressure in the reaction vessel was reduced to 5 kPa or less, and polycondensation was performed under the conditions of 210 ° C. and 5 kPa or less. 11 was obtained. At that time, the polymerization time was adjusted so that the softening point of the resulting polyester resin 11 was the value shown in Table 4. Table 4 shows the physical properties of the resin.

<Production Examples 12 to 18>
The monomer and the amount used were changed as shown in Table 3, and the others were the same as in Production Example 11 and the amorphous polyester resin No. 1 was used. 12 to No. 18 was obtained. Table 4 shows the physical properties of these resins.

<Example 1>
After thoroughly mixing the materials shown in Table 5 below with a Henschel mixer (“FM-75 type”, manufactured by Mitsui Miike Chemical Co., Ltd.), a twin-screw kneader (“PCM-30 type”) set at a temperature of 140 ° C., Kneaded by Ikekai Tekko 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.

  This coarsely crushed material was finely pulverized using a collision-type airflow pulverizer using high-pressure gas. Next, it classifies with a wind classifier (“Elbow Jet Lab EJ-L3”, manufactured by Nippon Steel Mining Co., Ltd.) using the Coanda effect, and fine particles and coarse particles are classified and removed simultaneously to obtain “toner mother particles 1”. It was.

  To 100.0 parts by mass of the obtained toner base particles, 1.0 part by mass of titanium oxide fine particles having a primary average particle diameter of 50 nm and surface-treated with 15.0% by mass of isobutyltrimethoxysilane, and 20.0 parts by mass of hexamethyldisilazane. 0.8 parts by weight of hydrophobic silica fine particles having a primary average particle diameter of 16 nm surface-treated with% and mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). Obtained.

  For toner 1, the following (1) evaluation of low-temperature fixability in high-speed development, (2) storage stability, and (3) paper discharge adhesion resistance were evaluated. Good results were obtained in all evaluations. It was.

[Evaluation]
(1) Low-temperature fixability in high-speed development A commercially available color laser printer Color Laser Jet CP4525 (manufactured by HP) was used as an evaluation machine. The fixing device was removed from the evaluation machine, and an external fixing device that can arbitrarily set the fixing temperature, fixing nip pressure, and process speed of the fixing device was attached. As a recording medium, 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.

In an environment of a temperature of 23 ° C. and a relative humidity of 50%, a solid black unfixed image was output so that the applied toner amount was 0.6 mg / cm ² .

The fixing temperature of the fixing device is 140 ° C., the fixing nip pressure is modified to 0.10 MPa, and the process speed is increased every 20 mm / sec in the range from 300 mm / sec to 500 mm / sec. Was fixed. The obtained solid black image was rubbed 5 times with Sylbon paper applied with a load of about 100 g, and the point at which the density reduction rate of the image density before and after the rub was 10% or less was set as the maximum process speed at which fixing can be performed. The faster the maximum process speed that can be fixed, the better the low-temperature fixability during high-speed development. The evaluation results are shown in Table 8. The evaluation results were ranked A to D according to the following criteria, but in the present invention, up to rank C is an acceptable level.
A (very good): The maximum process speed capable of fixing is 500 mm / sec or more.
B (good): The maximum process speed capable of fixing is 400 mm / sec or more and less than 500 mm / sec.
C (Normal): The maximum process speed capable of fixing is 300 mm / sec or more and less than 400 mm / sec.
D (Poor): The maximum process speed capable of fixing is less than 300 mm / sec.

(2) Evaluation of Storage Stability As a method for evaluating the long-term storage stability of the toner, a load of 1 kg is applied on a bag containing 10 g of toner for evaluation (Sun Zip D-4 bag manufactured by C-I Kasei Co., Ltd.) It was left for 1 month in an environment with a temperature of 45 ° C. and a relative humidity of 5%. After 1 month, the toner for evaluation was transferred to an environment of a temperature of 23 ° C. and a relative humidity of 60% and left overnight. As a measuring method, a toner for evaluation was placed on a set 200-mesh sieve, the displacement value of the digital vibrometer was adjusted to 0.50 mm (peak-to-peak), and vibration was applied for 30 seconds. . Thereafter, the long-term storage stability was evaluated from the amount of agglomerates of toner remaining on each sieve. The evaluation results are shown in Table 8. The evaluation results were ranked A to D according to the following criteria, but in the present invention, up to rank C is an acceptable level.
A (very good): The remaining amount of toner on the mesh is 0.2 g or less.
B (good): The amount of toner remaining on the mesh is more than 0.2 g and 0.5 g or less.
C (Normal): The remaining amount of toner on the mesh exceeds 0.5 g and is 1.0 g or less.
D (Poor): The amount of toner remaining on the mesh exceeds 1.0 g.

(3) Evaluation of paper discharge adhesion resistance A commercially available color laser printer Color Laser Jet CP4525 (manufactured by HP) was prepared as an evaluation machine. The fixing process speed, development process speed, and paper passing interval of this evaluation machine were changed, and modification was made so that printing could be performed at a speed of 60 sheets / minute. As the recording medium, high white paper GF-C081 (manufactured by Canon Marketing Japan, 81.4 g / m ² ) was used. The product toner was extracted from a commercially available cyan cartridge, the interior 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.

Amount of applied toner of 0.9 mg / cm in two environments: an environment having a temperature of 23 ° C. and a relative humidity of 50% (N / N environment) and an environment having a temperature of 30 ° C. and a relative humidity of 80% (H / H environment). 100 solid images were output by double-sided printing so as to be ² . After the output of 100 sheets, a load of about 2 kg was applied on the paper with the output images superimposed, and left for 10 minutes. After leaving for 10 minutes, whether or not the printed image is adhered was evaluated for each sheet. The evaluation results are shown in Table 8. The results were ranked A to D according to the following criteria, but in the present invention, up to rank C is an acceptable level.
A: There is no bonded image and good image quality is maintained.
B: Although there are adhered images, they are easily separated and maintain good image quality.
C: There are 3 or less images that have adhered images and have image defects after separation.
D: There are four or more images that have adhered images and have image defects after separation.

<Examples 2 to 12, Comparative Examples 1 to 8>
Toners 2 to 20 were obtained in the same manner as in Example 1 except that the formulation of the materials was changed as shown in Table 6. However, the toner 18 was annealed by obtaining a coarsely pulverized material and then leaving the obtained crushed material in a bucket and leaving it open in a constant temperature and high humidity tank for one day at 50 ° C. Table 7 shows the physical properties of Toners 1 to 20. Table 7 shows the results of evaluation performed in the same manner as in Example 1.

Claims (4)

A toner containing a binder resin and wax,
The binder resin includes a crystalline polyester resin and an amorphous polyester resin;
The crystalline polyester resin has a crystal nucleating agent site;
The crystal nucleating agent site is a site derived from an aliphatic monoalcohol having 10 to 30 carbon atoms and / or an aliphatic monocarboxylic acid having 11 to 31 carbon atoms,
The content of the amorphous polyester resin in the binder resin is 50% by mass or more,
The toner satisfying the following mathematical formulas (1) to (4):
TgA-TgB ≧ 10.0 (° C.) (1)
TgC-TgB ≧ 5.0 (° C.) (2)
TgA ≧ 45.0 (° C.) (3)
TgC ≧ 40.0 (° C.) (4)
[In the above formulas (1) to (4),
TgA represents the glass transition temperature (° C.) of the toner.
TgB is a glass transition temperature obtained by heating the toner to 150 ° C., cooling it with liquid nitrogen within 5 seconds after completion of heating, taking out the liquid nitrogen, and performing differential scanning calorimetry within 1 minute ( ° C).
TgC is a glass transition temperature (° C.) obtained by heating the toner to 150 ° C., cooling with liquid nitrogen within 5 seconds after the completion of heating, and holding the toner at 50 ° C. for 20 minutes, and then performing differential scanning calorimetry. ). ].   The toner according to claim 1, wherein the wax is a hydrocarbon wax. The toner according to claim 1, wherein a melting point Tw of the wax and a melting point Tc of the crystalline polyester resin satisfy the following formulas (5) and (6):
Tc <Tw <100.0 (° C.) (5)
Tw−Tc <20.0 (° C.) (6). A two-component developer comprising the toner according to any one of claims 1 to 3 and a magnetic carrier.