JP2016033648A - Crystalline copolymer resin, toner, developer, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which has not only excellent low-temperature fixability but also storage stability and image adhesion resistance.SOLUTION: A toner contains a crystalline resin. The crystalline resin contains a crystalline copolymer resin having a crystalline resin segment and a non-crystalline resin segment. In a differential scanning calorimetry (DSC) of the toner which is conducted on the following measurement condition, a crystallization heat quantity originating in the crystalline resin in a range of 10°C to 70°C in a temperature dropping step is 3 J/g to 40 J/g. [measurement condition] The toner is kept at -20°C, then is heated to 130°C at 10°C/min and is held for 1 minute, and then is cooled to -50°C at a temperature dropping rate of 10°C/min. A quantity of heat generation in a range of 10°C to 70°C in the temperature dropping step is determined to be the crystallization heat quantity originating in the crystalline resin in the range of 10°C to 70°C in the temperature dropping step.SELECTED DRAWING: None

Description

  The present invention relates to a crystalline copolymer resin, a toner, a developer, and an image forming apparatus.

  Conventionally, in an electrophotographic image forming apparatus or the like, a latent image formed electrically or magnetically has been visualized with an electrophotographic toner (hereinafter also simply referred to as “toner”). . For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed on the transfer material such as paper. In the fixing process for fixing the toner image on the transfer paper, a heat fixing method such as a heating roller fixing method or a heating belt fixing method is widely used because of its energy efficiency.

  In recent years, demands from the market for increasing the speed and energy saving of image forming apparatuses are increasing, and there is a demand for toners that are excellent in low-temperature fixability and can provide high-quality images. In order to achieve low-temperature fixability of the toner, it is necessary to lower the softening temperature of the binder resin of the toner. If the softening temperature of the binder resin is low, a part of the toner image is fixed on the surface of the fixing member at the time of fixing. So-called offset (hereinafter also referred to as hot offset) is liable to occur. Further, the heat-resistant storage stability of the toner is lowered, and so-called blocking occurs in which toner particles are fused with each other particularly in a high temperature environment. In addition, in the developing device, there are problems that the toner is fused and contaminated inside the developing device and the carrier, and that the toner is liable to film on the surface of the photoreceptor.

  As a technique that can solve these problems, it is known to use a crystalline resin as a binder resin for toner. Since the crystalline resin has a characteristic that it softens rapidly from the crystallized state at the melting point, the fixing temperature of the toner can be greatly lowered. However, when a crystalline resin is used as the binder resin of the toner, it is excellent in toughness while being soft and easily plastically deformed. For this reason, simply using a crystalline resin as a binder resin results in poor heat-resistant storage stability of the toner, and the toner aggregates in the toner storage container and the image forming apparatus, making it impossible to replenish the toner. The density may decrease and an abnormal image may be formed. On the other hand, many toners using a resin in which a crystalline segment and an amorphous segment are chemically bonded have been proposed. For example, a toner using a resin in which a crystalline polyester and an amorphous polyester are connected by an ester bond as a binder resin has been proposed (see, for example, Patent Document 1). In addition, a toner using a resin obtained by copolymerization with at least one of a urea bond and a urethane bond as a binder resin has been proposed (see, for example, Patent Documents 2 and 3). As a result, not only low-temperature fixability but also heat-resistant storage stability and mechanical stress have been improved.

  However, simply using a copolymer of a crystalline polyester resin and an amorphous polyester resin as a crystalline resin as a binder resin, the paper discharge roller, the conveying member, etc. in the paper discharge process after fixing are used. There have been problems such as contact and rubbing on the image surface due to rubbing, adhesion between copy papers printed in large quantities (image resistance).

  Therefore, the present situation is that there is a demand for a toner that not only excels in low-temperature fixing, but also has excellent storage stability and image adhesion resistance.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a toner not only excellent in low-temperature fixing but also excellent in storage stability and image adhesion resistance.

Means for solving the problems are as follows. That is,
The toner of the present invention is a toner containing a crystalline resin,
The crystalline resin contains a crystalline copolymer resin having a crystalline resin segment and an amorphous resin segment,
In the differential scanning calorimetry (DSC) of the toner performed under the following measurement conditions, the crystallization heat amount derived from the crystalline resin in the temperature lowering process range of 10 ° C. to 70 ° C. is 3 J / g to 40 J / g. It is characterized by being.
〔Measurement condition〕
The toner is held at −20 ° C., heated to 130 ° C. at 10 ° C./min, held for 1 minute, and then cooled to −50 ° C. at a temperature decreasing rate of 10 ° C./min. A calorific value in the range of 10 ° C. to 70 ° C. in the temperature lowering process is defined as a crystallization heat amount derived from the crystalline resin in a range of 10 ° C. to 70 ° C. in the temperature lowering process.

  According to the present invention, it is possible to solve the above-described problems, and to provide a toner that is excellent not only in low-temperature fixing but also in storage stability and image adhesion resistance.

FIG. 1 is a schematic configuration diagram showing an example of an image forming apparatus of the present invention. FIG. 2 is a partially enlarged view of FIG.

(Toner and crystalline copolymer resin)
The toner of the present invention contains at least a crystalline resin, and further contains other components as necessary.
The crystalline copolymer resin of the present invention has at least a crystalline resin segment and an amorphous resin segment.
In the description of the toner, the crystalline copolymer resin of the present invention will also be described.

In the differential scanning calorimetry (DSC) of the toner performed under the following measurement conditions, the crystallization heat amount (T) derived from the crystalline resin in the range of 10 ° C. to 70 ° C. in the temperature lowering process is 3 J / g to 40 J. / G.
〔Measurement condition〕
The toner is held at −20 ° C., heated to 130 ° C. at 10 ° C./min, held for 1 minute, and then cooled to −50 ° C. at a temperature decreasing rate of 10 ° C./min. A calorific value in the range of 10 ° C. to 70 ° C. in the temperature lowering process is defined as a crystallization heat amount derived from the crystalline resin in a range of 10 ° C. to 70 ° C. in the temperature lowering process.

  As a result of intensive studies, the present inventors have obtained a low-temperature fixability only by using a copolymer of a crystalline polyester resin and an amorphous polyester resin as a binder resin, which is a crystalline resin, It has been found that the hardness of the image surface cannot be quickly recovered because it takes time for the crystalline resin in the toner to crystallize again after the toner is melted on the fixing medium by heat fixing. For this reason, the use of a copolymer of a crystalline polyester resin and an amorphous polyester resin, which is a crystalline resin, only as a binder resin, the discharge roller, the conveying member, etc. in the discharge process after fixing. There have been problems such as contact and rubbing on the image surface due to rubbing, adhesion between copy papers printed in large quantities (image resistance).

  As a result of further intensive studies, the present inventors have found that, in a toner containing a crystalline copolymer resin having a crystalline resin segment and an amorphous resin segment as a binder resin, image strength after printing (image adhesion resistance, etc.) ) Greatly depends on the crystallinity of the crystalline part in the toner and the crystallization speed at the time of fixing. That is, the present inventors have found that the image strength after printing (image adhesion resistance, etc.) greatly depends on the amount of heat of crystallization when the heated toner is cooled. Then, in order to improve the image strength, the present invention has been completed by paying attention to promoting the crystallization degree and the crystallization speed of the crystalline part.

The heat of crystallization (T) in the differential scanning calorimetry (DSC) of the toner is 3 J / g to 40 J / g, preferably 10 J / g to 30 J / g. When the amount of crystallization heat (T) is less than 3 J / g, the crystallinity of the crystalline portion becomes poor, so that the image strength is reduced. When it exceeds 40 J / g, the crystalline portion in the binder resin is reduced. Therefore, the fixing width becomes narrow due to a significant decrease in viscoelasticity in a high temperature region.
The crystallization heat quantity (T) is a value calculated from the area of the DSC curve in the range of 10 ° C to 70 ° C, preferably in the range of 25 ° C to 70 ° C, more preferably in the range of 40 ° C to 70 ° C. It is a range.

  In the differential scanning calorimetry of the toner, the crystallization peak temperature derived from the crystalline resin in the temperature lowering process is preferably 10 ° C. or higher, more preferably 25 ° C. or higher, and particularly preferably 40 ° C. or higher. If the crystallization peak temperature is less than 10 ° C., the crystallinity of the crystalline part becomes poor at a temperature higher than that, so that the image strength tends to be lowered and the image adhesion resistance may be inferior. There is no restriction | limiting in particular as an upper limit of the said crystallization peak temperature, Although it can select suitably according to the objective, The said crystallization peak temperature has preferable 70 degrees C or less.

  There is no restriction | limiting in particular as melting | fusing point of the said toner, Although it can select suitably according to the objective, 50 to 75 degreeC is preferable and 60 to 70 degreeC is more preferable. When the melting point is less than 50 ° C., the crystalline resin tends to melt at a low temperature and the storage stability of the toner tends to be reduced. When the melting point exceeds 75 ° C., the crystalline resin is heated by heat during fixing. Melting may be insufficient, and the low-temperature fixability of the toner may be reduced.

  A transition temperature such as a crystallization heat amount derived from the crystalline resin in the toner, a crystallization peak temperature, and a melting peak temperature (melting point) of the toner, and a crystallization heat amount, a crystallization peak temperature of the crystalline resin, and Transition temperatures such as melting peak temperature (melting point) can be measured by differential scanning calorimetry (DSC). The measurement conditions are as follows.

<Differential scanning calorimetry (DSC)>
The measurement sample (toner or crystalline resin) is preferably annealed for 12 hours or more in the crystallization temperature region before measurement in order to stabilize the crystalline structure of the crystalline resin.
The measurement sample is held at −20 ° C., heated to 130 ° C. at 10 ° C./min, held for 1 minute, and then cooled to −50 ° C. at a temperature decrease rate of 10 ° C./min.
Draw a graph of “endothermic heat generation” and “temperature”, and let the peak temperature of the melting (endothermic) peak obtained in the heating process (1st. Heating) be the melting peak temperature (melting point). The peak of the obtained crystallization (exothermic) peak is defined as the crystallization peak temperature. In addition, the amount of heat of crystallization is calculated by setting the heat generation in the range of 10 ° C. to 70 ° C. in the temperature lowering process as the crystallization region. Further, as the glass transition temperature, a characteristic inflection observed in the temperature raising process (1st heating) is used as the glass transition temperature, and a value obtained from the DSC curve by the midpoint method is used.

<Crystalline resin>
The crystalline resin contains at least a crystalline copolymer resin, and further contains other crystalline resins as necessary.

<< Crystalline copolymer resin >>
The crystalline copolymer resin has at least a crystalline resin segment and an amorphous resin segment, preferably has at least one of a urethane bond and a urea bond, and, if necessary, other components Have
The crystalline copolymer resin is preferably a block copolymer resin having a crystalline resin segment and an amorphous resin segment.
In the crystalline copolymer resin, the crystalline resin segment and the amorphous resin segment are preferably bonded by at least one of a urethane bond and a urea bond.

-Crystalline resin segment-
The crystalline resin segment is not particularly limited as long as it is a segment made of a crystalline resin that constitutes the crystalline copolymer resin, and can be appropriately selected according to the purpose. It is preferable that it is a segment (crystalline polyester resin segment).

--- Crystalline polyester resin--
The crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polycondensed polyester resin synthesized from a polyol and a polycarboxylic acid, a lactone ring-opening polymer, An acid etc. are mentioned.
There is no restriction | limiting in particular as said crystalline polyester resin, Although it can select suitably according to the objective, The crystalline polyester which has a bivalent aliphatic alcohol component and a bivalent aliphatic carboxylic acid component as a structural component Resins are preferred.

--- Polyol ---
Examples of the polyol include divalent diols, trivalent to octavalent or higher polyols.

  The divalent diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic alcohols such as linear aliphatic alcohols and branched aliphatic alcohols (divalent aliphatic alcohols). ), An alkylene ether glycol having 4 to 36 carbon atoms, an alicyclic diol having 4 to 36 carbon atoms, an alkylene oxide of the alicyclic diol (hereinafter, “alkylene oxide” may be abbreviated as “AO”), Examples thereof include AO adducts of bisphenols, polylactone diols, polybutadiene diols, diols having carboxyl groups, diols having sulfonic acid groups or sulfamic acid groups, and diols having other functional groups such as salts thereof. Among these, an aliphatic alcohol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic alcohol having 2 to 36 chain carbon atoms is more preferable. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content with respect to the whole diol of the said linear aliphatic alcohol, Although it can select suitably according to the objective, 80 mol% or more is preferable and 90 mol% or more is more preferable. When the content is 80 mol% or more, the crystallinity of the resin is improved, the compatibility between the low temperature fixability and the heat resistant storage stability is good, and the resin hardness tends to be improved.

  The linear aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability. Among these, a linear aliphatic alcohol having 2 to 36 chain carbon atoms is preferable.

  The branched aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a branched aliphatic alcohol having 2 to 36 chain carbon atoms. Examples of the branched aliphatic alcohol include 1,2-propylene glycol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, and the like.

  The alkylene ether glycol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene Ether glycol etc. are mentioned.

  The alicyclic diol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

  The trivalent to octavalent or higher polyol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the trivalent to octavalent or higher polyvalent fat having 3 to 36 carbon atoms. Alcohol; AO adduct of trisphenol (addition mole number 2-30); AO adduct of novolak resin (addition mole number 2-30); Copolymerization of hydroxyethyl (meth) acrylate with other vinyl monomers Examples include acrylic polyols such as products.

  Examples of the trivalent to octavalent or higher polyhydric aliphatic alcohol having 3 to 36 carbon atoms include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin.

--- Polycarboxylic acid ---
Examples of the polycarboxylic acid include dicarboxylic acids, trivalent to hexavalent or higher polycarboxylic acids.

  There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, aliphatic dicarboxylic acid (divalent aliphatic carboxylic acid), aromatic dicarboxylic acid, etc. are mentioned. Examples of the aliphatic dicarboxylic acid include linear aliphatic dicarboxylic acid and branched aliphatic dicarboxylic acid. Among these, linear aliphatic dicarboxylic acid is preferable.

There is no restriction | limiting in particular as said aliphatic dicarboxylic acid, According to the objective, it can select suitably, For example, alkane dicarboxylic acid, alkenyl succinic acid, alkene dicarboxylic acid, alicyclic dicarboxylic acid etc. are mentioned. Of these, alkanedicarboxylic acids are preferred.
Examples of the alkanedicarboxylic acid include alkanedicarboxylic acid having 4 to 36 carbon atoms. Examples of the alkanedicarboxylic acid having 4 to 36 carbon atoms include succinic acid, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, and decylsuccinic acid.
Examples of the alkenyl succinic acid include dodecenyl succinic acid, pentadecenyl succinic acid, and octadecenyl succinic acid.
Examples of the alkene dicarboxylic acid include alkene dicarboxylic acids having 4 to 36 carbon atoms. Examples of the alkene dicarboxylic acid having 4 to 36 carbon atoms include maleic acid, fumaric acid, and citraconic acid.
As said alicyclic dicarboxylic acid, a C6-C40 alicyclic dicarboxylic acid etc. are mentioned, for example. Examples of the alicyclic dicarboxylic acid having 6 to 40 carbon atoms include dimer acid (dimerized linoleic acid).

  There is no restriction | limiting in particular as said aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, C8-36 aromatic dicarboxylic acid etc. are mentioned. Examples of the aromatic dicarboxylic acid having 8 to 36 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. It is done.

  Examples of the trivalent to hexavalent or higher polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms. Examples of the aromatic polycarboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

  In addition, as the dicarboxylic acid or the trivalent to hexavalent or higher polycarboxylic acid, the above acid anhydrides or alkyl esters having 1 to 4 carbon atoms may be used. Examples of the alkyl ester having 1 to 4 carbon atoms include methyl ester, ethyl ester, and isopropyl ester.

  Among the dicarboxylic acids, the aliphatic dicarboxylic acid is preferably used alone, and succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, and dodecanedicarboxylic acid are more preferably used alone. Also preferred are those obtained by copolymerizing the aromatic dicarboxylic acid together with the aliphatic dicarboxylic acid. As the aromatic dicarboxylic acid to be copolymerized, terephthalic acid, isophthalic acid, t-butylisophthalic acid, and alkyl esters of these aromatic dicarboxylic acids are preferable. Examples of the alkyl ester include methyl ester, ethyl ester, isopropyl ester, and the like. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

  There is no restriction | limiting in particular as a hydroxyl value of the said crystalline polyester resin which comprises the said crystalline polyester resin segment, Although it can select suitably according to the objective, 10 mgKOH / g-50 mgKOH / g are preferable.

  The molecular weight of the crystalline resin constituting the crystalline resin segment is preferably a weight average molecular weight (Mw) of 3,000 to 35,000 in Gel Permeation Chromatography (GPC) measurement, It is more preferable that it is 10,000-30,000. If the weight average molecular weight is too low, the toner tends to be inferior in blocking resistance and durability against stress such as stirring in the developing device. Tend to be inferior.

There is no restriction | limiting in particular as melting | fusing point (Tm) of the said crystalline resin which comprises the said crystalline resin segment, Although it can select suitably according to the objective, 50 to 80 degreeC is preferable. When the Tm is less than 50 ° C., the crystalline copolymer resin tends to melt at a low temperature and tends to reduce the blocking resistance of the toner. The melting of the copolymer resin is insufficient and the low-temperature fixability tends to decrease.
The melting point can be measured by an endothermic peak value of a DSC chart in a differential scanning calorimeter (DSC) measurement.

  About crystallinity, molecular structure, etc. of the crystalline resin segment, NMR measurement, differential scanning calorimeter (DSC) measurement, X-ray diffraction measurement, GC / MS measurement, LC / MS measurement, infrared absorption (IR) spectrum measurement, Etc. can be confirmed.

-Amorphous resin segment-
The amorphous resin segment is not particularly limited as long as it is a segment made of an amorphous resin constituting the crystalline copolymer resin, and can be appropriately selected according to the purpose. A segment made of polyester resin (amorphous polyester resin segment) is preferable.

--- Amorphous polyester resin--
There is no restriction | limiting in particular as said amorphous polyester resin, According to the objective, it can select suitably, For example, the polycondensation polyester resin etc. which are synthesize | combined from a polyol and polycarboxylic acid are mentioned.
The amorphous polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. The divalent aliphatic alcohol component and the divalent aromatic and aliphatic carboxylic acid component are constituent components. The amorphous polyester resin having is preferable.

--- Polyol ---
Examples of the polyol include divalent diols, trivalent to octavalent or higher polyols.

  The divalent diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic alcohols such as linear aliphatic alcohols and branched aliphatic alcohols (divalent aliphatic alcohols). ) And the like. Among these, aliphatic alcohols having 2 to 36 chain carbon atoms are preferable. These may be used individually by 1 type and may use 2 or more types together.

  The linear aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like. Among these, considering availability, ethylene glycol, 1,3-propanediol (propylene glycol), 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decane Diols are preferred. Among these, a linear aliphatic alcohol having 2 to 36 chain carbon atoms is preferable.

--- Polycarboxylic acid ---
Examples of the polycarboxylic acid include dicarboxylic acids, trivalent to hexavalent or higher polycarboxylic acids. Of these, divalent aromatic carboxylic acids are preferred.

  There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, etc. are mentioned. Examples of the aliphatic dicarboxylic acid include linear aliphatic dicarboxylic acid and branched aliphatic dicarboxylic acid. Of these, linear aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferred.

There is no restriction | limiting in particular as said aliphatic dicarboxylic acid, According to the objective, it can select suitably, For example, alkane dicarboxylic acid, alkenyl succinic acid, alkene dicarboxylic acid, alicyclic dicarboxylic acid etc. are mentioned.
Examples of the alkanedicarboxylic acid include alkanedicarboxylic acid having 4 to 36 carbon atoms. Examples of the alkanedicarboxylic acid having 4 to 36 carbon atoms include succinic acid, adipic acid, suberic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, and decylsuccinic acid.
Examples of the alkenyl succinic acid include dodecenyl succinic acid, pentadecenyl succinic acid, and octadecenyl succinic acid.
Examples of the alkene dicarboxylic acid include alkene dicarboxylic acids having 4 to 36 carbon atoms. Examples of the alkene dicarboxylic acid having 4 to 36 carbon atoms include maleic acid, fumaric acid, and citraconic acid.
As said alicyclic dicarboxylic acid, a C6-C40 alicyclic dicarboxylic acid etc. are mentioned, for example. Examples of the alicyclic dicarboxylic acid having 6 to 40 carbon atoms include dimer acid (dimerized linoleic acid).

  There is no restriction | limiting in particular as said aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, C8-36 aromatic dicarboxylic acid etc. are mentioned. Examples of the aromatic dicarboxylic acid having 8 to 36 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. It is done.

  Examples of the trivalent to hexavalent or higher polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms. Examples of the aromatic polycarboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

  In addition, as the dicarboxylic acid or the trivalent to hexavalent or higher polycarboxylic acid, the above acid anhydrides or alkyl esters having 1 to 4 carbon atoms may be used. Examples of the alkyl ester having 1 to 4 carbon atoms include methyl ester, ethyl ester, and isopropyl ester.

  There is no restriction | limiting in particular as a hydroxyl value of the said crystalline polyester resin which comprises the said amorphous polyester resin segment, Although it can select suitably according to the objective, 10 mgKOH / g-50 mgKOH / g are preferable.

  There is no restriction | limiting in particular as molecular weight of the said amorphous resin which comprises the said amorphous resin segment, Although it can select suitably according to the objective, In GPC measurement, a weight average molecular weight (Mw) 5000- 20,000 is preferable, and 7,000 to 15,000 are more preferable.

  There is no restriction | limiting in particular as glass transition temperature (Tg) of the said amorphous resin which comprises the said amorphous resin segment, Although it can select suitably according to the objective, 40 to 80 degreeC is preferable, 40 More preferably, the temperature is from 60 ° C to 60 ° C. When the Tg is less than 40 ° C., the heat resistance of the toner and durability against stress such as stirring in the developing device may be inferior. When the Tg exceeds 80 ° C., the viscoelasticity at the time of melting of the toner increases. In some cases, the low-temperature fixability is inferior.

  There is no restriction | limiting in particular as the softening temperature of the said amorphous resin which comprises the said amorphous resin segment, Although it can select suitably according to the objective, 60 to 160 degreeC is preferable and 80 to 140 degreeC is preferable. Is more preferable, and 100 to 120 ° C. is particularly preferable.

  The molecular structure of the amorphous resin constituting the amorphous resin segment can be confirmed by GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement using a solution or solid.

-Copolymerization-
There is no restriction | limiting in particular as a manufacturing method of the said crystalline copolymer resin, According to the objective, it can select suitably, For example, although any one of the following (1)-(3) methods etc. are mentioned, From the viewpoint of the degree of freedom in molecular design, (1) and (3) are preferable, and (1) is more preferable.
(1) An amorphous resin prepared in advance by a polymerization reaction and a crystalline resin prepared in advance by a polymerization reaction are dissolved or dispersed in a suitable solvent, and a hydroxyl group at the end of a polymer chain such as an isocyanate group, an epoxy group, or a carbodiimide group. Or a method of copolymerization by reacting with an extender having two or more functional groups that react with carboxylic acid.
(2) A method in which an amorphous resin prepared in advance by a polymerization reaction and a crystalline resin prepared in advance by a polymerization reaction are melt-kneaded and prepared by transesterification under reduced pressure.
(3) A method in which a hydroxyl group of a crystalline resin prepared in advance by a polymerization reaction is used as a polymerization initiation component, and an amorphous resin is subjected to ring-opening polymerization and copolymerization from a polymer chain end of the crystalline resin.

As the extender, polyisocyanate is preferable.
Examples of the polyisocyanate include diisocyanate.
Examples of the diisocyanate include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and araliphatic diisocyanates.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), crude TDI, 2, 4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenylmethane diisocyanate (MDI), crude MDI, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m-isocyanatophenyl Examples include sulfonyl isocyanate and p-isocyanatophenylsulfonyl isocyanate.

  Examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc. Can be mentioned.

  Examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanate). Natoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.

  Examples of the araliphatic diisocyanate include m-xylylene diisocyanate (XDI), p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like. .

  There is no restriction | limiting in particular as the usage-amount of the said polyisocyanate at the time of manufacturing the said crystalline copolymer resin, Although it can select suitably according to the objective, Of the hydroxyl group of the said crystalline resin and the said amorphous resin, The total number of moles / the total number of moles of isocyanate groups of the polyisocyanate (OH / NCO) is preferably in the range of 0.40 to 0.70, more preferably in the range of 0.45 to 0.65, and 0.45 to 0. A range of .55 is particularly preferred. When the OH / NCO is less than 0.4, the bonding between the amorphous resin and the crystalline resin is insufficient, the number of components present independently increases, and the stability of quality can be ensured. It may disappear. When the OH / NCO exceeds 0.8, the influence of the molecular weight of the crystalline copolymer resin and the interaction between the urethane groups becomes too strong, and the crystallization of the crystal part is inhibited, or the fluidity However, there are cases where sufficient fluidity and deformability cannot be ensured in situations where it is necessary.

  The mass ratio of the crystalline resin segment to the amorphous resin segment (crystalline resin segment / amorphous resin segment) in the crystalline copolymer resin is not particularly limited and is appropriately selected depending on the purpose. However, 10/90 to 40/60 is preferable, and 20/80 to 35/75 is more preferable.

When the crystalline resin segment increases in the crystalline copolymer resin, the melt viscosity is lowered and the low-temperature fixability is improved. Moreover, since the strength by crystallization is obtained, static storage stability is improved.
However, if there are too many crystalline resin segments in the crystalline copolymer resin, the restraint of the mobility during cooling becomes worse, and the rub resistance and stack storage stability may be reduced. Further, the fixing width tends to be narrowed due to a significant decrease in viscoelasticity in a high temperature region.

  There is no restriction | limiting in particular as softening temperature of the said crystalline copolymer resin, According to the amorphous resin (for example, amorphous polyester resin) and crystalline resin (for example, crystalline polyester resin) to be used, it selects suitably. However, 80 to 160 ° C is preferable, and 90 to 130 ° C is more preferable.

In the differential scanning calorimetry (DSC) of the crystalline copolymer resin performed under the following measurement conditions, the crystallization heat amount (R) of the crystalline copolymer resin in the range of 10 ° C. to 70 ° C. in the temperature lowering process is 3J. / G-40J / g is preferable, and 15J / g-30J / g is more preferable.
〔Measurement condition〕
The crystalline copolymer resin is held at −20 ° C., heated to 130 ° C. at 10 ° C./min, held for 1 minute, and then cooled to −50 ° C. at a temperature decreasing rate of 10 ° C./min. The calorific value in the range of 10 ° C. to 70 ° C. in the temperature lowering process is defined as the crystallization heat amount of the crystalline copolymer resin in the range of 10 ° C. to 70 ° C. in the temperature lowering process.

  The crystalline copolymer resin satisfying the crystallization heat quantity (R) of 3 J / g to 40 J / g can also be used as a nucleating agent.

The amount of crystallization heat (R) in the DSC cooling process of the crystalline copolymer resin is preferably a value calculated from the area of the DSC curve in the range of 10 ° C to 70 ° C, more preferably 25 ° C to 70 ° C. And is particularly preferably in the range of 40 ° C to 70 ° C.
In the differential scanning calorimetry of the crystalline copolymer resin, the crystallization peak temperature of the crystalline copolymer resin in the temperature lowering process is preferably 10 ° C. or higher, more preferably 25 ° C. or higher, and 40 ° C. or higher. Particularly preferred. If the crystallization peak temperature is less than 10 ° C., the crystallinity of the crystalline part becomes poor at a temperature higher than that, so that the image strength tends to be lowered and the image adhesion resistance may be inferior. There is no restriction | limiting in particular as an upper limit of the said crystallization peak temperature, Although it can select suitably according to the objective, The said crystallization peak temperature has preferable 70 degrees C or less.

  In the differential scanning calorimetry of the toner, the melting energy in the temperature rising process and the crystallization energy in the temperature lowering process preferably have “100 (%) × crystallization energy / melting energy” of 30% or more. It is more preferably 50% or more, and particularly preferably 70% or more. When the ratio is less than 30%, crystallization in the crystalline copolymer resin is insufficient, that is, there are a lot of amorphous parts, so that the image adhesion resistance due to a decrease in image strength may be inferior.

  There is no restriction | limiting in particular as melting | fusing point of the said crystalline copolymer resin, Although it can select suitably according to the objective, 50 to 75 degreeC is preferable and 60 to 70 degreeC is more preferable. When the melting point is less than 50 ° C., the crystalline resin tends to melt at a low temperature and the storage stability of the toner tends to be reduced. When the melting point exceeds 75 ° C., the crystalline resin is heated by heat during fixing. Melting may be insufficient, and the low-temperature fixability of the toner may be reduced.

<< Other crystalline resins >>
The crystalline resin may contain another crystalline resin in addition to the crystalline copolymer resin. There is no restriction | limiting in particular as said other crystalline resin, According to the objective, it can select suitably, For example, the crystalline resin which comprises the said crystalline resin segment described in description of the said crystalline copolymer resin (For example, crystalline polyester resin).

There is no restriction | limiting in particular as content of the said other crystalline resin in the said toner, Although it can select suitably according to the objective, 3 mass%-15 mass% are preferable.
When the toner contains the other crystalline resin, crystallization is promoted and strength is increased, so that static storage stability is improved. Moreover, since melt viscosity falls, low temperature fixability is more excellent.

<Other ingredients>
Examples of the other components include a colorant, a release agent, a charge control agent, and an external additive.

<< Colorant >>
There is no restriction | limiting in particular as said colorant, According to the objective, it can select suitably, For example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment etc. are mentioned. Among these, it is preferable to contain any of a yellow pigment, a magenta pigment, and a cyan pigment.
The black pigment is used for black toner, for example. Examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, magnetite, nigrosine dye, and iron black.
The yellow pigment is used for yellow toner, for example. Examples of the yellow pigment include CI Pigment Yellow (CI Pigment Yellow) 74, 93, 97, 109, 128, 151, 154, 155, 166, 168, 180, 185, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow and the like can be mentioned.
The magenta pigment is used for magenta toner, for example. Examples of the magenta pigment include quinacridone pigments, CI Pigment Red 48: 2, 57: 1, 58: 2, 5, 31, 146, 147, 150, 176, And monoazo pigments such as 184 and 269. Further, the quinacridone pigment may be used in combination with the monoazo pigment.
The cyan pigment is used for cyan toner, for example. Examples of the cyan pigment include a Cu-phthalocyanine pigment, a Zn-phthalocyanine pigment, and an Al-phthalocyanine pigment.

  There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toners, and 3 mass parts-10 parts. Part by mass is more preferable.

  The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded with the production of the master batch or the master batch include, for example, polymers of styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, or substitutes thereof; styrene-p-chlorostyrene copolymers, styrene- Propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene- Octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer Polymer, styrene-vinyl Styrene copolymers such as methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Combined; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin Aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The master batch can be obtained, for example, by mixing and kneading the master batch resin and the colorant under high shear. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method in which an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed is called a colorant. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

<< Releasing agent >>
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably, For example, a carbonyl group containing wax, polyolefin wax, a long chain hydrocarbon etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.

Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, and dialkyl ketones.
Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecane. Examples thereof include diol distearate.
Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate.
Examples of the polyalkanoic acid amide include dibehenyl amide.
Examples of the polyalkylamide include trimellitic acid tristearylamide.
Examples of the dialkyl ketone include distearyl ketone.
Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.

Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50 to 100 degreeC is preferable and 60 to 90 degreeC is more preferable. If the melting point is less than 50 ° C., the heat resistant storage stability may be adversely affected. If the melting point exceeds 100 ° C., a cold offset may easily occur during fixing at a low temperature.

  The melting point of the release agent can be measured using, for example, a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). First, 5.0 mg of the mold release agent is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, the temperature was raised from 0 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and then the temperature was lowered from 150 ° C. to 0 ° C. at a temperature lowering rate of 10 ° C./min. The temperature is raised to 150 ° C. in min and the DSC curve is measured. From the obtained DSC curve, using the analysis program in the DSC-60 system, the maximum peak temperature of the heat of fusion at the second temperature rise can be obtained as the melting point.

  The melt viscosity of the release agent is preferably 5 mPa · sec to 100 mPa · sec, more preferably 5 mPa · sec to 50 mPa · sec, and particularly preferably 5 mPa · sec to 20 mPa · sec as a measured value at 100 ° C. If the melt viscosity is less than 5 mPa · sec, the releasability may be lowered, and if it exceeds 100 mPa · sec, the hot offset resistance and the releasability at low temperatures may be lowered.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 1 mass part-20 mass parts are preferable with respect to 100 mass parts of said toner, 3 mass parts- 10 parts by mass is more preferable. When the content is less than 1 part by mass, the hot offset resistance may be reduced, and when it exceeds 20 parts by mass, the heat resistant storage stability, charging property, transferability, and stress resistance may be reduced. .

<< Charge Control Agent >>
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, Alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. Can be mentioned. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industries, Ltd.), LRA -901, LR-147 (manufactured by Nippon Carlit Co., Ltd.) which is a boron complex.

  There is no restriction | limiting in particular as content of the said charge control agent, Although it can select suitably according to the objective, 0.01 mass part-5 mass parts are preferable with respect to 100 mass parts of said toner. 02 parts by mass to 2 parts by mass is more preferable. When the content is less than 0.01 parts by mass, the charge rise property and the charge amount are not sufficient, and the toner image may be easily affected. When the content exceeds 5 parts by mass, the chargeability of the toner is too high, and the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density. .

<< External additive >>
The external additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silica, fatty acid metal salts, metal oxides, hydrophobized titanium oxide, and fluoropolymers.
Examples of the fatty acid metal salt include zinc stearate and aluminum stearate.
Examples of the metal oxide include titanium oxide, aluminum oxide, tin oxide, and antimony oxide.
Examples of the commercially available silica include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.).
Examples of commercially available titanium oxide include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (Fuji Titanium Industry Co., Ltd.). Company-made), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like.
Commercially available products of the hydrophobized titanium oxide include, for example, T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T. , TAF-1500T (all manufactured by Fuji Titanium Industrial Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

  Examples of the hydrophobic treatment method include a method of treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane.

  There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.1 mass part-5 mass parts are preferable with respect to 100 mass parts of the said toner. 3 mass parts-3 mass parts are more preferable.

  There is no restriction | limiting in particular as an average particle diameter of the primary particle of the said external additive, Although it can select suitably according to the objective, 100 nm or less is preferable and 3 nm-70 nm are more preferable. If the average particle size is less than 3 nm, the external additive may be buried in the toner and its function may not be exhibited effectively, and if it exceeds 100 nm, the surface of the photoreceptor may be damaged unevenly. .

  The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 μm to 16 μm. The upper limit is more preferably 11 μm and particularly preferably 9 μm. The lower limit is more preferably 0.5 μm and particularly preferably 1 μm.

  The ratio of the volume average particle diameter to the number average particle diameter of the toner [volume average particle diameter / number average particle diameter] is not particularly limited and may be appropriately selected depending on the intended purpose. In view of the above, 1.0 to 1.4 is preferable, and 1.0 to 1.3 is more preferable.

The volume average particle diameter (Dv) and the number average particle diameter (Dn) are measured by a Coulter counter method. Examples of the measuring device include Coulter Counter TA-II, Coulter Multisizer II, and Coulter Multisizer III (all manufactured by Coulter). The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic solution is prepared by preparing a 1% by mass NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles or toner are measured by the above measuring apparatus using a 100 μm aperture as an aperture. Calculate volume distribution and number distribution. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.

  As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

<Toner production method>
There is no restriction | limiting in particular as a manufacturing method of the said toner, According to the objective, it can select suitably, For example, a wet granulation method, a grinding method, etc. are mentioned. Examples of the wet granulation method include a dissolution suspension method and an emulsion aggregation method. From the difficulty of molecular kneading by kneading and uniform kneading of a high molecular weight resin and a low molecular weight resin, the dissolution suspension method and the emulsion aggregation method, which are production methods not involving the kneading of the binder resin, are preferable. The dissolution suspension method is more preferable from the viewpoint of resin uniformity.

  Further, the toner is produced by a particle production method as disclosed in Japanese Patent No. 4531076, that is, after the material constituting the toner is dissolved in carbon dioxide in a liquid or supercritical state, the liquid or supercritical state of carbon dioxide is dissolved. It can also be produced by a particle production method for obtaining toner particles by removing carbon.

<< Dissolution suspension method >>
The dissolution suspension method includes, for example, a toner material phase preparation step, an aqueous medium phase preparation step, an emulsification or dispersion preparation step, and an organic solvent removal step, and further includes other steps as necessary. The method of including is mentioned.

-Toner material phase (oil phase) preparation process-
The toner material phase preparation step includes at least the binder resin and, if necessary, further dissolves or disperses the toner material containing the colorant, the release agent, and the like in an organic solvent. There is no particular limitation as long as it is a step for preparing a dissolved or dispersed liquid (sometimes referred to as a toner material phase or an oil phase), and it can be appropriately selected according to the purpose.

There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The volatile thing whose boiling point is less than 150 degreeC is preferable at the point of the ease of removal.
Examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, and ethyl acetate. , Methyl ethyl ketone, methyl isobutyl ketone and the like. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable, and ethyl acetate is more preferable.
These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as the usage-amount of the said organic solvent, Although it can select suitably according to the objective, 0 mass part-300 mass parts are preferable with respect to 100 mass parts of said toner materials, 0 mass part-100 parts. Mass parts are more preferable, and 25 mass parts to 70 mass parts is particularly preferable.

-Aqueous medium phase (aqueous phase) preparation process-
The aqueous medium phase preparation step is not particularly limited as long as it is a step of preparing an aqueous medium phase, and can be appropriately selected according to the purpose. In this step, it is preferable to prepare an aqueous medium phase containing resin fine particles in the aqueous medium.

There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water, the solvent miscible with water, these mixtures etc. are mentioned. Among these, water is particularly preferable.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and can be appropriately selected according to the purpose. Examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. Is mentioned.
Examples of the alcohol include methanol, isopropanol, and ethylene glycol.
Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

The aqueous medium phase is prepared, for example, by dispersing the resin fine particles in the aqueous medium in the presence of a surfactant. The reason why the surfactant, the resin fine particles, and the like are appropriately added to the aqueous medium is to improve the dispersion of the toner material.
The amount of the anionic surfactant and the resin fine particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. The mass% to 10 mass% is preferable.

There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, anionic surfactant, a cationic surfactant, an amphoteric surfactant etc. are mentioned.
Examples of the anionic surfactant include fatty acid salt, alkyl sulfate ester salt, alkyl aryl sulfonate, alkyl diaryl ether disulfonate, dialkyl sulfosuccinate, alkyl phosphate, naphthalene sulfonic acid formalin condensate, poly Examples thereof include oxyethylene alkyl phosphate ester salts and glyceryl borate fatty acid esters.

The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. Examples of the material of the resin fine particles include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. Etc. These may be used individually by 1 type and may use 2 or more types together.
Among these, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and a combination thereof are preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.
Examples of the vinyl resin include polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, and (meth) acrylic acid-acrylic. Examples include acid ester polymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.
There is no restriction | limiting in particular as an average particle diameter of the said resin fine particle, Although it can select suitably according to the objective, 5 nm-200 nm are preferable and 20 nm-300 nm are more preferable.

  In the preparation of the aqueous medium phase, cellulose may be used as a dispersant. Examples of the cellulose include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and sodium carboxymethyl cellulose.

-Emulsification or dispersion preparation process-
The emulsification or dispersion preparation step is a step for preparing an emulsification or dispersion by mixing and dissolving and dispersing and dissolving the toner material (toner material phase) and the aqueous medium phase. There is no restriction | limiting in particular, According to the objective, it can select suitably.
There is no restriction | limiting in particular as the method of emulsification thru | or dispersion | distribution, According to the objective, it can select suitably, For example, it can carry out using a well-known disperser etc. Examples of the disperser include a low speed shear disperser and a high speed shear disperser.

  There is no restriction | limiting in particular as the usage-amount of the said aqueous medium phase with respect to 100 mass parts of said toner material phases, Although it can select suitably according to the objective, 50 mass parts-2,000 mass parts are preferable, 100 mass parts is preferable. -1,000 mass parts is more preferable. If the amount used is less than 50 parts by mass, the toner material phase may be poorly dispersed and toner particles having a predetermined particle size may not be obtained. If the amount used exceeds 2,000 parts by mass, it is not economical.

-Organic solvent removal process-
The organic solvent removing step is not particularly limited as long as it is a step of removing the organic solvent from the emulsified or dispersed liquid to obtain a desolvent slurry, and can be appropriately selected according to the purpose.
The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets of the emulsified or dispersed liquid, and (2) the emulsified or dispersed liquid is removed. Examples thereof include a method in which the organic solvent in the oil droplets of the emulsion or dispersion is completely removed by spraying in a dry atmosphere. When the organic solvent is removed, toner particles are formed.

-Other processes-
As said other process, a washing | cleaning process, a drying process, etc. are mentioned, for example.

-Cleaning process-
The washing step is not particularly limited as long as it is a step of washing the solvent-removed slurry with water after the organic solvent removing step, and can be appropriately selected depending on the purpose. Examples of the water include ion-exchanged water.

--- Drying process--
The drying step is not particularly limited as long as it is a step of drying the toner particles obtained in the washing step, and can be appropriately selected according to the purpose.

<< Crushing method >>
The pulverization method is, for example, a method of producing base particles of the toner by pulverizing and classifying a toner material containing at least a binder resin that has been melt-kneaded.
The melt kneading is performed by charging a mixture obtained by mixing the toner materials into a melt kneader. Examples of the melt kneader include a uniaxial or biaxial continuous kneader, a batch kneader using a roll mill, and the like. Specifically, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Kay Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works, manufactured by Bus Connieder and so on. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  The pulverization is a step of pulverizing the kneaded product obtained by the melt-kneading. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

  The classification is a step of adjusting the pulverized product obtained by the pulverization to particles having a predetermined particle size. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.

(Developer)
The developer of the present invention contains the toner of the present invention. The developer may be used as a one-component developer, or may be mixed with a carrier and used as a two-component developer. Among these, the two-component developer is preferable from the viewpoint of improving the service life when used in a high-speed printer or the like corresponding to the recent improvement in information processing speed.

In the case of the one-component developer using the toner, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, and a blade for thinning the toner The toner is not fused to the layer thickness regulating member such as the like, and good and stable developability and image can be obtained even when the developing means is used (stirred) for a long time.
Further, in the case of the two-component developer using the toner, even if the toner balance is maintained over a long period of time, the toner particle diameter in the developer is small, and even if it is stirred for a long time in the developing means, it is good and stable. Developability is obtained.

<Career>
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

<< Core material >>
The core material is not particularly limited as long as it has magnetic properties, and can be appropriately selected according to the purpose. Ferrite, magnetite, iron, and nickel are preferable. In addition, when considering the adaptability to environmental aspects that are remarkably advanced in recent years, the ferrite is not a conventional copper-zinc ferrite, but manganese ferrite, manganese-magnesium ferrite, manganese-strontium ferrite, manganese-magnesium-strontium ferrite Lithium ferrite is preferable.

<< Resin layer >>
The material of the resin layer is not particularly limited and may be appropriately selected depending on the purpose. For example, amino resin, polyvinyl resin, polystyrene resin, halogenated olefin resin, polyester resin, polycarbonate resin , Polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and vinyl fluoride For example, fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, and silicone resins. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said silicone resin, According to the objective, it can select suitably, For example, straight silicone resin which consists only of organosilosan bonds; alkyd resin, polyester resin, epoxy resin, acrylic resin, urethane resin, etc. Modified silicone resins modified with

A commercial item can be used as said silicone resin.
Examples of the straight silicone resin include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd.
Examples of the modified silicone resin include KR206 (alkyd modified silicone resin), KR5208 (acryl modified silicone resin), ES1001N (epoxy modified silicone resin), KR305 (urethane modified silicone resin) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified silicone resin), SR2110 (alkyd-modified silicone resin) manufactured by Dow Corning Silicone Co., Ltd. and the like can be mentioned.

  The silicone resin can be used alone, but a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like can also be used at the same time.

  As content in the said carrier of the component which forms the said resin layer, 0.01 mass%-5.0 mass% are preferable. When the content is less than 0.01% by mass, it may not be possible to form the uniform resin layer on the surface of the core material. When the content exceeds 5.0% by mass, the resin layer becomes thick. It becomes too much and granulation of carriers occurs, and uniform carrier particles may not be obtained.

  The content of the toner when the developer is a two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, but is 2.0 mass relative to 100 mass parts of the carrier. Parts to 12.0 parts by mass are preferable, and 2.5 parts to 10.0 parts by mass are more preferable.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention has at least an electrostatic latent image carrier (hereinafter sometimes referred to as a “photosensitive member”), an electrostatic latent image forming unit, and a developing unit, and if necessary. And have other means.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium. And organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, thermal CVD (chemical vapor deposition, Chemical Vapor Deposition) is formed on the support. ), A photo-CVD method, a plasma CVD method, or other film forming methods can be used to provide a photoconductor having a photoconductive layer made of a-Si. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

  There is no restriction | limiting in particular as a shape of the said electrostatic latent image carrier, Although it can select suitably according to the objective, A cylindrical shape is preferable. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, and more preferably 10 mm to 30 mm. Particularly preferred.

<Electrostatic latent image forming means and electrostatic latent image forming step>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples thereof include at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier imagewise.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. After the surface of the electrostatic latent image carrier is charged, the imagewise exposure can be performed, and the electrostatic latent image forming unit can be used.

<< Charging member and charging >>
The charging member is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotron and scorotron.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to a roller, and can be selected according to the specifications and form of the image forming apparatus.
When the magnetic brush is used as the charging member, as the magnetic brush, for example, various ferrite particles such as Zn-Cu ferrite are used as the charging member, and a non-magnetic conductive sleeve for supporting the ferrite member is included in the charging member. It consists of a magnet roll.
When the fur brush is used as the charging member, as the material of the fur brush, for example, a fur conductively treated with carbon, copper sulfide, metal, or metal oxide is used. A charging member can be obtained by winding or sticking to a cored bar.
The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

<< Exposure member and exposure >>
The exposure member is not particularly limited and may be appropriately selected depending on the purpose, as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed like an image to be formed. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
There is no restriction | limiting in particular as a light source used for the said exposure member, According to the objective, it can select suitably, For example, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser General light emitting materials such as (LD) and electroluminescence (EL).
In addition, various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure member.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Developing means and developing process>
The developing unit is not particularly limited as long as it is a developing unit including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image. Can be selected as appropriate.
The development step is not particularly limited as long as it is a step of developing the latent electrostatic image formed on the latent electrostatic image bearing member with toner to form a visible image. For example, it can be carried out by the developing means.

The developing means may be of a dry development type or a wet development type. Further, it may be a single color developing means or a multicolor developing means.
The developing means includes a stirrer for charging the toner by frictional stirring and a magnetic field generating means fixed inside, and a developer carrying that can carry and rotate the developer containing the toner on the surface. A developing device having a body is preferred.
In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrostatically attracted by the static force. It moves to the surface of the electrostatic latent image carrier. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier.

<Other means and other processes>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a static elimination means, a recycling means, and a control means.
Examples of the other processes include a transfer process, a fixing process, a cleaning process, a static elimination process, a recycling process, and a control process.

<< Transfer means and transfer process >>
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, the visible image is transferred onto an intermediate transfer member and combined. An embodiment having a primary transfer unit for forming a transfer image and a secondary transfer unit for transferring the composite transfer image onto a recording medium is preferable.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, an intermediate transfer member is used, and the transfer step can be performed on the intermediate transfer member. It is preferable that the visual image is firstly transferred and then the visible image is secondarily transferred onto the recording medium.
The transfer step can be performed by, for example, charging the visible image using a transfer charger and the transfer unit.
Here, when the image to be secondarily transferred onto the recording medium is a color image composed of a plurality of colors of toner, the toner of each color is sequentially superimposed on the intermediate transfer member by the transfer means. An image can be formed on the body, and the image on the intermediate transfer body can be collectively transferred onto the recording medium by the intermediate transfer unit.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least a transfer unit that peels and charges the visible image formed on the photoconductor toward the recording medium. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base or the like can also be used.

<< Fixing means and fixing process >>
The fixing unit is not particularly limited as long as it is a unit that fixes the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose. However, a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, the recording medium for each color toner May be performed each time the toner is transferred to the toner image, or may be performed simultaneously at the same time in a state in which the toner of each color is laminated.
The fixing step can be performed by the fixing unit. The heating in the heating and pressing member is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing unit depending on the purpose.

The surface pressure in the fixing step is not particularly limited and may be appropriately selected depending on the intended ^purpose, is preferably ^{10N / cm 2 ~80N / cm 2} .

<< Cleaning means and cleaning process >>
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoconductor, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, Examples thereof include a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, the cleaning step can be performed by the cleaning unit.

<< Static elimination means and static elimination process >>
The neutralizing means is not particularly limited as long as it is a means for neutralizing by applying a neutralizing bias to the photosensitive member, and can be appropriately selected according to the purpose. Examples thereof include a neutralizing lamp.
The neutralization step is not particularly limited as long as it is a step of neutralizing by applying a neutralization bias to the photoconductor, and can be appropriately selected according to the purpose. For example, it can be performed by the neutralization unit. .

<< Recycling means and recycling process >>
The recycling unit is not particularly limited as long as it is a unit that causes the developing device to recycle the toner removed in the cleaning step, and can be appropriately selected depending on the purpose. Can be mentioned.
The recycling process is not particularly limited as long as it is a process for recycling the toner removed in the cleaning process to the developing device, and can be appropriately selected according to the purpose. For example, the recycling unit performs the recycling process. Can do.

<< Control means and control process >>
The control means is not particularly limited as long as it can control the movement of each means, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.
The control process is not particularly limited as long as it can control the movement of each process, and can be appropriately selected according to the purpose. For example, the control process can be performed by the control means.

Next, one mode for carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 1 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 1. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. In the vicinity of the tandem developing device 120, an exposure device 21 as the exposure member is disposed. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. In the vicinity of the secondary transfer device 22, a fixing device 25 as the fixing means is arranged. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven. Then, the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Forming means). In each image forming unit, black, yellow, magenta, and cyan toner images are formed. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image carrier 10 is exposed to each color image-corresponding image on the basis of each color image information, with the charging device 160 as the charging means for uniformly charging the electrostatic latent image carrier 10 (FIG. 2). L), and an exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image for each color toner (black toner, yellow toner, magenta toner). And cyan tona ), A developing device 61 as the developing means for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, The static eliminator 64 is provided. Each image forming unit 18 can form each monochrome image (black image, yellow image, magenta image, and cyan image) based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one by the separation roller 145, sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying apparatus main body 150, and abutted against the registration roller 49 to stop. It is done. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. Then, the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device 22. By doing so, a color image is transferred and formed on the sheet (recording paper). The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by a switching claw 55 and discharged by a discharge roller 56 and is stacked on a discharge tray 57. Alternatively, the sheet is switched by the switching claw 55 and reversed by the sheet reversing device 28 and guided to the transfer position again. After the image is recorded on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57. Is done.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. “Part” represents “part by mass” unless otherwise specified. “%” Represents “% by mass” unless otherwise specified.

Molecular weight, softening point, glass transition temperature, melting point, crystallization (peak) temperature, and heat of crystallization were measured by the following methods.
<Molecular weight>
Apparatus: GPC (manufactured by Tosoh Corporation), detector: RI, measurement temperature: 40 ° C.,
Mobile phase: tetrahydrofuran, flow rate: 0.45 mL / min.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) are the number average molecular weight and the weight average molecular weight, respectively, measured by GPC (gel permeation chromatography) using a calibration curve prepared with a polystyrene sample with a known molecular weight as a standard. It is. In addition, the column used the thing which connected the exclusion limit 60,000, 20,000, and 10,000 things in series.

<Softening point>
Using a Koka flow tester (Shimadzu Corporation, CFT-500D), 1.5 g of the measurement sample was preheated at 50 ° C., and then heated to a plunger of 30 kg while heating at a heating rate of 5 ° C./min. Then, extrude from a nozzle with a diameter of 0.5 mm and a length of 1 mm, draw a graph of “plunger drop (flow value)” and “temperature”, and 1 / of the maximum value of plunger drop The temperature corresponding to 2 was read from the graph, and this value (temperature when half of the measurement sample flowed out) was taken as the softening point.

<Glass transition temperature, melting point, crystallization (peak) temperature, heat of crystallization>
The glass transition temperature, melting peak temperature (melting point), crystallization (peak) temperature, and crystallization heat amount of the resin and toner are as follows using a differential scanning calorimeter (DSC) (Q2000 manufactured by TA Instruments). Measured with Specifically, the measurement was performed as follows.
(Measurement condition)
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (empty container)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Starting temperature: -20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 130 ° C
Holding time: 1 min
Temperature drop rate: 10 ° C / min
End temperature: -50 ° C
Holding time: 5 min
Temperature increase rate: 10 ° C / min
End temperature: 130 ° C
Measurement was performed under the above measurement conditions, and a graph of “amount of heat absorbed and generated” and “temperature” was created.
The characteristic inflection observed in the temperature raising process (1st. Heating) was defined as the glass transition temperature (Tg). In addition, the value obtained by the midpoint method from DSC curve was used for Tg.
The melting point was the temperature at the top of the melting (endothermic) peak obtained in the temperature raising process (1st. Heating).
The crystallization peak temperature was the top of the crystallization (exothermic) peak obtained in the temperature lowering process.
The amount of crystallization heat was calculated by setting the heat generation in the range of 10 ° C. to 70 ° C. as the crystallization region in the temperature lowering process.

(Synthesis Example 1-1)
<Synthesis of Amorphous Polyester A1>
A 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, uses propylene glycol as a diol, terephthalic acid and adipic acid as dicarboxylic acids, and a molar ratio of terephthalic acid and adipic acid. (Terephthalic acid / adipic acid) was 85/15, and the molar ratio of diol to dicarboxylic acid was OH / COOH = 2.0. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm of titanium tetraisopropoxide is added to the monomer, and the temperature is raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over time, and the reaction was carried out until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 0.5 hour, and [Amorphous polyester A1] was obtained.
The resulting resin has an acid value (AV) of 0.25 mg KOH / g, a hydroxyl value (OHV) of 35.5 mg KOH / g, a glass transition temperature (Tg) of 49.0 ° C., a softening point of 110.4 ° C., and a weight average molecular weight ( Mw) 8,000.

(Synthesis Example 1-2)
<Synthesis of Amorphous Polyester A2>
A 5-L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, uses propylene glycol as a diol, terephthalic acid and succinic acid as dicarboxylic acids, and a molar ratio of terephthalic acid and succinic acid. (Terephthalic acid / succinic acid) was 80/20, and the diol / dicarboxylic acid molar ratio was OH / COOH = 2.0. Then, after sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm of titanium tetraisopropoxide is added to the monomer, and the temperature is raised to 200 ° C. in about 4 hours under a nitrogen gas stream, and then for 2 hours. The temperature was raised to 230 ° C over a period of time, and the reaction was continued until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 0.5 hour, and [Amorphous polyester A2] was obtained.
The resulting resin has an acid value (AV) of 0.27 mg KOH / g, a hydroxyl value (OHV) of 39.0 mg KOH / g, a glass transition temperature (Tg) of 50.2 ° C., a softening point of 113.7 ° C., and a weight average molecular weight ( Mw) 7,100.

(Synthesis Example 1-3)
<Synthesis of Amorphous Polyester A3>
A 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, uses propylene glycol as a diol, terephthalic acid and succinic acid as dicarboxylic acids, and a molar ratio of terephthalic acid and succinic acid. (Terephthalic acid / succinic acid) was 85/15, and the molar ratio of diol to dicarboxylic acid was OH / COOH = 2.0. Then, after sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm of titanium tetraisopropoxide is added to the monomer, and the temperature is raised to 200 ° C. in about 4 hours under a nitrogen gas stream, and then for 2 hours. The temperature was raised to 230 ° C over a period of time, and the reaction was continued until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30 mmHg for 0.5 hour, and [Amorphous polyester A3] was obtained.
The obtained resin has an acid value (AV) of 0.26 mg KOH / g, a hydroxyl value (OHV) of 24.1 mg KOH / g, a glass transition temperature (Tg) of 64.4 ° C., a softening point of 133.5 ° C., and a weight average molecular weight ( Mw) 10,000.

(Synthesis Example 1-4)
<Synthesis of Amorphous Polyester A4>
A 5-L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, uses propylene glycol as a diol, terephthalic acid and adipic acid as dicarboxylic acids, and a molar ratio of terephthalic acid and adipic acid. It was charged so that (terephthalic acid / adipic acid) was 80/20, and the molar ratio of diol to dicarboxylic acid was OH / COOH = 2.0. Then, after sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm of titanium tetraisopropoxide is added to the monomer, and the temperature is raised to 200 ° C. in about 4 hours under a nitrogen gas stream, and then for 2 hours. The temperature was raised to 230 ° C over a period of time, and the reaction was continued until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30 mmHg for 4 hours, and [Amorphous polyester A4] was obtained.
The obtained resin has an acid value (AV) of 0.5 mg KOH / g, a hydroxyl value (OHV) of 15.9 mg KOH / g, a glass transition temperature (Tg) of 48.8 ° C., a softening point of 123.4 ° C., and a weight average molecular weight ( Mw) 16,300.

(Synthesis Example 2-1)
<Synthesis of crystalline polyester B1>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,4-butanediol as a diol, dodecanedioic acid as a dicarboxylic acid, and a molar ratio of diol to dicarboxylic acid It was charged so that OH / COOH = 1.1. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm of titanium tetraisopropoxide is added to the monomer, and the temperature is raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over time, and the reaction was carried out until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 4 hours, and [crystalline polyester B1] was obtained.
The obtained resin had an acid value (AV) of 6.1 mgKOH / g, a hydroxyl value (OHV) of 25.9 mgKOH / g, a melting point (Tm) of 72.1 ° C., and a weight average molecular weight (Mw) of 16,600.

(Synthesis Example 2-2)
<Synthesis of crystalline polyester B2>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,4-butanediol as a diol, sebacic acid as a dicarboxylic acid, and a molar ratio of diol to dicarboxylic acid is OH It charged so that it might become /COOH=1.1. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm of titanium tetraisopropoxide is added to the monomer, and the temperature is raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over time, and the reaction was carried out until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30 mmHg for 4 hours, and [Crystalline polyester B2] was obtained.
The obtained resin had an acid value (AV) of 0.45 mg KOH / g, a hydroxyl value (OHV) of 26.3 mg KOH / g, a melting point (Tm) of 65.5 ° C., and a weight average molecular weight (Mw) of 16,700.

(Synthesis Example 2-3)
<Synthesis of crystalline polyester B3>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, ethylene glycol as a diol, sebacic acid as a dicarboxylic acid, and a molar ratio of diol to dicarboxylic acid is OH / COOH = 1. .1 was charged. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm of titanium tetraisopropoxide is added to the monomer, and the temperature is raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over time, and the reaction was carried out until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30 mmHg for 4 hours, and [Crystalline polyester B3] was obtained.
The obtained resin had an acid value (AV) of 0.67 mgKOH / g, a hydroxyl value (OHV) of 26.3 mgKOH / g, a melting point (Tm) of 77.3 ° C., and a weight average molecular weight (Mw) of 17,000.

(Synthesis Example 2-4)
<Synthesis of crystalline polyester B4>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, ethylene glycol as a diol, dodecanedioic acid as a dicarboxylic acid, and a molar ratio of diol to dicarboxylic acid is OH / COOH = We prepared to be 1.1. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm of titanium tetraisopropoxide is added to the monomer, and the temperature is raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over time, and the reaction was carried out until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30 mmHg for 4 hours, and [Crystalline polyester B4] was obtained.
The obtained resin had an acid value (AV) of 1.53 mgKOH / g, a hydroxyl value (OHV) of 24.5 mgKOH / g, a melting point (Tm) of 85.4 ° C., and a weight average molecular weight (Mw) of 16,300.

(Synthesis Example 2-5)
<Synthesis of Crystalline Polyester B-5>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,6-hexanediol as a diol, dodecanedioic acid as a dicarboxylic acid, and a molar ratio of the diol to the dicarboxylic acid It was charged so that OH / COOH = 1.05. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm of titanium tetraisopropoxide is added to the monomer, and the temperature is raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over time, and the reaction was carried out until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 4 hours, and [crystalline polyester B5] was obtained.
The obtained resin had an acid value (AV) of 1.2 mgKOH / g, a hydroxyl value (OHV) of 24.3 mgKOH / g, a melting point (Tm) of 75.0 ° C., and a weight average molecular weight (Mw) of 15,500.

(Synthesis Example 2-6)
<Synthesis of crystalline polyester B6>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,10-decanediol as a diol, sebacic acid as a dicarboxylic acid, and a molar ratio of diol to dicarboxylic acid is OH. It charged so that it might become /COOH=1.05. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm of titanium tetraisopropoxide is added to the monomer, and the temperature is raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over time, and the reaction was carried out until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 4 hours, and [crystalline polyester B6] was obtained.
The obtained resin had an acid value (AV) of 2.3 mgKOH / g, a hydroxyl value (OHV) of 25.2 mgKOH / g, a melting point (Tm) of 77.4 ° C., and a weight average molecular weight (Mw) of 15,800.

(Example A-1)
<Synthesis of Crystalline Copolymer Resin C1>
600 g of [Crystalline Polyester B1] was charged into a 5 L four-necked flask equipped with a nitrogen inlet tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 60 ° C. for 2 hours at 10 mmHg. After depressurization of nitrogen, 600 g of dehydrated ethyl acetate was added, and the temperature was raised to 75 ° C. under a nitrogen stream to obtain a homogeneous solution. Then, 88.1 g of 4,4′-diphenylmethane diisocyanate and dehydration treatment were performed. A dispersion composed of 88.1 g of ethyl acetate was added to the system. After the reaction system was homogenized, 500 ppm of tin 2-ethylhexanoate as a catalyst was added to the resin solid content and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,400 g of [amorphous polyester A1] prepared in advance and 1,400 g of ethyl acetate subjected to dehydration treatment was added, and the mixture was heated to reflux for 4 hours under a nitrogen stream. By removing ethyl acetate from the obtained resin solution under reduced pressure, [Crystalline copolymer resin C1] was obtained.
The obtained resin had a weight average molecular weight (Mw) of 21,000 and a softening point of 117.3 ° C. The other characteristics are shown in Table 1.

(Example A-2)
<Synthesis of Crystalline Copolymer Resin C2>
600 g of [Crystalline Polyester B1] was charged into a 5 L four-necked flask equipped with a nitrogen inlet tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 60 ° C. for 2 hours at 10 mmHg. After depressurizing nitrogen, 600 g of dehydrated ethyl acetate was added, heated to 75 ° C. under a nitrogen stream, and after becoming a homogeneous solution, 70.8 g of 4,4′-diphenylmethane diisocyanate and dehydration treatment were performed. A dispersion consisting of 70.8 g of ethyl acetate was added to the system. After the reaction system was homogenized, 500 ppm of tin 2-ethylhexanoate as a catalyst was added to the resin solid content and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,400 g of [amorphous polyester A1] prepared in advance and 1,400 g of ethyl acetate subjected to dehydration treatment was added, and the mixture was heated to reflux for 4 hours under a nitrogen stream. [Crystalline copolymer resin C2] was obtained by removing ethyl acetate from the obtained resin solution under reduced pressure.
The obtained resin had a weight average molecular weight (Mw) of 17,700 and a softening point of 113.6 ° C. The other characteristics are shown in Table 1.

(Example A-3)
<Synthesis of Crystalline Copolymer Resin C3>
600 g of [Crystalline Polyester B1] was charged into a 5 L four-necked flask equipped with a nitrogen inlet tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 60 ° C. for 2 hours at 10 mmHg. After depressurization of nitrogen, 600 g of ethyl acetate subjected to dehydration treatment was added, the temperature was raised to 75 ° C. under a nitrogen stream, and a homogeneous solution was obtained. Then, 93.9 g of 4,4′-diphenylmethane diisocyanate and dehydration treatment were performed. A dispersion consisting of 93.9 g of ethyl acetate was added to the system. After the reaction system was homogenized, 500 ppm of tin 2-ethylhexanoate as a catalyst was added to the resin solid content and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,400 g of [amorphous polyester A2] prepared in advance and 1,400 g of ethyl acetate subjected to dehydration treatment was added, and the mixture was heated to reflux for 4 hours under a nitrogen stream. By removing ethyl acetate from the obtained resin solution under reduced pressure, [Crystalline copolymer resin C3] was obtained.
The obtained resin had a weight average molecular weight (Mw) of 17,400 and a softening point of 113.8 ° C. The other characteristics are shown in Table 1.

(Example A-4)
<Synthesis of Crystalline Copolymer Resin C4>
600 g of [Crystalline Polyester B1] was charged into a 5 L four-necked flask equipped with a nitrogen inlet tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 60 ° C. for 2 hours at 10 mmHg. After depressurization of nitrogen, 600 g of dehydrated ethyl acetate was added, and the temperature was raised to 75 ° C. under a nitrogen stream to obtain a homogeneous solution, and then 66.0 g of 4,4′-diphenylmethane diisocyanate was dehydrated. A dispersion comprising 66.0 g of ethyl acetate was added to the system. After the reaction system was homogenized, 500 ppm of tin 2-ethylhexanoate as a catalyst was added to the resin solid content and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,400 g of [amorphous polyester A3] prepared in advance and 1,400 g of ethyl acetate subjected to dehydration treatment was added, and the mixture was heated to reflux for 4 hours under a nitrogen stream. [Crystalline copolymer resin C4] was obtained by removing ethyl acetate from the obtained resin solution under reduced pressure.
The obtained resin had a weight average molecular weight (Mw) of 22,500 and a softening point of 130.0 ° C. The other characteristics are shown in Table 1.

(Example A-5)
<Synthesis of Crystalline Copolymer Resin C5>
600 g of [Crystalline Polyester B1] was charged into a 5 L four-necked flask equipped with a nitrogen inlet tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 60 ° C. for 2 hours at 10 mmHg. After depressurization of nitrogen, 600 g of dehydrated ethyl acetate was added and heated to 75 ° C. under a nitrogen stream to obtain a homogeneous solution. Then, 52.3 g of 4,4′-diphenylmethane diisocyanate and dehydration treatment were performed. A dispersion comprising 52.3 g of ethyl acetate was added to the system. After the reaction system was homogenized, 500 ppm of tin 2-ethylhexanoate as a catalyst was added to the resin solid content and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,400 g of [amorphous polyester A4] prepared in advance and 1,400 g of ethyl acetate subjected to dehydration treatment was added, and the mixture was heated to reflux for 4 hours under a nitrogen stream. [Crystalline copolymer resin C5] was obtained by removing ethyl acetate from the obtained resin solution under reduced pressure.
The obtained resin had a weight average molecular weight (Mw) of 19,800 and a softening point of 127.5 ° C. The other characteristics are shown in Table 1.

(Example A-6)
<Synthesis of Crystalline Copolymer Resin C6>
600 g of [Crystalline Polyester B5] was charged into a 5 L four-necked flask equipped with a nitrogen inlet tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 10 mmHg at 60 ° C. for 2 hours. After depressurization of nitrogen, 600 g of dehydrated ethyl acetate was added, and the temperature was raised to 75 ° C. under a nitrogen stream to obtain a homogeneous solution. Then, 46.0′-diphenylmethane diisocyanate and 86.0 g of dehydration treatment were performed. A dispersion consisting of 86.0 g of ethyl acetate was added to the system. After the reaction system was homogenized, 500 ppm of tin 2-ethylhexanoate as a catalyst was added to the resin solid content and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,400 g of [amorphous polyester A1] prepared in advance and 1,400 g of ethyl acetate subjected to dehydration treatment was added, and the mixture was heated to reflux for 4 hours under a nitrogen stream. [Crystalline copolymer resin C6] was obtained by removing ethyl acetate from the obtained resin solution under reduced pressure.
The obtained resin had a weight average molecular weight (Mw) of 22,400 and a softening point of 119.6 ° C. The other properties are shown in Table 1.

(Example A-7)
<Synthesis of Crystalline Copolymer Resin C7>
600 g of [Crystalline Polyester B6] was charged into a 5 L four-necked flask equipped with a nitrogen inlet tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 60 ° C. for 2 hours at 10 mmHg. After depressurization of nitrogen, 600 g of dehydrated ethyl acetate was added, heated to 75 ° C. under a nitrogen stream, and after becoming a homogeneous solution, 86.8 g of 4,4′-diphenylmethane diisocyanate and dehydration treatment were performed. A dispersion composed of 86.8 g of ethyl acetate was added to the system. After the reaction system was homogenized, 500 ppm of tin 2-ethylhexanoate as a catalyst was added to the resin solid content and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,400 g of [amorphous polyester A1] prepared in advance and 1,400 g of ethyl acetate subjected to dehydration treatment was added, and the mixture was heated to reflux for 4 hours under a nitrogen stream. [Crystalline copolymer resin C7] was obtained by removing ethyl acetate from the obtained resin solution under reduced pressure.
The obtained resin had a weight average molecular weight (Mw) of 23,600 and a softening point of 120.3 ° C. The other characteristics are shown in Table 1.

(Comparative Example A-1)
<Synthesis of Crystalline Copolymer Resin C8>
600 g of [Crystalline Polyester B2] was charged into a 5 L four-necked flask equipped with a nitrogen introduction tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 60 ° C. for 2 hours at 10 mmHg. After depressurization of nitrogen, 600 g of ethyl acetate subjected to dehydration treatment was added, the temperature was raised to 75 ° C. under a nitrogen stream, and a homogeneous solution was obtained. Then, 89.5 g of 4,4′-diphenylmethane diisocyanate and A dispersion consisting of 89.5 g of ethyl acetate was added to the system. After the reaction system was homogenized, 500 ppm of tin 2-ethylhexanoate as a catalyst was added to the resin solid content and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,400 g of [amorphous polyester A1] prepared in advance and 1,400 g of ethyl acetate subjected to dehydration treatment was added, and the mixture was heated to reflux for 4 hours under a nitrogen stream. [Crystalline copolymer resin C8] was obtained by removing ethyl acetate from the obtained resin solution under reduced pressure.
The obtained resin had a weight average molecular weight (Mw) of 21,400 and a softening point of 107.7 ° C. The other characteristics are shown in Table 1.

(Comparative Example A-2)
<Synthesis of Crystalline Copolymer Resin C9>
600 g of [Crystalline Polyester B3] was charged into a 5 L four-necked flask equipped with a nitrogen inlet tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 10 mmHg at 60 ° C. for 2 hours. After depressurization of nitrogen, 600 g of ethyl acetate subjected to dehydration treatment was added, the temperature was raised to 75 ° C. under a nitrogen stream, and a homogeneous solution was obtained. Then, 89.5 g of 4,4′-diphenylmethane diisocyanate and A dispersion consisting of 89.5 g of ethyl acetate was added to the system. After the reaction system was homogenized, 500 ppm of tin 2-ethylhexanoate as a catalyst was added to the resin solid content and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,400 g of [amorphous polyester A1] prepared in advance and 1,400 g of ethyl acetate subjected to dehydration treatment was added, and the mixture was heated to reflux for 4 hours under a nitrogen stream. By removing ethyl acetate from the obtained resin solution under reduced pressure, [Crystalline copolymer resin C9] was obtained.
The obtained resin had a weight average molecular weight (Mw) of 20,700 and a softening point of 106.4 ° C. The other characteristics are shown in Table 1.

(Comparative Example A-3)
<Synthesis of Crystalline Copolymer Resin C10>
600 g of [Crystalline Polyester B4] was charged into a 5 L four-necked flask equipped with a nitrogen inlet tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 10 mmHg for 2 hours at 60 ° C. After depressurization of nitrogen, 600 g of dehydrated ethyl acetate was added, and the temperature was raised to 75 ° C. under a nitrogen stream to obtain a homogeneous solution. Then, 88.1 g of 4,4′-diphenylmethane diisocyanate and dehydration treatment were performed. A dispersion composed of 88.1 g of ethyl acetate was added to the system. After the reaction system was homogenized, 500 ppm of tin 2-ethylhexanoate as a catalyst was added to the resin solid content and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,400 g of [amorphous polyester A1] prepared in advance and 1,400 g of ethyl acetate subjected to dehydration treatment was added, and the mixture was heated to reflux for 4 hours under a nitrogen stream. By removing ethyl acetate from the obtained resin solution under reduced pressure, [Crystalline copolymer resin C10] was obtained.
The obtained resin had a weight average molecular weight (Mw) of 35,400 and a softening point of 115.0 ° C. The other characteristics are shown in Table 1.

(Comparative Example A-4)
<Synthesis of Crystalline Copolymer Resin C11>
400 g of [Amorphous Polyester A1] was charged into a 5 L four-necked flask equipped with a nitrogen inlet tube, a reflux tower, a stirrer, and a thermocouple, and dried under reduced pressure at 60 ° C. for 2 hours at 10 mmHg. After depressurization of nitrogen, 400 g of ethyl acetate subjected to dehydration treatment was added, and the temperature was raised to 75 ° C. under a nitrogen stream to obtain a homogeneous solution. Then, 73.8 g of 4,4′-diphenylmethane diisocyanate and A dispersion comprising 73.8 g of ethyl acetate was added to the system and stirred at 75 ° C. for 1 hour. Next, a resin solution consisting of 1,600 g of [Crystalline Polyester B2] prepared in advance and 1,600 g of ethyl acetate subjected to dehydration treatment was charged, and tin 2-ethylhexanoate was used as a catalyst in the amount of solid resin After adding 500 ppm to the solution, the mixture was heated to reflux for 4 hours under a nitrogen stream. By removing ethyl acetate from the obtained resin solution under reduced pressure, [Crystalline copolymer resin C11] was obtained.
The obtained resin had a weight average molecular weight (Mw) of 29,100 and a softening point of 78.7 ° C. The other characteristics are shown in Table 1.

(Synthesis Example 3)
<Manufacture of colorant master batch>
[Crystalline copolymer resin C1] 100 parts, 100 parts of cyan pigment (CI Pigment blue 15: 3) and 30 parts of ion-exchanged water were mixed well, and an open roll kneader (NIDEX, Nippon Coke) Kneading was performed using Kogyo Co., Ltd. The kneading temperature started kneading from 90 ° C. and then gradually cooled to 50 ° C. to prepare [Colorant masterbatch P1] in which the ratio (mass ratio) of the resin to the pigment was 1: 1.
[Crystalline copolymer resin C1] is similarly changed to [Crystalline copolymer resin C2] to [Crystalline copolymer resin C11]. [Colorant masterbatch P11] was produced.

(Synthesis Example 4)
<Manufacture of wax dispersion>
In a reaction vessel equipped with a condenser, a thermometer and a stirrer, 20 parts of paraffin wax (HNP-9 (melting point: 75 ° C.), manufactured by Nippon Seiwa Co., Ltd.) and 80 parts of ethyl acetate are placed and heated to 78 ° C. The solution was sufficiently dissolved and cooled to 30 ° C. with stirring for 1 hour, and further with an Ultra Visco Mill (manufactured by Imex), the liquid feeding speed was 1.0 kg / hour, the disk peripheral speed was 10 m / second, the diameter Wet pulverization was performed under the conditions of 80% by volume of 0.5 mm zirconia beads and 6 passes, and ethyl acetate was added to adjust the solid content concentration to produce a [wax dispersion] having a solid content concentration of 20%.

(Example B-1)
In a container equipped with a thermometer and a stirrer, 94 parts of [Crystalline Copolymer Resin C1] and 81 parts of ethyl acetate were added and heated to the melting point of the resin or higher to dissolve well. Further, 25 parts of [wax dispersion] and 12 parts of “colorant masterbatch P1” were added, and the mixture was stirred at 50 ° C. with a TK type homomixer (manufactured by Primics Co., Ltd.) at a rotation speed of 10,000 rpm. [Oil phase 1] was obtained by uniformly dissolving or dispersing. The temperature of [Oil Phase 1] was kept at 50 ° C. in the container.

  Next, in another container in which a stirrer and a thermometer are set, 75 parts of ion-exchanged water, organic resin fine particles for dispersion stabilization (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium, Salt of 25% dispersion (manufactured by Sanyo Chemical Industries, Ltd.), sodium carboxymethylcellulose (Serogen BS-H-3, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), sodium dodecyl diphenyl ether disulfonate An aqueous phase solution (aqueous phase 1) was prepared by mixing and stirring 16 parts of a 48.5% aqueous solution (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) and 5 parts of ethyl acetate at 40 ° C. 50 parts of [Oil Phase 1] maintained at 50 ° C. is added to the total amount of [Aqueous Phase 1], and mixed at 45 ° C. to 48 ° C. with a TK homomixer (manufactured by Primics Co., Ltd.) for 1 minute at 12,000 rpm. Thus, [Emulsified slurry 1] was obtained.

[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 50 ° C. for 2 hours to obtain [Slurry 1].
100 parts of [Slurry 1] of the obtained toner base particles was filtered under reduced pressure to obtain a filter cake. The following washing treatment was performed on the filter cake.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(2) 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 6,000 rpm for 5 minutes), and then filtered.
(4) 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered twice to obtain a filter cake 1 .

  The obtained “filter cake 1” was dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to prepare [Toner Base Particles 1].

  Next, 100 parts of the obtained [toner base particle 1] is added with 1.0 part of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) and 0.3% of titanium oxide (MT-150AI, manufactured by Teika Co., Ltd.). The parts were mixed using a Henschel mixer to prepare [Toner 1]. The properties of the obtained toner are shown in Table 2.

<Carrier production>
The following raw materials were dispersed with a homomixer for 20 minutes to prepare a resin layer coating solution. Thereafter, the resin layer coating solution was applied to the surface of 1,000 parts of spherical ferrite having a volume average particle size of 35 μm using a fluidized bed type coating apparatus to prepare [Carrier].
・ Silicone resin (organostraight silicone) 100 parts ・ γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts ・ Carbon black 10 parts ・ Toluene 100 parts

<Manufacture of developer>
[Carrier] 100 parts by weight [Toner 1] 7 parts uniformly at 48 rpm for 5 minutes using a type of tumbler mixer (made by Willy et Bacofen (WAB)) in which the container rolls and stirs Two-component developers corresponding to each were obtained by mixing. For [Toner 2] to [Toner 10], the corresponding developer was obtained through the same operation.

  For the produced two-component developer, the image of the tandem type image forming apparatus shown in FIG. 1 of the indirect transfer method adopting a contact charging method, a two-component development method, a secondary transfer method, a blade cleaning method, and a roller fixing method of external heating. The development unit was loaded to form an image, and the following performance evaluation was performed. The results are shown in Table 3.

<Evaluation>
<< Fixing temperature limit >>
Using the tandem type full-color image forming apparatus shown in FIG. 1, the toner adhesion amount after transfer is 0.85 ± 0.10 mg / cm ² on transfer paper (manufactured by Ricoh Business Expert Co., Ltd., copy printing paper <70>). A solid image (image size: 3 cm × 8 cm) was formed.
Fixing is performed by changing the temperature of the fixing belt, and the surface of the obtained fixed image is drawn with a ruby needle (tip radius 260 to 320 μmR, tip angle 60 degrees) using a drawing tester AD-401 (manufactured by Ueshima Seisakusho). Drawing was carried out with a load of 50 g, and the drawing surface was rubbed strongly 5 times with fibers (Hanicot # 440, manufactured by Hanilon Co., Ltd.), and the fixing belt temperature at which image shaving was almost eliminated was defined as the minimum fixing temperature. The solid image was created on the transfer paper at a position 3.0 cm from the front end in the paper passing direction. The speed of passing through the nip portion of the fixing device is 280 mm / s. The lower the fixing minimum temperature, the better the low-temperature fixing property.
〔Evaluation criteria〕
○: Fixing lower limit temperature is 120 ° C. or less Δ: Fixing lower limit temperature exceeds 120 ° C., 130 ° C. or less X: Fixing lower limit temperature exceeds 130 ° C.

<< Penetration (heat resistant storage stability) >>
Each toner was filled in a 50 mL glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated according to the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the value of penetration is large, and in the case of less than 5 mm, there is a high possibility of problems in use.
In the present invention, the penetration is expressed by the penetration depth (mm).
〔Evaluation criteria〕
○: Needle penetration is 10 mm or more △: Needle penetration is 5 mm or more and less than 10 mm ×: Needle penetration is less than 5 mm

<< Image adhesion (stackability) >>
Using the image forming apparatus shown in FIG. 1, 30 unfixed images of a full-color image (toner adhesion amount 0.85 mg / cm ² ) were continuously passed through A4 paper through a fixing machine. Then, the sheets were immediately overlapped, and 70 sheets of A4 paper were further placed thereon, and a load was applied. The image state after being left for 10 minutes was evaluated according to the following criteria.
〔Evaluation criteria〕
○: The papers are not bonded. It peels off immediately.
Δ: Slightly bonded, but no trace left on the image.
X: The toner on the image is peeled off when strongly adhered and forcibly removed.

(Examples B-2, B-4 to B-8, and Comparative Examples B-1 to B-4)
In the production of the toner of Example B-1, [Crystalline copolymer resin C1] is replaced with [Crystalline copolymer resin C2] to [Crystalline copolymer resin C11], respectively, as shown in Table 2 below. [Toner 2] in the same manner as in Example B-1, except that [Colorant masterbatch P1] is replaced with [Colorant masterbatch P2] to [Colorant masterbatch P11] as shown in Table 2 below. [Toner 4] to [Toner 12], and [Developer 2] and [Developer 4] to [Developer 12] were prepared, and the quality of the toner and developer was evaluated. The results are shown in Tables 2 and 3.

(Example B-3)
In the production of the toner of Example B-1, in the production of [Oil Phase 1], 94 parts of [Crystalline Copolymer Resin C1] are replaced with 89 parts of [Crystalline Copolymer Resin C1] and “Crystalline Polyester B1. “Toner 3” and “Developer 3” were prepared in the same manner as in Example B-1, except that the content was changed to 5 parts. The quality of the toner and developer was evaluated. The results are shown in Tables 2 and 3.

Aspects of the present invention are as follows, for example.
<1> A toner containing a crystalline resin,
The crystalline resin contains a crystalline copolymer resin having a crystalline resin segment and an amorphous resin segment,
In the differential scanning calorimetry (DSC) of the toner performed under the following measurement conditions, the crystallization heat amount derived from the crystalline resin in the temperature lowering process range of 10 ° C. to 70 ° C. is 3 J / g to 40 J / g. It is a toner characterized by being.
〔Measurement condition〕
The toner is held at −20 ° C., heated to 130 ° C. at 10 ° C./min, held for 1 minute, and then cooled to −50 ° C. at a temperature decreasing rate of 10 ° C./min. A calorific value in the range of 10 ° C. to 70 ° C. in the temperature lowering process is defined as a crystallization heat amount derived from the crystalline resin in a range of 10 ° C. to 70 ° C. in the temperature lowering process.
<2> The toner according to <1>, wherein in the differential scanning calorimetry of the toner, the crystallization peak temperature derived from the crystalline resin in the temperature lowering process is 10 ° C. or higher.
<3> The toner according to any one of <1> to <2>, wherein the crystalline resin has a melting point of 50 ° C to 75 ° C.
<4> The toner according to any one of <1> to <3>, wherein the crystalline resin segment and the amorphous resin segment are bonded by at least one of a urethane bond and a urea bond.
<5> The above <1, wherein the mass ratio of the crystalline resin segment to the amorphous resin segment (crystalline resin segment / amorphous resin segment) in the crystalline copolymer resin is 10/90 to 40/60 > To <4>.
<6> The toner according to any one of <1> to <5>, wherein the crystalline resin further contains another crystalline resin in addition to the crystalline copolymer resin.
<7> A crystalline copolymer resin having a crystalline resin segment and an amorphous resin segment,
In the differential scanning calorimetry (DSC) performed under the following measurement conditions, the crystallization heat amount in the range of 10 ° C. to 70 ° C. in the temperature lowering process is 3 J / g to 40 J / g. It is.
〔Measurement condition〕
The crystalline copolymer resin is held at −20 ° C., heated to 130 ° C. at 10 ° C./min, held for 1 minute, and then cooled to −50 ° C. at a temperature decreasing rate of 10 ° C./min. The calorific value in the range of 10 ° C. to 70 ° C. in the temperature lowering process is defined as the crystallization heat amount of the crystalline copolymer resin in the range of 10 ° C. to 70 ° C. in the temperature lowering process.
<8> The crystalline copolymer resin according to <7>, wherein a crystallization peak temperature in a temperature lowering process is 10 ° C. or higher in differential scanning calorimetry.
<9> A developer containing the toner according to any one of <1> to <6>.
<10> an electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising toner for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image;
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <6>.

JP 2004-138924 A JP 2008-052192 A JP 2010-0777419 A

Claims (10)

A toner containing a crystalline resin,
The crystalline resin contains a crystalline copolymer resin having a crystalline resin segment and an amorphous resin segment,
In the differential scanning calorimetry (DSC) of the toner performed under the following measurement conditions, the crystallization heat amount derived from the crystalline resin in the temperature lowering process range of 10 ° C. to 70 ° C. is 3 J / g to 40 J / g. A toner characterized by being.
〔Measurement condition〕
The toner is held at −20 ° C., heated to 130 ° C. at 10 ° C./min, held for 1 minute, and then cooled to −50 ° C. at a temperature decreasing rate of 10 ° C./min. A calorific value in the range of 10 ° C. to 70 ° C. in the temperature lowering process is defined as a crystallization heat amount derived from the crystalline resin in a range of 10 ° C. to 70 ° C. in the temperature lowering process.   The toner according to claim 1, wherein, in differential scanning calorimetry of the toner, the crystallization peak temperature derived from the crystalline resin in the temperature lowering process is 10 ° C. or higher.   The toner according to claim 1, wherein the crystalline resin has a melting point of 50 ° C. to 75 ° C. 4.   The toner according to claim 1, wherein the crystalline resin segment and the amorphous resin segment are bonded by at least one of a urethane bond and a urea bond.   The mass ratio (crystalline resin segment / amorphous resin segment) between the crystalline resin segment and the amorphous resin segment in the crystalline copolymer resin is 10/90 to 40/60. The toner according to any one of the above.   6. The toner according to claim 1, wherein the crystalline resin further contains another crystalline resin in addition to the crystalline copolymer resin. A crystalline copolymer resin having a crystalline resin segment and an amorphous resin segment,
In the differential scanning calorimetry (DSC) performed under the following measurement conditions, the crystallization heat amount in the range of 10 ° C. to 70 ° C. in the temperature lowering process is 3 J / g to 40 J / g. .
〔Measurement condition〕
The crystalline copolymer resin is held at −20 ° C., heated to 130 ° C. at 10 ° C./min, held for 1 minute, and then cooled to −50 ° C. at a temperature decreasing rate of 10 ° C./min. The calorific value in the range of 10 ° C. to 70 ° C. in the temperature lowering process is defined as the crystallization heat amount of the crystalline copolymer resin in the range of 10 ° C. to 70 ° C. in the temperature lowering process.   The crystalline copolymer resin according to claim 7, wherein, in differential scanning calorimetry, the crystallization peak temperature in the temperature lowering process is 10 ° C. or higher.   A developer comprising the toner according to claim 1. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising toner for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image;
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1.

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