JP2008281884A - Toner, developer, toner-containing container, process cartridge, image forming apparatus and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which is adaptable to a low-temperature fixing system, has good offset resistance, does not soil a fixing device and an image and can form high-quality images with good sharpness over a long period of time, and to provide a developer, a toner-containing container, a process cartridge, an image forming apparatus and an image forming method using the toner. <P>SOLUTION: The toner includes at least a binder resin, a release agent and a fixing aid, wherein the binder resin includes a polyester resin, this polyester resin is obtained by condensation polymerization of an alcohol component including ≥65 mol% of 1,2-propanediol in a dihydric alcohol component and a carboxylic acid component including purified rosin, the polyester resin has a softening point of 80 to <160°C, and the fixing aid has a melting point of 50 to <150°C and is included in a crystal domain state in the toner. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc., and a developer, a container containing the toner, a process cartridge, an image forming apparatus, and an image forming method using the toner About.

Image formation by electrophotography, electrostatic recording, electrostatic printing, etc. is generally performed on an electrostatic latent image on an electrostatic latent image carrier (hereinafter also referred to as “photosensitive member” or “electrophotographic photosensitive member”). The electrostatic latent image is developed with a developer to form a visible image (toner image), and then the visible image is transferred onto a recording medium such as paper and fixed to obtain a fixed image. It is performed by a series of processes.
Examples of the developer include a one-component developer using a magnetic toner or a non-magnetic toner alone, and a two-component developer composed of a toner and a carrier.

As a fixing method in the electrophotographic method, a heating heat roller method in which a heating roller is directly pressed against a toner image on a recording medium and fixed is generally used from the viewpoint of high energy efficiency. However, the heating heat roller system requires a large amount of power for fixing. Therefore, various studies have been made to reduce the power consumption of the heating roller from the viewpoint of energy saving. For example, a method of weakening the output of the heater for the heating roller when not outputting an image and increasing the output of the heater when outputting an image to raise the temperature of the heating roller is often used.
However, with this method, in order to raise the temperature of the heating roller to the temperature necessary for fixing from the sleep time, a waiting time of about several tens of seconds is required, and this waiting time becomes a stress for the user. In addition, when the image is not output, it is desired to suppress power consumption by completely turning off the heater. In order to achieve these requirements, it is necessary to lower the fixing temperature of the toner itself and lower the fixing temperature of the toner when it can be used.

  The toner used in the developer is required to have excellent low-temperature fixability and storage stability (blocking resistance) with the development of electrophotographic technology, and has been generally used as a binder resin for toner. Various attempts have been made to use a polyester resin having a higher affinity with a recording medium or the like than a styrene-based resin and excellent in low-temperature fixability. For example, a toner containing a linear polyester resin that defines physical properties such as molecular weight (see Patent Document 1), a toner containing a non-linear cross-linked polyester resin using a rosin as an acid component (see Patent Document 2), Etc. have been proposed.

In recent years, in order to further increase the speed and energy saving of the image forming apparatus, the conventional binder resin for toner is still insufficient for the market demand, shortening the fixing time in the fixing process, and Due to the lowering of the heating temperature by the fixing means, it is extremely difficult to maintain a sufficient fixing strength.
A toner containing a polyester resin using a rosin as described in Patent Document 2 is excellent in low-temperature fixability and has an advantage of improving toner productivity in the pulverization method because of excellent pulverizability. Further, by using 1,2-propanediol, which is a branched chain alcohol having 3 carbon atoms, as an alcohol component, low temperature fixability is improved while maintaining offset resistance as compared with alcohol having 2 or less carbon atoms. Therefore, it is effective for preventing deterioration in storage stability accompanying a decrease in glass transition temperature as compared with branched chain alcohols having 4 or more carbon atoms. By using such a polyester resin as a binder resin for toner, it is possible to fix at a low temperature and to improve the storage stability.

  However, the demand for energy saving tends to become more and more severe in the future, and the use of a polyester resin with excellent low-temperature fixability tends to improve the low-temperature fixability compared to the conventional one. It is expected that it will be difficult to sufficiently meet the demands for energy saving only by using it, and the actual situation is that further improvement and development are desired.

JP 2004-245854 A JP-A-4-70765

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention corresponds to a low-temperature fixing system, has good offset resistance, does not contaminate the fixing device and the image, and can form a high-quality image with good sharpness over a long period of time, Another object of the present invention is to provide a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method using the toner.

  As a result of intensive studies by the present inventors to solve the above-mentioned problems, an alcohol component containing 65 mol% or more of 1,2-propanediol in a divalent alcohol component, and a carboxylic acid component containing purified rosin In a toner using a polyester resin having a softening point of 80 ° C. or higher and lower than 160 ° C. obtained as a binder resin obtained by condensation polymerization of the toner, the toner has compatibility with the polyester resin having a melting point of 50 ° C. or higher and lower than 150 ° C. It has been found that the low-temperature fixability can be further improved by allowing the fixing aid to exist in a crystalline domain state in the toner. Further, since the fixing assistant present in the toner exists independently of the polyester resin before being heated in the fixing portion, the thermal characteristics of the polyester resin before being heated in the fixing portion may be deteriorated. It was also found that the heat-resistant storage stability can be maintained.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A toner containing at least a binder resin, a release agent, and a fixing aid,
The binder resin contains a polyester resin, and the polyester resin polycondenses an alcohol component containing 1,2-propanediol in an amount of 65 mol% or more of a divalent alcohol component and a carboxylic acid component containing a purified rosin. And the softening point of the polyester resin is 80 ° C. or higher and lower than 160 ° C.,
The toner is characterized in that the fixing assistant has a melting point of 50 ° C. or higher and lower than 150 ° C., and the fixing assistant is contained in the toner in a crystalline domain state.
<2> If the glass transition temperature of the polyester resin is Tgr, the glass transition temperature of the polyester resin after adding 10 parts by mass of a fixing aid to 90 parts by mass of the polyester resin and heating at 150 ° C. is Tgr ′. The toner according to <1>, wherein the toner satisfies the formula: Tgr−Tgr ′> 10 ° C.
<3> The toner according to any one of <1> to <2>, wherein the fixing assistant contains a crystalline polyester resin.
<4> The toner according to any one of <1> to <3>, wherein the fixing assistant contains a fatty acid having 16 to 24 carbon atoms.
<5> The toner according to any one of <1> to <4>, wherein the fixing aid contains an alcohol having 16 to 24 carbon atoms.
<6> The toner according to any one of <1> to <5>, wherein the fixing assistant contains an ester compound having an acid value of 20 mgKOH / g or more and less than 200 mgKOH / g.
<7> The toner according to any one of <1> to <6>, wherein the fixing assistant contains an ester compound having a hydroxyl value of 10 mgKOH / g or more and less than 200 mgKOH / g.
<8> The toner according to any one of <1> to <7>, wherein the fixing assistant contains a fatty acid amide formed by amide bond between a fatty acid and an amine.
<9> The toner according to any one of <1> to <8>, wherein the content of the fixing aid in the toner is 1% by mass or more and less than 20% by mass.
<10> Any one of <9> to <9>, wherein the polyester resin contains a polyester resin A having a softening point of 80 ° C. or higher and lower than 120 ° C. and a polyester resin B having a softening point of 120 ° C. or higher and 160 ° C. or lower. The toner described in 1.
<11> The toner according to any one of <1> to <10>, wherein the carboxylic acid component in the polyester resin further contains an aliphatic dicarboxylic acid compound having 2 to 4 carbon atoms.
<12> The toner according to any one of <1> to <11>, wherein the alcohol component in the polyester resin further contains glycerin.
<13> The above-mentioned obtained by removing at least a binder resin, a release agent, and a fixing aid in an aqueous medium by dispersing or dissolving a dispersion or dispersion in an aqueous medium. The toner according to any one of <1> to <12>.
<14> A developer comprising the toner according to any one of <1> to <13>.
<15> A toner-containing container filled with the toner according to any one of <1> to <13>.
<16> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, An image forming method comprising at least a transfer step of transferring a visible image to a recording medium and a fixing step of fixing the transfer image transferred to the recording medium,
The toner is the toner according to any one of <1> to <13>.
<17> An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to make it visible An image forming apparatus having at least developing means for forming an image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <13>.
<18> An electrostatic latent image carrier and at least developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image, and forming an image A process cartridge that is detachable from the apparatus body,
A process cartridge, wherein the toner is the toner according to any one of <1> to <13>.

The toner of the present invention contains at least a binder resin, a release agent, and a fixing aid,
The binder resin contains a polyester resin, and the polyester resin is a polycondensation of an alcohol component containing 1,2-propanediol in an amount of 65 mol% or more of a divalent alcohol component and a carboxylic acid component containing a purified rosin. And the softening point of the polyester resin is 80 ° C. or more and less than 160 ° C.,
The melting point of the fixing aid is 50 ° C. or higher and lower than 150 ° C., and the fixing aid is contained in the toner in a crystalline domain state.
The toner of the present invention contains at least a binder resin, a release agent, and a fixing aid. The polyester resin is obtained by polycondensing an alcohol component containing 1,2-propanediol as a divalent alcohol component and a purified rosin with a carboxylic acid component. 1,2-propanediol, which is a branched-chain alcohol having 3 carbon atoms used as the alcohol component, improves low-temperature fixability while maintaining offset resistance as compared with alcohol having 2 or less carbon atoms. It is effective and effective in preventing deterioration in storage stability accompanying a decrease in glass transition temperature as compared with a branched chain alcohol having 4 or more carbon atoms. In addition, since refined rosin is blended with the carboxylic acid component, fixing at an extremely low temperature is possible, and since the ester component is excessive compared to ordinary polyester resins, the miscibility with release agents is good. It becomes. As a result, the release agent dispersibility is excellent, there is no phase separation of the resin, the durability is excellent, and the low-temperature fixability is obtained while improving the heat-resistant storage stability of the resin. Furthermore, by using purified rosin, odors derived from impurities are suppressed, and heat resistant storage stability is improved.
In addition, the presence of a fixing aid in the toner in a crystalline domain state having compatibility with the polyester resin having a melting point of 50 ° C. or more and less than 150 ° C. can further improve the low-temperature fixability, Since the fixing assistant present in the toner is present independently of the polyester resin before being heated in the fixing portion, the thermal properties of the polyester resin before being heated in the fixing portion are not deteriorated. The heat-resistant storage stability can be maintained.
Therefore, according to the toner of the present invention, it is compatible with a low-temperature fixing system, has good offset resistance, does not contaminate the fixing device and the image, and can form a high-quality image with good sharpness over a long period of time. it can.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, it corresponds to a low-temperature fixing system, has good offset resistance, does not contaminate the fixing device and the image, and has good sharpness. High quality images can be formed over a long period of time.

The image forming apparatus of the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using toner. A developing unit that develops a visible image by development; a transfer unit that transfers the visible image to a recording medium; and a fixing unit that fixes the transferred image transferred to the recording medium. As the toner, the toner of the present invention is used.
In the image forming apparatus of the present invention, the electrostatic latent image forming unit forms an electrostatic latent image. The developing means develops the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. At this time, since the toner of the present invention is used as the toner, it is compatible with a low-temperature fixing system, has good offset resistance, does not contaminate the fixing device and the image, and has high sharpness and high quality. Images can be formed over a long period of time.

The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image. It includes at least a developing step, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium, and the toner of the present invention is used as the toner.
In the image forming method of the present invention, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image formed on the electrostatic latent image carrier is developed with toner to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. At this time, since the toner of the present invention is used as the toner, it is compatible with a low-temperature fixing system, has good offset resistance, does not contaminate the fixing device and the image, and has high sharpness and high quality. Images can be formed over a long period of time.

  The process cartridge of the present invention has at least an electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using toner to form a visible image. The image forming apparatus main body is detachable and excellent in convenience, and uses the toner of the present invention, so that it is compatible with a low-temperature fixing system and has good offset resistance. A high-quality image with good sharpness can be formed over a long period of time without contamination.

  According to the present invention, conventional problems can be solved, low-temperature fixing systems are compatible, offset resistance is good, fixing devices and images are not contaminated, and high-quality images with good sharpness are obtained. A toner that can be formed over a long period of time, a developer using the toner, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method can be provided.

(toner)
The toner of the present invention contains at least a binder resin, a release agent, and a fixing aid, and further contains other components as necessary.

<Fixing aid>
The fixing aid is a compound having a melting point of 50 ° C. or higher and lower than 150 ° C., and preferably 60 ° C. to 100 ° C. When the melting point of the fixing aid is less than 50 ° C., the fixing aid is likely to be melted and may be inferior in heat resistant storage stability. Since the toner needs to be heated at a high temperature, sufficient low-temperature fixability may not be obtained.
Here, the melting point of the fixing aid can be measured using, for example, a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation).
First, 5.0 mg of a fixing aid is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Then, it heated from 20 degreeC to 150 degreeC with the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. Then, it cooled to 0 degreeC from 150 degreeC with the temperature-fall rate of 10 degree-C / min, and also heated to 150 degreeC with the temperature increase rate of 10 degree-C / min, and measured the DSC curve. From the obtained DSC curve, using the analysis program in the DSC-60 system, the endothermic peak of the DSC curve at the second temperature rise can be selected, and the melting point (Tmp) of the fixing aid can be obtained.

  In the present invention, the glass transition temperature of the polyester resin is Tgr, and the glass transition temperature of the polyester resin after adding 10 parts by weight of a fixing aid to 90 parts by weight of the polyester resin and heating at 150 ° C. is Tgr ′. ΔTg = Tgr−Tgr ′> 10 ° C. is preferably satisfied, and ΔTg = Tgr−Tgr ′> 15 ° C. is more preferable.

Here, the glass transition temperature (Tgr) of the polyester resin and the glass transition temperature (Tgr ′) of the polyester resin when 10 parts by mass of the fixing aid are added are, for example, a DSC system (differential scanning calorimeter) (“DSC− 60 ", manufactured by Shimadzu Corporation).
First, about 5.0 mg of a polyester resin was put in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Subsequently, it heated from 20 degreeC to 150 degreeC with the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. Thereafter, the sample is cooled from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min, and a differential scanning calorimeter (“DSC-60”, manufactured by Shimadzu Corporation) Thus, the DSC curve was measured. From the obtained DSC curve, using the analysis program in the DSC-60 system, the shoulder of the DSC curve at the second temperature rise can be selected, and the glass transition temperature (Tgr) of the polyester resin can be calculated.
The glass transition temperature (Tgr ′) of the polyester resin when 10 parts by mass of the fixing aid is added can be measured in the same manner.
First, 0.5 mg of a fixing aid and 4.5 mg of a polyester resin were placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Subsequently, it heated from 20 degreeC to 150 degreeC with the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. Then, it cooled to 0 degreeC with the temperature-fall rate of 10 degree-C / min from 150 degreeC, and also heated to 150 degreeC with the temperature increase rate of 10 degree-C / min, and measured the DSC curve with the differential scanning calorimeter. From the obtained DSC curve, using the analysis program in the DSC-60 system, the shoulder of the DSC curve at the second temperature increase was selected, and the glass transition temperature (Tgr) of the polyester resin when the fixing aid was added. ') Can be calculated.

  The fixing aid is not particularly limited as long as it has a melting point of 50 ° C. or higher and lower than 150 ° C. and has crystallinity, and can be appropriately selected according to the purpose. For example, a crystalline polyester resin Long chain fatty acids, long chain alcohols, ester compounds, fatty acid amides and the like.

-Crystalline polyester resin-
The crystalline polyester resin comprises a polyvalent alcohol unit and a carboxylic acid _{unit, -OCOC-R-COO- (CH} 2) n- ( In the formula, R represents C2-20 straight-chain unsaturated An aliphatic group, and n represents an integer of 2 to 20) at least 60 mol% of all ester bonds in the entire resin. In the above formula, R preferably represents a linear unsaturated aliphatic divalent carboxylic acid residue, has 2 to 20 carbon atoms, and more preferably 2 to 4 linear unsaturated aliphatic. It is a group. n shows the integer of 2-20, and the integer of 2-6 is more preferable.

  Examples of the linear unsaturated aliphatic group are derived from linear unsaturated divalent carboxylic acids such as maleic acid, fumaric acid, 1,3-n-propene dicarboxylic acid, and 1,4-n-butene dicarboxylic acid. And a linear unsaturated aliphatic group.

The (CH ₂ ) n represents a linear aliphatic dihydric alcohol residue. Specific examples of the linear aliphatic dihydric alcohol residue include linear aliphatic dihydric alcohols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Can be derived from. Since the crystalline polyester resin uses a linear unsaturated aliphatic dicarboxylic acid unit as a carboxylic acid unit, the crystalline polyester resin has an effect of easily forming a crystal structure as compared with the case of using an aromatic dicarboxylic acid unit. Show.

The crystalline polyester resin is a polyvalent carboxylic acid comprising (1) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (an acid anhydride, a lower alkyl ester acid halide having 1 to 4 carbon atoms, etc.). It can be produced by subjecting the unit and (2) a polyhydric alcohol unit comprising a linear aliphatic diol to a polycondensation reaction by a conventional method. In this case, the polyvalent carboxylic acid unit may contain a small amount of other polyvalent carboxylic acid units as necessary. In this case, the polyvalent carboxylic acid unit includes (1) an unsaturated aliphatic divalent carboxylic acid unit having a branched chain, (2) a saturated aliphatic divalent carboxylic acid, a saturated aliphatic trivalent carboxylic acid, etc. In addition to aliphatic polyvalent carboxylic acid units, (3) aromatic polyvalent carboxylic acid units such as aromatic divalent carboxylic acids and aromatic trivalent carboxylic acids are included.
The content of these polyvalent carboxylic acid units is usually preferably 30 mol% or less, more preferably 10 mol% or less, based on the total carboxylic acid, and is suitably added within the range in which the resulting polyester has crystallinity. The

  Specific examples of polyvalent carboxylic acid units that can be added as needed include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid Divalent carboxylic acid units such as acids; trimetic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalene Trivalent or higher polyvalent carboxylic acid units such as tricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid, etc. Can be mentioned.

If necessary, the polyhydric alcohol unit may contain a trivalent or higher polyhydric alcohol unit in addition to a small amount of an aliphatic branched dihydric alcohol unit or cyclic dihydric alcohol unit. The content thereof is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total alcohol units, and is suitably added within the range in which the resulting polyester has crystallinity.
Examples of polyhydric alcohol units added as needed include 1,4-bis (hydroxymethyl) cyclohexane units, polyethylene glycol units, bisphenol A ethylene oxide adduct units, bisphenol A propylene oxide adduct units, glycerin units, etc. Is mentioned.

In the crystalline polyester resin, the molecular weight distribution is preferably sharp from the viewpoint of low-temperature fixability, and the molecular weight is preferably a relatively low molecular weight. The molecular weight of the crystalline polyester resin is such that its weight average molecular weight (Mw) is 5,500 to 6,500 and its number average molecular weight (Mn) is 1 in the molecular weight distribution by GPC of the o-dichlorobenzene soluble component. 300-1500 and its Mw / Mn ratio is preferably 2-5.
The molecular weight distribution of the crystalline polyester resin is based on a molecular weight distribution diagram in which the horizontal axis is log (M: molecular weight) and the vertical axis is mass part. In the case of the crystalline polyester resin used in the present invention, in this molecular weight distribution diagram, it is preferable to have a molecular weight peak in the range of 3.5 parts by mass to 4.0 parts by mass. 5 or less is preferable.

-Ester compound-
Examples of the ester compound include those obtained by esterifying the following alcohol component and fatty acid component.
As the alcohol component, for example, it is preferable to use a monomer of a polyol such as ethylene glycol, propylene glycol, butylene glycol, tetramethylene glycol, or glycerin, or a product obtained by condensation polymerization of the polyol as necessary. When the condensation polymer is used as an alcohol component, the degree of polymerization is preferably 2 or more and less than 20. When the degree of polymerization is 20 or more, the crystallinity is lowered, whereby the sharp melt property as a fixing aid is lost, and a sufficient low-temperature fixing effect may not be obtained.

  As the fatty acid, it is preferable to use a simple substance having a carbon number of 16 to 24 or a mixture thereof. Specific examples include simple substances such as lauric acid, palmitic acid, stearic acid, arachidic acid, eicosanoic acid, behenic acid, lignoceric acid, and mixtures thereof. When the number of carbon atoms is less than 12, the crystallinity is lowered, so that the melting point of the compound itself is lowered and sufficient heat-resistant storage stability may not be obtained. Further, the sharp melt property as a fixing aid is lost, and a sufficient low-temperature fixing effect may not be obtained.

The ester compound can be obtained by appropriately selecting the fatty acid and the alcohol component according to the purpose and esterifying. Further, the degree of esterification of the ester compound of the polyhydric alcohol can be appropriately selected according to the purpose.
The ester compound achieves low-temperature fixing by softening the polyester resin of the present invention, which is the main component of the toner. Therefore, the ester compound preferably has a certain acid value or hydroxyl value. When the ester compound has an acid value, the acid value is preferably 20 mgKOH / g or more and less than 200 mgKOH / g. When the acid value is less than 20 mgKOH / g, the compatibility with the polyester resin is not sufficient, and thus the effect for low-temperature fixing may not be sufficiently obtained. On the other hand, when the acid value is 200 mgKOH / g or more, there is a risk that the charging characteristics of the toner at high temperature and high humidity are deteriorated.
When the ester compound has a hydroxyl value, the hydroxyl value is preferably 10 mgKOH / g or more and less than 200 mgKOH / g. When the hydroxyl value is less than 10 mgKOH / g, the compatibility with the polyester resin is not sufficient, and the effect for low-temperature fixing may not be sufficiently obtained. On the other hand, if the hydroxyl value is 200 mgKOH / g or more, there is a risk that the charging characteristics of the toner at high temperature and high humidity are deteriorated.

  Here, the sample for measuring the acid value and the hydroxyl value is prepared by the following procedure. 0.5 g of fixing aid is added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution. Otherwise, the measurement is performed based on the measurement method described in JIS K0070.

-Long chain fatty acids-
The long chain fatty acid is preferably those having 16 to 24 carbon atoms. Specific examples thereof include simple substances such as palmitic acid, stearic acid, arachidic acid, eicosanoic acid, behenic acid, lignoceric acid, and mixtures thereof. When the number of carbon atoms is less than 16, the melting point is lowered and sufficient heat-resistant storage stability may not be obtained.

-Long chain alcohol-
As the long-chain alcohol, those having 16 to 24 carbon atoms are preferable. Specific examples thereof include simple substances such as hexyl alcohol, stearyl alcohol, eicosanol, and behenyl alcohol, or a mixture thereof. When the number of carbon atoms is less than 16, the melting point is lowered and sufficient heat-resistant storage stability may not be obtained.

-Fatty acid amide-
The fatty acid amide comprises an amide bond of a fatty acid and an amine. Examples of the fatty acid amide include ethylene bis stearic acid amide, oleic acid amide, erucic acid amide, stearic acid amide, behenic acid amide, and n-stearyl elca. Acid amide, n-oleyl palmitic acid amide, n-stearyl stearic acid amide, ethylene bisisostearic acid amide, methylol stearic acid amide, ethylene bisoleic acid amide, hexamethylene stearic acid amide, ethylene bisbehenic acid amide, methylene bis Examples thereof include a simple substance such as stearamide, ethylenebishydroxy stearamide, or a mixture thereof.

The fixing aid is present in the toner in a crystalline domain state and has a characteristic that it is compatible with the resin when heated.
In order to confirm that the fixing aid has crystallinity, the crystalline retention state (compatible or incompatible) can be measured from an X-ray diffraction chart.
Specifically, whether the fixing aid has crystallinity in the toner can be confirmed by a crystal analysis X-ray diffractometer (manufactured by X'Pert MRDX'Pert MRD Phillips). First, a fixing auxiliary agent is ground in a mortar to prepare a sample powder, and the obtained sample powder is uniformly applied to a sample holder. Thereafter, a sample holder is set in the diffractometer and measurement is performed to obtain a diffraction spectrum of the fixing aid. Next, toner powder is applied to the holder, and measurement is performed in the same manner. The fixing aid contained in the toner can be identified from the diffraction spectrum of the fixing aid obtained in advance. Moreover, in the said apparatus, the change of the diffraction spectrum at the time of changing temperature with an attached heating unit is measurable. Using the same unit, the proportion of compatible and incompatible components in the resin before and after heating of the fixing aid can be determined from the change in the peak area of the X-ray diffraction spectrum derived from the fixing aid at room temperature and 150 ° C. The larger the rate of change of the peak area derived from the fixing assistant before and after the heating, the more compatibilization with the toner resin is caused by the heating at the time of fixing, so that a larger effect for low-temperature fixing can be obtained.

  The dispersion diameter of the fixing aid is, for example, preferably 10 nm to 3 μm, more preferably 50 nm to 1 μm, in the maximum direction. When the dispersion diameter is less than 10 nm, the heat resistance storage stability may be inferior due to an increase in the contact surface area between the fixing aid and the binder resin. When the dispersion diameter exceeds 3 μm, Insufficient compatibility with the binder resin may result in poor low temperature fixability.

  The method for measuring the dispersion diameter of the fixing aid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the toner is embedded in an epoxy resin to form an ultrathin slice of about 100 nm, and tetraoxidation is performed. After dyeing with ruthenium, it is observed with a transmission electron microscope (TEM) at a magnification of 10,000 times, photographed, and this photograph is evaluated to observe the dispersion state of the fixing aid, and the dispersion The diameter can be measured. In order to distinguish between the fixing aid and the release agent in the toner, the toner is obtained by confirming the contrast difference obtained by dyeing the fixing aid and the release agent in the same manner with ruthenium tetroxide in advance. It can be identified by the difference in contrast between the fixing aid and the release agent.

  The content of the fixing aid in the toner is 1% by mass or more and 20% from the viewpoint that both low-temperature fixability and heat-resistant storage stability can be achieved and toner characteristics such as chargeability and resolution can be maintained at a high level. The content is preferably less than mass%, more preferably 3 mass% to 10 mass%. When the content is less than 1% by mass, the low-temperature fixability may be inferior, and when it is 20% by mass or more, the area of the fixing aid on the toner surface may increase and the fluidity may be inferior. .

<Polyester resin>
From the viewpoint that the polyester resin is excellent in low-temperature fixability and heat-resistant storage stability, an alcohol component containing 1,2-propanediol in an amount of 65 mol% or more in a divalent alcohol component and a carboxylic acid component containing a purified rosin Is a polyester resin having a softening point of 80 ° C. or more and less than 160 ° C. obtained by condensation polymerization.
Further, from the viewpoint of achieving both low-temperature fixability and anti-offset properties, a polyester resin (A) having a softening point Tm (A) of 120 ° C. or higher and 160 ° C. or lower, and a softening point Tm (B) of 80 ° C. or higher and 120 ° C. It is preferable to contain 2 types of polyester-type resin (B) which is less than degree C.

The polyester resin (A) has a softening point Tm (A) of 120 ° C or higher and 160 ° C or lower, preferably 130 ° C to 155 ° C, and more preferably 135 ° C to 155 ° C.
The polyester resin (B) has a softening point Tm (B) of 80 ° C or higher and lower than 120 ° C, preferably 85 ° C to 115 ° C, and more preferably 90 ° C to 110 ° C.
The difference [ΔTm; Tm (A) −Tm (B)] between Tm (A) and Tm (B) is preferably 10 ° C. or higher, more preferably 15 ° C. to 55 ° C., and further preferably 20 ° C. to 50 ° C. preferable.
Moreover, in order to combine low-temperature fixability, hot offset resistance, and heat-resistant storage stability, the mass ratio [(A) / (B)] of the polyester resin (A) and the polyester resin (B) is 10/90. -90/10 are preferable, 20 / 80-80 / 20 are more preferable, and 30 / 70-70 / 30 are still more preferable.
The high softening point polyester resin (A) having such characteristics contributes to improvement in offset resistance, and the low softening point polyester resin (B) contributes to improvement in low-temperature fixability. The combined use of the base resin (A) and the polyester base resin (B) is effective in achieving both low temperature fixability and offset resistance.

  In the present invention, at least one of the polyester-based resins (A) and (B) has a content of 1,2-propanediol in an alcohol component of 65 mol% or more, and substantially only an aliphatic alcohol. It is obtained by polycondensation of an alcohol component consisting of a carboxylic acid component containing purified rosin.

-Alcohol component-
1,2-propanediol, which is a branched-chain alcohol having 3 carbon atoms used for the alcohol component, improves low-temperature fixability while maintaining offset resistance as compared with alcohol having 2 or less carbon atoms. It is effective and effective in preventing deterioration of storage stability due to a decrease in glass transition temperature as compared with branched chain alcohols having 4 or more carbon atoms, fixing at an extremely low temperature, and improving storage stability. A surprising effect is produced. In addition, a polyester resin containing 1,2-propanediol as an alcohol component is excellent in compatibility with a release agent and easily finely dispersed. In particular, when the content of 1,2-propanediol is 65 mol% or more in the alcohol component, excellent low-temperature fixability and offset resistance are exhibited.

As the alcohol component, an alcohol other than 1,2-propanediol may be contained as long as the objects and effects of the present invention are not impaired. It is 65 mol% or more in a component, 70 mol% or more is preferable, 80 mol% or more is more preferable, and 90 mol% or more is still more preferable. Examples of the divalent alcohol component other than 1,2-propanediol include 1,3-propanediol, ethylene glycol having a different carbon number, hydrogenated bisphenol A, or alkylene (2 to 4 carbon atoms) oxide (average). Addition mole number 1-16) Aliphatic dialcohols, such as an adduct, etc. are mentioned.
The content of the divalent alcohol component is preferably 60 to 95 mol%, more preferably 65 to 90 mol% in the alcohol component.
In addition, it is preferable that the alcohol component of the said polyester-type resin (A) contains 1, 3- propanediol from a viewpoint of offset resistance. The molar ratio of 1,2-propanediol to 1,3-propanediol in the alcohol component of the polyester resin (A) (1,2-propanediol / 1,3-propanediol) is 99/1 to 65 / 35 is preferable, 95/5 to 70/30 is more preferable, 90/10 to 75/25 is still more preferable, and 85/15 to 77/23 is particularly preferable.
Examples of the alcohol component include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, and the like An aromatic alcohol such as an alkylene oxide adduct of bisphenol A may be contained, but at least one alcohol component of the polyester resins (A) and (B) is substantially composed only of an aliphatic alcohol. Preferably, both alcohol components of the polyester resins (A) and (B) are substantially composed only of aliphatic alcohols.
Here, in the present specification, the term “alcohol component consisting essentially of an aliphatic alcohol” means that the content of the aliphatic alcohol is 90 mol% or more in the alcohol component, and is 95 mol% or more. Is more preferable, 98 mol% or more is still more preferable, and especially 99 mol% or more is meant.

-Carboxylic acid component-
As the carboxylic acid component, purified rosin is used. As a result, the rosin having a polycyclic aromatic ring reduces the water absorption that the conventional aliphatic alcohol polyesters have, and further increases the effect of reducing the charge amount under high temperature and high humidity. Furthermore, by using purified rosin, odors derived from impurities are suppressed, and heat resistant storage stability is improved.

Here, the rosin is a natural resin obtained from pine, the main component of which is a resin such as abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, dehydroabietic acid An acid, or a mixture thereof.
The rosin is roughly classified into tall rosin obtained from tall oil obtained as a by-product in the process of producing pulp, gum rosin obtained from raw pine ani, wood rosin obtained from pine stumps, etc. From the viewpoint of low-temperature fixability, tall rosin is preferred.
In addition, a purified product of a modified rosin such as a disproportionated rosin or a hydrogenated rosin can be used, but in the present invention, a so-called raw rosin that is not modified is used from the viewpoint of low-temperature fixability and storage stability. It is preferable to do.

  The purified rosin is a rosin from which impurities have been removed by a purification process. Examples of main impurities include 2-methylpropane, acetaldehyde, 3-methyl-2-butanone, 2-methylpropanoic acid, butanoic acid, pentanoic acid, n-hexanal, octane, hexanoic acid, benzaldehyde, 2-pentylfuran, Examples include 2,6-dimethylcyclohexanone, 1-methyl-2- (1-methylethyl) benzene, 3,5-dimethyl-2-cyclohexene, 4- (1-methylethyl) benzaldehyde. In the present invention, among these, the peak intensity detected as a volatile component by the headspace GC-MS method of three types of impurities, 2-methylpropane, pentanoic acid and benzaldehyde, can be used as an indicator of purified rosin. . The reason why the volatile component, not the absolute amount of impurities, is used as an indicator is that the use of the purified rosin in the present invention makes odor one of the problems of improvement over the conventional polyester resin using rosin. .

The purified rosin has a peak intensity of hexanoic acid of 0.8 × 10 ⁷ or less and a peak intensity of pentanoic acid of 0.4 × 10 ⁷ or less under the measurement conditions of the headspace GC-MS method described later. Rosin having a peak intensity of benzaldehyde of 0.4 × 10 ⁷ or less. Furthermore, from the viewpoint of storage stability and odor, the peak intensity of hexanoic acid is preferably 0.6 × 10 ⁷ or less, and more preferably 0.5 × 10 ⁷ or less. The peak intensity of pentanoic acid is preferably 0.3 × 10 ⁷ or less, and more preferably 0.2 × 10 ⁷ or less. The peak intensity of benzaldehyde is preferably 0.3 × 10 ⁷ or less, and more preferably 0.2 × 10 ⁷ or less.

Furthermore, from the viewpoint of storage stability and odor, it is preferable that n-hexanal and 2-pentylfuran are reduced in addition to the above three substances. The peak intensity of n-hexanal is preferably 1.7 × 10 ⁷ or less, more preferably 1.6 × 10 ⁷ or less, and even more preferably 1.5 × 10 ⁷ or less. Further, the peak intensity of 2-pentylfuran is preferably 1.0 × 10 ⁷ or less, more preferably 0.9 × 10 ⁷ or less, and further preferably 0.8 × 10 ⁷ or less.

  The method for purifying the rosin is not particularly limited, and a known method can be used. Examples thereof include distillation, recrystallization, extraction, and the like, and purification by distillation is preferable. As the distillation method, for example, the method described in JP-A-7-286139 can be used, and examples thereof include vacuum distillation, molecular distillation, steam distillation, etc., but purification by vacuum distillation is preferable. For example, distillation is usually performed at a still temperature of 200 ° C. to 300 ° C. at a pressure of 6.67 kPa or less, and methods such as ordinary simple distillation, thin film distillation, rectification, and the like are applied. 2% by mass to 10% by mass of a high molecular weight product is removed as a pitch component with respect to rosin, and at the same time, an initial fraction of 2% by mass to 10% by mass is simultaneously removed.

  The softening point of the purified rosin is preferably 50 ° C to 100 ° C, more preferably 60 ° C to 90 ° C, and still more preferably 65 ° C to 85 ° C. Further, the impurities contained in the rosin are removed by purification. The softening point of the purified rosin in the present invention means a softening point measured when the rosin is once melted by the method described later and naturally cooled for 1 hour in an environment of a temperature of 25 ° C. and a relative humidity of 50%. .

The acid value of the purified rosin is preferably 100 mgKOH / g to 200 mgKOH / g, more preferably 130 mgKOH / g to 180 mgKOH / g, and still more preferably 150 mgKOH / g to 170 mgKOH / g.
The content of the purified rosin is preferably 2 mol% to 50 mol%, more preferably 5 mol% to 40 mol%, still more preferably 10 mol% to 30 mol% in the carboxylic acid component.

The carboxylic acid component preferably contains an aliphatic dicarboxylic acid compound having 2 to 4 carbon atoms. Examples of the aliphatic dicarboxylic acid compound having 2 to 4 carbon atoms include adipic acid, maleic acid, malic acid, succinic acid, fumaric acid, citraconic acid, itaconic acid, and anhydrides of these acids. Among these, it is more preferable that at least one aliphatic dicarboxylic acid compound selected from succinic acid, fumaric acid, citraconic acid and itaconic acid is contained. These aliphatic dicarboxylic acid compounds are effective in improving the low-temperature fixability, and itaconic acid is preferred among the aliphatic dicarboxylic acid compounds in the present invention.
The content of the aliphatic dicarboxylic acid is preferably 0.5 mol% to 20 mol%, preferably 1 mol% to 10 mol% in the carboxylic acid component, from the viewpoint of improving low-temperature fixability and suppressing the decrease in glass transition temperature. Is more preferable.

  The carboxylic acid component may contain a carboxylic acid compound other than the purified rosin as long as the effects of the present invention are not impaired. From the viewpoint of securing the glass transition temperature, phthalic acid, isophthalic acid, terephthalic acid An aromatic dicarboxylic acid such as an acid is preferably contained. The content of the aromatic dicarboxylic acid is preferably 40 mol% to 95 mol%, more preferably 50 mol% to 90 mol%, and still more preferably 60 mol% to 80 mol% in the carboxylic acid component.

  The polyester resin is preferably a crosslinked polyester resin. As a crosslinking agent, it is preferable that a trivalent or higher valence monomer is contained in at least one of the alcohol component and the carboxylic acid component. The content of the trivalent or higher raw material monomer is preferably 0 mol% to 40 mol%, and more preferably 5 mol% to 30 mol% in the total amount of the alcohol component and the carboxylic acid component.

  In the trivalent or higher raw material monomer, as the trivalent or higher polyvalent carboxylic acid compound, for example, trimellitic acid or a derivative thereof is preferable. Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, sorbitol, or an alkylene (2 to 4 carbon) oxide (average added mole number 1 to 16) adduct thereof. Among these, glycerin is particularly preferable because it not only acts as a crosslinking agent but is also effective in improving low-temperature fixability. From this viewpoint, it is preferable that glycerin is contained as at least one alcohol component of the polyester resins (A) and (B). The content of the glycerin is preferably 5 mol% to 40 mol%, more preferably 10 mol% to 35 mol%, in the alcohol component.

-Esterification catalyst-
The condensation polymerization of the alcohol component and the carboxylic acid component is preferably performed in the presence of an esterification catalyst. Examples of the esterification catalyst include Lewis acids such as p-toluenesulfonic acid, titanium compounds, and tin (II) compounds having no Sn—C bond, and these are used alone or in combination. . Among these, a titanium compound and a tin (II) compound having no Sn—C bond are particularly preferable.

As said titanium compound, the titanium compound which has a Ti-O bond is preferable, and the compound which has a C1-C28 alkoxy group, an alkenyloxy group, or an acyloxy group is more preferable.
Examples of the titanium compound include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diethylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) _2], titanium distearate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 18 H 37 O) 2 ], Chitanto Isopropylate triethanolaminate _{[Ti (C 6 H 14 O 3} N) 1 (C 3 H 7 O) 3 ], titanium monopropylate tris (triethanolaminate) _{[Ti (C 6 H 14 O 3} N) ₃ (C ₃ H ₇ O) ₁ ] and the like. Among these, titanium diisopropylate bistriethanolaminate, titanium diisopropylate bisdiethanolamate, and titanium dipentylate bistriethanolaminate are particularly preferable. It is.

Other preferred titanium compounds include, for example, tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti (C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate, and dioctyl dihydroxy octyl titanate are preferable. These can be obtained by reacting, for example, titanium halide with a corresponding alcohol. It is also available as a commercial product.
The abundance of the titanium compound is preferably 0.01 parts by mass to 1.0 part by mass, and 0.1 parts by mass to 0.7 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Is more preferable.

Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, and a tin (II) having a Sn—X bond (where X represents a halogen atom). A compound etc. are preferable and the tin (II) compound which has a Sn-O bond is more preferable.
Examples of the tin (II) compound having a Sn-O bond include tin (II) oxalate, tin (II) diacetate, tin (II) dioctanoate, tin (II) dilaurate, and tin (II) distearate. Tin (II) having a carboxylic acid group having 2 to 28 carbon atoms, such as tin (II) dioleate; dioctyloxy tin (II), dilauroxy tin (II), distearoxy tin (II), dioleioxy tin (II) Dialkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms, such as tin oxide (II) and tin sulfate (II).
Examples of the compound having the Sn-X (wherein X represents a halogen atom) bond include tin (II) halides such as tin (II) chloride and tin (II) bromide, among these. And fatty acid tin (II) represented by (R ¹ COO) ₂ Sn (where R ¹ represents an alkyl or alkenyl group having 5 to 19 carbon atoms), (R ¹ COO) ₂ Sn ² O) ₂ Sn (provided that, ^{R 2} is dialkoxy tin represented by an alkyl group or alkenyl group having 6 to 20 carbon atoms) (II), tin oxide represented by SnO (II) are preferred, ( Fatty acid tin (II) and tin (II) oxide represented by R ¹ COO) ₂ Sn are more preferable, and tin (II) dioctanoate, tin (II) distearate, and tin (II) oxide are more preferable.
The abundance of the tin (II) compound having no Sn-C bond is preferably 0.01 parts by mass to 1.0 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 0.1 parts by mass to 0.7 parts by mass is more preferable.

When the titanium compound and the tin (II) compound having no Sn—C bond are used in combination, the total amount of the titanium compound and the tin (II) compound is 100% of the total amount of the alcohol component and the carboxylic acid component. 0.01 mass part-1.0 mass part is preferable with respect to a mass part, and 0.1 mass part-0.7 mass part is more preferable.
The polycondensation of the alcohol component and the carboxylic acid component can be performed, for example, at a temperature of 180 ° C. to 250 ° C. in an inert gas atmosphere in the presence of the esterification catalyst. The softening point of the polyester resin can be adjusted by the reaction time.

  The glass transition temperatures of the polyester resins (A) and (B) are preferably 45 ° C to 75 ° C, more preferably 50 ° C to 70 ° C, and more preferably 50 ° C to 65 ° C from the viewpoints of fixability, storage stability and durability. More preferred is ° C. The acid value is preferably 1 mgKOH / g to 80 mgKOH / g, more preferably 10 mgKOH / g to 50 mgKOH / g, from the viewpoints of chargeability and environmental stability.

  In the present invention, the polyester resins (A) and (B) are preferably amorphous polyesters different from crystallinity. In this specification, “amorphous polyester” refers to a polyester having a difference between the softening point and the glass transition temperature (Tg) of 30 ° C. or more.

  The polyester resins (A) and (B) may be modified polyester resins. The modified polyester resin refers to a polyester resin grafted or blocked with phenol, urethane or the like.

  The binder resin is used in combination with a known binder resin, for example, a vinyl resin such as styrene-acrylic resin, an epoxy resin, a polycarbonate, a polyurethane, or the like, as long as the effects of the present invention are not impaired. However, the total content of the polyester resin (A) and the polyester resin (B) is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more in the binder resin. Further preferred.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, Although it can select suitably according to the objective from well-known things, A wax is preferable. Examples of the wax include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, and sazol wax; oxidation of aliphatic hydrocarbon waxes such as oxidized polyethylene wax. Or plant copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; animal waxes such as beeswax, lanolin, spermaceti; mineral waxes such as ozokerite, ceresin, petrolatum; Examples thereof include waxes mainly composed of fatty acid esters such as montanic acid ester wax and caster wax; those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax.

Examples of the release agent include saturated straight chain fatty acids such as palmitic acid, stearic acid, montanic acid, straight chain alkyl carboxylic acids having a straight chain alkyl group; plandic acid, eleostearic acid, valinal acid, and the like. Unsaturated fatty acids; Stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, long chain alkyl alcohol and other saturated alcohols; sorbitol and other polyhydric alcohols; linoleic acid amide, olefinic acid amide, lauric acid Fatty acid amides such as acid amides; saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N'- Unsaturated fatty acid amides such as dioleyl adipic acid amide and N, N′-dioleyl sepacic acid amide; Aromatic bisamides such as m-xylene bis-stearic acid amide and N, N-distearyl isophthalic acid amide; Fatty acid metal salts such as calcium phosphate, calcium laurate, zinc stearate, magnesium stearate; wax grafted with aliphatic hydrocarbon wax using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglyceride and the like Examples include partial ester compounds of polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and the like.
Furthermore, polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, polyolefins polymerized using catalysts such as Ziegler catalysts and metallocene catalysts under low pressure, radiation, electromagnetic waves Or synthesized using light-polymerized polyolefin, low-molecular-weight polyolefin obtained by pyrolyzing high-molecular-weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, age method, etc. Hydrocarbon waxes, synthetic waxes having a compound having 1 carbon atom as a monomer, hydrocarbon waxes having a functional group such as a hydroxyl group or a carboxyl group, a mixture of a hydrocarbon wax and a hydrocarbon wax having a functional group Things, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with vinyl monomers such as maleic anhydride.
In addition, these release agents may be obtained by using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a liquid crystal deposition method, or a low molecular weight solid fatty acid. , Low molecular weight solid alcohol, low molecular weight solid compound, and other impurities are preferably used.
In particular, in the case of a toner manufactured by a pulverization method, since it is easily pulverized at the interface between the binder resin and the release agent, the release agent is exposed on the surface of the toner, causing filming on the photosensitive member or carrier. Although there is a problem, the binder resin in the present invention has very good dispersibility of the release agent, and the release agent is hardly detached from the toner due to the compatible action of the binder resin and the release agent. For this reason, the occurrence of filming is extremely small as compared with the conventional toner. Particularly for the binder resin used in the present invention, among the above release agents, carnauba wax is more preferable because it exhibits the best dispersibility. Among the carnauba waxes, those from which free fatty acids have been eliminated are particularly preferred.

The melting point of the release agent is preferably 60 ° C. to 120 ° C., more preferably 70 ° C. to 110 ° C., in order to balance the fixability and the offset resistance. When the melting point is less than 60 ° C., the blocking resistance may be lowered, and when it exceeds 120 ° C., the anti-offset effect may be hardly exhibited.
Further, by using two or more different types of release agents in combination, the plasticizing action and the release action, which are the actions of the release agent, can be expressed simultaneously. Examples of the type of release agent having a plasticizing action include a release agent having a low melting point, a branch having a molecular structure, and a structure having a polar group. Examples of the mold release agent having a mold release action include a mold release agent having a high melting point, and examples of the molecular structure include a linear structure and a non-polar one having no functional group. Examples of use include a combination of two or more different release agents having a melting point difference of 10 to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.
When selecting two types of release agents, in the case of a release agent having the same structure, a release agent having a relatively low melting point exerts a plasticizing action, and a release agent having a high melting point is released. Demonstrate the effect. At this time, when the difference in melting point is 10 ° C. to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect may be difficult to appear, and if it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one mold release agent is preferably 60 ° C to 120 ° C, and more preferably 70 ° C to 110 ° C, since it tends to easily exhibit the function separation effect.

As the release agent, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exhibit a plastic action, and have a more linear structure, Nonpolar or non-denatured straight ones that do not have a functional group exhibit a releasing action. Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, carnauba wax, can Delila wax, rice wax or montan wax and hydrocarbon wax The combination of the scan and the like.
In any case, since it becomes easy to balance the toner storage stability and the fixing property, the peak top temperature of the maximum peak is in the region of 60 ° C. to 120 ° C. in the endothermic peak observed in the DSC measurement of the toner. It is more preferable that it has a maximum peak in the region of 70 ° C to 110 ° C. In the present invention, the temperature of the peak top of the maximum endothermic peak of the release agent (wax) measured by DSC is defined as the melting point of the release agent.
Here, a differential scanning calorimeter (manufactured by Shimadzu Corp., TA-60WS and DSC-60) was used as a DSC measuring device for the release agent or toner, and it was obtained from the measured DSC curve. As a measuring method, it was performed according to ASTM D3418-82. The DSC curve used in the present invention was one that was measured when the temperature was raised at a temperature rate of 10 ° C./min after raising and lowering the temperature once and taking a previous history.
The total content of the release agent in the toner of the present invention is preferably 0.2 to 30 parts by mass with respect to 100 parts by mass of the binder resin. Is more preferable, and 3 to 15 parts by mass is still more preferable.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as a color of the said coloring agent, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the black material include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), and titanium oxide. And organic pigments such as aniline black (CI Pigment Black 1).
Examples of the magenta coloring pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like.
Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate resin, polybutyl Methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polypropylene resin, polyester resin, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral resin, polyacrylic acid resin, rosin, modified rosin, terpene Examples thereof include resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffins. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene resin, poly p-chlorostyrene resin, and polyvinyl toluene resin. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, 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, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - like maleic acid ester copolymer.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and the organic solvent component. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

-Charge control agent-
In the present invention, a charge control agent for controlling the charge amount of the toner may be used. The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material is preferable. For example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone Or the compound, a fluorine-type activator, the metal salt of a salicylic acid, the metal salt of a salicylic acid derivative, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of phenol-based condensate (both manufactured by Orient Chemical Co., Ltd.); TP-302, TP-415 of quaternary ammonium salt molybdenum complex (both manufactured by Hodogaya Chemical Co., Ltd.) ); Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, boron Complex LR-147 (Nippon Carlit Co., Ltd.); quinacridone, azo face Examples thereof include polymeric compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or the toner. You may fix to the toner surface after particle manufacture.
The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1 mass part-10 mass parts are preferable, and 0.2 mass part-5 mass parts are more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large and the effect of the main charge control agent is reduced. As a result, the electrostatic attraction 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 from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, zinc stearate, And aluminum oxide stearate); metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); Examples include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation). Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.); IT-S (produced by Ishihara Sangyo Co., Ltd.) and the like.

In order to obtain the hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles, the hydrophilic fine particles are made of silane cups such as methyltrimethoxysilane, methyltriethoxysilane, and octyltrimethoxysilane. It can be obtained by treating with a ring agent.
Examples of the hydrophobizing agent include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and silane couplings having a fluorinated alkyl group. Agents, organic titanate coupling agents, aluminum coupling agents, silicone oils, silicone varnishes and the like.

Further, silicone oil-treated inorganic fine particles obtained by treating the inorganic fine particles with silicone oil if necessary are also suitable.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Examples include silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic or methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.

The average particle size of primary particles of the inorganic fine particles is preferably 1 nm to 100 nm, and more preferably 3 nm to 70 nm. When the average particle size is less than 1 nm, the inorganic fine particles are embedded in the toner, and the function may not be effectively exhibited. When the average particle size exceeds 100 nm, the surface of the electrostatic latent image carrier is damaged unevenly. May end up. As the external additive, inorganic fine particles and hydrophobized inorganic particles can be used in combination. The average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, and more preferably 5 nm to 70 nm. More preferably, the primary particles subjected to the hydrophobization treatment include at least two types of inorganic fine particles having an average particle size of 20 nm or less and at least one type of inorganic fine particles of 30 nm or more. Further, BET specific surface area of the inorganic fine particles ^is preferably 20m ² / g~500m 2 / g.
The amount of the external additive added is preferably 0.1% by mass to 5% by mass and more preferably 0.3% by mass to 3% by mass with respect to the toner.

  Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; condensation polymerization system such as silicone, benzoguanamine, nylon; polymer particles by thermosetting resin It is done. By using such resin fine particles in combination, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01% by mass to 5% by mass, and more preferably 0.1% by mass to 2% by mass with respect to the toner.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, etc. are mentioned.

The fluidity improver is capable of surface treatment to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, a fluorine Examples thereof include silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the electrostatic latent image carrier or the intermediate transfer member. For example, fatty acid such as zinc stearate, calcium stearate, stearic acid, etc. Metal salts; polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

-Toner production method-
The method for producing the toner is not particularly limited and can be appropriately selected according to the purpose from conventionally known toner production methods. For example, a kneading / pulverizing method, a polymerization method, a dissolution suspension method, The spray granulation method etc. are mentioned. Among these, the polymerization method is particularly preferable.

--Kneading and grinding method--
In the kneading and pulverizing method, for example, a toner material containing at least a binder resin, a release agent, and a fixing aid is melt-kneaded, and the obtained kneaded material is pulverized and classified, whereby the base material of the toner is obtained. A method for producing particles.
In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay, a PCM type twin screw extruder manufactured by Ikegai Co., Ltd. Used. 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.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. 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.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

  Next, the external additive is externally added to the toner base particles. By mixing and stirring the toner base particles and the external additive using a mixer, the surface of the toner base particles is coated while being crushed. At this time, it is important from the viewpoint of durability that the external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the toner base particles.

--- Polymerization method--
As a method for producing a toner by the polymerization method, for example, a toner material containing at least a modified polyester resin capable of urea or urethane bonding, a release agent, and a fixing aid is dissolved or dispersed in an organic solvent. Then, the solution or dispersion is dispersed in an aqueous medium, subjected to a polyaddition reaction, and the solvent of the dispersion is removed and washed.

  Examples of the modified polyester resin capable of being bonded with urea or urethane include, for example, polyester prepolymer having an isocyanate group obtained by reacting a carboxyl group or a hydroxyl group at a terminal of a polyester with a polyvalent isocyanate compound (PIC). Can be mentioned. The modified polyester resin obtained by crosslinking and / or extending the molecular chain by the reaction of this polyester prepolymer and amines can improve the hot offset property while maintaining the low temperature fixability.

Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane). Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; And those blocked with oxime, caprolactam, and the like. These may be used individually by 1 type and may use 2 or more types together.
The ratio of the polyvalent isocyanate compound (PIC) is preferably 5/1 to 1/1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group, 4/1 to 1.2 / 1 is more preferable, and 2.5 / 1 to 1.5 / 1 is still more preferable.

  The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having the isocyanate group is preferably 1 or more, more preferably 1.5 to 3 on average, and 1.8 to 2.5 on average. Is more preferable.

As amines (B) to be reacted with the polyester prepolymer, divalent amine compound (B1), trivalent or higher polyvalent amine compound (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5) ), B1 to B5 amino groups blocked (B6), and the like.
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-). Dimethyl dicyclohexyl methane, diamine cyclohexane, isophorone diamine, etc.); aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazolidine compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). . Among these amines (B), B1 and a mixture of B1 and a small amount of B2 are particularly preferable.

  The ratio of the amines (B) is equivalent to the equivalent ratio [NCO] / [NHx of the isocyanate group [NCO] in the polyester prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B). ] Is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and still more preferably 1.2 / 1 to 1 / 1.2.

  According to the method for producing a toner by the polymerization method as described above, a toner having a small particle diameter and a spherical shape can be produced at low cost with little environmental load.

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

The volume average particle diameter of the toner is preferably 4 μm to 12 μm, and more preferably 4 μm to 10 μm. When the volume average particle size is less than 4 μm, it is advantageous for obtaining a high-resolution and high-quality image, but it may be disadvantageous for transferability and cleaning properties. Also, the smaller the toner particle size, the easier it is for the toner to fuse to the carrier surface, and the chargeability of the carrier may decrease more quickly. On the other hand, if the volume average particle size exceeds 12 μm, it may be difficult to obtain a high-resolution image.
The same applies to the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) of the toner. That is, if the number average particle diameter is too large with respect to the volume average particle diameter, the toner may be easily fused to the carrier surface because there are many fine powders. Accordingly, the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) of the toner is preferably 1.20 or less.
Here, the volume average particle diameter of the toner and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) can be measured, for example, as follows.
Measuring instrument: Coulter Multisizer III (Beckman Coulter, Inc.)
・ Aperture diameter: 100μm
・ Analysis software: Beckman Coulter Multisizer 3 Version 3.51 (Beckman Coulter)
・ Electrolyte: Isoton III (Beckman Coulter, Inc.)
-Dispersion: 10% by mass surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
-Dispersion condition: Add 10 mg of a measurement sample to 5 mL of the dispersion, and disperse with an ultrasonic disperser for 1 minute. Thereafter, 25 mL of an electrolytic solution is added and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: 100 mL of electrolyte and dispersion were added to a beaker, and 30,000 particles were measured at a concentration capable of measuring the particle size of 30,000 particles in 20 seconds. The diameter and number average particle diameter can be determined.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, the filming of the toner on the developing roller as the developer carrying member, and the thinning of the toner are performed. There is no fusion of toner to a layer thickness regulating member such as a blade for layering, and good and stable developability and images can be obtained even when the developing means is used for a long time (stirring). 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.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 μm to 200 μm, and more preferably 40 μm to 100 μm. When the average particle size (volume average particle size (D ₅₀ )) is less than 10 μm, in the distribution of carrier particles, the number of fine powder systems increases, and the magnetization per particle may be lowered to cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may be reduced and toner scattering may occur. In the case of a full color having many solid portions, the reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and may be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyesters 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 Copolymers with vinyl fluoride, fluoroterpolymers (triple fluoride (multiple) copolymer) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. . These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin, Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.
Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin, such as KR206 (alkyd modified), KR5208 (acrylic modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. 98 mass% is preferable and 93 mass%-97 mass% are more preferable.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 part by mass to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

(Toner container)
The toner-containing container of the present invention contains the toner or the developer of the present invention in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.
The size, shape, structure, material and the like of the container body containing toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral irregularity is formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable, and among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The container containing toner is easy to store and transport, has excellent handling properties, and can be attached to a process cartridge, an image forming apparatus, etc., which will be described later, detachably and can be suitably used for replenishing toner.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a toner to produce a visible image. And at least developing means to be formed, and other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge can be detachably mounted on various electrophotographic image forming apparatuses, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

Here, for example, as shown in FIG. 1, the process cartridge includes an electrostatic latent image carrier 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and further, if necessary. And other means. In FIG. 1, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.
Next, the image forming process using the process cartridge shown in FIG. 1 will be described. The electrostatic latent image carrier 101 is charged by the charging unit 102 while being rotated in the direction of the arrow, and exposure 103 by the exposure unit (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Including recycling process, control process, etc.
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The material, shape, structure, size, etc. of the electrostatic latent image carrier (hereinafter, sometimes referred to as “electrophotographic photoreceptor”, “photoreceptor”, “image carrier”) are particularly limited. However, it can be appropriately selected from known ones, and the shape thereof is preferably a drum shape. Examples of the material thereof include inorganic photoconductors such as amorphous silicon and selenium, polysilane, and phthalopolymethine. Organic photoreceptors, and the like. Among these, amorphous silicon or the like is preferable in terms of long life.

  The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

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

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
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.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developer capable of bringing the toner or the developer into contact or non-contact with the electrostatic latent image is provided. Etc. are more preferable.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. 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 (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means, the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
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 not particularly limited and can be appropriately selected from known recording media (recording paper).

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is 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 step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Preferred examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode of carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier, a charging roller 20 as the charging unit, an exposure device 30 as the exposure unit, and a developing unit. A developing device 40, an intermediate transfer member 50, a cleaning device 60 as the cleaning unit having a cleaning blade, and a static elimination lamp 70 as the static elimination unit.

  The intermediate transfer member 50 is an endless belt, and is designed so as to be movable in the direction of the arrow in the figure by three rollers 51 that are arranged on the inner side and stretch the belt. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. An intermediate transfer member cleaning blade 90 is disposed in the vicinity of the intermediate transfer member 50, and a transfer bias for transferring a visible image (toner image) to the recording medium 95 (secondary transfer) is applied. Possible transfer rollers 80 as the transfer means are arranged to face each other. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 in the rotation direction of the intermediate transfer member 50. The contact portion between the intermediate transfer member 50 and the contact portion between the intermediate transfer member 50 and the recording medium 95 is disposed.

  The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Yes. The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. Further, the developing belt 41 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer body 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 4 is a tandem type color image forming apparatus. The tandem image forming apparatus 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. 4. 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 body 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged in parallel and facing each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. 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. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. 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, and 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. Each of the image forming units forms black, yellow, magenta, and cyan toner images. 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 bearing member 10 is uniformly charged, and the electrostatic latent image bearing member is exposed (L in FIG. 5) for each color image corresponding to each color image information. An exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) Develop with A developing device 61 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, and a static eliminator 64 are provided. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the color image information. The black image, the yellow image, the magenta image, and the cyan image formed in this manner 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. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. 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 145, 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. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. 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 the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  The image forming apparatus and the image forming method of the present invention are compatible with a low-temperature fixing system, have good offset resistance, and use the toner of the present invention that does not contaminate the fixing apparatus and the image. Images can be formed efficiently.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples and comparative examples, “softening point of polyester resin”, “softening point of rosin”, “glass transition temperature of polyester resin (Tgr)”, “glass transition temperature of polyester resin when fixing aid is added” (Tgr ′) ”,“ melting point of fixing aid (Tmp) ”, and“ acid value of polyester resin and rosin ”were measured as follows.

<Measurement of softening point of polyester resin>
Using a flow tester (manufactured by Shimadzu Corporation, CFT-500D), 1 g of resin was heated at a heating rate of 3 ° C./min. Extrusion, the amount of plunger drop of the flow tester against temperature was plotted, and the temperature at which half of the sample flowed out was taken as the softening point.

<Measurement of softening point of rosin>
(1) Preparation of sample 10 g of rosin was melted on a hot plate at 170 ° C. for 2 hours. Thereafter, the sample was naturally cooled for 1 hour in an open state at a temperature of 25 ° C. and a relative humidity of 50%, and pulverized for 10 seconds with a coffee mill (National MK-61M) to prepare a sample.
(2) Measurement Using a flow tester (manufactured by Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C./min. The sample was extruded from a 1 mm nozzle, and the plunger drop amount of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.

<Measurement of Glass Transition Temperature (Tgr) of Polyester Resin and Glass Transition Temperature (Tgr ′) of Polyester Resin When Adding Fixing Aid>
The glass transition temperature (Tgr) of the polyester resin and the glass transition temperature (Tgr ′) of the polyester resin when 10 parts by mass of the fixing aid are added are DSC system (differential scanning calorimeter) (“DSC-60”, Shimadzu Corporation). ).
About 5.0 mg of polyester resin was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Subsequently, it heated from 20 degreeC to 150 degreeC with the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. Thereafter, the sample is cooled from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min, and a differential scanning calorimeter (“DSC-60”, manufactured by Shimadzu Corporation) Thus, the DSC curve was measured. From the obtained DSC curve, using the analysis program in the DSC-60 system, the shoulder of the DSC curve at the second temperature increase was selected, and the glass transition temperature (Tgr) of the polyester resin was calculated.
Further, the glass transition temperature (Tgr ′) of the polyester resin when 10 parts by mass of the fixing aid was added was measured in the same manner. Fixing aid 0.5 mg and polyester resin 4.5 mg were placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Subsequently, it heated from 20 degreeC to 150 degreeC with the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. Then, it cooled to 0 degreeC with the temperature-fall rate of 10 degree-C / min from 150 degreeC, and also heated to 150 degreeC with the temperature increase rate of 10 degree-C / min, and measured the DSC curve with the differential scanning calorimeter. From the obtained DSC curve, using the analysis program in the DSC-60 system, the shoulder of the DSC curve at the second temperature increase was selected, and the glass transition temperature (Tgr) of the polyester resin when the fixing aid was added. ') Was calculated.

<Melting point of fixing aid (Tmp)>
Similarly, the melting point of the fixing aid was measured using a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation).
About 5.0 mg of fixing aid is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Subsequently, it heated from 20 degreeC to 150 degreeC with the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. Then, it cooled to 0 degreeC from 150 degreeC with the temperature-fall rate of 10 degree-C / min, and also heated to 150 degreeC with the temperature increase rate of 10 degree-C / min, and measured the DSC curve. From the obtained DSC curve, using the analysis program in the DSC-60 system, the endothermic peak of the DSC curve at the second temperature increase was selected, and the melting point (Tmp) of the fixing aid was determined.

<Measurement of acid value of polyester resin, acid value of rosin, and acid value of fixing aid>
Measurement was performed based on the method described in JIS K0070. However, only the measurement solvent was changed from a mixed solvent of ethanol and ether specified in JIS K0070 to a mixed solvent of ethanol and toluene (ethanol: toluene = 1: 4 (volume ratio)).

(Synthesis Example 1)
-Purification of rosin-
Add 1,000 g of tall rosin to a 2,000 mL distillation flask equipped with a fractionation tube, reflux condenser, and receiver, perform distillation under reduced pressure of 13.3 kPa, and distill at 195 ° C. to 250 ° C. Minutes were collected as the main fraction. The rosin before purification was unpurified rosin A, and the main fraction obtained by distillation under reduced pressure of 13.3 kPa was used as purified rosin B in the examples and comparative examples described later.

  20 g of each rosin was pulverized with a coffee mill (National MK-61M) for 5 seconds, and 0.5 g was measured in a headspace vial (20 mL) through a sieve having an opening of 1 mm. The headspace gas was sampled, and impurities in rosin A and rosin B were analyzed by the headspace GC-MS method as follows. The results are shown in Table 1.

<Measurement conditions of the headspace GC-MS method>
A. Headspace sampler (manufactured by Agilent, HP7694)
Sample temperature: 200 ° C
・ Loop temperature: 200 ℃
・ Transfer line temperature: 200 ℃
・ Sample heating equilibrium time: 30 min
・ Vial pressurization gas: Helium (He)
・ Vial pressurization time: 0.3 min
-Loop filling time: 0.03 min
-Loop equilibration time: 0.3 min
・ Injection time: 1 min

B. GC (gas chromatography) (manufactured by Agilent, HP6890)
Analytical column: DB-1 (60 m-320 μm-5 μm)
・ Carrier: Helium (He)
・ Flow rate conditions: 1mL / min
・ Inlet temperature: 210 ° C
Column head pressure: 34.2 kPa
・ Injection mode: split
・ Split ratio: 10: 1
Oven temperature condition: 45 ° C. (3 min) -10 ° C./min-280° C. (15 min)

C. MS (mass spectrometry) (manufactured by Agilent, HP5973)
-Ionization method: EI (electron ionization) method-Interface temperature: 280 ° C
-Ion source temperature: 230 ° C
-Quadrupole temperature: 150 ° C
Detection mode: Scan 29-350 m / s

(Synthesis Example 2)
-Synthesis of polyester resins A0 and B4-
The alcohol component, terephthalic acid, and esterification catalyst shown in Tables 2 and 3 were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, The reaction was allowed to undergo a condensation polymerization reaction at 230 ° C. for 15 hours, and then the reaction was performed at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 180 ° C., purified rosin B or unpurified rosin A was added and reacted at 200 ° C. for 15 hours. After cooling to 180 ° C., itaconic acid was added and reacted at 200 ° C. for 8 hours. After cooling to 180 ° C., trimellitic anhydride is added, the temperature is raised to 210 ° C. over 2 hours, and the reaction is carried out at 210 ° C. and 10 kPa to the desired softening point to synthesize polyester resins A0 and B4. Went.

(Synthesis Example 3)
-Synthesis of polyester resin B0-
The alcohol component, terephthalic acid, and esterification catalyst shown in Table 3 were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and 230 ° C. under a nitrogen atmosphere. And then subjected to a condensation polymerization reaction for 15 hours at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 180 ° C., purified rosin B was added and reacted at 200 ° C. for 15 hours. After cooling to 180 ° C., itaconic acid was added, the temperature was raised to 210 ° C. over 2 hours, and the reaction was carried out at 210 ° C. and 10 kPa to the desired softening point to synthesize polyester resin B0.

(Synthesis Example 4)
-Synthesis of polyester resin B1-
The alcohol component, terephthalic acid, and esterification catalyst shown in Table 3 were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and 230 ° C. under a nitrogen atmosphere. And then subjected to a condensation polymerization reaction for 15 hours at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 180 ° C., itaconic acid was added, the temperature was raised to 210 ° C. over 2 hours, and the reaction was carried out at 210 ° C. and 10 kPa to the desired softening point to synthesize polyester resin B1.

(Synthesis Example 5)
-Synthesis of polyester resins A1 and A3-
The alcohol component, terephthalic acid, and esterification catalyst shown in Table 2 were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, rectification, stirrer, and thermocouple, and a nitrogen atmosphere Then, the polycondensation reaction was performed at 230 ° C. for 15 hours, and then the reaction was performed at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 180 ° C., trimellitic anhydride is added, heated to 210 ° C. over 3 hours, reacted at normal pressure for 10 hours, and then reacted to the desired softening point at 210 ° C. and 20 kPa. The polyester resins A1 and A3 were synthesized.

(Synthesis Example 6)
-Synthesis of polyester resins A2 and B2, B3-
Place the alcohol component, terephthalic acid, and esterification catalyst shown in Table 2 and Table 3 in a 5-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, rectification, stirrer, and thermocouple. Polyester resins A2, B2, and B3 were synthesized by performing a condensation polymerization reaction at 230 ° C. for 15 hours in a nitrogen atmosphere and then reacting at 230 ° C. and 20 kPa to a desired softening point.

＊アルコール成分及びカルボン酸成分の使用量における括弧内の値はモル比を表す。
＊エステル化触媒の使用量は、アルコール成分及びカルボン酸成分の総量１００質量部に対する質量比を表す。

* The values in parentheses in the amounts of alcohol component and carboxylic acid component used represent the molar ratio.
* The amount of the esterification catalyst used represents a mass ratio with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

Example 1
<Preparation of Toner 1>
-Preparation of resin fine particle emulsion-
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 79 parts by mass of styrene Part, 79 parts by weight of methacrylic acid, 105 parts by weight of butyl acrylate, 13 parts by weight of divinylbenzene, and 1 part by weight of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). An aqueous dispersion [fine particle dispersion] was obtained.
The obtained [fine particle dispersion] was measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.), and the volume average particle diameter was 105 nm. A part of the [fine particle dispersion] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 95 ° C., the number average molecular weight 140,000, and the mass average molecular weight 980,000.

-Preparation of toner composition liquid A-
50 parts by mass of polyester resin A0, 50 parts by mass of polyester resin B0, C.I. I. 4 parts by weight of Pigment Blue 15: 3, crystalline polyester A as a fixing aid [acid component: 90% fumaric acid, 5% succinic acid, 5% trimellitic anhydride, alcohol component: 1,4-butanediol 100 % (All molar ratio), melting point 120 ° C., weight average molecular weight (Mw) = 6,000] 10 parts by mass, paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-09) 5 parts by mass as a release agent, Then, 110 parts by mass of ethyl acetate was dispersed with a ball mill for 48 hours, and this liquid was designated as toner composition liquid A.

-Preparation of aqueous medium A-
10 parts by weight of the fine particle dispersion, 4 parts by weight of sodium dodecylbenzenesulfonate, and 100 parts by weight of a 2% by weight aqueous solution of carboxymethylcellulose (trade name “Serogen BS-H”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) The liquid was designated as an aqueous medium A.

-Preparation of emulsion or dispersion-
150 parts by mass of the aqueous medium A is put in a container, and stirred at 8,000 rpm using a TK homomixer (manufactured by Primics). Emulsification or dispersion (emulsion slurry) was prepared by mixing.

-Removal of organic solvent-
100 parts by mass of the emulsified slurry was charged in a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min.

-Washing and drying-
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake and mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) for 10 minutes at 12,000 rpm. ) And then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. To the obtained filter cake, 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. Furthermore, 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with an opening of 75 μm mesh to prepare toner base particles.

-External additive treatment-
With respect to 100 parts by mass of the obtained toner base particles, 1.0 part by mass of hydrophobic silica (“H2000”, manufactured by Clariant Japan Co., Ltd.) as an external additive was added using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Toner 1 was prepared by mixing for 30 seconds at a speed of 30 m / s and performing 5 cycles of resting for 1 minute, and sieving with an opening of 35 μm mesh.

(Example 2)
-Production of Toner 2-
In the “preparation of toner composition liquid A” in Example 1, the same procedure as in Example 1 was performed except that the fixing aid was changed from crystalline polyester A to behenic acid (NAA222S, melting point: 78 ° C., manufactured by NOF Corporation). Thus, Toner 2 was produced.

(Example 3)
-Production of Toner 3-
In the “Preparation of Toner Composition Liquid A” of Example 1, the same procedure as in Example 1 was performed except that the fixing aid was changed from crystalline polyester A to behenyl alcohol (NAA 180, melting point 62 ° C., manufactured by NOF Corporation). Toner 3 was produced.

Example 4
-Production of Toner 4-
In Example 1 “Preparation of toner composition liquid A”, except that the fixing aid was changed from crystalline polyester A to diglycerin distearate (hydroxyl value 80 mg KOH / g, melting point 62 ° C.). Thus, Toner 4 was produced.

(Example 5)
-Production of Toner 5-
In Example 1 “Preparation of toner composition liquid A”, except that the fixing aid was changed from crystalline polyester A to distearyl monostearate (acid value 120 mg KOH / g, melting point 72 ° C.). Thus, Toner 5 was produced.

(Example 6)
-Production of Toner 6-
Example 1 except that the fixing aid was changed from crystalline polyester A to oleic acid amide (manufactured by Nippon Seika Co., Ltd., Neutron, melting point 74 ° C.) in “Preparation of toner composition liquid A” in Example 1. In the same manner, Toner 6 was produced.

(Example 7)
-Production of Toner 7-
In “Preparation of Toner Composition Liquid A” in Example 1, the fixing aid was changed from crystalline polyester A to stearyl stearate (manufactured by Matsumoto Yushi Co., Ltd., Brian DPS-60, acid value 10 mgKOH / g, melting point 62 ° C.). A toner 7 was produced in the same manner as in Example 1 except that.

(Example 8)
-Production of Toner 8-
In Example 1 “Preparation of toner composition liquid A”, the fixing aid was changed from 10 parts by mass of crystalline polyester A to 2 parts by mass of behenic acid (NAA222S, melting point 78 ° C., manufactured by NOF Corporation). In the same manner as in Example 1, toner 8 was produced.

(Comparative Example 1)
-Production of Comparative Toner 1-
A comparative toner 1 was produced in the same manner as in Example 5 except that the polyester resin A0 was changed to the polyester resin A1 and the polyester resin B0 was changed to the polyester resin B1 in “Preparation of toner composition liquid A” in Example 5. .

(Comparative Example 2)
-Preparation of Comparative Toner 2-
A comparative toner 2 was produced in the same manner as in Example 1 except that the addition of the fixing aid was changed to 0 part by mass in “Preparation of Toner Composition Liquid A” in Example 1.

(Comparative Example 3)
-Production of Comparative Toner 3-
In the “Preparation of Toner Composition Liquid A” in Example 1, except that the polyester resin A0 was changed to the polyester resin A2, the polyester resin B0 was changed to the polyester resin B2, and the addition amount of the fixing aid was changed to 0 parts by mass. Comparative toner 3 was produced in the same manner as in Example 1.

(Comparative Example 4)
-Production of Comparative Toner 4-
A comparative toner 4 was produced in the same manner as in Example 5 except that the polyester resin A0 was changed to the polyester resin A2 and the polyester resin B0 was changed to the polyester resin B2 in “Preparation of toner composition liquid A” in Example 5. .

(Comparative Example 5)
-Production of Comparative Toner 5-
Comparative toner 5 was produced in the same manner as in Example 1 except that the fixing aid was changed from crystalline polyester A to lauric acid (melting point: 45 ° C.) in “Preparation of toner composition liquid A” of Example 1. .

(Comparative Example 6)
-Production of Comparative Toner 6-
The same procedure as in “Preparation of toner composition liquid A” in Example 1 was carried out except that the fixing aid was changed from crystalline polyester A to ethylenebiscapric amide (Nihon Seika Co., Ltd., SLIPAX C10, melting point 161 ° C.). Comparative toner 6 was produced in the same manner as in Example 1.

(Comparative Example 7)
-Production of Comparative Toner 7-
A comparative toner 7 was produced in the same manner as in Example 5 except that the polyester resin A0 was changed to the polyester resin A3 in “Preparation of toner composition liquid A” in Example 5.

(Comparative Example 8)
-Production of Comparative Toner 8-
A comparative toner 8 was produced in the same manner as in Example 5 except that the polyester resin B0 was changed to the polyester resin B3 in “Preparation of Toner Composition Liquid A” in Example 5.

(Comparative Example 9)
-Production of Comparative Toner 9-
A comparative toner 9 was produced in the same manner as in Example 5 except that the polyester resin B0 was changed to the polyester resin B4 in “Preparation of Toner Composition Liquid A” in Example 5.

  Next, Table 4 summarizes the types of resins and the mass ratios of the toners of Examples 1 to 8 and Comparative Examples 1 to 9.

  Further, for the toners of Examples 1 to 8 and Comparative Examples 1 to 9, the type, amount, melting point, ΔTg (Tgr−Tgr ′) of the fixing aid, and the crystallinity of the fixing aid determined as follows. Are summarized in Table 5.

-Determination of crystallinity of fixing aid-
In order to confirm that the fixing aid has crystallinity, a crystalline retention state (compatible or incompatible) was measured from an X-ray diffraction chart.
Specifically, whether or not the fixing aid has crystallinity in the toner was confirmed by a crystal analysis X-ray diffractometer (X'Pert MRDX'Pert MRD manufactured by Philips).
First, a sample of fixing aid was ground with a mortar to prepare a sample powder, and the obtained sample powder was uniformly applied to a sample holder. Thereafter, a sample holder was set in the diffractometer and measurement was performed to obtain a diffraction spectrum of the fixing aid. Next, the toner powder was applied to the holder and measured in the same manner. Similarly, the binder resin alone used for each toner was applied to a holder and measured in the same manner. In the diffraction spectrum of the obtained fixing aid, the peak of the wave number that does not overlap with the peak of the binder resin alone is selected as the identification peak, and the case where the identification peak is observed in the toner is defined as “with crystallinity” The case where no peak was observed was judged as “no crystallinity”. The results are shown in Table 5.

＊ΔＴｇ（Ｔｇｒ−Ｔｇｒ’）：ポリエステル樹脂のガラス転移温度をＴｇｒとし、該ポリエステル樹脂９０質量部に対し定着助剤を１０質量部加えて１５０℃で加熱した後のポリエステル樹脂のガラス転移温度をＴｇｒ’とする。

* ΔTg (Tgr−Tgr ′): The glass transition temperature of the polyester resin after adding 10 parts by mass of a fixing aid to 90 parts by mass of the polyester resin and heating at 150 ° C. Let Tgr ′.

-Production of carrier-
To 100 parts by mass of toluene, 100 parts by mass of a silicone resin (“organostraight silicone”), 5 parts by mass of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black are added. A coating layer forming solution was prepared by dispersing for a minute. The obtained coating layer forming liquid was coated on a surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluid bed type coating apparatus to prepare a magnetic carrier.

-Production of developer-
5 parts by mass of each of the toners of Examples and Comparative Examples that had been subjected to external additive treatment and 95 parts by mass of the carrier were mixed by a ball mill to produce the two-component developers of Examples 1 to 8 and Comparative Examples 1 to 9. .
Using each of the obtained two-component developers, fixability (offset generation temperature and fixing lower limit temperature) and heat-resistant storage stability were evaluated as follows. The results are shown in Table 6.

<Fixability (offset generation temperature and fixing lower limit temperature)>
A device that has been tuned so that the temperature and linear velocity can be adjusted by removing the silicone oil coating mechanism from the fixing unit of the tandem color image forming apparatus (“Imagio Neo C350”; manufactured by Ricoh Co., Ltd.) and remodeling it to an oilless fixing system. Then, the fixing property (offset non-occurrence temperature and fixing lower limit temperature) was evaluated using plain paper (“TYPE 6000 <70W> Y eyes”; manufactured by Ricoh Co., Ltd.).
The tandem color image forming apparatus can continuously print 35 sheets of A4 size paper per minute. At this time, the linear velocity of the fixing roller was set to 125 mm / s, and the evaluation was performed by changing the roller temperature.

−Offset generation temperature−
For image formation, the solid image of each single color of yellow, magenta, cyan, and black on each plain paper is 0.85 ± 0.3 mg / cm ^{2 on} the plain paper using the tandem color image forming apparatus. The toner was adjusted so as to be developed. The obtained image was fixed by changing the temperature of the heating roller, and the fixing temperature at which hot offset occurs (offset generation temperature) was measured and evaluated based on the following criteria.
〔Evaluation criteria〕
◎: 210 ° C or more ○: Less than 210 ° C 190 ° C or more △: Less than 190 ° C 170 ° C or more ×: Less than 170 ° C

-Minimum fixing temperature-
For the image, the plain paper was set using the tandem type color image forming apparatus, and a copy test was performed. The obtained fixed image was rubbed with a special cloth pad, and the fixing roll temperature at which the residual ratio of the image density was 70% or more was defined as the minimum fixing temperature, and evaluated based on the following criteria.
〔Evaluation criteria〕
◎: Less than 120 ° C ○: Less than 140 ° C 120 ° C or more △: Less than 160 ° C 140 ° C or more ×: 160 ° C or more

<Heat resistant storage stability (Penetration)>
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 based on a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, it shows that heat-resistant storage stability is excellent, so that the said penetration value is large, and when a penetration is 5 mm or less, possibility that a problem in use will generate | occur | produce is high.
〔Evaluation criteria〕
○: Needle penetration 25 mm or more △: Needle penetration 15 mm or more and less than 25 mm ×: Needle penetration less than 15 mm

From the above results, in Examples 1 to 8 which are toners of the present invention, by introducing each fixing aid into a binder resin excellent in low-temperature fixability, hot offset resistance, and heat storage stability, Further, it was confirmed that the low-temperature fixability was improved. Also at that time, neither the offset resistance deterioration nor the heat resistant storage stability was confirmed.
On the other hand, in Comparative Example 1, since a polyester resin not containing purified rosin was used, hot offset resistance and heat resistant storage stability deteriorated.
Moreover, in the comparative example 4, since the polyester resin which does not use 1, 2- propanediol was used, the hot offset resistance and the heat-resistant storage stability deteriorated.
In Comparative Examples 2 and 3, since no fixing aid was added, sufficient low-temperature fixability could not be obtained.
Moreover, in Comparative Example 5, since the melting point of the fixing aid was too low, deterioration in heat resistant storage stability was confirmed.
In Comparative Example 6, since the melting point of the fixing aid was too high, sufficient low-temperature fixability could not be obtained.
Further, in Comparative Example 7, the softening point of the polyester resin was too high, so that sufficient low-temperature fixability could not be obtained.
Moreover, in the comparative example 8, since the softening point of the polyester resin was too low, the hot offset resistance and the heat resistant storage stability were deteriorated.
Moreover, in the comparative example 9, since the polyester resin using the unpurified rosin was used, the hot offset resistance and the heat-resistant storage stability deteriorated.

The toner of the present invention is compatible with a low-temperature fixing system, has good offset resistance, does not contaminate the fixing device and the image, and can form a high-quality image with good sharpness over a long period of time. It is suitably used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like.
Since the image forming apparatus, the image forming method, and the process cartridge of the present invention use the toner of the present invention and can form an extremely high quality image, for example, a laser printer, a direct digital plate making machine, It can be widely used in full-color copiers, full-color laser printers, full-color plain paper fax machines, etc. using an indirect electrophotographic multicolor image development system.

FIG. 1 is a schematic view showing an example of the process cartridge of the present invention. FIG. 2 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory view showing an example of carrying out the image forming method of the present invention by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 5 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

Explanation of symbols

10 Electrostatic latent image carrier (photosensitive drum)
10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling body 34 Second Traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development roller La 44Y Development roller 44M Development roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 switching claw 56 discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 photoconductor cleaning device 64 discharger 70 discharge lamp 80 transfer roller 90 cleaning device 95 transfer paper 100 image forming device 101 photoconductor DESCRIPTION OF SYMBOLS 102 Charging means 103 Exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem type developer 121 Heating roller 122 Fixing roller 123 Fixing belt 124 Addition Roller 125 Heating source 126 Cleaning roller 127 Temperature sensor 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier main body 160 Charging device 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (18)

A toner containing at least a binder resin, a release agent, and a fixing aid,
The binder resin contains a polyester resin, and the polyester resin is a polycondensation of an alcohol component containing 1,2-propanediol in an amount of 65 mol% or more of a divalent alcohol component and a carboxylic acid component containing a purified rosin. And the softening point of the polyester resin is 80 ° C. or more and less than 160 ° C.,
A toner, wherein the fixing assistant has a melting point of 50 ° C. or higher and lower than 150 ° C., and the fixing assistant is contained in the toner in a crystalline domain state.   When the glass transition temperature of the polyester resin is Tgr, and the glass transition temperature of the polyester resin after adding 10 parts by weight of a fixing aid to 90 parts by weight of the polyester resin and heating at 150 ° C. is Tgr ′, the following formula, Tgr The toner according to claim 1, wherein the toner satisfies −Tgr ′> 10 ° C.   The toner according to claim 1, wherein the fixing aid contains a crystalline polyester resin.   The toner according to claim 1, wherein the fixing assistant contains a fatty acid having 16 to 24 carbon atoms.   The toner according to claim 1, wherein the fixing assistant contains an alcohol having 16 to 24 carbon atoms.   The toner according to claim 1, wherein the fixing aid contains an ester compound having an acid value of 20 mgKOH / g or more and less than 200 mgKOH / g.   The toner according to claim 1, wherein the fixing assistant contains an ester compound having a hydroxyl value of 10 mgKOH / g or more and less than 200 mgKOH / g.   The toner according to claim 1, wherein the fixing aid contains a fatty acid amide formed by amide bond between a fatty acid and an amine.   The toner according to claim 1, wherein the content of the fixing aid in the toner is 1% by mass or more and less than 20% by mass.   The toner according to claim 1, wherein the polyester resin contains a polyester resin A having a softening point of 80 ° C. or higher and lower than 120 ° C. and a polyester resin B having a softening point of 120 ° C. or higher and 160 ° C. or lower.   The toner according to any one of claims 1 to 10, wherein the carboxylic acid component in the polyester resin further contains an aliphatic dicarboxylic acid compound having 2 to 4 carbon atoms.   The toner according to claim 1, wherein the alcohol component in the polyester resin further contains glycerin.   2. The resin composition obtained by removing at least a binder resin, a release agent, and a fixing aid in an aqueous medium by dispersing or dissolving the dispersion or dispersion in an aqueous medium. The toner according to any one of 12 above.   A developer comprising the toner according to claim 1.   A toner-containing container filled with the toner according to claim 1. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible image An image forming method including at least a transfer step of transferring the image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium,
An image forming method, wherein the toner is the toner according to claim 1. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image An image forming apparatus having at least developing means for transferring, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1. The image forming apparatus main body includes at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A removable process cartridge,
The process cartridge according to claim 1, wherein the toner is the toner according to claim 1.

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