JP4808694B2 - Toner, developer, image forming apparatus, image forming method, and process cartridge - Google Patents

Description

  The present invention relates to a toner used for electrophotographic image formation such as a copying machine, electrostatic printing, printer, facsimile, electrostatic recording, and the like, and a developer, an image forming apparatus, an image forming method, and a process using the toner. It relates to the cartridge.

  In an electrophotographic image forming apparatus, an electrostatic recording apparatus, and the like, an electrostatic latent image formed on an electrostatic latent image carrier (hereinafter also referred to as “photosensitive member” or “electrophotographic photosensitive member”). A toner image having toner attached to the image is transferred onto a recording medium. Next, the transferred toner image is fixed on a recording medium by heating and pressing to form a toner image. In general, full-color image formation uses four color toners of black, yellow, magenta, and cyan, develops each color, heats and presses a toner image in which each toner layer is superimposed on a recording medium, and fixes it. By doing so, a full-color image is formed.

  In recent years, toners with excellent low-temperature fixability have been demanded for image forming apparatuses such as printers, copiers, and facsimiles as energy savings and speed-ups are achieved, while offset resistance and storage stability (blocking resistance). Therefore, a toner having characteristics contrary to the low-temperature fixability is required. As a toner satisfying these requirements, for example, a toner containing a polyester resin using a rosin as an acid component in a polyester resin has been reported (see Patent Documents 1 and 2).

In addition, in so-called capsule toners composed of a core material and an outer shell, it has been reported that the chargeability and developability are improved by treating the colorant in the core material with rosins such as natural rosin and abietic acid derivatives. (See Patent Document 3). Further, it has been reported that a color toner containing a colorant surface-treated with abietic acid is excellent in transferability, cleaning property, and charging stability, and a good full-color image can be obtained (see Patent Document 4).
In these technologies, rosin derivatives such as abietic acid having a heteroaromatic ring are added, and by adding these rosin derivatives, the dispersion of the colorant is improved, and in the initial stage, good transfer And charging stability are exhibited. However, these rosin derivatives are low molecular weight substances and are not chemically bonded to the binder resin. Toners containing a large amount of low molecular weight rosin derivatives at the time of abrasion resistance are used in two-component development systems. In addition, the one-component development method has a drawback that it easily adheres to the charging roller and gradually deteriorates developability.

  Further, in a fixing process by a contact heating method performed using a heating member such as a heat roller, toner releasability with respect to the heating member (hereinafter also referred to as “offset resistance”) is required. Such offset resistance can be improved by including a release agent in the toner, and the presence state of the release agent in the toner greatly affects the release property. The release agent is desirably dispersed uniformly in the toner from the standpoint of quality stability, but if it is excessively finely dispersed, it becomes difficult for the release agent to ooze out on the toner surface during heating, so it has an appropriate dispersion diameter. Better. A polyester resin using an aliphatic alcohol has a problem of high compatibility with a general release agent and poor release properties. However, due to the rigidity due to the structure, the molecular weight can be increased at the same fixing temperature, and the heat resistant storage stability tends to be superior to that of styrene-acrylic resin. On the other hand, when the styrene-acrylic resin imparts meltability at low temperatures, it is necessary to lower the molecular weight. As a result, there are problems such as the brittleness of the resin and the deterioration of heat-resistant storage stability, but it is inexpensive, and it can be compared with the previous release agent due to the freedom of structural design, such as the addition of functional groups. There is an aspect that it is easy to control the compatibility.

Thus, for example, many methods of using a mixture of styrene-acrylic resin and polyester resin have been proposed (see, for example, Patent Document 5).
Further, a method using a crystalline polyester resin and a styrene-acrylic resin has been proposed (see, for example, Patent Document 6).
However, in any proposal, from the point of compatibility between the styrene-acrylic resin and the polyester resin, contamination of the resin component to the carrier and changes in physical properties are likely to occur with the separation of the resin in the toner. There are challenges.

In addition, an example using a copolymer of a styrene-acrylic resin and a polyester resin has been proposed, but it is necessary to introduce a styrene-acrylic resin into the polyester resin as long as the low-temperature fixability is not hindered. Is not sufficient, and low temperature fixability cannot be obtained.
In addition, an example in which a crystalline polyester resin and a styrene-acrylic resin are used in combination has been proposed in order to improve low-temperature fixability. However, this proposal has problems such as separation of resins and separation of pigments because of the crystallinity of the polyester resin.
In order to improve the compatibility between the styrene-acrylic resin and the polyester resin, a method using a block polymer or copolymer of the polyester resin and the styrene-acrylic resin has been proposed (see, for example, Patent Document 7).
In addition, as a method for introducing a styrene-acrylic resin component during toner granulation, it has been proposed to use a chemical toner manufacturing method (see Patent Documents 8 and 9). However, in this proposal, when the styrene-acrylic resin component is introduced while maintaining the fixing property of the polyester resin, there are problems such as brittleness of the styrene-acrylic resin portion and heat-resistant storage stability.

  Furthermore, a toner containing a non-linear cross-linked polyester resin using a rosin as an acid component in a polyester resin has been proposed (see Patent Document 10). According to this proposal, in addition to rosins, aliphatic alcohols, aromatic alcohols, and other carboxylic acids such as unsaturated dicarboxylic acids having 4 to 10 carbon atoms, terephthalic acid and trimellitic acid are combined. There is a problem that a odor peculiar to rosins is generated during heating, and there is a problem that a component of rosin, which is a low molecular weight substance, easily adheres to a member such as a charging roller.

  Therefore, it is excellent in low-temperature fixability, there is no contamination of the toner and the release agent on the carrier and other members even after long-term use, and a toner having excellent low-temperature fixability and heat-resistant storage stability and related technology are still provided. However, the present situation is that further improvement and development are desired.

JP-A-4-70765 Japanese Patent Laid-Open No. 2007-139813 JP-A-8-54755 JP-A-7-128911 JP 2003-255611 A JP 2006-171364 A JP 2005-266400 A JP 2001-265058 A Japanese Patent No. 3203451 JP-A-4-70765

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, a toner having excellent low-temperature fixability, no contamination of the carrier and other members with toner and release agent even in long-term use, and having both excellent low-temperature fixability and heat-resistant storage stability, and development using the toner An object is to provide an agent, an image forming apparatus, an image forming method, and a process cartridge.

Means for solving the problems are as follows. That is,
<1> A toner comprising at least a binder resin, a colorant, and a release agent,
The binder resin contains a styrene-acrylic resin and a polyester resin,
The polyester resin is obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
The toner is characterized in that the content of abietic acid in the toner is 1% by mass or less.
<2> The toner according to <1>, wherein the alcohol component contains an aliphatic diol in an amount of 65 mol% or more of the divalent alcohol component.
<3> The toner according to <2>, wherein the aliphatic diol contains 65 mol% or more of 1,2-propanediol.
<4> The toner according to any one of <1> to <3>, wherein the carboxylic acid component further contains an aromatic dicarboxylic acid.
<5> A polyester resin obtained by polycondensing 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, and the polyester resin The toner according to any one of <1> to <4>, wherein the softening point of the toner is 80 ° C. or higher and lower than 120 ° C.
<6> The toner according to any one of <1> to <5>, wherein the styrene-acrylic resin contains a styrene-methyl acrylate copolymer.
<7> The toner according to any one of <1> to <5>, wherein the styrene-acrylic resin contains a styrene-butyl acrylate copolymer.
<8> The toner according to any one of <1> to <7>, wherein the styrene-acrylic resin contains a crosslinking component.
<9> From <1> to <8>, wherein the mass ratio [(B) / (A)] of the styrene-acrylic resin (A) and the polyester resin (B) is 5/5 to 1/9. The toner according to any one of the above.
<10> The toner according to any one of <1> to <9>, wherein the release agent contains at least one of carnauba wax and rice wax.
<11> A developer comprising the toner according to any one of <1> to <10> and a carrier.
<12> 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 <10>.
<13> 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,
An image forming method, wherein the toner is the toner according to any one of <1> to <10>.
<14> A process cartridge having 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. And
A process cartridge, wherein the toner is the toner according to any one of <1> to <10>.
<15> A toner-containing container, wherein the toner according to any one of <1> to <10> is contained in a container.

The toner of the present invention contains at least a binder resin, a colorant, and a release agent,
The binder resin contains a styrene-acrylic resin and a polyester resin,
The polyester resin is obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
The content of abietic acid in the toner is 1% by mass or less.
The toner of the present invention contains at least a polyester resin, a styrene-acrylic resin, a colorant, and a release agent. The polyester resin is obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound. Since the content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component, and the content of abietic acid in the toner is 1% by mass or less, the temperature is extremely low. Since the ester component is excessive as compared with a normal polyester resin, the miscibility with acrylic acid or its ester and a release agent is improved. As a result, the dispersibility of the release agent 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.
Further, it is possible to obtain a toner having a low-temperature fixability with a polyester resin while maintaining a relatively good release agent dispersibility with a styrene-acrylic resin. That is, by using a relatively short-chain diol and using a polyester resin having a rosin structure in its skeleton, the compatibility with the acrylic component and the release agent is improved, and the low-temperature fixability and the release agent are improved. Separation can be suppressed.

  The developer of the present invention includes the toner of the present invention and a carrier. For this reason, when an image is formed by electrophotography using the developer, it has excellent low-temperature fixability, and there is no contamination of the toner and release agent on the carrier and other members even in long-term use, and excellent low-temperature fixing. High-quality images can be obtained.

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, there is no contamination of the carrier and other members with the toner and the release agent even during long-term use, and abnormal images such as density reduction and background contamination are seen. An extremely high quality image can be formed.

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, there is no contamination of the carrier and other members with the toner and the release agent even during long-term use, and abnormal images such as density reduction and background contamination are seen. An extremely high quality image can be formed.

  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. In addition, the image forming apparatus main body is detachable and excellent in convenience, and since the toner of the present invention is used, there is no contamination of the toner and the release agent on the carrier and other members even in long-term use. Therefore, it is possible to form an extremely high-quality image in which abnormal images such as density reduction and background contamination are not seen.

  According to the present invention, conventional problems can be solved, excellent in low-temperature fixability, no contamination of the carrier and other members with toner and release agent, and excellent low-temperature fixability and heat-resistant storage even in long-term use. And a developer using the toner, an image forming apparatus, an image forming method, and a process cartridge can be provided.

The toner of the present invention contains at least a binder resin, a colorant, and a release agent, preferably contains a charge control agent and an external additive, and further contains other components as necessary. .
The binder resin contains a styrene-acrylic resin and a polyester resin, and is characterized in that the content of abietic acid in the toner is controlled.

<Polyester resin>
The polyester resin is formed by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound.

In the present invention, the rosin compound as the carboxylic acid component contains abietic acid as a main component, and when abietic acid derived from the rosin compound remains in the toner, the toner adheres to the carrier and the charging roller and is contaminated. It becomes easy and the charge reduction with time increases. On the other hand, rosin has a remarkable effect for improving the compatibility between the pigment and the release agent and the resin, and in particular, maintains an appropriate dispersion diameter of the release agent. Although it is an area, it contributes to the low-temperature fixability from the improvement of the affinity with a recording medium such as paper. In the present invention, by introducing the rosin skeleton into the polyester resin, it is possible to obtain a toner having an excellent fixing property by appropriately dispersing the release agent, and further reducing the amount of abietic acid remaining in the toner. This prevents contamination of the carrier and the charging roller and does not lower the function of the charge control agent, so that it is possible to maintain excellent charge rising property, charge stability, and transferability over a long period of time. It is done. In addition, it is possible to form a high-quality image in which abnormal images such as a change in color tone, a decrease in density, and fogging are not observed over a long period of time.
From the above viewpoint, in the toner of the present invention, the content of abietic acid is 1.0% by mass or less, preferably 0.9% by mass or less, more preferably 0.5% by mass or less in the toner. 3 mass% or less is further more preferable, and it is especially preferable that it does not contain abietic acid substantially.

  In the present invention, as described above, the rosin compound contained in the carboxylic acid component contains abietic acid as a main component, and only by reducing the rosin compound used within the range where the effects of the present invention are exhibited, A toner in which the content of abietic acid is controlled within a predetermined range cannot be obtained. Therefore, in the present invention, for example, as a method of reducing the amount of abietic acid in the toner, for example, (1) a method of increasing the reaction rate of the rosin compound by using an aliphatic diol having excellent reactivity as the alcohol component (2) A method using a modified rosin modified with an unsaturated fatty acid and preliminarily reduced in the amount of abietic acid, (3) In the production of polyester, the reaction time, reaction temperature, and degree of vacuum are adjusted, and the reaction rate of the rosin compound (4) A method of removing low molecular weight components contained in polyester by performing steam distillation or water dripping after reaction of raw material monomers, (5) Alcohol component has any of two hydroxyl groups. And a method using an aliphatic diol which is a primary hydroxyl group.

-Alcohol component-
As described above, the alcohol component of the polyester resin is preferably an aliphatic diol. By using an aliphatic diol, which is more reactive than an aromatic alcohol, as an alcohol component, the rosin compound is easily taken into the polyester resin, and the abietic acid content can be reduced. Furthermore, by adding the rosin compound together with the aliphatic alcohol to the reaction system first and reacting the rosin compound and the aliphatic alcohol, the rosin compound is more easily taken into the polyester resin.

  As described above, the alcohol component of the polyester resin is preferably an aliphatic diol. By using an aliphatic diol, which is more reactive than an aromatic alcohol, as an alcohol component, the rosin compound is easily taken into the polyester resin, and the abietic acid content can be reduced. Further, the rosin compound is first easily added to the polyester resin by adding the rosin compound together with the aliphatic alcohol to the reaction system to react the rosin compound and the aliphatic alcohol.

  There is no restriction | limiting in particular as said aliphatic diol, According to the objective, it can select suitably, For example, a C2-C6 aliphatic alcohol is suitable, These may be used individually by 1 type. Two or more kinds may be used in combination. Among these, ethylene glycol, 1,2-propanediol, and 1,3-propanediol are more preferable. From the viewpoint of keeping the glass transition temperature of the resin high and ensuring the storage stability of the toner, 1,2-propanediol is preferred. Is particularly preferred. 1,2-propanediol, which is an alcohol having a secondary hydroxyl group having 3 carbon atoms, has a lower glass transition temperature of the resin and toner storage stability than an alcohol having a secondary hydroxyl group having 4 or more carbon atoms. The effect of preventing the reduction is great. The 1,2-propanediol content in the aliphatic diol is preferably 65 mol% or more, more preferably 70 mol% or more, and still more preferably 80 to 100 mol%.

When an unmodified rosin compound is used as the rosin compound described later, from the viewpoint of reactivity, the alcohol component is 1,3-propanediol, etc. together with 1,2-propanediol as an aliphatic diol. It is preferable that both of these two hydroxyl groups contain an aliphatic diol which is a primary hydroxyl group, and the content thereof is preferably 30 mol% or less in the aliphatic diol, and preferably 10 mol% to 20 mol%. More preferred.
The aliphatic diol is preferably 65 mol% or more, more preferably 80 mol% to 100 mol% in the divalent alcohol component.

  Examples of the divalent alcohol component other than the aliphatic diol include bisphenols such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane. Aromatic alcohols such as an alkylene oxide adduct of A, hydrogenated bisphenol A and its alkylene (2 to 4 carbon atoms) oxide (average number of added moles 1 to 16) adduct and the like.

  The content of the divalent alcohol component is preferably 60 mol% to 100 mol%, more preferably 60 mol% to 95 mol%, still more preferably 65 mol% to 90 mol% in the alcohol component.

-Carboxylic acid component-
As described above, the carboxylic acid component contains a rosin compound.
In the present invention, rosin is a natural resin obtained from rosin, and its main component is abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, dehydroabietic acid, lepopimaric acid, etc. A resin acid or a mixture thereof.
In addition to natural rosin, which is roughly divided into tall rosin obtained from tall oil obtained as a by-product in the pulp manufacturing process, gum rosin obtained from raw pine resin, wood rosin obtained from pine stumps, etc. Modified rosins such as rosin, dimerized rosin, polymerized rosin, disproportionated rosin, and hydrogenated rosin are also included.In the present invention, the content of abietic acid has been reduced in advance. Modified rosin is preferred.
A modified rosin modified with an unsaturated fatty acid is obtained by addition reaction of an unsaturated fatty acid to rosin, and specifically, repopimaric acid, abietic acid, neodymium having a conjugated double bond among the main components of rosin. It can be obtained through a Diels-Alder reaction or an ene reaction under heating with abietic acid and parastrinic acid and an unsaturated fatty acid.
As the modified rosin, the above-mentioned known rosin can be used, but natural rosin is preferable from the viewpoint of color, and tall rosin is more preferable from the viewpoint of low-temperature fixability.
Examples of the unsaturated fatty acid that modifies rosin include (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and the like.
In the present specification, “(meth) acryl” means acryl or methacryl. Therefore, (meth) acrylic acid means acrylic acid or methacrylic acid, and a modified rosin modified with (meth) acrylic acid is an acrylic having little steric hindrance from the viewpoint of reaction activity in Diels-Alder reaction or ene reaction. An acrylic acid-modified rosin modified with an acid is preferred.

  There is no restriction | limiting in particular as a manufacturing method of the modified | denatured rosin by an unsaturated fatty acid, According to the objective, it can select suitably, For example, a rosin and an unsaturated fatty acid are mixed and Diels are heated by heating to 180 to 260 degreeC. -A modified rosin can be obtained by adding an unsaturated fatty acid to an acid having a conjugated double bond contained in the rosin by an alder reaction or an ene reaction. The obtained modified rosin may be used as it is, or a purified rosin purified through an operation such as distillation may be used.

  The purified rosin is a rosin whose impurities are reduced by a purification process. By purifying rosin in this manner, impurities contained in rosin are removed. 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, and the like. In the present invention, among these, the peak intensity of three types of impurities, hexanoic acid, pentanoic acid, and benzaldehyde, detected as a volatile component by the headspace GC-MS method, 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 the odor one of the problems of improvement with respect to the conventional polyester resin using the rosin. .

Specifically, the purified rosin means that the hexanoic acid peak intensity is 0.8 × 10 ⁷ or less and the pentanoic acid peak intensity is 0 under the measurement conditions of the headspace GC-MS method of Examples described later. .4 × is 10 ⁷ or less, a peak intensity of benzaldehyde refers to rosin is 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 kinds of 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 to 300 ° C. at a pressure of 6.67 kPa or less, and methods such as ordinary simple distillation, thin film distillation, rectification, etc. are applied. In contrast, 2 to 10% by mass of a high molecular weight substance is removed as a pitch component, and at the same time, 2 to 10% by mass of an initial fraction is simultaneously removed.

  The content of the rosin compound is preferably 5% by mass or more, more preferably 5% by mass to 40% by mass, still more preferably 10% by mass to 40% by mass, and more preferably 15% by mass in the total mass of the alcohol component and the carboxylic acid component. % To 40% by weight is particularly preferable, and 25% to 40% by weight is most preferable.

As the carboxylic acid component other than the rosin compound, aromatic dicarboxylic acid compounds such as phthalic acid, isophthalic acid and terephthalic acid are preferable from the viewpoint of obtaining a resin having a high glass transition temperature. The content of the aromatic dicarboxylic acid compound is preferably 40 mol to 95 mol, more preferably 50 mol to 90 mol, and still more preferably 60 to 80 mol with respect to 100 mol of the alcohol component.
In the present invention, carboxylic acid, anhydride of carboxylic acid, and alkyl ester of carboxylic acid are collectively referred to as a carboxylic acid compound.

At least one of the alcohol component and the carboxylic acid component may contain a trivalent or higher raw material monomer. The content of the trivalent or higher raw material monomer is preferably 40 mol or less, more preferably 5 to 30 mol, per 100 mol of the divalent alcohol component.
In the trivalent or higher raw material monomer, as the trivalent or higher polyvalent carboxylic acid compound, trimellitic acid or a derivative thereof is preferable, and as the trivalent or higher polyhydric alcohol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, Or the alkylene (2-4 carbon atoms) oxide adduct (average addition mole number 1-16) etc. are mentioned, In these, since it is effective for the improvement of low temperature fixability, glycerol is preferable.

-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 the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group having 1 to 28 carbon atoms, 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 bistriethanolamate are particularly preferred, and these are also available as, for example, commercial products manufactured by Matsumoto Kosho Co., Ltd. It is.

Specific examples of other preferable titanium compounds include 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], tetra myristyl titanate _{[Ti (C 14 H 29 O)} 4 ], tetraoctyl titanate _{[Ti (C 8 H 17 O)} 4 ], dioctyl-dihydroxy-octyl 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, tetra Preferred are myristyl titanate, tetraoctyl titanate, dioctyl dihydroxy octyl titanate, For example, the titanium halide may be obtained by reacting a corresponding alcohol, are also commercially available, such as Nisso Corporation.
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 0.5 parts by mass with respect to 100 parts by mass of the total mass of the alcohol component and the carboxylic acid component. Part is more preferred.

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) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms, such as tin (II) dioleate; dioctyloxytin (II), dilauroxytin (II), distearoxytin (II), dioleoxytin (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 (wherein R ¹ represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R 1 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 0.01 parts by mass to 1.0 part by mass with respect to 100 parts by mass of the total mass of the alcohol component and the carboxylic acid component. Preferably, 0.1 mass part-0.5 mass part 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 the total mass of the alcohol component and the carboxylic acid component. 0.01 mass part-1.0 mass part is preferable with respect to 100 mass parts, and 0.1 mass part-0.5 mass part is more preferable.

  The condensation polymerization 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.

As described above, steam distillation may be performed as a means for reducing the amount of abietic acid by reducing unreacted rosin.
In the steam distillation, water mixed with the resin may be liquid or gaseous (steam), and the amount of water mixed is obtained from the viewpoint of controlling the influence on the physical properties of the resin. 0.1 mass part-50 mass parts are preferable with respect to 100 mass parts of resin obtained, 0.5 mass part-40 mass parts are more preferable, and 1 mass part-30 mass parts are still more preferable.
The mixing of the resin and water is preferably 100 ° C. to 300 ° C., more preferably 130 ° C. to 250 ° C., particularly 150 ° C. to 240 ° C. It is preferable.
In the mixing of the resin and water, the water addition rate is preferably 0.002 to 0.5 parts by mass / min with respect to 100 parts by mass of the resin obtained from the viewpoint of the share given to the release agent, and is 0.008. -0.3 mass part / min is more preferable, and 0.008-0.2 mass part / min is still more preferable.
The mixing of the resin and water is not particularly limited as long as it is from the addition of rosin to the time when the reaction product is withdrawn from the reaction vessel after the completion of the entire reaction. In addition, it is preferable to be in a mixed state with water until just before the resin is extracted.

  There is no restriction | limiting in particular as a method of mixing resin and water, According to the objective, it can select suitably, 100 to 260 degreeC is preferable, Especially the method of blowing in water vapor | steam of 120 to 180 degreeC in resin. preferable. In the method of bubbling by blowing air and nitrogen or the like, if the resin viscosity is high, each of the bubbles increases and there is no interaction between the bubbles and the resin, so that a sufficient effect cannot be obtained. On the other hand, when water vapor is blown in, water becomes fine water vapor bubbles and uniformly diffuses over a wide area in the resin, so it is estimated that unreacted rosin compounds can be released from the resin. Is done.

The softening point of the polyester resin is preferably 80 ° C. or higher and lower than 160 ° C., more preferably 90 ° C. to 150 ° C., and still more preferably 95 ° C. to 150 ° C., from the viewpoint of reducing adhesion of the toner to the carrier and the charging roller. . The softening point can be easily adjusted by, for example, the polymerization time.
In addition, the glass transition temperature of the polyester resin is preferably 45 ° C to 75 ° C, more preferably 50 ° C to 65 ° C, from the viewpoints of fixability, storage stability, and durability. The acid value of the polyester resin is preferably 1 to 90 mgKOH / g, more preferably 10 to 50 mgKOH / g, from the viewpoints of chargeability and environmental stability.
The polyester resin is obtained by polycondensation of 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. The softening point is preferably 80 ° C. or higher and lower than 120 ° C.

  In the present invention, the polyester resin may be a polyester resin that has been modified to such an extent that its properties are not substantially impaired. Examples of the modified polyester resin include grafting or blocking with phenol, urethane, epoxy or the like by the method described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. And a composite resin having two or more types of resin units including a polyester unit.

  The content of the polyester resin obtained by using a predetermined amount of the rosin compound is preferably 50% by mass or more, and more preferably 70% by mass or more in the binder resin.

-Styrene-Acrylic resin-
The styrene-acrylic resin used in combination with the polyester resin is not particularly limited, and generally known styrene-acrylic resins can be used. For example, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate Copolymer, styrene-propyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, or a mixture thereof, a copolymer of these, Derivatives and the like. Among these, a styrene-butyl acrylate copolymer and a styrene-methyl acrylate copolymer are particularly preferable from the viewpoint of fixability and heat-resistant storage stability.

  The styrene-acrylic resin preferably has a crosslinking component. As a result, while enjoying the low-temperature fixability by the polyester resin, it exhibits appropriate elasticity at the time of heat melting, and an effect excellent in hot offset resistance can be obtained without impairing heat-resistant storage stability. The introduction of the crosslinking component into the styrene-acrylic resin is easy, for example, by copolymerizing a radical polymerizable ethylenic polyfunctional monomer, such as divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol. Examples include dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, and neopentyl glycol acrylate. In addition, monomers having a reactive group in a pendant group, such as glycidyl methacrylate, methylol acrylamide, acrolein and the like, can be used, and radical polymerizable ethylenic polyfunctional monomers can be used. Among these, divinylbenzene, hexane Diol diacrylate is particularly preferred.

  The mass ratio [(B) / (A)] of the styrene-acrylic resin (A) and the polyester resin (B) is preferably 5/5 to 1/9, more preferably 3/7 to 1/9. preferable. Within the range of the mass ratio, good low-temperature fixability is exhibited, and excellent heat-resistant storage stability is obtained.

  In addition, as said binder resin, in the range which does not impair the effect of this invention, other resin, such as a well-known binder resin, for example, an epoxy resin, a polycarbonate resin, a polyurethane resin, may be used together.

-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 especially 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; and oxidation of aliphatic hydrocarbon waxes such as oxidized polyethylene wax. Or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, rice wax, wax wax, jojoba wax; animal waxes such as beeswax, lanolin, whale wax; minerals such as ozokerite, ceresin, petrolatum, etc. Waxes based on fatty acid esters such as montanic acid ester wax and caster wax; and 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 bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic 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.
Further, 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. A hydrocarbon wax, a synthetic wax using a compound having one carbon atom as a monomer, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group, a hydrocarbon wax and a hydrocarbon wax having a functional group Compounds, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.
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. For the binder resin used in the present invention, among the above release agents, carnauba wax and rice wax are more preferable because they exhibit 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, combinations of 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, in the endothermic peak observed in the DSC measurement of the toner, the peak top temperature of the maximum peak is in the region of 60 ° C. to 120 ° C. 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 at 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 instrument for the release agent or toner, and the DSC curve was measured. 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 content of the release agent in the toner is not particularly limited and may be appropriately selected depending on the purpose. A preferable dispersion is 0.2 to 30 parts by mass with respect to 100 parts by mass of the binder resin. Although a state is obtained, 1 mass part-20 mass parts are more preferable, and 3 mass parts-15 mass parts are 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 degreen 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 color 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 styrene or substituted polymer 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 a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. 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 attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

-External additive-
The external additive is not particularly limited and may be appropriately selected 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, the hydrophobized titania fine particles, and the 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 thereof 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 diameter 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 can be surface-treated to increase hydrophobicity and prevent deterioration of fluidity and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, 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 property 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 may be appropriately selected from conventionally known toner production methods according to the purpose. The spray granulation method etc. are mentioned. Among these, the kneading and pulverization method is particularly preferable from the viewpoints of dispersibility and productivity of the release agent and the colorant.

--Kneading and grinding method--
The kneading and pulverization method includes, for example, melt-kneading a toner material containing at least a binder resin, a release agent, and a colorant, and pulverizing and classifying the obtained kneaded material, whereby the base particles of the toner are obtained. It is a method of manufacturing.
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 Co., Ltd., 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--
Examples of the method for producing a toner by the polymerization method include dissolution or dispersion of a toner material containing a modified polyester resin capable of at least urea or urethane bond in an organic solvent, a styrene-acrylic resin, a release agent, and a colorant. Let Then, the solution or dispersion is dispersed in an aqueous medium, subjected to a polyaddition reaction, the solvent of this 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.

Examples of amines (B) to be reacted with the polyester prepolymer include a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4), an 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 blocked B1-B5 amino group (B6) include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 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 weight average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose.However, in order to obtain a high-quality image with excellent granularity, sharpness, and fine line reproducibility, the weight average particle diameter The particle size is preferably 3 μm to 10 μm, more preferably 4 μm to 7 μm. When the weight average particle size is less than 3 μm, the sharpness and fine line reproducibility of the image are excellent, but the fluidity and transferability of the toner may be deteriorated.
Here, the weight average particle diameter of the toner 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 solution and dispersion liquid 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 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 diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  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. For example, KR206 (alkyd modified), KR5208 (acryl 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 used in the present invention contains the toner or 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 preferably used. 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 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 provided in various electrophotographic image forming apparatuses, and is preferably provided detachably in 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 electrostatic latent image carrier (hereinafter, also referred to as “electrophotographic photoreceptor”, “photoreceptor”, “image carrier”) is particularly limited in terms of material, shape, structure, size, and the like. However, it can be suitably selected from known ones, and the shape thereof is preferably a drum shape, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, polysilane, phthalopolymethine and the like. 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 using 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 and 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. Suitable 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 member 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 member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. 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 way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. 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, the image forming method, and the process cartridge of the present invention are excellent in low-temperature fixability, have no contamination of the carrier and other members with toner and release agent, and have excellent low-temperature fixability and heat resistance. Since the toner of the present invention having storability is used, a high-quality image can be obtained efficiently.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following synthesis examples, examples, and comparative examples, “resin softening point”, “resin glass transition temperature (Tg)”, “resin acid value”, “toner weight average particle size and particle size distribution (D ₄ / Dn) ”and“ content of abietic acid in rosin or toner ”were measured as follows.

<Softening point of resin>
The softening point of the resin was measured by using a flow tester (manufactured by Shimadzu Corporation, CFT-500D) and applying a load of 1.96 MPa with a plunger while heating 1 g of resin as a sample at a heating rate of 6 ° C./min. Extrusion was performed from a nozzle having a length of 1 mm and a length of 1 mm, and the amount of plunger drop of the flow tester was plotted against the temperature. The temperature at which half of the sample flowed out was taken as the softening point.

<Glass transition temperature (Tg) of resin>
The glass transition temperature (Tg) of the resin was measured using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), weighing 0.01 to 0.02 g of the sample into an aluminum pan, and the temperature was raised to 200 ° C. The sample cooled from the temperature to 0 ° C at a temperature decrease rate of 10 ° C / min is heated at a rate of temperature increase of 10 ° C / min, and the peak is extended from the baseline extension line below the endothermic peak temperature and from the peak rising portion. The temperature at the point of intersection with the tangent indicating the maximum slope until was taken as the glass transition temperature.

<Resin acid value>
The acid value of the resin was measured based on the method described in JIS K0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

<Toner Weight Average Particle Size (D ₄ ) and Particle Size Distribution (D ₄ / Dn)>
The weight average particle diameter (D ₄ ) and the particle size distribution (D ₄ / Dn) of the toner are measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) at an aperture diameter of 100 μm, and analysis software (Beckman The analysis was performed with Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml beaker made of glass, and 0.5 g of each toner is added. Stir in a micropartel. Next, 80 ml of ion exchange water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2% by mass. In this measurement method, it is important that the concentration is 8% by mass ± 2% by mass from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm were used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm were targeted.
After measuring the weight and number of toners, the weight distribution and number distribution were calculated. From the obtained weight distribution and number distribution, the weight average particle diameter (D ₄ ) and particle size distribution (D ₄ / Dn) of the toner were determined.

<Content of abietic acid in rosin or toner>
The sample was dissolved in acetone, adjusted to be a 0.3 mass% solution, methyl esterified with diazomethane, and then GC (gas chromatography, Agilent, HP6890) under the following measurement conditions. Analysis was carried out.
-GC measurement conditions-
Analytical column: HP-5 (30 m-250 μm-0.25 μm)
・ Carrier: Helium (He)
・ Flow rate conditions: 1 ml / min
・ Inlet temperature: 250 ° C
Column head pressure: 126.8 kPa
Injection mode: split
-Oven temperature condition: after holding at 180 ° C. for 5 min, increase to 200 ° C. at a rate of 2 ° C./min and hold at 200 ° C. for 5 min

(Synthesis Example 1)
-Purification of rosin-
1,000 g of tall rosin was added into a 2,000 mL distillation flask equipped with a fractionation tube, a reflux condenser, and a receiver, and distillation was carried out under a reduced pressure of 1 kPa to distill at 195 ° C. to 250 ° C. Was collected as the main fraction. Hereinafter, tall rosin subjected to purification is referred to as unpurified rosin, and rosin collected as a main fraction is referred to as purified rosin A.

  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 the unpurified rosin and purified rosin A 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 pressurized gas: Helium (He)
・ Bial 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 conditions: 1 mL / min
・ Inlet temperature: 210 ° C
Column head pressure: 34.2 kPa
Injection mode: split
Split ratio: 10: 1
-Oven temperature conditions: 45 ° C (3min) -10 ° C / min-280 ° C (15min)

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

(Synthesis Example 2)
-Synthesis of acrylic acid-modified rosin-
In a 10-liter flask equipped with a fractionation tube, a reflux condenser, and a receiver, 5312 g (16 mol) of unpurified tall rosin and 573.6 g (8 mol) of acrylic acid were added. After raising the temperature over time and reacting at 210 ° C. for 3 hours, distillation was further performed under reduced pressure at 210 ° C. and 4 kPa to synthesize modified rosin modified with acrylic acid (acrylic acid modified rosin).
The content of abietic acid in the unpurified tall rosin used for the production of the acrylic acid-modified rosin was 34.9% by mass, and the content of abietic acid in the acrylic acid-modified rosin was 12.5% by mass. there were.

(Synthesis Example 3)
-Synthesis of itaconic acid-modified rosin-
In a 10-liter flask equipped with a fractionation tube, a reflux condenser, and a receiver, 5312 g (16 mol) of unpurified tall rosin used in the production of acrylic acid-modified rosin and 1040.8 g (8 mol) of itaconic acid were added. In addition, the temperature was raised from 160 ° C. to 210 ° C. over 2 hours, reacted at 210 ° C. for 3 hours, further distilled at 210 ° C. under reduced pressure of 4 kPa, and modified rosin modified with itaconic acid (Itacone Acid-modified rosin) was synthesized.
The content of abietic acid in the obtained itaconic acid-modified rosin was 3.6% by mass.

(Synthesis Example 4)
-Synthesis of fumaric acid-modified rosin-
In a 10-liter flask equipped with a fractionation tube, a reflux condenser, and a receiver, 5312 g (16 mol) of unpurified tall rosin used for the production of acrylic acid-modified rosin and 928 g (8 mol) of fumaric acid were added. The temperature was raised from 160 ° C. to 210 ° C. over 2 hours, reacted at 210 ° C. for 3 hours, further distilled at 210 ° C. under reduced pressure of 4 kPa, and modified rosin modified with fumaric acid (fumaric acid modified) Rosin) was synthesized.
The content of abietic acid in the obtained fumaric acid-modified rosin was 2.8% by mass.

(Synthesis Example 5)
-Synthesis of resins A to C-
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the alcohol component shown in Table 2-1 below, a carboxylic acid component other than trimellitic anhydride, and an esterification catalyst And subjected to a condensation polymerization reaction at 235 ° C. for 15 hours in a nitrogen atmosphere, and then the reaction was performed at 235 ° C. for 1 hour under 8.0 kPa. After cooling to 210 ° C., trimellitic anhydride shown in Table 2-1 was added, the reaction was performed at 210 ° C. for 1 hour under normal pressure (101.3 kPa), and the desired softening point at 210 ° C. and 10 kPa. The polyester resin (resins A to C) was synthesized.

(Synthesis Example 6)
—Synthesis of Resins D to I—
Carboxylic acid components other than the alcohol components and trimellitic anhydride shown in Table 2-1 and Table 2-2 below (unpurified tall rosin uses the unpurified tall rosin used for the production of acrylic acid-modified rosin), and esterification catalyst Was placed in a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a rectifying column, a stirrer, and a thermocouple, and subjected to a condensation polymerization reaction at 235 ° C. for 10 hours in a nitrogen atmosphere. The reaction was performed at 235 ° C. for 2 hours under 0.0 kPa. After cooling to 210 ° C., trimellitic anhydride shown in Table 2-1 and Table 2-2 was added, and the reaction was performed at 210 ° C. for 2 hours under normal pressure (101.3 kPa). The polyester resin (resins D to I) was synthesized by reacting to a desired softening point.

(Synthesis Example 7)
-Synthesis of Resins J and K-
Carboxylic acid components other than the alcohol components and trimellitic anhydride shown in Table 2-2 below (unrefined tall rosin uses the unpurified tall rosin used in the production of acrylic acid-modified rosin), and the esterification catalyst were introduced into a nitrogen inlet tube. In a 5 L four-necked flask equipped with a dehydration tube, rectifying column, stirrer, and thermocouple, subjected to a condensation polymerization reaction at 235 ° C. for 10 hours in a nitrogen atmosphere, then at 8.0 kPa under 235 ° C. For 2 hours. After cooling to 210 ° C., trimellitic anhydride shown in Table 2-2 was added, the reaction was performed at 210 ° C. for 2 hours under normal pressure (101.3 kPa), and steam at 140 ° C. was fed at a rate of 5 g / min. The polyester resin (resins J and K) was synthesized by carrying out the reaction at 210 ° C. and 20 kPa to the desired softening point while adding dropwise (water vapor distillation). The water addition rate (5 g / min) corresponds to 0.11 part by mass / min with respect to 100 parts by mass of the obtained polyester resin, and the total dripping amount of water is 896 g, that is, 100 parts by mass of the binder resin. It was 20 mass parts with respect to this.

(Synthesis Example 8)
-Synthesis of resin L-
Carboxylic acid components other than the alcohol components shown in Table 2-2 below, unpurified tall rosin (using the unpurified tall rosin used for the production of acrylic acid-modified rosin), and the esterification catalyst, nitrogen introduction tube, dehydration tube, rectification Place in a 5 L four-necked flask equipped with a tower, a stirrer, and a thermocouple, perform a condensation polymerization reaction at 230 ° C. for 15 hours under a nitrogen atmosphere, and then react at 230 ° C. for 1 hour under 8.0 kPa. went. After cooling to 180 ° C., the unpurified tall rosin shown in Table 2-2 was added, the temperature was raised to 210 ° C. over 3 hours, and the reaction was performed at normal pressure (101.3 kPa) for 10 hours. 210 ° C., 20 kPa The polyester resin (resin L) was synthesized by reacting to a desired softening point.

（＊１）：エステル化触媒の使用量において、括弧内の数値はアルコール成分とカルボン酸成分との総質量１００質量部に対する質量比を示す。
（＊２）：アルコール成分とカルボン酸成分との総質量中の含有量

(* 1): In the amount of the esterification catalyst used, the numerical value in parentheses indicates the mass ratio of the alcohol component and the carboxylic acid component to the total mass of 100 parts by mass.
(* 2): Content in the total mass of alcohol component and carboxylic acid component

(Synthesis Example 9)
-Synthesis of Resin M-
748 g of terephthalic acid, 144 g of trimellitic anhydride, 1808 g of bisphenol A (2,2) propylene oxide, 712 g of bisphenol A (2,2) ethylene oxide, and 17 g of dibutyltin oxide as an esterification catalyst, A polyester resin (resin M) was placed in a 5-liter four-necked flask equipped with a stirrer, dropping funnel and thermocouple, and reacted to a desired softening point at 210 ° C. and 10 kPa in a nitrogen atmosphere. Was synthesized.
The obtained resin M had a softening point of 145.0 ° C., a glass transition temperature of 63.1 ° C., and an acid value of 12.2 mgKOH / g.

(Toner Production Example 1)
The toner 1 formulation shown in Table 3 below was premixed using a Henschel mixer (Mitsui Miike Chemical Co., Ltd., FM10B), and then mixed with a biaxial kneader (Ikegai Co., Ltd., PCM-30). Melting and kneading were carried out at a temperature of from C to 130C. The obtained kneaded product was cooled to room temperature and then coarsely pulverized to 200 μm to 400 μm with a hammer mill. Next, the mixture is finely pulverized using a supersonic jet pulverizer, Labo Jet (manufactured by Nippon Pneumatic Industry Co., Ltd.), and then classified by an airflow classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I). Produced.
To 100 parts by mass of the obtained toner base particles, 1.0 part by mass of an additive (HDK-2000, manufactured by Clariant Co., Ltd.) was stirred and mixed with a Henschel mixer to prepare toner 1.

(Toner Production Examples 2 to 16)
In the toner production example 1, toners 2 to 16 were produced in the same manner as in the toner production example 1 except that the raw material combinations and prescription amounts shown in Table 3 below were changed.

The obtained toners 1 to 16 all have a weight average particle diameter D ₄ = 6.5 μm ± 0.5 μm, a particle content of 5 μm or less = 20 number% or less, and a particle size distribution (D ₄ / Dn) of 1.3. It was in the range of -1.6.

＊ＳＡ−１：スチレン−メチルアクリレート共重合体（ガラス転移温度（Ｔｇ）＝６１℃、軟化点＝１１５℃、ＴＨＦ不溶分＝０％）
＊ＳＡ−２：スチレン−ブチルアクリレート共重合体（ガラス転移温度（Ｔｇ）＝６２℃、軟化点＝１２２℃、ＴＨＦ不溶分＝０％）
＊ＳＡ−３：スチレン−ブチルアクリレート共重合体（ガラス転移温度（Ｔｇ）＝６１℃、軟化点＝１１８℃、ＴＨＦ不溶分＝２８％（架橋成分））
＊部は質量部を表す。
＊帯電制御剤：ＣＣＡ１

ただし、前記式中、ｔ−Ｂｕはターシャリーブチル基を表す。

* SA-1: Styrene-methyl acrylate copolymer (glass transition temperature (Tg) = 61 ° C., softening point = 115 ° C., THF insoluble content = 0%)
* SA-2: Styrene-butyl acrylate copolymer (glass transition temperature (Tg) = 62 ° C., softening point = 122 ° C., THF insoluble content = 0%)
* SA-3: Styrene-butyl acrylate copolymer (glass transition temperature (Tg) = 61 ° C., softening point = 118 ° C., THF insoluble content = 28% (crosslinking component))
* Part represents part by mass.
* Charge control agent: CCA1

However, in the above formula, t-Bu represents a tertiary butyl group.

-Fabrication of carrier-
As a core material, 5,000 parts by mass of Mn ferrite particles (weight average particle size = 35 μm), and as a coating material, a solid content amount of a mixed solution of tetrabutoxymethylated benzoguanamine in toluene and butanol (solid content concentration: 70 mass%) 5 Equivalent to part by mass, acrylic resin solution (solid content 50% by mass) equivalent to 5% by mass solid content, methyl silicone resin having a silanol group as methyl silicone resin [solid content 23% by mass] solid content equivalent to 15 parts by mass And mixed at room temperature.
5 parts by mass of carbon black (Mitsubishi Carbon Black # 44, manufactured by Mitsubishi Chemical Corporation) is added to the solid content of this solution, and the liquid diluted with 80 parts by mass of toluene is stirred with a homogenizer, dispersed, and coated. A liquid was prepared. Further, 10 parts by weight of aminosilane (SH6020, manufactured by Toray Dow Corning Silicone Co., Ltd.) was added and the coating liquid prepared by dispersing for 10 minutes was used to rotate the core material, the coating liquid, and the fluid bed. The coating liquid was applied to the core material by introducing it into a coating apparatus for coating while forming a swirling flow provided with a bottom plate disk and stirring blades. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to prepare Carrier A.

-Preparation of two-component developer-
Using the prepared carrier A, 7 parts by mass of each of the toners prepared above with respect to 100 parts by mass of the carrier A is a type of tumbler mixer in which the container rolls and stirs (Willie et Bacofen (WAB)). For 3 minutes at 48 rpm and charged. In the present invention, 200 g of carrier A and 14 g of toner were placed in an ointment bottle having an internal volume of 500 ml and mixed.

(Examples 1-14 and Comparative Examples 1-2)
The two-component developer containing each of the toners of Examples 1 to 14 and Comparative Examples 1 and 2 produced as described above is applied to a black (Bk) unit of an image forming apparatus (manufactured by Ricoh Co., Ltd., Image Neo Neo C285). After loading, image formation was performed, and various performance evaluations were performed as follows. All the evaluations were performed on black (Bk) images. The results are shown in Tables 4-1 and 4-2.

<Low temperature fixability>
A solid image with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² is created on a thick transfer paper (manufactured by NBS Ricoh Co., Ltd., copy printing paper <135>), and fixing is performed by changing the temperature of the fixing belt. The surface of the obtained fixed image was drawn with a ruby needle (tip radius 260 to 320 μmR, tip angle 60 degrees) and a load of 50 g using a drawing tester (AD-401, manufactured by Ueshima Seisakusho), and a fiber (Hanikot # 440). (Manufactured by Hanilon Co., Ltd.), the drawing surface was rubbed strongly 5 times, and the fixing belt temperature at which the image was hardly scraped was determined as the minimum fixing temperature. Further, the solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction.
〔Evaluation criteria〕
Regarding low-temperature fixability, ◎ when the lower limit fixing temperature is 125 ° C. or lower, ◯ when it is 126 ° C. or higher and 135 ° C. or lower, Δ when it is 136 ° C. or higher and 145 ° C. or lower, and × when it is 146 ° C. or higher and 155 ° C. or lower. In the case of 156 ° C. or higher, it is indicated by xx.

<Hot offset resistance>
Create a solid image with a toner adhesion of 0.85 ± 0.1 mg / cm ^{2 on} plain paper transfer paper (type 6200, manufactured by Ricoh Co., Ltd.), perform a fixing test by changing the temperature of the fixing belt, and perform hot offset. The upper limit temperature at which hot offset does not occur was determined as the fixing upper limit temperature. Further, the solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction.
〔Evaluation criteria〕
Regarding hot offset resistance, ◎ when the upper limit fixing temperature is 230 ° C. or higher, ○ when the temperature is 210 ° C. or higher and lower than 230 ° C., Δ when 190 ° C. or higher and lower than 210 ° C., × when 180 ° C. or higher and lower than 190 ° C. In the case of 180 ° C. or lower, it is indicated by xx.

<Initial image quality>
An image evaluation chart was output, and the presence or absence of background contamination, image density, blurring, etc. was evaluated. The presence / absence of abnormality and the rank evaluation of image quality were visually evaluated, and the determination was made in the following five stages.
〔Evaluation criteria〕
A: Image abnormalities are not observed at all and are good. O: Differences in image density are observed as compared with the original image, but it is satisfactory without problems in practical use.
Δ: Some change in image density is felt ×: The density change is obvious XX: The density change is severe, and a normal image cannot be obtained

<Stability over time>
50,000 character image charts with an image area ratio of 15% are output by running using the image forming apparatus, and then the same evaluation as the initial image quality evaluation is performed and compared with the initial image. did.
〔Evaluation criteria〕
A: Image abnormality is not observed at all and is good.
○: Compared with the initial image, a slight difference in hue and image density are observed, but there is no problem.
Δ: A slight change in color tone (tone), image density, etc. is felt compared to the initial image.
X: Compared with the initial image, color tone change, density change, etc. are obvious and problematic.
XX: Compared with the initial image, the color tone change, density change, etc. are severe, and a normal image cannot be obtained.

<Carrier contamination>
The carrier contamination property (referred to as carrier spent) is a characteristic that serves as an index of toner carrier contamination. The higher the mechanical strength of the toner, the less the carrier contamination.
As an evaluation method, specifically, using the above-mentioned image forming apparatus, the developer after 100 sheets running output of 50% image area and after 30,000 sheets running output are extracted, and the developer is checked. An appropriate amount was placed in a gauge with a mesh having an opening of 32 μm, and air blowing was performed to separate the toner and the carrier. 1.0 g of the obtained carrier was put in a 50 ml glass bottle, 10 ml of chloroform was added, and the mixture was shaken 50 times and allowed to stand for 10 minutes. Thereafter, the supernatant chloroform solution was placed in a glass cell, and the transmittance of the chloroform solution was measured using a turbidimeter.
〔Evaluation criteria〕
When the transmittance is 95% or more, ◎, 90% to 94%, ◯, 80% to 89%, Δ, 70% to 79%. In the case of x and 69% or less, it was indicated by x.

<Photoconductor filming>
After 100 sheets of 50% image chart running output and 50,000 sheets running output, the filming state of the toner on the photoreceptor was visually evaluated. Considering the presence or absence of abnormality in the output image, the determination was made in the following five stages.
〔Evaluation criteria〕
◎: No image abnormality and no toner filming on the photoconductor ○: No image abnormality but slight toner filming on the photoconductor Δ: Some abnormal image is seen and the photoconductor Clear toner filming is also observed. ×: Clear image abnormality is observed, toner filming on the photoconductor is severe, and there is a problem level. XX: Clear image abnormality is seen, on the photoconductor Toner filming is bad and normal images cannot be obtained.

<Heat resistant storage stability>
4 g of toner was put in a glass bottle with a volume of 30 mL and filled by tapping 150 times, and stored in an environment of temperature 45 ° C. and humidity 60% RH for 24 hours. This was taken out and allowed to stand at room temperature for 2 hours, and then the toner was taken out on white paper, and the presence or absence of aggregates in the toner was visually confirmed. The determination was made by dividing into the following four stages.
〔Evaluation criteria〕
(Double-circle): The aggregate is not recognized at all.
○: Slight agglomerates are observed, but all are loosely agglomerated and disintegrate with slight vibration.
(Triangle | delta): Although an aggregate is recognized, if it touches with tweezers, an aggregate will collapse | disintegrate easily.
X: A clear aggregate is recognized, and a part is blocked. Does not collapse when touched with tweezers

<Odor>
The odor generated during fixing was evaluated according to the following criteria.
〔Evaluation criteria〕
○: Unpleasant odor is not recognized ×: Unpleasant odor is recognized

The toner of the present invention is excellent in low-temperature fixability and has no low-temperature fixability and heat-resistant storage stability without contamination of the carrier and other members with toner and release agent even when the developer is used for a long time. Therefore, it is suitably used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method 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 for 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 developer 121 Heating roller 122 Fixing roller 123 Fixing belt 124 Addition Roller 125 Heat 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 Conveyance roller 148 Paper feed path 150 Copier main body 160 Charging device 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (14)

A toner comprising at least a binder resin, a colorant, and a release agent,
The binder resin contains a styrene-acrylic resin and a polyester resin,
The polyester resin is obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a rosin compound,
The content of the rosin compound is 5% by mass or more based on the total mass of the alcohol component and the carboxylic acid component,
A toner characterized in that the content of abietic acid in the toner is 1% by mass or less.   The toner according to claim 1, wherein the alcohol component contains an aliphatic diol in an amount of 65 mol% or more of the divalent alcohol component.   The toner according to claim 2, wherein the aliphatic diol contains 65 mol% or more of 1,2-propanediol.   The toner according to claim 1, wherein the carboxylic acid component further contains an aromatic dicarboxylic acid.   The polyester resin is obtained by polycondensing 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, and the softening point of the polyester resin The toner according to claim 1, wherein the toner is 80 ° C. or higher and lower than 120 ° C.   The toner according to claim 1, wherein the styrene-acrylic resin contains a styrene-methyl acrylate copolymer.   The toner according to claim 1, wherein the styrene-acrylic resin contains a styrene-butyl acrylate copolymer.   The toner according to claim 1, wherein the styrene-acrylic resin contains a crosslinking component.   The toner according to any one of claims 1 to 8, wherein a mass ratio [(B) / (A)] of the styrene-acrylic resin (A) and the polyester resin (B) is 5/5 to 1/9. .   The toner according to claim 1, wherein the release agent contains at least one of carnauba wax and rice wax.   A developer comprising the toner according to claim 1 and a carrier. 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. 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,
The image forming method, wherein the toner is the toner according to claim 1. A process cartridge having 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 process cartridge according to claim 1, wherein the toner is the toner according to claim 1.

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