JP2014059453A - Toner, developer, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that exhibits excellent low-temperature fixability and heat-resistant storage stability, as well as excellent image intensity, even when a binder resin contains a large amount of crystalline resin.SOLUTION: A toner contains a binder resin, and the binder resin contains 50 mass% or more of a crystalline resin having at least one of a urethane bond and a urea bond. In a molecular weight distribution measured by gel permeation chromatography, the toner contains 5% to 15% of components with a molecular weight of 300 to 1,500 at a peak area ratio.

Description

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

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

  In recent years, demands from the market for increasing the speed and energy saving of image forming apparatuses are increasing, and there is a demand for toners that are excellent in low-temperature fixability and can provide high-quality images. In order to achieve low-temperature fixability of the toner, it is necessary to lower the softening temperature of the binder resin of the toner. However, if the softening temperature of the binder resin is low, the heat-resistant storage stability of the toner is lowered, particularly in a high temperature environment. There is a problem in that so-called blocking occurs where the toner particles are fused together.

  As a technique that can solve this problem, a technique that uses a crystalline resin as a binder resin of toner is known. The crystalline resin can be rapidly softened at the melting point of the resin, and the softening temperature of the toner can be lowered to the vicinity of the melting point while ensuring heat-resistant storage stability below the melting point. Therefore, both low-temperature fixability and heat-resistant storage stability can be achieved.

  For example, as a toner using a crystalline resin, a toner using a crystalline resin obtained by extending a crystalline polyester resin with diisocyanate as a binder resin has been proposed (see, for example, Patent Documents 1 and 2). In addition, a toner using a crystalline resin containing a sulfonic acid group and having a crosslinked structure with an unsaturated bond has been proposed (see, for example, Patent Document 3). In addition, resin particles in which the ratio between the softening temperature and the melting heat peak temperature and the viscoelastic properties are defined within a specific range and a toner using the resin particles have been proposed (for example, see Patent Document 4). In addition, toners using two types of crystalline resins having different storage elastic modulus or molecular weight have been proposed (see, for example, Patent Documents 5 and 6).

  However, when the content of the crystalline resin in the binder resin is increased in order to meet the demand for further low-temperature fixability in recent years, in the toner using these proposed techniques, indentation hardness such as Vickers hardness is used. Is weak, and the image is weak against scratching and rubbing, that is, there is a problem that the image strength is low.

  Therefore, even when the content of the crystalline resin in the binder resin is large, it is currently required to provide a toner that is excellent in low-temperature fixability and heat-resistant storage stability and also excellent in image strength.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a toner that is excellent in low-temperature fixability and heat-resistant storage stability and in image strength even when the content of the crystalline resin in the binder resin is large.

Means for solving the problems are as follows. That is,
The toner of the present invention is a toner containing a binder resin,
The binder resin contains 50% by mass or more of a crystalline resin containing at least one of a urethane bond and a urea bond,
The molecular weight distribution measured by gel permeation chromatography is characterized by containing a component having a molecular weight of 300 to 1,500 in a peak area ratio of 5% to 15%.

  According to the present invention, the above-described problems can be solved, and a toner having excellent low-temperature fixability and heat-resistant storage stability and excellent image strength even when the content of the crystalline resin in the binder resin is large. Can be provided.

FIG. 1 is a schematic cross-sectional view of the image forming apparatus used in the embodiment.

(toner)
The toner of the present invention contains a binder resin, and further contains other components as necessary.
The binder resin contains 50% by mass or more of a crystalline resin containing at least one of a urethane bond and a urea bond.
The toner contains a component having a molecular weight of 300 to 1,500 in a molecular weight distribution measured by gel permeation chromatography in a peak area ratio of 5% to 15%.

  When the content of the crystalline resin in the binder resin is increased in the toner (for example, when the binder resin contains 50% by mass or more of the crystalline resin), the low-temperature fixability due to the crystalline resin tends to be excellent. However, there is a problem that the indentation hardness such as Vickers hardness becomes weak and the image becomes weak against scratching and rubbing, that is, the image strength is weak.

Accordingly, as a result of intensive studies, the present inventors have determined that the amount of oligomer components (components having a molecular weight of 300 to 1,500) in the toner is low-temperature fixing when the binder resin contains 50% by mass or more of a crystalline resin. It has been found that it has an effect on the property, heat storage stability, and image strength.
In the toner in which the binder resin contains 50% by mass or more of a crystalline resin containing at least one of a urethane bond and a urea bond, the toner has a molecular weight of 300 to 300 in a molecular weight distribution measured by gel permeation chromatography. It has been found that by including 1,500 components in a peak area ratio of 5% to 15%, a toner having excellent low-temperature fixability, heat-resistant storage stability, and image strength can be obtained, and the present invention has been completed. It was.

  The peak area ratio is not particularly limited as long as it is 5% to 15%, and can be appropriately selected according to the purpose, but is preferably 5% to 10%, and more preferably 6% to 9%. When the peak area ratio is less than 5%, the image strength is lowered and the low-temperature fixability is not sufficient. When the peak area ratio exceeds 15%, the image intensity decreases. When the peak area ratio is within the preferable range, the low-temperature fixability, heat-resistant storage stability, and image strength are all excellent, and when the peak area ratio is within the more preferable range, the low-temperature fixability, heat-resistant storage stability, and image An excellent toner with a good balance of strength can be obtained.

The oligomer component (component having a molecular weight of 300 to 1,500) of the toner is considered to have the following influence on the toner.
Since the oligomer component has a relatively low melting point, it deteriorates the thermal characteristics of the toner. Therefore, the low temperature fixability of the toner is improved. On the other hand, the heat resistant storage stability of the toner is reduced.
Further, the oligomer component improves the affinity with the recording medium. Therefore, the low temperature fixability of the toner is improved.
The oligomer component affects the crystallinity of the crystalline resin. When the main molecular weight portion of the crystalline resin is crystallized, if the oligomer component is moderate, the oligomer component is still soft, so that the oligomer component assists the alignment of the molecular chain of the crystalline resin, It is thought that the crystallinity increases. Therefore, it affects the image strength and low-temperature fixability of the toner.

Therefore, if the peak area ratio is small (less than 5%), since the oligomer component is small, the affinity with the recording medium is reduced, and the crystallinity of the crystalline resin does not increase. It is considered that the low-temperature fixability of the toner is lowered. Further, it is considered that the image strength of the toner is lowered by the crystallinity of the crystalline resin not increasing.
Further, when the peak area ratio is large (exceeding 15%), since the oligomer component is large, the crystallization of the crystalline resin is hindered, and the crystallinity of the crystalline resin is not increased, and the image strength of the toner is increased. Is expected to decrease. Further, it is considered that the heat resistant storage stability of the toner is lowered.

The method for controlling the peak area ratio to 5% to 15% is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the reaction time and temperature in the binder resin production stage are adjusted. Examples thereof include controlling the generation of a low molecular weight component by controlling, and removing the low molecular weight component by exposing the binder resin to a solvent such as alcohol.
In the conventional toner having a high content of crystalline resin, the amount of the oligomer component is larger than the above range.

Here, in the molecular weight distribution measured by gel permeation chromatography (GPC), whether or not the toner contains a component having a molecular weight of 300 to 1,500 in a peak area ratio of 5% to 15% is, for example, It can be measured by the method.
Specifically, the produced toner is dissolved in tetrahydrofuran (THF), allowed to stand overnight, and then the colorant is separated using a centrifuge, and then GPC measurement is performed. Then, the peak area ratio is obtained from the ratio of the peak areas having a molecular weight of 300 to 1,500 when the peak area of the entire toner is 100%. The molecular weight is calculated using a monodisperse polystyrene standard sample. As said monodisperse polystyrene standard sample, the monodisperse polystyrene standard sample used in the measurement of the weight average molecular weight mentioned later, etc. are mentioned, for example.

<Binder resin>
The binder resin is not particularly limited as long as it contains 50% by mass or more of the crystalline resin containing at least one of the urethane bond and the urea bond with respect to the binder resin. A crystalline resin containing at least one of the urethane bond and the urea bond and an amorphous resin may be used in combination. Further, the binder resin may contain a crystalline resin other than the crystalline resin including at least one of the urethane bond and the urea bond.
The content of the crystalline resin containing at least one of the urethane bond and the urea bond with respect to the binder resin is not particularly limited as long as it is 50% by mass or more, and can be appropriately selected according to the purpose. , 65% by mass or more is preferable, and 80% by mass or more is preferable from the viewpoint of maximizing the compatibility between excellent low-temperature fixability and heat-resistant storage stability due to the crystalline resin containing at least one of the urethane bond and the urea bond. Is more preferable, and 95% by mass or more is particularly preferable. When the content is less than 50% by mass, the thermal steepness of the crystalline resin containing at least one of the urethane bond and the urea bond cannot be expressed on the viscoelastic properties of the toner, and the low temperature fixability and the heat resistant storage stability are not obtained. It is difficult to balance.

Here, “crystallinity” in the present invention is a property that softens sharply by heat. The resin having this property is referred to as “crystalline resin”. Whether or not the crystalline resin is, for example, the ratio of the softening temperature measured by the Koka flow tester and the maximum peak temperature of the melting heat measured by the differential scanning calorimeter (DSC) (softening temperature / heat of melting It can be confirmed that the maximum peak temperature is 0.80 to 1.55.
“Non-crystalline” means a property of being softened gently by heat. The resin having this property is referred to as “non-crystalline resin”. Whether the resin is an amorphous resin is determined by, for example, the ratio of the softening temperature measured by the Koka flow tester and the maximum peak temperature of the melting heat measured by the differential scanning calorimeter (DSC) (softening temperature / heat of melting) (The maximum peak temperature of) is greater than 1.55.
The softening temperature of the resin and toner can be measured using a Koka flow tester (for example, CFT-500D (manufactured by Shimadzu Corporation)). While heating 1 g of resin as a sample at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. Plot, and let the temperature at which half of the sample flowed out be the softening temperature.
The maximum peak temperature of the heat of fusion of the resin and toner can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). As a pretreatment, a sample to be used for measurement of the maximum peak temperature of heat of fusion is melted at 130 ° C., then lowered from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./minute, and then from 70 ° C. to 10 ° C. The temperature is lowered at a rate of 0.5 ° C./min. Here, by DSC, the temperature is increased at a rate of temperature increase of 20 ° C./min to measure the endothermic change, and a graph of “endothermic amount” and “temperature” is drawn. The endothermic peak temperature at 100 ° C. is defined as “Ta *”. When there are a plurality of endothermic peaks, the temperature of the peak with the largest endothermic amount is Ta *. Thereafter, the sample is stored at (Ta * −10) ° C. for 6 hours, and further stored at (Ta * −15) ° C. for 6 hours. Next, the sample was cooled to 0 ° C. by DSC at a temperature decrease rate of 10 ° C./min, and then the temperature was increased at a temperature increase rate of 20 ° C./min to measure the endothermic change. The temperature corresponding to the maximum peak of the calorific value is taken as the maximum peak temperature of the heat of fusion.

-Crystalline resin containing at least one of urethane bond and urea bond-
The crystalline resin containing at least one of the urethane bond and the urea bond is not particularly limited as long as it is a resin containing at least one of the urethane bond and the urea bond and having crystallinity. Examples thereof include a crystalline polyester resin containing at least one of a urethane bond and a urea bond, a crystalline polyurethane resin, and a crystalline polyurea resin. These resins may be modified or may not be modified. These may be used individually by 1 type and may use 2 or more types together. Among these, a crystalline polyester resin containing at least one of a urethane bond and a urea bond is preferable from the viewpoint of increasing the hardness of the resin by generating a hydrogen bond between molecular chains.

  The maximum peak temperature of the heat of fusion of the crystalline resin containing at least one of the urethane bond and the urea bond is not particularly limited and may be appropriately selected depending on the intended purpose. From the point of coexistence of these, 45 to 70 degreeC is preferable, 53 to 65 degreeC is more preferable, and 58 to 62 degreeC is especially preferable. When the maximum peak temperature is less than 45 ° C., the low temperature fixability is improved, but the heat resistant storage stability may be deteriorated. When it exceeds 70 ° C., the heat resistant storage stability is improved, but the low temperature fixability is deteriorated. There is.

  The ratio between the softening temperature of the crystalline resin containing at least one of the urethane bond and the urea bond and the maximum peak temperature of the heat of fusion (softening temperature / maximum peak temperature of the heat of fusion) is not particularly limited and depends on the purpose. 0.80 to 1.55 is preferable, 0.85 to 1.25 is more preferable, 0.90 to 1.2 is still more preferable, and 0.90 to 1.19 is particularly preferable preferable. The smaller the ratio, the softer the resin, the better the low temperature fixability and heat resistant storage stability.

In the viscoelastic properties of the crystalline resin containing at least one of the urethane bond and the urea bond, the storage elastic modulus G ′ at (maximum peak temperature of heat of fusion) + 20 ° C. is not particularly limited and is appropriately determined depending on the purpose. Although it can be selected, 5.0 × 10 ⁶ Pa · s or less is preferable, 1.0 × 10 ¹ Pa · s to 5.0 × 10 ⁵ Pa · s is more preferable, and 1.0 × 10 ¹ Pa. -S-1.0 * 10 < ⁴ > Pa * s is especially preferable.
Further, the loss elastic modulus G ″ at (the maximum peak temperature of heat of fusion) + 20 ° C. is not particularly limited and can be appropriately selected according to the purpose, but is 5.0 × 10 ⁶ Pa · s or less. Preferably, 1.0 × 10 ¹ Pa · s to 5.0 × 10 ⁵ Pa · s is more preferable, and 1.0 × 10 ¹ Pa · s to 1.0 × 10 ⁴ Pa · s is particularly preferable.
Further, in the viscoelastic properties of the toner, the values of G ′ and G ″ at (maximum melting heat peak temperature) + 20 ° C. are 1.0 × 10 ³ Pa · s to 5.0 × 10 ⁶ Pa · s. It is preferable from the viewpoint of fixing strength and hot offset resistance.

  The viscoelastic property of the crystalline resin containing at least one of the urethane bond and the urea bond can be obtained by adjusting the ratio of the crystalline monomer to the amorphous monomer constituting the resin, the molecular weight of the resin, or the like. it can. For example, when the ratio of the crystalline monomer is increased, the value of G ′ decreases.

  The dynamic viscoelastic characteristic values (storage elastic modulus G ′, loss elastic modulus G ″) of the resin and toner are measured using a dynamic viscoelasticity measuring apparatus (for example, ARES (manufactured by TA Instruments)). it can. The measurement is performed under a frequency of 1 Hz. The sample was molded into a pellet having a diameter of 8 mm and a thickness of 1 mm to 2 mm, fixed to a parallel plate having a diameter of 8 mm, stabilized at 40 ° C., a frequency of 1 Hz (6.28 rad / s), and a strain amount of 0.1% (strain In the amount control mode), the temperature is increased to 200 ° C. at a temperature increase rate of 2.0 ° C./min.

  The weight average molecular weight (Mw) of the crystalline resin containing at least one of the urethane bond and the urea bond is not particularly limited and may be appropriately selected depending on the intended purpose. 000-100,000 are preferable, 5,000-60,000 are more preferable, and 8,000-30,000 are especially preferable. When the weight average molecular weight is less than 2,000, the hot offset resistance may be deteriorated, and when it exceeds 100,000, the low-temperature fixability may be deteriorated.

  In this specification, the weight average molecular weight (Mw) of the resin can be measured using a gel permeation chromatography (GPC) measuring device (for example, GPC-8220 GPC (manufactured by Tosoh Corporation)). As a column, TSKgel SuperHZM-H 15 cm triple (made by Tosoh Corporation) is used. The resin to be measured is made into a 0.15 mass% solution with tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.), filtered through a 0.2 μm filter, and the filtrate is used as a sample. 100 μL of the THF sample solution is injected into a measuring apparatus, and the measurement is performed at a flow rate of 0.35 mL / min in an environment at a temperature of 40 ° C. In measuring the molecular weight of the sample, the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. Examples of the monodisperse polystyrene standard sample include Showdex STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 are used. An RI (refractive index) detector is used as the detector.

--- Crystalline polyester resin containing at least one of urethane bond and urea bond--
The crystalline polyester resin containing at least one of the urethane bond and the urea bond is preferably a block polymer having a crystalline polyester component and a polyurethane component. The block copolymer can be obtained, for example, by reacting a crystalline polyester resin having a hydroxyl group at a terminal with polyisocyanate.
The crystalline polyester resin containing at least one of the urethane bond and the urea bond is obtained, for example, by reacting a crystalline polyester resin containing a functional group capable of reacting with an active hydrogen group and an active hydrogen group-containing compound. be able to. Examples of the functional group capable of reacting with the active hydrogen group include an isocyanate group. Examples of the active hydrogen group-containing compound include a compound having an amino group and water. The compound having an amino group may be a ketimine in which the amino group is blocked with a ketone.

--- Crystalline polyester resin ---
The crystalline polyester resin is obtained using, for example, a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester, or a derivative thereof.

---- Polyhydric alcohol ----
There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated fats having 2 to 12 carbon atoms are preferred. Group diols are more preferred. When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin may be lowered, and the melting point may be lowered. Further, when the saturated aliphatic diol has more than 12 carbon atoms, it is difficult to obtain a practical material. The number of carbon atoms is more preferably 12 or less.
The saturated aliphatic diol is not particularly limited and may be appropriately selected depending on the intended purpose.However, the crystalline polyester resin obtained has high crystallinity and is excellent in sharp melt properties. 4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used individually by 1 type and may use 2 or more types together.

---- Polyvalent carboxylic acid ----
There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and anhydrides and lower (C1 to C3) alkyl esters thereof.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. Lower (carbon number 1 to 3) alkyl ester and the like.
In addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the polyvalent carboxylic acid may include a dicarboxylic acid having a sulfonic acid group. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained.
These may be used individually by 1 type and may use 2 or more types together.

  The crystalline polyester resin is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. . By doing so, since crystallinity is high and it is excellent in sharp melt property, it is preferable at the point which can exhibit the outstanding low-temperature fixability.

The crystalline polyester resin containing at least one of the urethane bond and the urea bond is preferably a block polymer having a crystalline polyester component and a polyurethane component. The block copolymer can be obtained, for example, by reacting a crystalline polyester resin having a hydroxyl group at a terminal with polyisocyanate.
There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably, For example, diisocyanate, trivalent or more polyisocyanate etc. are mentioned.
There is no restriction | limiting in particular as said diisocyanate, According to the objective, it can select suitably, For example, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate etc. are mentioned. Among these, the carbon number excluding carbon in the NCO group is 6-20 aromatic diisocyanate, 2-18 aliphatic diisocyanate, 4-15 alicyclic diisocyanate, 8-15 araliphatic diisocyanate, these Of these, a modified product of diisocyanate (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product), and a mixture of two or more of these are preferable.

The crystalline polyester resin containing at least one of the urethane bond and the urea bond is obtained, for example, by reacting a crystalline polyester resin containing a functional group capable of reacting with an active hydrogen group and an active hydrogen group-containing compound. be able to. Examples of the functional group capable of reacting with the active hydrogen group include an isocyanate group. Examples of the active hydrogen group-containing compound include a compound having an amino group and water.
Examples of the compound having an amino group include diamines and trivalent or higher polyamines.
There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aliphatic diamine and aromatic diamine are mentioned. Among these, an aliphatic diamine having 2 to 18 carbon atoms and an aromatic diamine having 6 to 20 carbon atoms are preferable.
The compound having an amino group may be a ketimine in which the amino group is blocked with a ketone.

  When the crystalline polyester resin containing at least one of the urethane bond and the urea bond is obtained by reacting a crystalline polyester resin containing a functional group capable of reacting with an active hydrogen group and an active hydrogen group-containing compound, this reaction The toner may be produced in the course of toner production, for example, when particles that are dispersed or emulsified in an aqueous medium are granulated. In this case, the resin containing the functional group capable of reacting with the active hydrogen group including the crystalline polyester resin containing the functional group capable of reacting with the active hydrogen group may be referred to as a binder resin precursor.

--- Crystalline polyurethane resin--
The crystalline polyurethane resin is obtained, for example, by reacting a polyol and a polyisocyanate.
Examples of the polyol include diols, trivalent to octavalent or higher polyols.
Examples of the polyisocyanate include diisocyanate, trivalent or higher polyisocyanate, and the like.
As the crystalline polyurethane resin, a crystalline polyurethane resin synthesized from the diol and the diisocyanate is preferable.

--- Polyol ---
Examples of the polyol include diols, trivalent to octavalent or higher polyols.
There is no restriction | limiting in particular as said diol, According to the objective, it can select suitably, For example, aliphatic diols, such as a linear aliphatic diol and a branched aliphatic diol; C4-C36 carbon number 4 -36 alkylene ether glycol; alicyclic diol having 4 to 36 carbon atoms; alkylene oxide of the alicyclic diol (hereinafter abbreviated as AO); AO adduct of bisphenols; polylactone diol; polybutadiene diol; carboxyl group Diols having sulfonic acid groups or sulfamic acid groups, and diols having other functional groups such as salts thereof.
Among these, aliphatic diols having 2 to 36 chain carbon atoms are preferable.
These may be used individually by 1 type and may use 2 or more types together.

--- Polyisocyanate ---
Examples of the polyisocyanate include diisocyanate, trivalent or higher polyisocyanate, and the like.
There is no restriction | limiting in particular as said diisocyanate, According to the objective, it can select suitably, For example, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate etc. are mentioned. Among these, the carbon number excluding carbon in the NCO group is 6-20 aromatic diisocyanate, 2-18 aliphatic diisocyanate, 4-15 alicyclic diisocyanate, 8-15 araliphatic diisocyanate, these Of these, a modified product of diisocyanate (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product), and a mixture of two or more of these are preferable.

--- Crystalline polyurea resin--
The crystalline polyurea resin can be obtained, for example, by reacting a polyamine with a polyisocyanate.
Examples of the polyamine include diamines and trivalent or higher polyamines.
Examples of the polyisocyanate include diisocyanate, trivalent or higher polyisocyanate, and the like.
The crystalline polyurea resin is preferably a polyurea resin synthesized from the diamine and the diisocyanate.

--- Polyisocyanate ---
As said polyisocyanate, the thing similar to the said diisocyanate and the said trivalent or more polyisocyanate mentioned in description of the said crystalline polyurethane resin is mentioned, for example.

--- Polyamine ---
Examples of the polyamine include diamines and trivalent or higher polyamines.
There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aliphatic diamine, aromatic diamine, etc. are mentioned. Among these, an aliphatic diamine having 2 to 18 carbon atoms and an aromatic diamine having 6 to 20 carbon atoms are preferable. Moreover, you may use the said trivalent or more amine as needed.

-Amorphous resin-
The non-crystalline resin is not particularly limited as long as it is non-crystalline, and can be appropriately selected according to the purpose. For example, styrene such as polystyrene, poly-p-styrene, polyvinyltoluene, or a substituted product thereof. Homopolymer, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-meta Acrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene -Acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl Styrene copolymers such as ketone copolymers, styrene-butadiene copolymers, styrene-isopropyl copolymers, styrene-maleic acid ester copolymers, polythyme methacrylate resins, polybutyl methacrylate resins, polyvinyl chloride resins , Polyvinyl acetate resin, polyethylene resin, polyester resin, polyurethane resin, epoxy resin, polyvinyl butyral resin, polyacrylic acid resin, rosin resin, modified rosin resin, terpene resin, phenol resin, aliphatic or aromatic hydrocarbon resin, aromatic These resins are modified so as to have a functional group capable of reacting with an active hydrogen group. These may be used individually by 1 type and may use 2 or more types together.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a coloring agent, a mold release agent, a charge control agent, an external additive etc. are mentioned.

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

  There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable with respect to the said toner, and 3 mass%-10 mass% are preferable. More preferred. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner may occur. The characteristics may be degraded.

  The colorant can also be used as a master batch combined with a resin. There is no restriction | limiting in particular as manufacture of a masterbatch, or resin kneaded with a masterbatch, According to the objective, it can select suitably.

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

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

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

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

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40 to 160 degreeC is preferable, 50 to 120 degreeC is more preferable, and 60 to 90 degreeC is especially preferable. preferable. If the melting point is less than 40 ° C., the heat resistant storage stability may be adversely affected. If the melting point exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melting point of the release agent is, for example, raised to 200 ° C. (first time) using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), and is 0 ° C. at a temperature lowering rate of 10 ° C./min. The sample is cooled to a temperature of 10 ° C./min (second time). And the maximum peak temperature of the heat of fusion in the second temperature rise can be obtained as the melting point.

  The melt viscosity of the release agent is preferably 5 mPa · sec to 1,000 mPa · sec, more preferably 10 mPa · sec to 100 mPa · sec, as a measured value at a temperature 20 ° C. higher than the melting point of the release agent. If the melt viscosity is less than 5 mPa · sec, the releasability may be lowered, and if it exceeds 1,000 mPa · sec, the effect of improving hot offset resistance and low-temperature fixability cannot be obtained. There is.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 0 mass%-40 mass% are preferable with respect to the said toner, and 3 mass%-30 mass%. Is more preferable. When the content exceeds 20% by mass, heat-resistant storage stability, charging property, transferability, and stress resistance may be deteriorated.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, Alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. Can be mentioned. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industries, Ltd.), LRA -901, LR-147 (manufactured by Nippon Carlit Co., Ltd.) which is a boron complex. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said charge control agent, Although it can select suitably according to the objective, 0.1 mass%-10 mass% are preferable with respect to the said toner, 0.2 mass%. -5 mass% is more preferable. When the content is less than 0.1% by mass, the charge rising property and the charge amount are not sufficient, and the toner image may be deteriorated. When the content exceeds 10% by mass, the chargeability of the toner is too high, the electrostatic attraction with the developing roller increases, and the fluidity of the developer and the image density may decrease. .

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

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

  There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.01 mass%-5 mass% are preferable with respect to the said toner, 0.1 mass% -2 mass% is more preferable.

  There is no restriction | limiting in particular as an average particle diameter of the primary particle of the said external additive, Although it can select suitably according to the objective, 1 nm-100 nm are preferable, and 3 nm-70 nm are more preferable. If the average particle size is less than 1 nm, the external additive may be buried in the toner and its function may not be effectively exhibited. If it exceeds 100 nm, the surface of the photoreceptor may be damaged unevenly. .

  The toner is preferably a toner obtained by forming particles from a toner material liquid containing the binder resin. The toner material liquid contains, for example, the binder resin and an organic solvent, and further contains the colorant, the release agent, the binder resin precursor, and the like as necessary.

<Toner production method>
There is no restriction | limiting in particular as a manufacturing method of the said toner, According to the objective, it can select suitably, For example, what is called a chemical construction method etc. which granulate a toner particle in an aqueous medium and a granulation method etc. are mentioned.
Further, the toner is produced by a particle production method as disclosed in Japanese Patent No. 4531076, that is, after the material constituting the toner is dissolved in carbon dioxide in a liquid or supercritical state, the liquid or supercritical state of carbon dioxide is dissolved. It can also be produced by a particle production method for obtaining toner particles by removing carbon.

In the chemical method, the crystalline resin can be easily granulated.
Examples of the chemical method for granulating toner particles in the aqueous medium include, for example, a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, and a dispersion polymerization method in which a monomer is used as a starting material; a resin or a resin precursor Dissolution suspension method in which it is dissolved in an organic solvent and dispersed or emulsified in an aqueous medium; phase inversion emulsification method in which water is added to a solution comprising a resin or resin precursor and an appropriate emulsifier; and by these methods Examples include an agglomeration method in which the obtained resin particles are aggregated in a state of being dispersed in an aqueous medium and granulated into particles of a desired size by heating and melting. Among these, a toner obtained by a dissolution suspension method is more preferable from the viewpoint of granulation properties (easiness of control of particle size distribution, control of particle shape, etc.) using a crystalline resin.

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

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

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

-Chemical method-
The chemical method is not particularly limited and may be appropriately selected depending on the intended purpose. However, at least the toner material liquid containing the binder resin is dispersed or emulsified in an aqueous medium, and the toner base particles. The method of granulating is preferable.
Further, as the chemical method, an oil phase (toner material liquid) obtained by dissolving or dispersing a toner material containing at least one of the binder resin and the binder resin precursor in an organic solvent is used as an aqueous medium. A method of granulating the toner base particles by dispersing or emulsifying in the toner is preferable.
In the dissolution suspension method and the ester elongation method, the crystalline resin can be easily granulated.

--Organic solvent--
The organic solvent used for dissolving or dispersing the binder resin or the binder resin precursor is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later.
Examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, and ethyl acetate. , Methyl ethyl ketone, methyl isobutyl ketone and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, ester solvents such as methyl acetate and ethyl acetate, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable.

  The solid content concentration of the toner material liquid containing the binder resin or the binder resin precursor is preferably 40% by mass to 80% by mass. When the solid content concentration is less than 40% by mass, the amount of toner produced may be reduced, and when it exceeds 80% by mass, it becomes difficult to dissolve or disperse the binder resin or the binder resin precursor. In addition, the viscosity may be high and difficult to handle.

  The toner material other than the resin such as the colorant and the release agent, and the masterbatch thereof may be individually dissolved or dispersed in an organic solvent and mixed with the toner material liquid.

--- Aqueous medium--
As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.

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

  In the aqueous medium, it is preferable that the inorganic dispersant or the organic resin fine particles are previously dispersed in the aqueous medium in view of the sharpness of the particle size distribution of the obtained toner and the dispersion stability.

Examples of the inorganic dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
As the resin that forms the organic resin fine particles, any resin that can form an aqueous dispersion can be used, and it may be a thermoplastic resin or a thermosetting resin, For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, and the like can be given. These resins may be used alone or in combination of two or more. Among these, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and a combination thereof are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained.

  The method for emulsifying or dispersing the toner material liquid in the aqueous medium is not particularly limited, but known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave may be used. Applicable. Among these, the high-speed shearing type is preferable from the viewpoint of reducing the particle size of the particles. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1,000 rpm to 30,000 rpm, preferably 5,000 rpm to 20,000 rpm. As temperature at the time of dispersion | distribution, it is 0 to 150 degreeC (under pressure) normally, and 20 to 80 degreeC is preferable.

  When the toner material liquid has the binder resin precursor, the active hydrogen group-containing compound necessary for the binder resin precursor to undergo an elongation or cross-linking reaction is dispersed in the aqueous medium. The toner material liquid may be mixed in advance before mixing, or may be mixed in an aqueous medium.

  In order to remove the organic solvent from the obtained emulsified dispersion, a known method can be used. For example, the whole system is gradually heated under normal pressure or reduced pressure, and the organic in the droplets A method in which the solvent is completely removed by evaporation can be employed. By doing so, toner base particles can be obtained.

  A known technique is used for the step of washing and drying the toner base particles dispersed in the aqueous medium. That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at about room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, or a desired particle size distribution may be obtained using a known classifier as necessary after drying.

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

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

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

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

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

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

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

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

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

  The content of the toner when the developer is a two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, but is 2.0% by mass to 12% with respect to the carrier. 0.0 mass% is preferable, and 2.5 mass% to 10.0 mass% is more preferable.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, and a developing unit, and further includes other units as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

<Electrostatic latent image carrier>
The material, shape, structure, and size of the latent electrostatic image bearing member are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape, Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

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

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

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

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

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

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

<Developing means and development process>
The developing unit is not particularly limited as long as it is a unit including toner that develops the electrostatic latent image to form a visible image, and can be appropriately selected according to the purpose.
The development step is not particularly limited as long as it is a step of developing the electrostatic latent image using toner to form a visible image, and can be appropriately selected according to the purpose. It can be carried out by developing means.
The toner is the toner of the present invention.

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

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

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

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

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

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

-Cleaning means and cleaning process-
The cleaning means is not particularly limited as long as it can remove the toner remaining on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, static Examples thereof include an electric brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
The cleaning step is not particularly limited as long as the toner remaining on the latent electrostatic image bearing member can be removed, and can be appropriately selected according to the purpose. For example, the cleaning unit performs the cleaning step. be able to.

-Static elimination means and static elimination process-
The neutralizing means is not particularly limited as long as it is a means for eliminating static electricity by applying a neutralizing bias to the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Can be mentioned.
The neutralization step is not particularly limited as long as it is a step of neutralizing by applying a neutralization bias to the electrostatic latent image carrier, and can be appropriately selected according to the purpose. It can be carried out.

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

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

(Process cartridge)
The process cartridge according to the present invention is not particularly limited as long as it has at least an electrostatic latent image carrier and a developing unit and can be attached to and detached from the image forming apparatus, and can be appropriately selected according to the purpose.
The developing unit is a unit including toner that develops the electrostatic latent image to form a visible image.
The toner is the toner of the present invention.

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

(Production Example 1)
<Manufacture of crystalline resin 1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 283 parts of sebacic acid, 215 parts of 1,6-hexanediol, and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added. The reaction was carried out for 8 hours at 180 ° C. while distilling off the produced water under an air stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the number average molecular weight Mn was further reduced under a reduced pressure of 5 mmHg to 20 mmHg. The reaction was carried out until the value reached 5,200 to obtain a base resin.
250 parts of the obtained base resin and 200 parts of ethyl acetate were mixed uniformly at 60 ° C. to prepare a base resin solution.

  Next, 7.5 parts of diphenylmethane-4,4′-diisocyanate (MDI) and 75 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and 450 parts of the base resin solution are further added. In addition, the mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off to obtain [Crystalline Resin 1] (crystalline polyester resin containing a urethane bond) having a melting point of 67 ° C.

(Production Example 2)
<Manufacture of crystalline resin 2>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 310 parts of sebacic acid, 115 parts of 1,6-hexanediol, 65 parts of ethylene glycol, and titanium dihydroxybis (triethanolaminate) 1 as a condensation catalyst The reaction was allowed to proceed for 5 hours at 160 ° C. while distilling off the water produced, and then further reacted at 180 ° C. for 3 hours. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water produced under nitrogen stream and 1,6-hexanediol and ethylene glycol, and further under reduced pressure of 5 mmHg to 20 mmHg, The reaction was carried out until the average molecular weight Mn reached 5,900 to obtain a base resin.
250 parts of the obtained base resin and 200 parts of ethyl acetate were mixed uniformly at 60 ° C. to prepare a base resin solution.

  Next, 6.0 parts of diphenylmethane-4,4′-diisocyanate (MDI) and 75 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and 450 parts of the base resin solution is further added. In addition, the mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off to obtain [Crystalline Resin 2] (crystalline polyester resin containing a urethane bond) having a melting point of 71 ° C.

(Production Example 3)
<Manufacture of crystalline resin 3>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 260 parts of adipic acid, 255 parts of 1,6-hexanediol, and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added, and nitrogen was added. The reaction was carried out for 8 hours at 180 ° C. while distilling off the produced water under an air stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the number average molecular weight Mn was further reduced under a reduced pressure of 5 mmHg to 20 mmHg. The reaction was continued until 5,000 reached 5,000 to obtain a base resin.
250 parts of the obtained base resin and 200 parts of ethyl acetate were mixed uniformly at 60 ° C. to prepare a base resin solution.

  In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 8.3 parts of diphenylmethane-4,4′-diisocyanate (MDI) and 75 parts of ethyl acetate were added, and 450 parts of the base resin solution was further added. The reaction was performed at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off to obtain [Crystalline Resin 3] (crystalline polyester resin containing a urethane bond) having a melting point of 59 ° C.

(Production Example 4)
<Manufacture of crystalline resin 4>
In a reaction vessel equipped with a stirrer, 10 parts of crystalline resin 1 and 100 parts of tetrahydrofuran (THF) were placed and stirred until the crystalline resin 1 was completely dissolved to prepare a THF solution. Next, 2,000 parts of methanol was placed in a reaction vessel equipped with a stirrer, and the THF solution prepared above was added dropwise to perform reprecipitation. [Crystalline resin 4] having a melting point of 65 ° C. (including a urethane bond) as a precipitate A crystalline polyester resin) was obtained.

(Production Example 5)
<Manufacture of oligomer components>
In Production Example 4, THF and methanol were removed from the filtrate from which [Crystalline Resin 4] (precipitate) was removed, and [Oligomer Component] having a weight average molecular weight Mw of 821 was obtained.

(Production Example 6)
<Production of crystalline resin prepolymer>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 283 parts of sebacic acid, 215 parts of 1,6-hexanediol, and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added. The reaction was carried out for 8 hours at 180 ° C. while distilling off the produced water under an air stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the number average molecular weight Mn was further reduced under a reduced pressure of 5 mmHg to 20 mmHg. The reaction was continued until 5,000 reached 5,000 to obtain a base resin.
The softening temperature of the base resin measured by an elevated flow tester is 72.2 ° C., the maximum peak temperature of the heat of fusion measured by a differential scanning calorimeter (DSC) is 66.9 ° C., and the ratio (softening temperature / Maximum peak temperature of heat of fusion) was 1.08.
250 parts of the obtained base resin and 200 parts of ethyl acetate were mixed uniformly at 60 ° C. to prepare a base resin solution.

In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 37 parts of diphenylmethane-4,4′-diisocyanate (MDI) and 87 parts of ethyl acetate were added, and 450 parts of the base resin solution was added, and a nitrogen stream was added. The mixture was reacted at 80 ° C. for 5 hours to obtain a 50% ethyl acetate solution (prepolymer solution) of [crystalline resin prepolymer 1] (modified polyester resin) having an isocyanate group at the terminal.
After crushing the isocyanate at the end of the prepolymer by adding 0.5 part of n-dibutylamine to 10 parts of the resulting prepolymer solution and mixing it uniformly, the solvent and the remaining n- Although the dibutylamine was removed, the weight average molecular weight of the THF soluble component was 45,700.

(Production Example 7)
<Manufacture of amorphous resin 1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 215 parts of a propylene oxide 2 mol adduct of bisphenol A, 132 parts of an ethylene oxide 2 mol adduct of bisphenol A, 126 parts of terephthalic acid, and tetrabutoxy as a condensation catalyst 1.8 parts of titanate was added and reacted for 6 hours at 230 ° C. under a nitrogen stream while distilling off the water produced. Next, after reacting under reduced pressure of 5 mmHg to 20 mmHg for 1 hour and cooling to 180 ° C., 8 parts of trimellitic anhydride was added, and under reduced pressure of 5 mmHg to 20 mmHg, the weight average molecular weight Mw was about 10,000. The reaction was continued until it reached [noncrystalline resin 1] (noncrystalline polyester resin).

(Production Example 8)
<Manufacture of non-crystalline resin prepolymer>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] has a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5 mgKOH / g, a hydroxyl value of 49 mgKOH / g, and a softening temperature measured by Koka flow tester. Was 92 ° C., the maximum peak temperature of heat of fusion measured by a differential scanning calorimeter (DSC) was 58 ° C., and the ratio (softening temperature / maximum peak temperature of heat of fusion) was 1.58.
Next, 411 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. A prepolymer solution containing an amorphous resin prepolymer 1] was obtained. [Amorphous resin prepolymer 1] had a free isocyanate% of 1.53%.
After crushing the isocyanate at the end of the prepolymer by adding 0.5 part of n-dibutylamine to 10 parts of the resulting prepolymer solution and mixing it uniformly, the solvent and the remaining n- The weight-average molecular weight of the THF soluble matter after removing dibutylamine was 51,300.

(Production Example 9)
<Production of Colorant Dispersion 1>
In a beaker, 20 parts of copper phthalocyanine, 4 parts of a colorant dispersant (Solspers 28000; manufactured by Avicia Co., Ltd.) and 76 parts of ethyl acetate were stirred and uniformly dispersed. Then, copper phthalocyanine was finely dispersed by a bead mill. [Colorant dispersion 1] was obtained. The volume average particle size of [Colorant Dispersion Liquid 1] measured by a particle size measuring device LA-920 manufactured by Horiba, Ltd. was 0.3 μm.

(Production Example 10)
<Manufacture of wax dispersion>
In a reaction vessel equipped with a condenser, a thermometer and a stirrer, 15 parts of paraffin wax (HNP-9, melting point 75 ° C., Nippon Seiwa Co., Ltd.) and 85 parts of ethyl acetate are placed and heated to 78 ° C. After sufficiently dissolving and cooling to 30 ° C. with stirring for 1 hour, the solution was further fed with an ultra visco mill (manufactured by IMEX Co., Ltd.) at a liquid feeding speed of 1.0 kg / hr, a disk peripheral speed: 10 m / sec, a diameter of 0 0.5 mm zirconia bead filling amount 80 volume%, wet-grinding under conditions of 6 passes. Finally, ethyl acetate was added to adjust the solid content concentration to 15% to obtain [Wax Dispersion 1].

Example 1
<Production of resin solution>
In a reaction vessel equipped with a thermometer and a stirrer, 100 parts of [Crystalline Resin 1] and 100 parts of ethyl acetate are placed, heated to 50 ° C. and stirred to prepare a homogeneous phase [Resin Solution 1] Got.

<Manufacture of toner 1>
In a beaker, 45 parts of [resin solution 1], 15 parts of 50% ethyl acetate solution of [crystalline resin prepolymer 1], 14 parts of [wax dispersion 1], and 10 parts of [colorant dispersion 1] The mixture was stirred at 8,000 rpm with a TK homomixer at 50 ° C., and uniformly dissolved and dispersed to obtain [Toner Material Liquid 1].

99 parts of ion-exchanged water in a beaker and 6 parts of a 25% aqueous dispersion of organic resin fine particles for dispersion stabilization (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) Then, 1 part of sodium carboxymethylcellulose and 10 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, Ltd., Eleminol MON-7) were uniformly dissolved. Next, at 50 ° C., while stirring the TK homomixer at 10,000 rpm, 75 parts of [Toner material liquid 1] was added and stirred for 2 minutes to obtain a mixed solution.
Subsequently, the obtained mixed liquid was transferred to a Kolben equipped with a stirrer and a thermometer, and ethyl acetate was distilled off at 55 ° C. until the concentration was 0.5% or less. [Aqueous resin dispersion 1 of resin particles] Got.
Next, as a pre-cleaning step, [Aqueous resin dispersion 1 of resin particles] was cooled to room temperature, filtered, and 300 parts of ion-exchanged water was added to the obtained filter cake, and a TK homomixer was used. The mixture was filtered at 12,000 rpm for 10 minutes and then filtered twice.
Next, 300 parts of ion-exchanged water is added to the obtained filter cake, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered three times. 300 parts of 1% hydrochloric acid was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered. Finally, 300 parts of ion-exchanged water was added to the obtained filter cake, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer, the operation of filtering was performed twice to obtain a filter cake.
The obtained filter cake was crushed and then dried at 40 ° C. for 22 hours to obtain [Resin Particle 1] having a volume average particle size of 5.6 μm.
Using 100 parts of the obtained [resin particles 1] and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive, a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) was used. After 5 cycles of mixing at 30 m / second for 30 seconds and resting for 1 minute, a sieve having a mesh size of 35 μm was sieved to prepare toner 1.

<Evaluation>
The obtained toner was evaluated as follows. The results are shown in Table 1.
<< Oligomer amount (peak area ratio of oligomer component) >>
The amount of the component (oligomer component) having a molecular weight of 300 to 1,500 in the toner was determined as a peak area ratio by GPC measurement. Details of the measurement method are shown below.
Specifically, the produced toner was dissolved in tetrahydrofuran (THF), allowed to stand overnight, and then the colorant was separated using a centrifuge, and then GPC measurement was performed. Then, the peak area ratio was determined from the ratio of the peak areas having a molecular weight of 300 to 1,500 when the peak area of the entire toner was taken as 100%.

<< Low-temperature fixability (fixing minimum temperature) >>
Using the image forming apparatus A shown below, a solid image having a toner adhesion amount after transfer of 0.85 ± 0.1 mg / cm ² on transfer paper (manufactured by Ricoh Business Expert Co., Ltd., copy printing paper <70>) (Image size: 3 cm × 8 cm), fixing by changing the temperature of the fixing belt, and using the drawing tester AD-401 (manufactured by Ueshima Seisakusho Co., Ltd.) as a ruby needle (Tip radius 260 μmR to 320 μmR, tip angle 60 degrees), drawing with a load of 50 g, rubbing the drawing surface strongly 5 times with fibers (Hanicot # 440, manufactured by Hanilon), fixing belt temperature with almost no image shaving It was 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. The speed of passing through the nip portion of the fixing device is 280 mm / s. The lower the fixing minimum temperature, the better the low-temperature fixability.

-Image forming apparatus A-
The image forming apparatus A (image forming apparatus 100) shown in FIG. 1 is a color printer that uses a tandem method in which image forming units that form a plurality of color images are juxtaposed along the belt extending direction.
In FIG. 1, an image forming apparatus 100 includes photosensitive drums 20Y, 20C, 20M as image carriers that can form images as images corresponding to colors separated into yellow, cyan, magenta, and black, respectively. A tandem structure with 20 Bk arranged side by side is adopted.
In the image forming apparatus 100 having the configuration shown in FIG. 1, the visible images formed on the photosensitive drums 20Y, 20C, 20M, and 20Bk are in the direction of arrow A1 while facing the photosensitive drums 20Y, 20C, 20M, and 20Bk. A recording sheet S on which an intermediate transfer body (hereinafter referred to as a transfer belt) 11 using a movable endless belt is subjected to a primary transfer process to superimpose and transfer respective images, and thereafter a recording sheet or the like is used. On the other hand, batch transfer is performed by executing a secondary transfer process.
Around each photosensitive drum, an apparatus for image formation processing is arranged according to the rotation of the photosensitive drum. Now, the photosensitive drum 20Bk that performs black image formation will be described as an object. A charging device 30Bk, a developing device 40Bk, a primary transfer roller 12Bk, and a cleaning device 50Bk that perform image forming processing along the rotation direction are arranged. For the writing performed after charging, the optical writing device 8 is used.
In the superimposing transfer to the transfer belt 11, the visible image formed on each photoconductive drum 20 </ b> Y, 20 </ b> C, 20 </ b> M, 20 </ b> Bk is transferred to the same position on the transfer belt 11 in the process of moving the transfer belt 11 in the A1 direction. As described above, voltage application by the primary transfer rollers 12Y, 12C, 12M, and 12Bk disposed to face the respective photosensitive drums 20Y, 20C, 20M, and 20Bk with the transfer belt 11 interposed therebetween causes the A1 direction upstream. The timing is shifted toward the downstream side.
The photosensitive drums 20Y, 20C, 20M, and 20Bk are arranged in this order from the upstream side in the A1 direction. Each of the photosensitive drums 20Y, 20C, 20M, and 20Bk is provided in an image station for forming yellow, cyan, magenta, and black images.
The image forming apparatus 100 is disposed so as to face four image stations that perform image forming processing for each color and above each of the photosensitive drums 20Y, 20C, 20M, and 20Bk, and includes a transfer belt 11 and a primary transfer roller 12Y. , 12C, 12M, and 12Bk, a secondary transfer roller 5 that is a transfer roller as a transfer member that is arranged to face the transfer belt 11 and that is driven by the transfer belt 11 and rotates. An intermediate transfer belt cleaning device 13 disposed opposite to the transfer belt 11 for cleaning the transfer belt 11, and an optical writing device 8 serving as an optical writing device disposed below these four image stations. And have.
The optical writing device 8 is equipped with a semiconductor laser as a light source, a coupling lens, an fθ lens, a toroidal lens, a folding mirror, a rotating polygon mirror as a deflecting means, etc., and each of the photosensitive drums 20Y, 20C, 20M, Write light Lb corresponding to each color with respect to 20 Bk (in the figure, for convenience, the reference is applied only to the image station of the black image, but the same applies to the other image stations), and the photosensitive drum An electrostatic latent image is formed on 20Y, 20C, 20M, and 20Bk.
The image forming apparatus 100 includes a sheet feeding device 61 as a sheet feeding cassette on which recording sheets S transported between the photosensitive drums 20Y, 20C, 20M, and 20Bk and the transfer belt 11 are stacked, and a sheet feeding device. The transfer section between each of the photosensitive drums 20Y, 20C, 20M, and 20Bk and the transfer belt 11 is fed with the recording sheet S conveyed from the feeding device 61 at a predetermined timing in accordance with the toner image formation timing by the image station. A registration roller pair 4 that is fed out toward the registration roller 4 and a sensor (not shown) that detects that the leading edge of the recording paper S has reached the registration roller pair 4 are provided.
The image forming apparatus 100 includes a fixing device 101 as a roller fixing type fixing unit for fixing the toner image onto the recording sheet S on which the toner image is transferred, and the main body of the image forming apparatus 100 with the fixed recording sheet S A paper discharge roller 7 that discharges to the outside, a paper discharge tray that is disposed on the top of the main body of the image forming apparatus 100 and that stacks the recording paper S discharged to the outside of the main body of the image forming apparatus 100 by the discharge roller 7, and paper discharge There are provided toner bottles 9Y, 9C, 9M, and 9Bk, which are located on the lower side of the tray and filled with toners of yellow, cyan, magenta, and black.
The transfer belt unit 10 includes a drive roller 72 and a driven roller 73 around which the transfer belt 11 is wound, in addition to the transfer belt 11 and the primary transfer rollers 12Y, 12C, 12M, and 12Bk.
The driven roller 73 also has a function as a tension urging unit for the transfer belt 11. For this reason, the driven roller 73 is provided with an urging unit using a spring or the like. Such a transfer belt unit 10, the primary transfer rollers 12Y, 12C, 12M, and 12Bk, the secondary transfer roller 5, and the cleaning device 13 constitute a transfer device 71.
The sheet feeding device 61 is disposed at the lower part of the main body of the image forming apparatus 100, and includes a feeding roller 3 as a feeding roller that contacts the upper surface of the uppermost recording sheet S. The uppermost recording sheet S is fed toward the registration roller pair 4 by being rotationally driven 3 in the counterclockwise direction.
Although not shown in detail, the cleaning device 13 provided in the transfer device 71 has a cleaning brush and a cleaning blade disposed so as to face and contact the transfer belt 11. The transfer belt 11 is cleaned by scraping and removing foreign matter such as residual toner on the top with a cleaning brush and a cleaning blade.
The cleaning device 13 also has a discharge means (not shown) for carrying out and discarding the residual toner removed from the transfer belt 11.

<< Image intensity >>
The state of scratches after a pencil scratch test using a pencil of hardness B in accordance with JIS K5600-5-4 for the test paper fixed at a fixing belt temperature of 160 ° C. in the low temperature fixability test. From the evaluation, the following criteria were used.
〔Evaluation criteria〕
◎: Scratch marks are not seen at all, and no image is lost even if rubbed with an eraser ○: Scratch marks are not seen at all, but a slight loss of image occurs when rubbed with an eraser △: Scratch marks are almost seen Although there is no clear image missing when rubbed with an eraser ×: Scratch marks are seen, and there is a clear image missing even without rubbing with an eraser

<< Heat resistant storage stability >>
A 50 mL glass container is filled with toner, left in a constant temperature bath at 50 ° C. for 24 hours, then cooled to 24 ° C., and the penetration (mm) is measured by a penetration test (JIS K2235-1991). The heat resistant storage stability was evaluated according to the following criteria. In addition, it means that heat resistance preservability is excellent, so that the penetration degree is large, and the penetration degree of less than 10 mm is highly likely to cause a problem in use.
〔Evaluation criteria〕
◎: Needle penetration is 25 mm or more ○: Needle penetration is 20 mm or more and less than 25 mm △: Needle penetration is 15 mm or more and less than 20 mm ×: Needle penetration is 10 mm or more and less than 15 mm XX: Needle penetration is less than 10 mm

(Example 2)
A toner 2 was obtained in the same manner as in Example 1 except that the crystalline resin 1 was replaced with the crystalline resin 2 in Example 1.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
A toner 3 was obtained in the same manner as in Example 1 except that the crystalline resin 1 was replaced with the crystalline resin 3 in Example 1.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
In Example 1, the toner 4 was obtained in the same manner as in Example 1 except that the crystalline resin 1 was replaced with the crystalline resin 4 and 2 parts of the [oligomer component] were added when the [toner material liquid 1] was produced. .
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
In Example 1, Toner 5 was obtained in the same manner as in Example 1 except that 4 parts of [Oligomer component] were added when [Toner material liquid 1] was prepared.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 6)
A toner 6 was obtained in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 2] below in Example 1.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 1.

-Manufacture of toner material liquid 2-
In a reaction vessel equipped with a thermometer and a stirrer, 100 parts of [Amorphous Resin 1] and 100 parts of ethyl acetate were added, and the mixture was heated to 50 ° C. and stirred to prepare a uniform phase [Resin Solution 2]. Got.
Subsequently, 15 parts of [resin solution 2], 30 parts of [resin solution 1], 15 parts of prepolymer solution containing [amorphous resin prepolymer 1], 14 parts of [wax dispersion 1], and 10 parts of [Colorant Dispersion Liquid 1] was added, stirred at 8,000 rpm with a TK homomixer at 50 ° C., and uniformly dissolved and dispersed to obtain [Toner Material Liquid 2].

(Comparative Example 1)
A toner a was obtained in the same manner as in Example 1 except that the crystalline resin 1 was replaced with the crystalline resin 4 in Example 1.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
In Example 1, a toner b was obtained in the same manner as in Example 1 except that 6 parts of [oligomer component] were added when [Toner material liquid 1] was prepared.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
In Example 1, a toner c was obtained in the same manner as in Example 1 except that 10 parts of [oligomer component] was added when [Toner material liquid 1] was produced.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 1.

In Table 1, the “crystalline resin in the binder resin content” refers to a crystalline resin containing at least one of a urethane bond and a urea bond.

As an aspect of this invention, it is as follows, for example.
<1> A toner containing a binder resin,
The binder resin contains 50% by mass or more of a crystalline resin containing at least one of a urethane bond and a urea bond,
The toner comprises a component having a molecular weight of 300 to 1,500 in a molecular weight distribution measured by gel permeation chromatography in a peak area ratio of 5% to 15%.
<2> The toner according to <1>, wherein the crystalline resin including at least one of a urethane bond and a urea bond includes a crystalline polyester resin including at least one of a urethane bond and a urea bond.
<3> The toner according to <2>, wherein the crystalline polyester resin containing at least one of a urethane bond and a urea bond is a block polymer having a crystalline polyester component and a polyurethane component.
<4> The toner according to any one of <1> to <3>, wherein the peak area ratio is 5% to 10%.
<5> The toner according to any one of <1> to <4>, wherein particles are formed from a toner material liquid containing a binder resin in an aqueous medium.
<6> A developer containing the toner according to any one of <1> to <5>.
<7> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image to form a visible image. And an image forming apparatus, wherein the toner is the toner according to any one of <1> to <5>.

Japanese Patent Publication No. 4-024702 JP-B-4-024703 Japanese Patent No. 3910338 JP 2010-0777419 A JP 2009-014926 A JP 2010-151996 A

Claims (7)

A toner containing a binder resin,
The binder resin contains 50% by mass or more of a crystalline resin containing at least one of a urethane bond and a urea bond,
A toner comprising a component having a molecular weight of 300 to 1,500 in a molecular weight distribution measured by gel permeation chromatography in a peak area ratio of 5% to 15%.   The toner according to claim 1, wherein the crystalline resin containing at least one of a urethane bond and a urea bond includes a crystalline polyester resin containing at least one of a urethane bond and a urea bond.   The toner according to claim 2, wherein the crystalline polyester resin containing at least one of a urethane bond and a urea bond is a block polymer having a crystalline polyester component and a polyurethane component.   The toner according to claim 1, wherein a peak area ratio is 5% to 10%.   The toner according to claim 1, wherein particles are formed from a toner material liquid containing a binder resin in an aqueous medium.   A developer comprising the toner according to claim 1.   An electrostatic latent image bearing member; an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image bearing member; and a toner that develops the electrostatic latent image to form a visible image. An image forming apparatus comprising: a developing unit provided at least; and the toner is the toner according to claim 1.