JP2014032232A - Toner - Google Patents

Abstract

A toner capable of preventing low-temperature offset and achieving both low-temperature fixability and heat-resistant storage stability.
A piston having a core-shell structure toner particle in which a shell phase containing a resin B is formed on the surface of a core containing a binder resin A, a colorant and a wax, and pressurizing the sample In measurement of the flow characteristics of binder resin A and resin B using a constant load extrusion type capillary rheometer with an area of the pressure surface to 1.0 cm ² and a diameter of the die hole through which the sample is extruded is 1.0 mm. When A is pressurized by a piston at a pressure of 5.0 MPa, the temperature until the displacement of the piston reaches 2.0 mm is 10 seconds after the start of pressurization. TA and tB satisfy a specific relationship, where tB is the time from the start of pressurization until the displacement of the piston reaches 2.0 mm. Toner, characterized in that.
[Selection figure] None

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, and a toner jet recording method. Specifically, a toner used in an image forming method for forming a toner image on an electrostatic latent image carrier and then transferring the image onto a transfer material to form a toner image and fixing the image under thermal pressure to obtain a fixed image About.

In recent years, also in the field of electrophotographic apparatuses such as copying machines and printers, energy saving has been considered as a major technical problem, and a great reduction in the amount of heat applied to the fixing apparatus has been cited. Accordingly, there is an increasing need for low-temperature fixability that enables a toner to be sufficiently fixed with a low heat quantity.
Conventionally, in order to enable fixing at a lower temperature, it is known as an effective method to contain a component having a crystal structure in a binder resin. Crystalline polyester does not show a clear glass transition due to the regular arrangement of molecular chains, it is difficult to soften in a temperature range lower than the crystalline melting point, and it exhibits meltability at a slight temperature rise from the melting point. It has the property to do. Focusing on this point, studies have been made to introduce crystalline polyester into the core or shell of a toner having a core-shell structure, and a toner for achieving both low-temperature fixability and heat-resistant storage stability has been proposed.
Patent Document 1 proposes a toner in which a crystalline polyester having a melting point of 50 ° C. to 100 ° C. is used for the core and a shell of amorphous polyester is formed on the core.
Patent Document 2 proposes a toner using a crystalline resin produced using a non-crystalline polyester for the core and a monomer containing the crystalline polyester for the shell.
Patent Document 3 proposes a toner using a block polymer in which a crystalline part and an amorphous part are bonded as a core and a crystalline resin as a shell.

JP 2006-91379 A JP 2010-150535 A JP 2011-94135 A

The toner described in Patent Document 1 is thought to have a thick shell layer and poor sharp melt properties on the toner surface, and has a problem that the low-temperature fixing effect by the core is not fully utilized.
In addition, although the toner described in Patent Document 2 has a sharp melt property in the shell layer, it is considered that good low temperature fixability cannot be obtained because the sharp melt property of the core itself is not sufficient. Therefore, it is considered necessary to improve the low-temperature fixing property by using a resin having a crystal structure for both the core and the shell in the toner having the core-shell structure.
On the other hand, when the present inventors evaluated the toner produced according to the indication of the said patent document 3, it turned out that it has favorable sharp-melt property. However, in the evaluation of fixability, it was found that low temperature offset is likely to occur. The reason is that the melting rate of the shell is faster than the melting rate of the core because the melting point of the crystalline component contained in the shell is low, the proportion of the crystalline component is too high, and the molecular weight (Mn) is low. Can be considered. That is, at the stage where the shell layer is melted, the core is not sufficiently melted, and the wax contained in the core does not ooze out efficiently, so it is considered that low temperature offset is likely to occur.
As described above, there is still a problem in realizing a toner having both low-temperature fixability and heat-resistant storage stability in a toner incorporating crystalline polyester.
Accordingly, an object of the present invention is to provide a toner that can prevent low-temperature offset and can achieve both low-temperature fixability and heat-resistant storage stability.

The present invention is a toner having core-shell structured toner particles in which a shell phase containing a resin B is formed on the surface of a core containing a binder resin A, a colorant and a wax,
The area of the pressing surface for the sample of the piston that pressurizes the sample is 1.0 cm. ² In the measurement of the flow characteristics of the binder resin A and the resin B by a constant load extrusion type capillary rheometer whose diameter of the die hole into which the sample is extruded is 1.0 mm, a pressure of 5.0 MPa is applied to the binder resin A by a piston. When pressurizing with the pressure, the temperature when the displacement until the displacement of the piston reaches 2.0 mm is 10 seconds after the start of pressurization is TA (° C.); the resin B heated to the TA (° C.) is the piston. When the time from the start of pressurization until the displacement of the piston reaches 2.0 mm is tB (seconds) when TA is pressurized at 5.0 MPa, TA (° C.) and tB (seconds) are expressed by the following formulas: The present invention relates to a toner satisfying (1) and (2).
Formula (1) 65.0 <= TA <= 90.0
Formula (2) 20.0 ≦ tB ≦ 200.0

  According to the present invention, it is possible to provide a toner capable of preventing low temperature offset during fixing and achieving both low temperature fixability and heat resistant storage stability.

Schematic diagram of toner particle manufacturing equipment Example of temperature-time curve used when calculating TA of binder resin A with a constant load extrusion type capillary rheometer

The toner of the present invention is a toner having toner particles having a core-shell structure in which a shell phase containing resin B is formed on the surface of a core containing binder resin A, colorant and wax.
The core-shell structure in the present invention includes a form in which the shell phase may not completely cover the surface of the core and the core is partially exposed. Moreover, the shell phase does not cover the core as a layer having a clear interface, and includes a form in which the interface is not clearly defined.
The present inventors have conducted detailed studies on the melting behavior of the core and the shell in the core-shell toner.
Conventionally, physical properties such as a softening point, a melt viscosity, a storage elastic modulus, and a loss elastic modulus have been used as an index for determining the sharp melt property of a toner. However, these measurements are a method that starts from a state where a sufficient amount of heat is applied, or a method that measures while gradually raising the temperature from the low temperature side, so the obtained physical property values include time factors at all. Not. Therefore, it has been difficult to grasp the speed in the melting behavior of the toner during heating.
On the other hand, the fixing step in the electrophotographic process is to fix the toner onto the transfer material by applying heat and pressure to the toner. In general, the process speed in the fixing step is 100 mm / second to 200 mm / second, and the time during which heat and pressure are actually applied to the toner on the transfer material is extremely short.
Therefore, the present inventors considered that it is necessary to observe the melting behavior of the toner at the initial stage of heating in consideration of a time factor.
Therefore, we started by measuring the melting rate of the toner in consideration of the time factor by devising the measurement conditions of the constant load extrusion type capillary rheometer. Details are described below.

In the present invention, the measurement of the melting rate of the toner is performed according to a manual attached to the apparatus using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation). In this device, while applying a constant load from the top of the measurement sample filled in the cylinder by the piston, the inside of the cylinder is heated to melt the measurement sample, and the molten measurement sample is pushed out from the die at the bottom of the cylinder. Alternatively, it is possible to obtain a flow curve indicating the relationship between time and the piston lowering amount (hereinafter also referred to as “displacement”).
As a test mode in a capillary tube rheometer, there is a constant temperature method in which measurement is performed under a constant temperature condition in addition to a temperature increase method in which measurement is performed while increasing the temperature at a constant speed that is generally used in the toner field. In the present invention, a constant temperature method is used. In the normal constant temperature method, the preheating time after filling the sample to be measured is set to 3 to 5 minutes, the measurement is started after the sample has sufficiently melted, and the flow curve is calculated from the time and the piston drop (displacement). Get. This method obtains the melt viscosity of the measurement sample under a constant temperature condition, and does not reproduce the behavior of the toner in the actual fixing process.
On the other hand, in the present invention, by setting the time from the sample filling to the measurement start without providing a preheating time to 15 seconds, the melting rate including the time until the measurement sample is heated and the melting starts is included. Can be measured. That is, by shortening preheating as much as possible, it has become possible to measure physical property values that correlate with toner behavior under a short pressurization and heating condition in the actual fixing process.
In the fixing process, when the nip width (the contact portion between the pressure roller and the fixing roller of the fixing device) is about 5 mm to 15 mm and the process speed is 100 mm / second to 200 mm / second, the time for the transfer material to pass between the nips is 25 It is about milliseconds to 150 milliseconds. That is, the fixing is achieved by the toner layer on the transfer material being melted and deformed within the passage time. Therefore, the present inventors assumed that the thickness of the toner layer on the transfer material is 5 μm and passes through a fixing device having a nip width of 10 mm in 25 milliseconds. Then, in the measurement of the capillary rheometer where the area of the pressing surface is 1.0 cm ² and the diameter of the die hole is 1.0 mm, when the toner is pressed at a pressure of 5.0 MPa, 10 seconds after the start of pressing Attention was paid to the temperature at which the displacement was 2.0 mm. As a result of the examination, it was found that the correlation between the temperature and the low-temperature fixability for the above conditions was high.
Based on the above, the present inventors measured under various conditions, and further focused on measuring the flow characteristics of the binder resin A and the resin B constituting the toner. The correlation was examined.

Since the low-temperature fixability of the toner is strongly influenced by the thermal characteristics of the binder resin A, the present inventors first focused on the melting rate of the binder resin A. When the binder resin A was pressurized at a pressure of 5.0 MPa under the above conditions, the temperature at which the displacement of the piston 10 seconds after the start of pressurization was 2.0 mm was defined as TA (° C.).
Then, the correlation between the TA value and the low-temperature fixability and heat-resistant storage stability of the toner using the binder resin A is examined, and the TA of the binder resin A is 65.0 ≦ TA ≦ 90.0 [formula It was found that it is important to satisfy (1)].
That is, when the TA value exceeds 90.0 ° C., good low-temperature fixability cannot be obtained. On the other hand, when the value of TA is less than 65.0 ° C., the heat resistant storage stability deteriorates.
Here, in order to lower the value of TA, for example, when an amorphous resin is used as the binder resin A, there is a measure to lower the glass transition temperature of the resin. However, when the glass transition temperature is lowered, the heat resistant storage stability tends to decrease.
On the other hand, for example, when a resin having crystallinity is contained in the binder resin A, the melting point of the resin having crystallinity and the content ratio in the binder resin A are listed as control factors for lowering the TA value. It is done. That is, the melting point of the resin having crystallinity contained in the binder resin A is lowered, or the content ratio in the binder resin A is increased. However, if the melting point of the resin having crystallinity contained in the binder resin A is excessively lowered or the content ratio is excessively increased, the heat resistant storage stability tends to be lowered.
In terms of achieving both low-temperature fixability and heat-resistant storage stability of the toner, the binder resin A may contain a resin having crystallinity in that the TA value can be designed more widely. preferable. That is, when the binder resin A contains a resin having crystallinity, the toner using the binder resin A can more easily achieve both low-temperature fixability and heat-resistant storage stability.

Next, attention was focused on the molten state of the resin B in a state where the binder resin A melts rapidly. Specifically, in the measurement by a constant temperature method using a constant load extrusion type capillary rheometer having a pressure surface area of 1.0 cm ² and a die hole diameter of 1.0 mm, the binder resin is used. The displacement of the piston when the resin B is pressurized at a pressure of 5.0 MPa at a temperature [ie, TA (° C.)] at which the displacement of A after 10 seconds from the start of pressurization becomes 2.0 mm is 2.0 mm. The time to reach is tB (seconds). That is, when the tB is 10.0 seconds, the thermal melting rate of the binder resin A is the same as that of the resin B.
As described above, in order to efficiently exude the wax during fixing, the binder resin A needs to be sufficiently melted when the resin B is melted. That is, in order to prevent low temperature offset, it is necessary to make the melting rate of the resin B slower than that of the binder resin A.
Here, if an amorphous resin is used as the resin B, it is easy to design the resin B to have a melting rate slower than that of the binder resin A. However, the low-temperature fixability tends to decrease.
When the resin B contains a resin having crystallinity, as control factors for achieving the above conditions, the melting point and content ratio of the resin having crystallinity contained in the resin B, and the glass transition temperature contained in the resin B Examples thereof include the content and molecular weight of vinyl monomers at 105.0 ° C. or higher. Specifically, the melting point of the resin having crystallinity contained in the resin B is increased, the content ratio is decreased, and the content of the vinyl monomer having a glass transition temperature of 105.0 ° C. or more contained in the resin B And a design that increases the molecular weight. However, the melting point of the resin having the crystallinity of the resin B is excessively increased, the content ratio is excessively decreased, and the content of the vinyl monomer having a glass transition temperature of 105.0 ° C. or more to be included in the resin B is If the design is excessively increased and the molecular weight is excessively increased, the toner surface becomes difficult to be softened, which tends to be disadvantageous for low-temperature fixability.
As a result of investigations by the present inventors based on the above, in order for the toner using the shell phase containing the resin B to prevent low temperature offset and to exhibit excellent low temperature fixability, the above tB is expressed by the following formula. It was found that (2) should be satisfied.
Formula (2) 20.0 ≦ tB ≦ 200.0
When the value of tB is less than 20.0 seconds, it is difficult to prevent low temperature offset. On the other hand, when the value of tB exceeds 200.0 seconds, it is disadvantageous for low-temperature fixability.

  From the above examination results, the toner is designed so that the TA and tB satisfy the formulas (1) and (2), thereby preventing a low temperature offset at the time of fixing, as well as low temperature fixability and heat resistant storage stability. It was found that both can be achieved. Preferably, the TA and tB satisfy 70.0 ≦ TA ≦ 85.0 and 50.0 ≦ tB ≦ 150.0. By setting the toner design within such a range, the above-described effect can be expressed more favorably.

In the toner of the present invention, as the binder resin A, any of a crystalline resin and an amorphous resin can be used. These may be mixed or used. Among these, as described above, the binder resin A preferably contains a resin having crystallinity. In this case, the resin having crystallinity means a resin having a crystal structure in which polymer molecular chains are regularly arranged. Therefore, it is difficult to soften in a temperature range lower than the melting point of the crystal, and meltability is manifested by a slight temperature rise at the melting point. In this invention, it is preferable that resin which has crystallinity is resin which has the polyester site | part which can take a crystalline structure.
Further, the binder resin A used in the present invention has a maximum endothermic peak peak temperature (hereinafter referred to as TpA) at the first temperature increase of 50.0 ° C. in the measurement with a differential scanning calorimeter (DSC). It is preferably 75.0 ° C. or lower.
When TpA is higher than 75.0 ° C., it is difficult to control the TA value in the above formula (1) below the upper limit, and the toner using the binder resin A tends to have low-temperature fixability.
On the other hand, when the value of TpA is smaller than 50.0 ° C., it becomes difficult to control the TA value in the above formula (1) to the lower limit or more, and the toner using the binder resin A has low heat resistance storage stability. There is a tendency.
That is, as one means for designing the TA value to satisfy the formula (1), the TpA value is set in the above range. A more preferable range of the TpA is 55.0 ° C. or higher and 70.0 ° C. or lower.

In the toner of the present invention, the binder resin A preferably contains 50.0% by mass or more and 90.0% by mass or less of a resin having crystallinity. Furthermore, it is more preferable that the binder resin A contains 50.0% by mass or more and 90.0% by mass or less of a resin having a polyester portion capable of taking a crystal structure.
When the content of the resin having crystallinity in the binder resin A is more than 90.0% by mass, it becomes difficult to control the TA value in the formula (1) to the lower limit or more, and the binder resin A is used. The toner that has been used tends to decrease the heat-resistant storage stability.
On the other hand, when the content of the resin having crystallinity in the binder resin A is less than 50.0% by mass, it becomes difficult to control the value of TA in the formula (1) below the upper limit, and the binder resin A The toner using the toner tends to be disadvantageous for low-temperature fixability.
That is, as one means for designing the TA value to satisfy the formula (1), the content of the resin having crystallinity in the binder resin A can be included in the above range. A more preferable range of the content of the resin having crystallinity in the binder resin A is 60.0% by mass or more and 85.0% by mass or less.

As one form of the resin having crystallinity, a resin having a polyester portion capable of taking a crystal structure can be given. Moreover, crystalline polyester is mentioned as one form of resin which has the polyester site | part which can take a crystal structure.
In a resin having a polyester moiety capable of taking a crystal structure, an aliphatic diol and a polyvalent carboxylic acid are preferably used as raw materials for the synthesis of the polyester moiety capable of taking a crystal structure.
The aliphatic diol is preferably a linear aliphatic diol having 4 to 20 carbon atoms, and examples thereof include the following. Ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Diol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol. These may be used alone or in combination of two or more.
An aliphatic diol having a double bond can also be used as the aliphatic diol. Examples of the aliphatic diol having a double bond include the following compounds. 2-butene-1,4-diol, 3-hexene-1,6-diol, 4-octene-1,8-diol.
Of these, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol can be preferably exemplified from the viewpoint of adjusting the TpA that affects low-temperature fixability to the above range.
As the polyvalent carboxylic acid, an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid are preferable, an aliphatic dicarboxylic acid is more preferable, and a linear aliphatic dicarboxylic acid is particularly preferable.
Examples of the linear aliphatic dicarboxylic acid include the following. Succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid. Or its lower alkyl ester and acid anhydride.
Examples of the aromatic dicarboxylic acid include the following. Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid. These may be used alone or in combination of two or more.
A dicarboxylic acid having a double bond can also be used as the polyvalent carboxylic acid. Examples of such dicarboxylic acids include fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters and acid anhydrides are also included.
Of these, adipic acid, sebacic acid, 1,10-decanedicarboxylic acid, and 1,12-dodecanedicarboxylic acid can be preferably exemplified from the viewpoint of adjusting the TpA that affects low-temperature fixability to the above range.
There is no restriction | limiting in particular in the method of producing the polyester part which can take the said crystal structure, It can produce by the general polymerization method of the polyester resin which makes an alcohol component and an acid component react. For example, direct polycondensation and transesterification methods can be used, and they can be prepared depending on the type of diol or dicarboxylic acid used.
The production of the polyester part capable of taking the crystal structure is preferably carried out at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower, while reducing the pressure in the reaction system as necessary, while removing water and alcohol generated during condensation. It is preferable to react. When the monomer is not dissolved or compatible at the reaction temperature, a high boiling point solvent may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If there is a monomer with poor compatibility in the copolymerization reaction, the monomer with poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component. preferable.
As a catalyst which can be used at the time of manufacture of the polyester part which can take the said crystal structure, the following can be mentioned, for example. Titanium catalyst of titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide. Tin catalyst of dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide.

The amorphous resin that can be used for the binder resin A will be described. Examples of the amorphous resin used for the binder resin A include, but are not limited to, vinyl resins such as polyurethane resin, polyester resin, styrene acrylic resin, and polystyrene. These resins may be modified with urethane, urea, or epoxy. Of these, polyester resins and polyurethane resins are preferably used from the viewpoint of maintaining elasticity with respect to the resin.
Examples of the monomer used in the polyester resin as the non-crystalline resin include divalent or trivalent or higher carboxylic acids as described in “Polymer Data Handbook: Basic Edition” (Edited by Polymer Society: Bafukan). And divalent or trivalent or higher alcohols. Specific examples of these monomer components include the following compounds.
Divalent carboxylic acids include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, dimethyl terephthalate, dibasic acid of malonic acid, anhydrides thereof and lower alkyl esters thereof, maleic acid Aliphatic unsaturated dicarboxylic acids of acids, fumaric acid, itaconic acid, citraconic acid. Examples of the trivalent or higher carboxylic acid include trimellitic acid and its anhydride and lower alkyl ester. These may be used individually by 1 type and may use 2 or more types together.
Examples of the divalent alcohol include the following compounds. Bisphenol A, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, propylene glycol. Examples of the trivalent or higher alcohols include the following compounds. Glycerin, trimethylol ethane, trimethylol propane, pentaerythritol. These may be used individually by 1 type and may use 2 or more types together. If necessary, a monovalent acid such as acetic acid or benzoic acid, or a monovalent alcohol such as cyclohexanol or benzyl alcohol can be used for the purpose of adjusting the acid value or the hydroxyl value.
The polyester resin can be synthesized by a conventionally known method using the monomer component.
Next, the polyurethane resin as the non-crystalline resin will be described. The polyurethane resin is a reaction product of an aliphatic diol and a diisocyanate, and the functionality of the resulting resin can be changed by changing the aliphatic diol and the diisocyanate.
Examples of the diisocyanate include diisocyanates that can be used for the resin. Moreover, the following are mentioned as an aliphatic diol which can be used for a polyurethane resin.
Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol); alkylene ether glycol (polyethylene glycol, polypropylene glycol); alicyclic diol (1,4-cyclohexanedimethanol); bisphenols (bisphenol) A); alkylene oxide (ethylene oxide, propylene oxide) adduct of the alicyclic diol; the alkyl portion of the alkylene ether glycol may be linear or branched. In the present invention, an alkylene glycol having a branched structure can also be preferably used.
In the present invention, as long as the binder resin A does not affect low-temperature fixability, the non-crystalline resin is included so that the elasticity of the binder resin A after the toner is melted during fixing can be maintained. It becomes.
The glass transition temperature (Tg) of the amorphous resin in the binder resin A is preferably 50.0 ° C. or higher and 130.0 ° C. or lower. More preferably, it is 70.0 degreeC or more and 120.0 degreeC or less. By being in this range, the elasticity in the fixing region is easily maintained.

In the toner of the present invention, as one form of the resin having crystallinity contained in the binder resin A, a block obtained by chemically bonding a polyester part capable of taking a crystal structure and a part not taking a crystal structure Examples thereof include polymers (hereinafter also simply referred to as block polymers). Therefore, it is also a preferable aspect that the binder resin A contains the block polymer.
The block polymer is a polymer in which polymers are linked by a covalent bond within one molecule. Here, the polyester part which can take a crystal structure is a part which regularly arrange | positions by gathering many itself, and expresses crystallinity, A crystalline polyester is mentioned as a preferable example. In addition, the part where the crystal structure cannot be taken is a part where a regular arrangement does not occur even when a large number of the parts are collected, and preferred examples include polyester and polyurethane as an amorphous resin. It is done.
The block polymer includes an AB type diblock polymer, an ABA type triblock polymer, an BAB type triblock polymer, an ABAB type, which has a polyester part (A) capable of taking a crystal structure and a part (B) not capable of taking a crystal structure. Type multi-block polymers, and any form can be used in the present invention.
In the block polymer, examples of the bonding form in which a polyester portion capable of taking a crystal structure and a portion not taking a crystal structure are covalently bonded include an ester bond, a urea bond, and a urethane bond. Among these, a block polymer bonded with a urethane bond is more preferable because it can easily maintain elasticity after the toner is melted during fixing.
In the present invention, when a block polymer is used as the binder resin A, the ratio of the polyester portion capable of taking a crystal structure is 50.0% by mass or more and 90.0% by mass or less with respect to the binder resin A. It is preferable.
As a method for preparing a block polymer, a method of separately preparing a component that forms a polyester site that can take a crystal structure and a component that forms a site that cannot take a crystal structure and bonding them together (two-step method) is used. be able to. Also, a method (one-step method) in which a raw material of a component that forms a polyester portion capable of taking a crystal structure and a raw material of a component that forms a portion that cannot take a crystal structure are simultaneously prepared and prepared at one time can be used.
The block polymer in the present invention can be synthesized by selecting from various methods in consideration of the reactivity of each terminal functional group.
In the case of a block polymer in which both a polyester part capable of taking a crystal structure and a part not taking a crystal structure are polyester resins, each component can be prepared separately and then bonded using a binder. In particular, when the acid value of one polyester is high and the hydroxyl value of the other polyester is high, it is not necessary to use a binder, and the condensation reaction can proceed while heating and reducing pressure as it is. At this time, the reaction temperature is preferably about 200.0 ° C.
When the binder is used, the following binders are exemplified. Polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, polyfunctional epoxy, polyhydric acid anhydride. These binders can be used for synthesis by dehydration reaction or addition reaction.
In addition, in the case of a block polymer in which the polyester part that can take a crystal structure is a crystalline polyester and the part that cannot take a crystal structure is a polyurethane, after preparing each part separately, the alcohol terminal of the crystalline polyester and the polyurethane It can be prepared by subjecting an isocyanate terminal to a urethanization reaction. The synthesis can also be performed by mixing a crystalline polyester having an alcohol terminal and a diol and diisocyanate constituting polyurethane and heating. In this case, at the initial stage of the reaction when the concentrations of the diol and the diisocyanate are high, these selectively react to form a polyurethane, and after the molecular weight increases to some extent, the urethane between the isocyanate terminal of the polyurethane and the alcohol terminal of the crystalline polyester. Happens.

  The number average molecular weight (Mn) of the block polymer is preferably 3000 or more and 40000 or less, and more preferably 7000 or more and 25000 or less. The weight average molecular weight (Mw) of the block polymer is preferably 10,000 or more and 60,000 or less, and more preferably 20,000 or more and 50,000 or less. By being in these ranges, it is possible to maintain good heat-resistant storage stability and to impart sharp melt properties to the toner.

In the present invention, the block polymer may have an acid value. When the block polymer has an acid value, a more uniform particle size distribution can be obtained when toner particles are produced in an aqueous medium. In this case, the acid value of the block polymer is preferably 3.0 mgKOH / g or more and 30.0 mgKOH / g or less, more preferably 5.0 mgKOH / g or more and 20.0 mgKOH / g or less.
The adjustment of the acid value can be achieved, for example, by changing the terminal isocyanate group, hydroxyl group and carboxyl group of the block polymer to polyhydric carboxylic acids, polyhydric alcohols, polyhydric isocyanates, polyfunctional epoxies, polyanhydrides, and polyhydric acids. This can be done by modifying with a polyvalent amine.

In the toner of the present invention, the resin B preferably contains a crystalline resin. The resin B has a maximum endothermic peak peak temperature (hereinafter referred to as TpB) in the first temperature increase in a measurement with a differential scanning calorimeter (DSC) of 55.0 ° C. or higher and 80.0 ° C. or lower. It is preferable.
When TpB is higher than 80.0 ° C., it becomes difficult to control the value of tB in the formula (2) below the upper limit, and the low-temperature fixability tends to decrease.
On the other hand, when the value of TpB is lower than 55.0 ° C., it becomes difficult to control the tB of the above formula (2) to the lower limit or more, and low temperature offset tends to occur.
That is, as one means for setting the value of tB to satisfy the equation (2),
It is mentioned that the value of TpB is within the above range.
In the present invention, it is more preferable that the TpA and the TpB satisfy the relationship of the following formula (3).
Formula (3) TpA ≧ TpB
By satisfying the expression (2) and also satisfying the expression (3), it is possible to achieve both a low-temperature fixability and a heat-resistant storage stability in a more favorable manner.

In the toner of the present invention, one form of the resin having crystallinity in the resin B is a resin having a polyester portion capable of taking a crystal structure. Moreover, crystalline polyester is mentioned as one form of resin which has the polyester site | part which can take a crystal structure.
Examples of a method for introducing a crystalline polyester component that is one form of a polyester moiety capable of taking a crystal structure into the resin B include the following methods.
(A) A method of copolymerizing a vinyl monomer a having a molecular structure with a polyester moiety capable of taking a crystal structure and another vinyl monomer b.
(B) After copolymerization using a vinyl monomer a ′ which is a precursor for introducing a polyester moiety capable of taking a crystal structure and another vinyl monomer b, the polyester moiety capable of taking the crystal structure is reacted. Method.
Among these methods, the method (A) is preferable from the viewpoint of easy introduction of the polyester moiety. The vinyl monomers a, a ′, and b will be described below.

The vinyl monomer a contains a polyester site capable of taking a crystal structure in the molecular structure. As one form of the polyester part which can take the crystal structure contained in the vinyl-type monomer a, the crystalline polyester obtained by reacting C4-C20 aliphatic diol and aliphatic polycarboxylic acid is mentioned. In addition, the aliphatic diol is preferably a linear aliphatic diol that easily improves crystallinity.
As the aliphatic diol and the aliphatic polyvalent carboxylic acid, those similar to those used for the binder resin A can be used.
Examples of the method for producing the vinyl monomer a include the following methods.
(1) The vinyl monomer having a hydroxyl group or the vinyl monomer having a carboxyl group and the crystalline polyester component are esterified to produce a vinyl monomer containing a polyester moiety capable of forming a crystal structure in the molecular structure. Method.
(2) A method for producing a vinyl monomer having a molecular structure containing a polyester moiety capable of taking a crystal structure by urethanizing a vinyl monomer having an isocyanate group and the crystalline polyester component.
(3) A method for producing a vinyl monomer containing in its molecular structure a polyester moiety capable of forming a crystal structure by urethanizing the vinyl monomer having a hydroxyl group and the crystalline polyester component with a diisocyanate as a binder.
Among these methods, the methods (2) and (3) are particularly preferable from the viewpoint of reactivity with the crystalline polyester component.
Here, when the crystalline polyester component is introduced by an esterification reaction with a carboxyl group or by a urethanization reaction with an isocyanate group, the crystalline polyester component is preferably alcohol-terminated. Therefore, the crystalline polyester component preferably has a diol / dicarboxylic acid molar ratio (diol / dicarboxylic acid) of 1.02 or more and 1.20 or less. On the other hand, when the crystalline polyester component is introduced by an esterification reaction with a hydroxyl group, it is preferably an acid terminal, and the molar ratio of the diol to the dicarboxylic acid is preferably the opposite.
Examples of the vinyl monomer having a hydroxyl group include the following.
Hydroxystyrene, N-methylolacrylamide, N-methylolmethacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene glycol monomethacrylate, allyl alcohol, methacryl alcohol, crotyl alcohol, iso Crotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether. Among these, hydroxyethyl methacrylate is particularly preferable.
The vinyl monomer having a carboxyl group is preferably an unsaturated monocarboxylic acid having 30 or less carbon atoms, an unsaturated dicarboxylic acid, or an anhydride thereof, and examples thereof include the following.
Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, itaconic acid, cinnamic acid, and anhydrides thereof. Among these, acrylic acid, methacrylic acid, maleic acid, and fumaric acid are particularly preferable.
Examples of the vinyl monomer having an isocyanate group include the following.
2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, 2
-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate. Among these, particularly preferred are 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.

The polyester portion capable of taking the crystal structure of the vinyl monomer a preferably has a peak temperature of the maximum endothermic peak in DSC measurement of 55.0 ° C. or higher and 80.0 ° C. or lower.
The polyester moiety capable of taking a crystal structure included in the molecular structure of the vinyl monomer a has a number average molecular weight (Mn) of 1,000 or more in gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF), It is preferable that it is 20,000 or less and a weight average molecular weight (Mw) is 2,000 or more and 40,000 or less. A more preferable range of Mn is 2,000 or more and 15,000 or less, and a more preferable range of Mw is 3,000 or more and 20,000 or less.

A preferred example of the resin B is a copolymer obtained by copolymerizing a vinyl monomer a having a molecular structure with a polyester moiety capable of forming a crystal structure and another vinyl monomer b, and When the total amount of monomers used in the copolymer is 100.0 parts by mass, the ratio of the vinyl monomer a is 20.0 parts by mass or more and 50.0 parts by mass or less.
When the ratio of the vinyl monomer a is less than 20.0 parts by mass, it becomes difficult to control the value of tB in the formula (2) below the upper limit, and the toner using the resin B has low temperature fixability. Tend to.
On the other hand, when the proportion of the vinyl monomer a is more than 50.0 parts by mass, it becomes difficult to control the tB of the formula (2) to the lower limit or more, and the toner using the resin B causes a low temperature offset. It tends to be easier.
That is, as one means for designing the value of the tB to satisfy the formula (2), the ratio of the vinyl monomer a in the resin B is set in the above range.

  The vinyl monomer a ′ is not particularly limited as long as it can be a precursor for introducing a polyester moiety capable of taking the crystal structure. The vinyl monomer containing a hydroxyl group described above and a vinyl monomer containing a carboxyl group. A monomer or a vinyl monomer having an isocyanate group can be used. The polyester part which can take a crystal structure can be introduce | transduced by esterification reaction or urethanation reaction of these groups and the alcohol terminal or acid terminal of polyester.

As the vinyl monomer b, the following monomers can be used.
Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins; alkadienes such as butadiene, isoprene, 1,4- Pentadiene, 1,6-hexadiene and 1,7-octadiene.
Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene; terpenes such as pinene, limonene, indene.
Aromatic vinyl hydrocarbons: styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutions such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butyl Styrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene; and vinylnaphthalene.
Vinyl monomer having a carboxyl group and / or a salt thereof: unsaturated monocarboxylic acid having 3 to 30 carbon atoms, unsaturated dicarboxylic acid and anhydride thereof, such as maleic acid, maleic anhydride, fumaric acid, crotonic acid, Carboxyl group-containing vinyl monomers of itaconic acid, citraconic acid, and cinnamic acid.
Vinyl esters: for example vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, vinyl Methoxy acetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl acrylate and alkyl methacrylate having 1 to 30 carbon atoms (linear or branched) (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, 2- Tylhexyl acrylate, 2-ethylhexyl methacrylate, stearyl acrylate, behenyl acrylate), vinyl monomers having a polyalkylene glycol chain (polyethylene glycol (molecular weight 300) monoacrylate, polyethylene glycol (molecular weight 300) monomethacrylate, polypropylene glycol (molecular weight 500) mono Acrylate, polypropylene glycol (molecular weight 500) monomethacrylate), methyl alcohol ethylene oxide (ethylene oxide is abbreviated as EO) 10 mol adduct acrylate, methyl alcohol ethylene oxide (ethylene oxide is abbreviated as EO) 10 mol adduct Methacrylate, lauryl alcohol EO 30 mol adduct acrylate, lauryl al Cole EO 30 mole adduct methacrylate, polyacrylates and polymethacrylates (polyacrylates and polymethacrylates of polyhydric alcohols: ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, neopentyl glycol di Acrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate.
These vinyl monomers may be used alone or in combination of two or more.

In the present invention, the vinyl monomer b preferably contains two or more kinds of vinyl monomers. The vinyl monomer b is a homopolymer obtained by polymerizing alone, a vinyl monomer having a glass transition temperature of 105 ° C. or higher (hereinafter referred to as a vinyl monomer x) It is preferable to contain 1.0 to 9.0 parts by mass with respect to 100.0 parts by mass of all monomers used for coalescence.
When the content of the vinyl monomer x is more than 9.0 parts by mass with respect to 100 parts by mass of all the monomers used in the copolymer, the value of tB in the formula (2) is controlled to the upper limit or less. The toner using the resin B tends to be disadvantageous for low-temperature fixability.
On the other hand, when the content of the vinyl monomer x is less than 1.0 part by mass, it becomes difficult to control the tB of the formula (2) to the lower limit or more, and the toner using the resin B causes a low temperature offset. It tends to be easier.
That is, as one means for setting the value of tB to satisfy the formula (2), the content of the vinyl monomer x is set in the above range.
Examples of the vinyl monomer x include dimethylacrylamide (Tg = 114 ° C.), acrylamide (Tg = 191 ° C.), monomethylacrylamide (Tg = 171 ° C.), tert-butyl methacrylate (Tg = 107 ° C.), vinyl benzoic acid (Tg = 177 ° C), 2-methylstyrene (Tg = 127 ° C), acrylic acid (Tg = 111 ° C), methacrylic acid (Tg = 170 ° C), methyl methacrylate (Tg = 107 ° C), 4-hydroxystyrene (Tg) = 156 ° C.). In the present invention, methacrylic acid (Tg = 170 ° C.) can be preferably used.
In addition, as the glass transition temperature Tg in the said homopolymer, the average value (neat resin) of the result measured as a homopolymer single-piece | unit in the value of the high molecular database (polyinfo) in NIMS (National Institute for Materials Science). Of the median).

As the vinyl monomer b, in addition to the above monomers, vinyl monomers having an organic polysiloxane structure can also be used.
The organic polysiloxane is a material having a low interfacial tension. Therefore, a toner using a vinyl monomer having an organic polysiloxane structure as one element of vinyl monomer b is expected to have a release effect from the photoreceptor during fixing, and is more effective for suppressing low temperature offset. It is thought that.
In addition, the use of the vinyl monomer having the organic polysiloxane structure is also suitable for using the resin B as a dispersant material in the production of toner particles using carbon dioxide in a high-pressure state, which will be described later, as a dispersion medium. It is.
Here, the organic polysiloxane structure is a structure having a repeating unit of Si—O bond and two monovalent organic groups bonded to each Si atom.
Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and these organic groups may have a substituent. In addition, each organic group may be the same or different. Among these organic groups, an alkyl group and an aryl group are preferable because the characteristics of the organic polysiloxane described later are easily expressed, and an alkyl group having 1 to 3 carbon atoms is more preferable. Particularly preferred is a methyl group.
A preferred example of the vinyl monomer having the organic polysiloxane structure is shown in the following chemical formula (1).

Here, in the above chemical formula (1), R ₁ and R ₂ each independently represent an alkyl group, preferably each having 1 to 3 carbon atoms, and R ₁ having 1 carbon atom. Further preferred. R ₃ is preferably an alkylene group, and more preferably 1 to 3 carbon atoms. R ₄ represents hydrogen or a methyl group. N is the degree of polymerization, and the degree of polymerization n is preferably an integer of 2 or more and 18 or less.

In the present invention, the number average molecular weight (Mn) measured using gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF) of the resin B is preferably 8000 or more and 40000 or less, and the weight average The molecular weight (Mw) is preferably 20000 or more and 100,000 or less.
When the weight average molecular weight is larger than 100,000, it is difficult to control the value of tB in the formula (2) below the upper limit, and the toner using the resin B tends to be disadvantageous for low-temperature fixability.
On the other hand, if the weight average molecular weight is smaller than 20000, it becomes difficult to control the tB in the formula (2) to be lower than the lower limit, and the toner using the resin B tends to cause a low temperature offset.
That is, as one means for designing the tB value to satisfy the formula (2), the weight average molecular weight may be within the above range.
Furthermore, the more preferable range of the Mn is 8000 or more and 25000 or less, and the more preferable range of Mw is 40000 or more and 80000 or less.
In the present invention, it is preferable that the resin B is not dissolved in a dispersion medium when toner particles are produced by a method described later. Therefore, a crosslinked structure may be introduced into the resin B. In the present invention, the content of the resin B in the shell phase is not particularly limited, but is preferably 50.0% by mass or more, and it is particularly preferable not to use a resin other than the resin B as the shell phase.

In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. Further, it may be added when the toner particles are produced. By blending the charge control agent, the charge characteristics are stabilized, and it becomes easy to control the optimum triboelectric charge amount according to the development system.
As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable.
Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. The toner of the present invention can contain these charge control agents alone or in combination of two or more.
A preferable blending amount of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass with respect to 100.0 parts by mass of the binder resin A. It is below mass parts.

The toner particles used in the present invention contain a wax. The wax is not particularly limited, and examples thereof include the following.
Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat A wax mainly composed of a fatty acid ester such as an aromatic hydrocarbon ester wax; and a partially or completely deoxidized fatty acid ester such as a deoxidized carnauba wax; a partial ester of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.
In the present invention, as a form of the wax, in the case of the dissolution suspension method, the ease of preparation of the wax dispersion, the ease of incorporation into the prepared toner, the leachability from the toner during fixing, the release From the viewpoint of moldability, aliphatic hydrocarbon waxes and ester waxes can be preferably exemplified. The ester wax is preferably an ester wax having a functionality of 3 or more, more preferably an ester wax having a functionality of 4 or more, and further preferably an ester wax having a functionality of 6 or more.
The tri- or higher functional ester wax is obtained, for example, by condensation of a tri- or higher functional acid and a long-chain linear saturated alcohol, or synthesis of a tri- or higher-functional alcohol and a long-chain linear saturated fatty acid.
In the present invention, trifunctional or higher functional alcohols that can be used include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. Glycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitol. Moreover, as these condensates, diglycerin condensed with glycerin, triglycerin, tetraglycerin, hexaglycerin and decaglycerin, etc. Examples thereof include condensed dipentaerythritol and trispentaerythritol. Among these, a structure having a branched structure is preferable, pentaerythritol or dipentaerythritol is more preferable, and dipentaerythritol is particularly preferable.
Preferred examples of the long-chain straight-chain saturated fatty acid that can be used in the present invention include those represented by the general formula C _n H _{2n + 1} COOH, where n is 5 or more and 28 or less. For example, the following can be mentioned, but the invention is not limited to these. Depending on the case, it is also possible to use a mixture. Examples include caproic acid, caprylic acid, octylic acid, nonylic acid, decanoic acid, dodecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and behenic acid.
The wax is a myristic acid, palmitic acid, stearin from the viewpoint of optimizing the peak temperature of the maximum endothermic peak (hereinafter referred to as TpW) in the first temperature increase in the measurement with a differential scanning calorimeter (DSC). Acid and behenic acid are preferred.
Examples of the trifunctional or higher functional acid that can be used in the present invention include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. Trimellitic acid, butanetetracarboxylic acid.
The long-chain linear saturated alcohol that can be used in the present invention is represented by C _n H _{2n + 1} OH, and those in which n is 5 or more and 28 or less are preferably used. Examples include, but are not limited to: Depending on the case, it is also possible to use a mixture. Examples include capryl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol. In view of the TpW, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol are preferable.
In the present invention, the wax content in the toner is preferably 1.0% by mass or more and 20.0% by mass or less, and more preferably 2.0% by mass or more and 15.0% by mass. When the wax content is less than 1.0% by mass, the releasability of the toner tends to be lowered, and the transfer paper is likely to be wound when the fixing body is at a low temperature. When the wax content is more than 20.0% by mass, the wax tends to be exposed on the toner surface, and the heat resistant storage stability tends to be lowered.
The wax preferably has a TpW of 60.0 ° C. or more and the TA or less. When the value of TpW is less than 60 ° C., the wax tends to be exposed on the toner surface, and the heat resistant storage stability tends to be lowered. On the other hand, if the value of TpW is higher than the value of TA, it becomes difficult for the wax to melt properly at the time of fixing, and low-temperature offset property tends to occur or it tends to be disadvantageous for low-temperature fixability.

The toner of the present invention contains a colorant in order to impart coloring power. Examples of the colorant used in the present invention include the following organic pigments, organic dyes, and inorganic pigments. Further, a colorant conventionally used for toner can be used. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.
Examples of the colorant for yellow include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following. C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 213, 214. These can be used alone or in combination of two or more.
Examples of the colorant for magenta include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following. C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19. These can be used alone or in combination of two or more.
Examples of the colorant for cyan include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following. C. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66. These can be used alone or in combination of two or more.
Examples of black colorants include the following. Furnace black, channel black, acetylene black, thermal black, lamp black carbon black. Further, metal oxides such as magnetite and ferrite are also used.
In the present invention, when used as a colorant for a normal color toner, the content of the colorant is preferably 2.0% by mass or more and 15.0% by mass or less based on the toner. When the amount is less than 2.0% by mass, the coloring power tends to decrease. On the other hand, when it is more than 15.0% by mass, the color space tends to be small. More preferably, it is 2.5 mass% or more and 12.0 mass% or less. Further, a light color toner having a reduced density can be preferably used in combination with a normal color toner. In this case, the content of the colorant is preferably 0.5% by mass or more and 5.0% by mass or less with respect to the toner.

It is preferable to add inorganic fine powder as a fluidity improver to the toner particles used in the present invention. Examples of the inorganic fine powder include fine powder such as silica fine powder, titanium oxide fine powder, alumina fine powder, and double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.
Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside of the silica fine powder and less Na ₂ O and SO ₃ ²⁻ is preferable. The dry silica may be a composite fine powder of silica and another metal oxide produced by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process. Specific examples of the inorganic fine particles include the following.
Silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara , Antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride.
The inorganic fine powder is preferably externally added to the toner particles in order to improve the fluidity of the toner and make the charge uniform. In addition, the hydrophobic treatment of the inorganic fine powder makes it possible to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics in a high-humidity environment. More preferably, the body is used. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner is reduced, and the developability and transferability are easily lowered.
Treatment agents for hydrophobic treatment of inorganic fine powders include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, An organic titanium compound is mentioned. These treatment agents may be used alone or in combination.
Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, when the inorganic fine powder is hydrophobized with a coupling agent, or simultaneously with the treatment, the hydrophobized inorganic fine powder treated with silicone oil treated with silicone oil increases the charge amount of the toner even in a high humidity environment. It is good for maintaining and reducing selective developability.
The amount of the inorganic fine powder added is preferably 0.1 parts by mass or more and 4.0 parts by mass or less, more preferably 0.2 parts by mass or more and 3.5 parts by mass or less with respect to 100.0 parts by mass of the toner particles. It is below mass parts.

The toner of the present invention is a toner having toner particles having a core-shell structure in which a shell phase containing resin B is formed on the surface of a core containing binder resin A, colorant and wax.
The shell phase may be formed at the same time as the core formation step or after the core is formed. From the viewpoint of simplicity, it is preferable to simultaneously perform the core manufacturing process and the shell phase forming process.
The method for forming the shell phase is not limited at all. For example, when the shell phase is provided after the core is formed, the resin fine particles containing the core and the resin B are dispersed in an aqueous medium, and then the core surface. There is a method of agglomerating and adsorbing resin fine particles containing the resin B.
Here, the toner particles preferably contain the resin B in a range of 3.0 parts by weight to 15.0 parts by weight with respect to 100.0 parts by weight of the binder resin A.
When the content of the resin B is more than 15.0 parts by mass, the low-temperature fixability tends to be lowered. On the other hand, when the resin B is less than 3.0 parts by mass, the heat resistant storage stability tends to be lowered.
That is, it is preferable to set the content of the resin B in the above range from the viewpoint of achieving both low temperature fixability and heat resistant storage stability.
In the present invention, a dissolution suspension method in which toner particles having a core-shell structure can be prepared in one step is preferable. In the dissolution suspension method, a resin composition obtained by dissolving a binder resin A serving as a core, a colorant, and a wax in an organic medium in an aqueous medium in which resin fine particles containing the resin B serving as a shell phase are dispersed. To disperse. Then, the organic medium is removed to obtain toner particles.
The method for preparing the resin fine particles is not particularly limited, and it can be prepared by dissolving the emulsion polymerization method or the resin in a solvent or liquefying it and suspending it in an aqueous medium. it can. At this time, known surfactants and dispersants can be used, and the resin constituting the resin fine particles can be made self-emulsifying.
Solvents that can be used as an organic medium for dissolving the binder resin A include hydrocarbon solvents such as ethyl acetate, xylene and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane, methyl acetate and ethyl acetate. And ester solvents such as butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane.
As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve), and lower ketones (acetone, 1-butanone).
The method for dispersing the resin composition or the like in the dispersion medium is not particularly limited, and general-purpose devices such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be used. It is preferable to use a general-purpose emulsifier and disperser.
For example, Ultra Turrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Special Mechanized Industry Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Homomic Line Flow (Made by Special Machine Industries Co., Ltd.), colloid mill (made by Shinko Pantech Co., Ltd.), thrasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Cavitron (made by Eurotech), fine flow mill Examples thereof include a continuous emulsifier (manufactured by Taiheiyo Kiko Co., Ltd.), a clear mix (manufactured by M Technique Co., Ltd.), a batch type of Philmix (manufactured by Tokushu Kika Kogyo Co., Ltd.), or a continuous dual-use emulsifier.
When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 rpm to 30000 rpm, preferably 3000 rpm to 20000 rpm. In the case of a batch method, the dispersion time is usually from 0.1 minutes to 5.0 minutes. The temperature during dispersion is usually 10.0 ° C or higher and 55.0 ° C or lower, preferably 10.0 ° C or higher and 40.0 ° C or lower.

The toner particles of the present invention are more preferably produced in a non-aqueous medium. Therefore, in the production of the toner particles of the present invention, a dissolution suspension method using high-pressure carbon dioxide as a dispersion medium can be particularly preferably exemplified.
That is, in the present invention, the toner particles contain a resin composition in which the binder resin A, the colorant and the wax are dissolved or dispersed in a medium containing an organic solvent, and resin fine particles containing the resin B. The toner particles are preferably formed by dispersing in a dispersion medium mainly composed of carbon dioxide in a high-pressure state and removing the organic solvent from the obtained dispersion.
Here, the high-pressure carbon dioxide is carbon dioxide in a supercritical state or a liquid state. The carbon dioxide in the liquid state is a gas-liquid that passes through a triple point (temperature = −57 ° C., pressure = 0.5 MPa) and a critical point (temperature = 31 ° C., pressure = 7.4 MPa) on the phase diagram of carbon dioxide. This represents carbon dioxide under boundary temperature, critical temperature isotherm, and temperature and pressure conditions of the portion surrounded by the solid-liquid boundary line. Moreover, the carbon dioxide in the supercritical state represents carbon dioxide under temperature and pressure conditions above the critical point of carbon dioxide. Further, liquid or supercritical carbon dioxide may be used alone as a dispersion medium, and an organic solvent may be contained as another component. In this case, it is preferable that the high-pressure carbon dioxide and the organic solvent form a homogeneous phase.

Hereinafter, a method for producing toner particles using a dispersion medium containing carbon dioxide in a high pressure state, which is suitable for obtaining the toner particles, will be described as an example.
First, a colorant, wax, and other additives as necessary are added to an organic solvent capable of dissolving the binder resin A, and uniform by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser. Dissolve or disperse in Next, the thus-dissolved or dispersed liquid (hereinafter simply referred to as a resin composition) is dispersed in a dispersion medium containing carbon dioxide in a high pressure state to form oil droplets.
At this time, it is preferable to disperse a dispersing agent in a dispersion medium containing carbon dioxide in a high pressure state. Examples of the dispersant include resin fine particles containing resin B for forming a shell phase, but other components may be mixed as a dispersant. For example, any of an inorganic fine particle dispersant, an organic fine particle dispersant, and a mixture thereof may be used, and two or more kinds may be used in combination according to the purpose.
Examples of the inorganic fine particle dispersant include inorganic particles of alumina, zinc oxide, titania, and calcium oxide.
As the organic fine particle dispersant, in addition to resin B, for example, vinyl resin, urethane resin, epoxy resin, ester resin, polyamide, polyimide, silicone resin, fluorine resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, Examples include aniline resins, ionomer resins, polycarbonates, celluloses, and mixtures thereof. These may have a crosslinked structure.
Although the said dispersing agent may be used as it is, in order to improve the adsorptivity to the said oil droplet surface at the time of granulation, you may use what was surface-modified by various processes. Specifically, surface treatment with a silane-based, titanate-based, or aluminate-based coupling agent, surface treatment with various surfactants, and coating treatment with a polymer are exemplified. Since the organic fine particles as the dispersant adsorbed on the surface of the oil droplets remain as they are after the toner particles are formed, the resin B and other resins used as the dispersant form a shell phase of the toner particles.

In the present invention, the resin fine particles containing the resin B preferably have a volume average particle diameter of 30 nm or more and 300 nm or less. More preferably, it is 50 nm or more and 200 nm or less. When the particle size of the resin fine particles containing the resin B is too small, the stability of oil droplets during granulation tends to be lowered. When the particle size of the resin fine particles containing the resin B is too large, it is difficult to control the particle size of the oil droplets to a desired size.
In the present invention, any method may be used for dispersing the dispersant in a dispersion medium containing carbon dioxide in a high pressure state. Specific examples include a method in which a dispersion medium containing the dispersant and high-pressure carbon dioxide is charged into a container and directly dispersed by stirring or ultrasonic irradiation. Another example is a method in which a dispersion liquid in which the dispersant is dispersed in an organic solvent is introduced into a container charged with a dispersion medium containing carbon dioxide in a high-pressure state using a high-pressure pump.
In the present invention, any method may be used as a method of dispersing the resin composition in a dispersion medium containing carbon dioxide in a high pressure state. As a specific example, there is a method of introducing the resin composition into a container containing a dispersion medium containing high-pressure carbon dioxide in a state where the dispersant is dispersed, using a high-pressure pump. Moreover, you may introduce | transduce into the dispersion medium containing the carbon dioxide of the high voltage | pressure state of the state which disperse | distributed the said dispersing agent to the container prepared with the said resin composition.

In the present invention, the dispersion medium containing carbon dioxide in a high pressure state is preferably a single phase. When granulating by dispersing the resin composition in carbon dioxide in a high pressure state, a part of the organic solvent in the oil droplets moves into the dispersion. At this time, it is not preferable that the carbon dioxide phase and the organic solvent phase exist in a separated state, which causes the stability of the oil droplets to be impaired. Therefore, it is preferable to adjust the temperature and pressure of the dispersion medium and the amount of the resin composition with respect to the high-pressure carbon dioxide within a range in which the carbon dioxide and the organic solvent can form a homogeneous phase.
In addition, regarding the temperature and pressure of the dispersion medium, it is preferable to pay attention to granulation properties (ease of oil droplet formation) and solubility of the constituent components in the resin composition in the dispersion medium. For example, the binder resin A and wax in the resin composition may be dissolved in the dispersion medium depending on temperature conditions and pressure conditions. Usually, the lower the temperature and the lower the pressure, the more the solubility of the above components in the dispersion medium is suppressed, but the formed oil droplets are likely to agglomerate and coalesce, and the granulation property is lowered. On the other hand, although the granulation property is improved as the temperature and pressure are increased, the component tends to be easily dissolved in the dispersion medium. Therefore, in the production of the toner particles of the present invention, the temperature of the dispersion medium is preferably in the temperature range of 10 ° C. or more and 40 ° C. or less.
Moreover, the pressure in the container forming the dispersion medium is preferably 1.0 MPa or more and 20.0 MPa or less, and more preferably 2.0 MPa or more and 15.0 MPa or less. In addition, the pressure in this invention shows the total pressure, when components other than a carbon dioxide are contained in a dispersion medium.
After granulation is completed in this way, the organic solvent remaining in the oil droplets is removed through a dispersion medium of carbon dioxide in a high pressure state. Specifically, carbon dioxide in a higher pressure state is further mixed with the dispersion medium in which oil droplets are dispersed, and the remaining organic solvent is extracted into a carbon dioxide phase, and the carbon dioxide containing the organic solvent is further increased in pressure. By replacing with carbon dioxide in the state.
In the mixing of the dispersion medium and the high-pressure carbon dioxide, carbon dioxide having a higher pressure may be added to the dispersion medium, and the dispersion medium may be added to carbon dioxide having a lower pressure. Also good.
And as a method of substituting the carbon dioxide containing an organic solvent with the carbon dioxide of a high pressure state, the method of distribute | circulating a high pressure carbon dioxide is mentioned, keeping the pressure in a container constant. At this time, the toner particles formed are captured while being captured by a filter.
When the replacement with carbon dioxide in the high-pressure state was not sufficient and the organic solvent remained in the dispersion medium, it was dissolved in the dispersion medium when the container was decompressed to recover the obtained toner particles. In some cases, the organic solvent may condense and the toner particles may be redissolved or the toner particles may coalesce. Therefore, the substitution with carbon dioxide in the high pressure state is preferably performed until the organic solvent is completely removed. The amount of high-pressure carbon dioxide to be circulated is preferably 1.0 to 100.0 times, more preferably 1.0 to 50.0 times, most preferably the mass of the dispersion medium. Is 1.0 times or more and 30.0 times or less.
When removing the toner particles from the dispersion containing high-pressure carbon dioxide in which the toner particles are dispersed, the container may be decompressed to room temperature and normal pressure at once. The pressure may be reduced stepwise by providing. The decompression speed is preferably set within a range where the toner particles do not foam.
The organic solvent and carbon dioxide used in the present invention can be recycled.

  The toner of the present invention preferably has a number average molecular weight (Mn) of 5,000 or more and 40,000 or less, as measured using gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF). Mw) is preferably 15000 or more and 60000 or less. By being in this range, it is possible to maintain good heat-resistant storage stability and to impart an appropriate sharp melt property to the toner. A more preferable range of Mn is 10,000 or more and 25000 or less, and a more preferable range of Mw is 20000 or more and 50000 or less. Further, Mw / Mn is preferably 6 or less. A more preferable range of Mw / Mn is 4 or less.

Hereinafter, methods for measuring various physical properties of the toner and toner material of the present invention will be described.
<Measurement method of peak temperature (TpA, TpB, TpW) of maximum endothermic peak>
The peak temperature of the maximum endothermic peak in the present invention is measured under the following conditions using DSC Q1000 (manufactured by TA Instruments).
Temperature increase rate: 10.0 ° C / min
Measurement start temperature: 20.0 ° C
Measurement end temperature: 180.0 ° C
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 5.0 mg of a sample is precisely weighed, placed in a silver pan, and measured once. A silver empty pan is used as a reference. In the present invention, the peak temperature (TpA, TpB, TpW) of the maximum endothermic peak at the first temperature increase is read.
The “melting point” of the crystalline resin (for example, crystalline polyester) in the present invention is the peak temperature of the maximum endothermic peak at the first temperature rise of the crystalline substance in the above method.

<Method of measuring TA and tB using a constant load extrusion type capillary rheometer>
The TA and tB are measured using a constant-load extrusion type capillary rheometer “Flow Characteristic Evaluation Device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample filled in the cylinder by the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is extruded from the die at the bottom of the cylinder. A flow curve showing the relationship between the amount of piston lowering (displacement) and time can be obtained.
As a measurement sample, about 0.22 g of the material used for the binder resin A or the material used for the resin B in a 25.0 ° C. environment in a tablet molding compressor (for example, NT-100H, manufactured by NP System Co., Ltd.) Is compression molded at about 12.0 MPa for about 60.0 seconds, and the bottom area is 1.0 cm ² (
A cylindrical shape having a diameter of about 11.3 mm and a thickness of about 2.2 mm is used.
The measurement conditions of CFT-500D when measuring TA are as follows.
Test mode: Constant temperature method Measurement temperature: Measurement is started from 50.0 ° C., and measured up to 120.0 ° C. in increments of 5.0 ° C.
Piston bottom area (measured pressure surface area): 1.0 cm ²
Test load (piston load): 5.0 MPa
Preheating time: 0 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm
Measurement start: The measurement sample is put into the cylinder, and measurement (pressurization) is started 15.0 seconds after the piston is set.

When determining the TA value, first set the test load (pressure) to 5.0 MPa and a temperature of 50 ° C.
Then, the time from the start of pressurization until the displacement of the measurement sample reaches 2.0 mm is measured. The same operation is performed on other measurement samples except that the temperature is changed to each temperature divided by 5 ° C. from 50 ° C. to 120 ° C., and the displacement becomes 2.0 mm from the start of pressurization at each temperature. Measure the time to reach. About the obtained measurement results, the temperature is plotted on the horizontal axis and the time until the displacement reaches 2.0 mm is plotted on the vertical axis to create a temperature-time curve as shown in FIG. From the obtained temperature-time curve, the temperature when the time from the start of pressurization until the displacement reaches 2.0 mm is 10 seconds is read, and this temperature is defined as TA [° C.].
For tB, the measurement temperature is TA and the test load (pressure) is 5.0 MPa, and the time from the start of pressurization until the displacement reaches 2.0 mm is read from the obtained flow curve. Is tB [seconds].

<Method for Measuring Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with an aperture tube of 100.0 μm is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.
On the “Pulse to particle size conversion setting” screen of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bin, and the particle size range from 2.0 μm to 60.0 μm. .
The specific measurement method is as follows.
(1) About 200.0 ml of the electrolytic solution is put in a glass-made 250.0 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30.0 ml of the electrolytic aqueous solution is placed in a glass-made 100.0 ml flat bottom beaker. As a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10.0 mass% aqueous solution of a neutral detergent for cleaning a precision measuring instrument having a pH of 7.0 consisting of an organic builder, Jun Wako) About 0.3 ml of a diluted solution obtained by diluting about 3.0 times by mass with ion exchange water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. About 3.3 L of ion exchange water is placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. In the beaker, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution is maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10.0 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in a sample stand, the electrolytic aqueous solution of (5) in which toner is dispersed is dropped using a pipette so that the measured concentration becomes about 5.0% by mass. Adjust to. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Method of measuring number average molecular weight (Mn) and weight average molecular weight (Mw) using gel permeation chromatography (GPC)>
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin by gel permeation chromatography (GPC) were measured by GPC using THF as a solvent for the tetrahydrofuran (THF) soluble content of the resin. The measurement conditions are as follows.
(1) Preparation of measurement sample Resin (sample) and THF are mixed at a concentration of about 0.5 to 5.0 mg / mL (for example, about 5.0 mg / mL), and at room temperature for several hours (for example, 5 to 6). After standing), the mixture was sufficiently shaken and the THF and the sample were mixed well until the sample was no longer united. Furthermore, it left still at room temperature for 12 hours or more (for example, 24 hours). At this time, the time from the start of mixing the sample and THF to the end of standing was set to 24 hours or longer.
Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, Mysori Disc H-25-2 [manufactured by Tosoh Corp.], Excro Disc 25CR [manufactured by Gelman Science Japan Ltd.] can be preferably used) is passed. Was used as a GPC sample.
(2) Sample measurement The column was stabilized in a 40.0 ° C. heat chamber, and THF as a solvent was passed through the column at this temperature at a flow rate of 1.0 ml / min. Measurement was performed by injecting 50.0 to 200.0 μl of a THF sample solution of the resin adjusted to 5.0 mg / mL.
In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts.
As a standard polystyrene sample for creating a calibration curve, Pressure Chemical
Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6.0 × 10 ² , 2.1 × 10 ³ , 4.0 × 10 ³ , 1.7 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2.0 × 10 ⁶ , 4.5 × 10 ⁶ were used. The detector also has RI (
A refractive index detector was used.
In addition, as a column, in order to accurately measure a molecular weight region of 1.0 × 10 ^{3 to} 2.0 × 10 ⁶ , a plurality of commercially available polystyrene gel columns were used in combination as described below. The measurement conditions of GPC in the present invention are as follows.
[GPC measurement conditions]
Apparatus: LC-GPC 150C (manufactured by Waters)
Column: KF801, 802, 803, 804, 805, 806, 807 (manufactured by Shodex) Column connection temperature: 40.0 ° C
Mobile phase: THF (tetrahydrofuran)

<Measurement method of particle diameter of colorant particle, wax particle, resin fine particle for shell>
The particle diameter of resin fine particles is measured using a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.) with a range setting of 0.001 μm to 10.0 μm, and a volume average particle diameter (μm or nm). In addition, as a dilution solvent, the composition was matched with the solvent of each dispersion liquid.

<Calculation method of the ratio (mass%) of the polyester part which can take a crystal structure>
The ratio (mol%) of the polyester moiety capable of taking a crystal structure in the binder resin A is measured by ¹ H-NMR under the following conditions.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times Measurement temperature: 30.0 ° C
Sample: Prepare 50.0 mg of a sample in a sample tube having an inner diameter of 5.0 mm, add deuterated chloroform (CDCl ₃ ) as a solvent, and dissolve it in a 40.0 ° C. constant temperature bath. From the obtained ¹ H-NMR chart, a peak independent of the peaks attributed to the other constituent elements is selected from the peaks attributed to the constituent elements of the polyester moiety capable of taking a crystal structure. to calculate the integral value _{S 1.} Similarly, among the peaks attributed to the components of the non-crystalline region, select the independent peaks and peak attributable to other components an integrated value S ₂ is calculated for this peak. The proportion of the polyester portion capable of forming a crystal structure, by using the integrated value S ₁ and the integrated value S _2, obtained as follows. Note that n ₁ and n ₂ are the number of hydrogens in the constituent element to which the focused peak belongs.
Percentage of the polyester part capable of taking a crystal structure (mol%) =
_{{(S 1 / n 1)} / ((S 1 / n 1) + (S 2 / n 2))} × 100
The ratio (mol%) of the polyester moiety capable of taking the crystal structure thus obtained is converted to mass% by the molecular weight of each component.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this at all. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.

<Synthesis of crystalline polyester 1>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-Sebacic acid 124.0 parts by mass-1,6-hexanediol 76.0 parts by mass-Dibutyltin oxide 0.1 parts by mass The system was purged with nitrogen by depressurization, and then stirred at 180 ° C for 6 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing the stirring, and the temperature was further maintained for 2 hours. Crystalline polyester 1 was synthesize | combined by air-cooling when it became a viscous state and stopping reaction. Table 1 shows the physical properties of the crystalline polyester 1.

<Synthesis of crystalline polyesters 2 to 10>
In the synthesis of the crystalline polyester 1, the crystalline polyesters 2 to 10 were synthesized in the same manner except that the acid component, the alcohol component, and the input amount thereof were changed as shown in Table 1. Table 1 shows the physical properties of the crystalline polyesters 2 to 10.

<Synthesis of crystalline polyesters 11 to 15>
In the synthesis of crystalline polyester 1, an acid component, an alcohol component, and the amount of the input component changed as shown in Table 1 were charged, the system was purged with nitrogen by depressurization, and then stirred at 250 ° C. for 1 hour. It was. The crystalline polyesters 11 to 15 were synthesized by air-cooling at a viscous state and stopping the reaction. The physical properties of the obtained crystalline polyesters 11 to 15 are shown in Table 1.

<Synthesis of Amorphous Polyester 1>
In a reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube,
-39.0 parts by mass of dimethyl terephthalate-15.0 parts by mass of isophthalic acid-35.0 parts by mass of dodecenyl succinic anhydride-6.0 parts by mass of trimellitic anhydride-10.0 parts by mass of bisphenol A ethylene oxide adduct -Bisphenol A propylene oxide adduct was charged at a ratio of 95.0 parts by mass, and the inside of the reaction vessel was replaced with dry nitrogen gas. Thereafter, 0.15 parts by mass of dibutyltin oxide was added as a catalyst, and the mixture was stirred and reacted at about 190 ° C. for about 7 hours under a nitrogen gas stream. Furthermore, the temperature was raised to about 250 ° C., the reaction was stirred for 5.0 hours, the inside of the reaction vessel was depressurized to 10.0 mmHg, and the reaction was stirred for about 0.5 hours under reduced pressure to obtain amorphous polyester 1. . The number average molecular weight Mn of the amorphous polyester 1 was 3,500, the weight average molecular weight Mw was 6,500, and the glass transition temperature Tg was 55 ° C.

<Synthesis of Amorphous Polyurethane 1>
-Xylylene diisocyanate (XDI) 64.0 parts by mass-Cyclohexanedimethanol (CHDM) 36.0 parts by mass-Tetrahydrofuran (THF) 100.0 parts by mass In a reaction vessel equipped with a stirrer and a thermometer, nitrogen substitution was performed. While charging the above. The mixture was heated to 50 ° C. and subjected to urethanization reaction for 10 hours. Thereafter, 3.0 parts by mass of tertiary butyl alcohol was added to modify the terminal isocyanate group with alcohol. After cooling, the solvent was distilled off with an evaporator to obtain amorphous polyurethane 1. The number average molecular weight Mn of the amorphous polyurethane 1 was 3,500, the weight average molecular weight Mw was 6,500, and the glass transition temperature Tg was 140 ° C.

<Synthesis of block polymer 1>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
· Xylylene diisocyanate (XDI) 48.0 parts by mass · Cyclohexanedimethanol (CHDM) 27.0 parts by mass · Tetrahydrofuran (THF) 80.0 parts by mass Heating to 50.0 ° C and urethanization over 10.0 hours Reaction was performed. Thereafter, a solution prepared by dissolving 1,25.0 parts by mass of crystalline polyester in 220.0 parts by mass of THF was gradually added, and further stirred at 50.0 ° C. for 5 hours. Then, it cooled to room temperature and the block polymer 1 was synthesize | combined by distilling THF which is a solvent off.

<Synthesis of block polymers 2 to 11>
In the synthesis of block polymer 1, block polymers 2 to 11 were obtained by changing the materials and blending amounts shown in Table 2. Table 2 shows the physical properties of the obtained block polymers 1 to 11.

<Preparation of Binder Resin A Solution 1>
Block polymer 1 100.0 parts by mass Acetone 100.0 parts by mass The above materials are put into a beaker and heated to a temperature of 40.0 ° C., and stirred at 3000 rpm for 10 minutes using a disper (manufactured by Tokushu Kika Co., Ltd.). Binder resin A solution 1 was obtained.

<Preparation of Binder Resin A Solutions 2 to 12>
In the preparation of the binder resin A solution 1, binder resin A solutions 2 to 12 were obtained by changing the materials and blending amounts shown in Table 3 instead of the block polymer 1.

<Preparation of Binder Resin A Solution 13>
-Amorphous polyester 1 100.0 parts by mass-Methyl ethyl ketone 50.0 parts by mass-Ethyl acetate 50.0 parts by mass The above materials are placed in a beaker and heated to 40.0 ° C. The binder resin A solution 13 was obtained by stirring at 3000 rpm for 10 minutes.

<Preparation of Binder Resin A Dispersion 1>
40.0 parts by mass of the crystalline polyester 9 was added to 160.0 parts by mass of ion-exchanged water, and the mixture was stirred with a homogenizer while heating at 85 ° C. to obtain a binder resin A dispersion 1.

  For the block polymer, crystalline polyester, and amorphous polyester as the binder resin A used in the binder resin A solutions 1 to 13 and the binder resin A dispersion 1, the peak temperature TpA of the maximum endothermic peak determined by DSC and Table 5 shows TA values obtained by a constant load extrusion type capillary rheometer. For the binder resin A solution 8, a part of the prepared solution was dried under reduced pressure at 40 ° C. for 5 hours by a rotary evaporator, and then the taken out resin was measured.

<Synthesis of vinyl monomer a1>
Crystalline polyester 11 100.0 parts by mass Tetrahydrofuran 100.0 parts by mass In a reaction vessel equipped with a stirrer and a thermometer, the above materials were charged and dissolved at 40 ° C while purging with nitrogen. 6.2 parts by mass of 2-isocyanatoethyl methacrylate (Karenz MOI manufactured by Showa Denko KK) was dropped and reacted at 40 ° C. for 2 hours to obtain a vinyl monomer a1 solution. Subsequently, tetrahydrofuran was removed under reduced pressure at 40 ° C. for 5 hours by a rotary evaporator to obtain a vinyl monomer a1.

<Synthesis of vinyl monomers a2 to a5>
In the synthesis of the vinyl monomer a1, the crystalline monomers 12 to 15 were used in place of the crystalline polyester 11 to obtain vinyl monomers a2 to a5.

<Synthesis of Shell Resin B Dispersion 1>
In a beaker, a vinyl monomer a1 as a vinyl monomer a, a vinyl-modified silicone monomer as a vinyl monomer b, styrene, methacrylic acid, and other materials are charged in the following blending ratio, and stirred and mixed at 20 ° C. A monomer solution was prepared.
-40.0 parts by mass of vinyl-based monomer a1-15.0 parts by mass of vinyl-modified silicone monomer (X-22-2475: manufactured by Shin-Etsu Chemical Co., Ltd.)
-Styrene (St) 38.5 parts by mass-Methacrylic acid (MAA) 6.5 parts by mass-Azobismethoxydimethylvaleronitrile 0.3 parts by mass-Normal hexane 80.0 parts by mass Next, the monomer solution is heated in advance. It was introduced into a dropping funnel that had been dried. Separately from this, 300.0 parts by mass of normal hexane was charged into a heat-dried two-necked flask. After the atmosphere was replaced with nitrogen, a dropping funnel was attached, and the monomer solution was added dropwise at 40 ° C. for 1 hour in a sealed state. Stirring was continued for 3 hours from the end of dropping, and a mixture of 0.3 parts by mass of azobismethoxydimethylvaleronitrile and 20.0 parts by mass of normal hexane was added again, followed by stirring at 40 ° C. for 3 hours. Then, the resin B dispersion 1 for shells with a solid content of 20.0 mass% was obtained by cooling to room temperature.
X-22-2475, which is a vinyl monomer having an organic polysiloxane structure, has the following formula (1): R ₁ is a methyl group, R ₂ is a methyl group, R ₃ is a propylene group, and R ₄ is a methyl group. , A vinyl monomer having a structure in which n is 3.

<Synthesis of Resin B Dispersions 2 to 25 for Shell>
In the synthesis of the shell resin B dispersion 1, the compositions and addition amounts of the vinyl monomer a and the vinyl monomer b were changed to those shown in Table 4 to obtain shell resin B dispersions 2 to 25.

<Synthesis of Shell Resin B Dispersion 26>
In the synthesis of the shell resin B dispersion 1, the composition and addition amount of the vinyl monomer a and the vinyl monomer b were changed to those shown in Table 4, and the monomer solution was added dropwise and stirred for 3 hours. A mixture of 1.0 part by mass of methoxydimethylvaleronitrile and 20.0 parts by mass of normal hexane was dropped again, and the mixture was stirred at 80 ° C. for 3 hours to obtain a resin B dispersion 26 for shell.

<Synthesis of Shell Resin B Dispersion 27>
In the synthesis of the shell resin B dispersion 1, the composition and addition amount of the vinyl monomer a and the vinyl monomer b were changed to those shown in Table 4, and the monomer solution was added dropwise and stirred for 3 hours. A mixture of 3.0 parts by mass of methoxydimethylvaleronitrile and 20.0 parts by mass of normal hexane was dropped again, and the mixture was stirred at 80 ° C. for 3 hours to obtain a resin B dispersion 27 for shells.

<Synthesis of Shell Resin B Dispersion 28>
In the synthesis of the shell resin B dispersion 1, the composition and addition amount of the vinyl monomer a and the vinyl monomer b were changed to those shown in Table 4, and the monomer solution was added dropwise and stirred for 3 hours. A mixture of 0.1 part by mass of methoxydimethylvaleronitrile and 20.0 parts by mass of normal hexane was dropped again, and the mixture was stirred at 40 ° C. for 3 hours to obtain a resin B dispersion for shell 28.

<Synthesis of Shell Resin B Dispersion 29>
In the synthesis of the shell resin B dispersion 1, the composition and addition amount of the vinyl monomer a and the vinyl monomer b were changed to those shown in Table 4, and the monomer solution was added dropwise and stirred for 3 hours. Methoxydimethylvaleronitrile 0.08 parts by mass and normal hexane 20
. The resin B dispersion 29 for shells was obtained by performing the change which dripped a 0 mass part mixture again and stirred at 40 degreeC for 3 hours.

Table 4 shows the volume average particle diameters of the resin fine particles in the obtained shell resin B dispersions 1 to 29.
Subsequently, a part of the shell resin B dispersions 1 to 29 were dried under reduced pressure at 40 ° C. for 5 hours by a rotary evaporator to obtain shell resins B1 to B29. For the shell resins B1 to B29, the number average molecular weight Mn and the weight average molecular weight Mw were measured. The results are shown in Table 4. Table 5 shows the peak temperature TpB of the maximum endothermic peak obtained by DSC and the value of tB obtained by a constant load extrusion type capillary rheometer.

<Synthesis of Shell Resin B Dispersion 30>
-Styrene 74.0 mass parts-n-butyl acrylate 6.0 mass parts-Acrylic acid 1.0 mass part-Dodecanethiol 4.8 mass parts-Carbon tetrabromide 1.0 mass part The above is mixed and dissolved. It was. This was ionized with 1.2 parts by weight of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and 2.0 parts by weight of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC). What was melt | dissolved in 100.0 mass parts of exchange water was disperse | distributed in the flask. This solution was emulsified and slowly mixed for 10 minutes, and then 10.0 parts by mass of ion-exchanged water in which 1.0 part by mass of ammonium persulfate was dissolved was added to perform nitrogen substitution. Thereafter, the contents in the flask were heated with an oil bath until the contents reached 70 ° C. while stirring, and the emulsion polymerization was continued for 5 hours. Then, ion-exchange water was added and it adjusted so that solid content might be 20.0 mass%. Thus, a resin B dispersion 30 for shell was obtained. The volume average particle diameter of the resin fine particles in the shell resin B dispersion 30 was 150 nm.
Subsequently, a part of the shell resin B dispersion 30 was filtered to obtain a solid content, thereby obtaining a shell resin B30. The resin B30 for shell had a glass transition temperature Tg of 59.0 ° C., a number average molecular weight Mn of 4000, and a weight average molecular weight Mw of 15000.
Further, when the value of tB of the shell resin B dispersion 30 was measured by a constant load extrusion type capillary rheometer, no outflow was observed.

<Preparation of wax dispersion 1>
Dipentaerythritol palmitate wax 20.0 parts by mass (TpW value is 70 ° C.)
-Wax dispersant 8.0 parts by weight (in the presence of 15.0 parts by weight of polyethylene, 50.0 parts by weight of styrene, 25.0 parts by weight of n-butyl acrylate, 10.0 parts by weight of acrylonitrile were copolymerized, Copolymer with a peak molecular weight of 8,500)
Acetone 72.0 parts by mass The above was put into a glass beaker (made by IWAKI glass) with a stirring blade, and the system was heated to 50 ° C. to dissolve the wax in acetone. Then, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.
This solution is put into a heat-resistant container together with 20.0 parts by mass of 1.0 mm glass beads, dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki), glass beads are removed with a nylon mesh, and the solid content is A 20.0 mass% wax dispersion 1 was obtained.
The wax particle size in the wax dispersion 1 was 200 nm in terms of volume average particle size.

<Preparation of wax dispersion 2>
In the preparation of the wax dispersion 1, a wax was prepared in the same manner as the wax dispersion 1 except that the dipentaerythritol palmitate wax was changed to a dipentaerythritol stearate wax (TpW value was 78 ° C.). Dispersion 2 was obtained.

<Preparation example of wax dispersion 3>
In the preparation of the wax dispersion 1, the wax was prepared in the same manner as the wax dispersion 1 except that the dipentaerythritol palmitate wax was changed to a dipentaerythritol myristic ester wax (TpW value was 62 ° C.). Dispersion 3 was obtained.

<Preparation of wax dispersion 4>
Dipentaerythritol palmitate wax 20.0 parts by mass (TpW value is 70 ° C.)
Cationic surfactant 10.0 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion-exchanged water 70.0 parts by mass The above was mixed, heated to 95 ° C, and sufficiently dispersed by IKA Ultra Turrax T50. Then, it was dispersed with a pressure discharge type gorin homogenizer to obtain a wax dispersion 4 having a wax content of 20.0% by mass. The wax particle size in the wax dispersion 4 was 200 nm in terms of volume average particle size.

<Preparation of Colorant Dispersion 1>
・ C. I. Pigment Blue 15: 3 100.0 parts by mass, acetone 150.0 parts by mass, glass beads (1.0 mm) 200.0 parts by mass The above materials are put into a heat-resistant glass container and dispersed for 5 hours with a paint shaker. The glass beads were removed with a nylon mesh to obtain a colorant dispersion 1 having a solid content of 40.0% by mass. The volume average particle diameter of the colorant particles was 100 nm.

<Preparation of Colorant Dispersion 2>
・ C. I. Pigment Blue 15: 3 50.0 parts by mass / Anionic surfactant 7.5 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK; 20.0% by mass)
-Ion-exchanged water 450.0 parts by mass The above was mixed and dissolved. Thereafter, a colorant dispersion 2 was prepared by dispersing the colorant by dispersing for about 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). The volume average particle diameter of the colorant particles was 130 nm, and the solid content was 25.0% by mass.

<Manufacture of toner particles 1>
In the apparatus shown in FIG. 1, first, the valves V1 and V2 and the pressure regulating valve V3 are closed, and the resin B for shell is dispersed in a pressure resistant granulation tank T1 having a filter and a stirring mechanism for capturing toner particles. Liquid 1 35.0 mass parts was prepared, and internal temperature was adjusted to 25 degreeC. Next, the valve V1 was opened, carbon dioxide (purity 99.99%) was introduced into the pressure vessel T1 from the carbon dioxide cylinder B1 using the pump P1, and the valve V1 was closed when the internal pressure reached 3.0 MPa. .
On the other hand, in the resin solution tank T2,
-Binder resin solution 1 180.0 parts by mass-Wax dispersion 1 25.0 parts by mass-Colorant dispersion 1 12.5 parts by mass-Acetone 15.0 parts by mass, adjusting the internal temperature to 25 ° C did.
Next, the valve V2 is opened and the contents of the resin solution tank T2 are introduced into the granulation tank T1 using the pump P2 while stirring the inside of the granulation tank T1 at 1000 rpm. Valve V2 was closed. After the introduction, the internal pressure of the granulation tank T1 was 5.0 MPa. It was 250.0 mass parts when the sum total of the introduced carbon dioxide was read by the value of the mass flow meter.
After the introduction of the contents of the resin solution tank T2 to the granulation tank T1, granulation was performed by further stirring for 10 minutes at 2000 rpm.
Next, the valve V1 was opened, and carbon dioxide was introduced into the granulation tank T1 from the cylinder B1 using the pump P1. At this time, the pressure regulating valve V3 was set to 10.0 MPa, and carbon dioxide was further circulated while maintaining the internal pressure of the granulation tank T1 at 10.0 MPa. By this operation, carbon dioxide containing the organic solvent (mainly acetone) extracted from the granulated droplets was discharged to the solvent recovery tank T3, and the organic solvent and carbon dioxide were separated.
The introduction of carbon dioxide into the granulation tank T1 was stopped when it reached 15.0 times the amount of carbon dioxide initially introduced into the granulation tank T1. At this point, the operation of replacing carbon dioxide containing an organic solvent with carbon dioxide containing no organic solvent was completed.
Further, the pressure regulating valve V3 was opened little by little, and the internal pressure of the granulation tank T1 was reduced to atmospheric pressure, whereby the toner particles 1 captured by the filter were collected. It was confirmed that the toner particles 1 have a core-shell structure.

<Manufacture of toner particles 2 to 33>
In the production of toner particles 1, toner particles 2 to 33 were obtained in the same manner except that the types of binder resin A solution, shell resin B dispersion and wax dispersion used were changed as shown in Table 5. . In addition, it was confirmed that the toner particles 2 to 33 have a core-shell structure.

<Production Example of Toner Particles 34>
Binder resin A dispersion 1 160.0 parts by weight Colorant dispersion 2 5.5 parts by weight Wax dispersion 4 10.0 parts by weight 10 mass% polyaluminum chloride aqueous solution 0.8 parts by weight Ion exchange 20.0 parts by weight of water The above was placed in a round stainless steel flask and adjusted to pH 4.0. This was dispersed using a homogenizer, heated in an oil bath for heating to 55 ° C. with stirring, and kept at this temperature for 60 minutes. When this was observed with an optical microscope, it was confirmed that aggregated particles having a volume average particle diameter of 6.5 μm were formed.
Therefore, 26.0 parts by mass of the resin B dispersion 30 for shells was added to the dispersion with stirring. Therefore, an aqueous solution obtained by diluting sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.5% by mass was gently added to adjust the pH to 5.0. While continuing stirring, the temperature was raised to 65 ° C. and held for 30 minutes, and then observed with an optical microscope, and it was confirmed that the volume average particle diameter had grown to 6.9 μm. When the temperature was further raised to 80 ° C. and held for 60 minutes, observation with an optical microscope revealed coated spherical toner particles. The temperature was lowered to 20 ° C. at a rate of 100 ° C./min while adding ion-exchanged water. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and then dried using a vacuum dryer, whereby toner particles 34 were obtained.

<Manufacture of toner particles 35 to 44>
In the production of toner particles 1, toner particles 35 to 44 were obtained in the same manner except that the types of binder resin A solution, shell resin B dispersion and wax dispersion used were changed as shown in Table 5. . In addition, it was confirmed that the toner particles 35 to 44 have a core-shell structure.

<Manufacture of carrier particles>
4.0% by mass of a silane coupling agent (3- (2-aminoethylaminopropyl) trimethyl) with respect to a magnetite powder having a number average particle diameter of 0.25 μm and a hematite powder having a number average particle diameter of 0.60 μm. Methoxysilane) was added, and the mixture was stirred and mixed at a high speed at 100 ° C. or higher to make each fine particle lipophilic.
・ Phenol 10.0 parts by mass ・ Formaldehyde solution (formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass)
6.0 parts by mass / lipophilic magnetite 63.0 parts by mass / lipophilic hematite 21.0 parts by mass The above materials, 28.0% by mass of ammonia water 5.0 parts by mass, water 10.0 A mass part was put into a flask, heated and maintained at 85 ° C. for 30 minutes while stirring and mixing, and cured by polymerization reaction for 3 hours. Then, after cooling to 30 degreeC and adding water, the supernatant liquid was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (5 mmHg or less) at 60 ° C. to obtain spherical magnetic resin particles in which a magnetic material was dispersed.
Next, as a coating resin, a copolymer of methyl methacrylate having methyl methacrylate and a perfluoroalkyl group (CF _3- (CF ₂ ) _m −: m = 7) (copolymerization ratio [mass basis] 8: 1 weight average) Molecular weight 45,000) was used. 10.0 parts by mass of melamine particles having a particle size of 290.0 nm, 6.0% of carbon particles having a specific resistance of 1.0 × 10 ⁻² Ω · cm and 30.0 nm in particle size are added to 100.0 parts by mass of the coating resin. Mass parts were added and dispersed for 30 minutes with an ultrasonic disperser. Further, a mixed solvent coating solution of methyl ethyl ketone and toluene was prepared so that the coating resin content was 2.5 parts by mass with respect to the magnetic resin particles (solution concentration 10.0% by mass).
The coating solution was applied to the surface of the magnetic resin particles by volatilizing the solvent at 70 ° C. while continuously applying shear stress. The resin-coated magnetic carrier particles were heat-treated with stirring at 100 ° C. for 2 hours, cooled and pulverized, and then classified by a 200-mesh sieve to obtain a number average particle diameter of 33.0 μm and a true specific gravity of 3.53 g / cm. ³ , a carrier having an apparent specific gravity of 1.84 g / cm ³ and a magnetization strength of 42.0 Am ² / Kg was obtained.

<Example 1>
(Preparation of toner 1 and two-component developer 1)
Next, anatase-type titanium oxide fine powder (BET specific surface area 80.0 m ² / g, number average particle size: 15.0 nm, isobutyltrimethoxysilane 12.0% by mass with respect to 100.0 parts by mass of toner particles 1 Treatment) First, 0.9 part by mass is externally added by a Henschel mixer, and further, oil-treated silica fine particles (BET specific surface area 95.0 m ² / g, silicone oil 15.0% by mass treatment) 1.2 parts by mass, sol-gel silica fine particles (BET specific surface area 24.0 m ² / g, number average particle size: 110.0 nm) 1.5 parts by mass are mixed with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) FM-10B to obtain toner 1. It was.
In the present invention, a two-component developer 1 prepared by mixing 8.0 parts by mass of the toner 1 and 92.0 parts by mass of the carrier was prepared. Various evaluations to be described later were performed using the toner 1 or the two-component developer 1. The various evaluation results are shown in Table 6.

<Examples 2 to 31>
(Preparation of toners 2 to 31 and two-component developers 2 to 31)
Toner particles 2 to 31 were externally added in the same manner as in Example 1 to obtain toners 2 to 31. Further, two-component developers 2 to 31 were prepared by mixing with the carrier as in Example 1. Various evaluations described later were performed using the toners 2 to 31 or the two-component developers 2 to 31. The various evaluation results are shown in Table 6.

<Comparative Examples 1 to 13>
(Preparation of toners 32 to 44 and two-component developers 32 to 44)
The toner particles 32 to 44 were externally added in the same manner as in Example 1 to obtain toners 32 to 44. Further, in the same manner as in Example 1, two-component developers 32 to 44 were prepared by mixing with the above. Various evaluations described below were performed using the toners 32 to 44 or the two-component developers 32 to 44. The various evaluation results are shown in Table 6.

<Image evaluation>
A method for evaluating the obtained toner or two-component developer will be described. For image evaluation, a commercially available color copying machine (trade name: CLC5000) manufactured by Canon Inc. was used.
<Evaluation of low-temperature fixability>
For the evaluation, the above two-component developer and color laser copying machine CLC5000 (manufactured by Canon Inc.) were used. The development contrast of the copying machine was adjusted so that the amount of toner applied on the paper was 0.6 / cm ² , and in the single color mode, the end margin was 5.0 mm, the width was 100.0 mm, and the length was 28.0 mm. The unfixed image was prepared in a room temperature and normal humidity environment (23.0 ° C./60.0% RH). As the paper, A4 paper ("Prober bond paper": 105.0 g / m ² , manufactured by Fox River) was used.
Next, the fixing device of LBP5900 (manufactured by Canon Inc.) was modified so that the fixing temperature can be manually set, and the rotation speed of the fixing device was changed to 300.0 mm / s. Further, the pressure at the time of fixing was set to 0.75 kgf / cm ² . Using the modified fixing device, the above fixing temperature is increased by 5.0 ° C. in a range of 80.0 ° C. to 180 ° C. in a normal temperature and normal humidity environment (23.0 ° C./60.0% RH). A fixed image was obtained at each temperature of the solid unfixed image.
The image area of the obtained fixed image is covered with a soft thin paper (trade name “Dasper”, manufactured by Ozu Sangyo Co., Ltd.), and the image area is rubbed three times while applying a load of 1.0 KPa on the thin paper. did. The image density before and after rubbing was measured, respectively, and the reduction rate ΔD (%) of the image density was calculated by the following formula. The temperature at which ΔD (%) was less than 10.0% was defined as the fixing start temperature, and the low temperature fixability was evaluated according to the following evaluation criteria.
The image density was measured with a color reflection densitometer (Color reflection densitometer X-Rite 404A: manufacturer X-Rite).
(Expression): ΔD (%) = {(Image density before rubbing−Image density after rubbing) / Image density before rubbing} × 100
In the present invention, A rank to D rank were judged as good low temperature fixability.
(Evaluation criteria)
A: Fixing start temperature is less than 100 ° C. B: Fixing start temperature is between 100 ° C. and less than 105 ° C. C: Fixing start temperature is between 105 ° C. and less than 110 ° C. D: Fixing start temperature is between 110 ° C. and less than 120 ° C. E: Fixing start temperature Is over 120 ℃

<Evaluation of low temperature offset property>
The fixed image obtained in the evaluation of the fixing start temperature was evaluated for low temperature offset. In the evaluation, the density change was confirmed at a portion where the portion of the solid image after one rotation of the fixing belt was a white background. The measurement was performed using DENSOMETER TC-6DS manufactured by Tokyo Denshoku Technical Center, and the reflectance (%) was measured to obtain a concentration value. The place where the density changed by 0.5% was defined as the low temperature offset generation point, and the minimum temperature at which the density did not occur was defined as the fixing temperature.
(Evaluation criteria)
A: Generated at less than 100 ° C. B: Generated at 100 ° C. or higher and lower than 105 ° C. C: Generated at 105 ° C. or higher and lower than 110 ° C. D: Generated at 110 ° C. or higher and lower than 120 ° C. E: Generated at 120 ° C. or higher. From A rank to D rank, it was judged as having good low temperature offset resistance.

<Evaluation of heat-resistant storage stability>
About 10.0 g of toner was put in a 100.0 ml polycup and allowed to stand at 53 ° C. for 3 days, and then each left sample was visually evaluated. In the present invention, it was judged that A rank to D rank had good heat-resistant storage stability.
(Evaluation criteria)
A: Agglomerates are not seen.
B: Agglomerates are seen but easily collapse.
C: It will not collapse unless shaken lightly.
D: If it is not shaken strongly, it will not collapse.
E: Immobilization.

T1: Granulation tank, T2: Resin solution tank, T3: Solvent recovery tank, B1: Carbon dioxide cylinder, P1, P2: Pump, V1, V2: Valve, V3: Pressure adjustment valve

Claims (13)

A toner having core-shell structure toner particles in which a shell phase containing a resin B is formed on the surface of a core containing a binder resin A, a colorant and a wax,
The binding resin A and the resin B were measured by a constant load extrusion type capillary rheometer having an area of a pressure surface with respect to a sample of a piston for pressurizing the sample of 1.0 cm ² and a diameter of a die hole into which the sample was extruded of 1.0 mm. In measuring flow characteristics,
When the binder resin A is pressurized with a piston at a pressure of 5.0 MPa, the temperature when the time until the displacement of the piston becomes 2.0 mm is 10 seconds after the start of pressurization is TA (° C.), When the resin B heated to TA (° C.) is pressurized with a piston at a pressure of 5.0 MPa, the time from the start of pressurization until the displacement of the piston becomes 2.0 mm is tB (seconds).
The toner, wherein the TA (° C.) and tB (second) satisfy the following expressions (1) and (2).
Formula (1) 65.0 <= TA <= 90.0
Formula (2) 20.0 ≦ tB ≦ 200.0   The binder resin A is characterized in that the peak temperature TpA of the maximum endothermic peak at the first temperature rise is 50.0 ° C. or higher and 75.0 ° C. or lower as measured by a differential scanning calorimeter (DSC). Item 2. The toner according to Item 1.   The toner according to claim 2, wherein the binder resin A contains a resin having a polyester portion capable of taking a crystal structure.   The toner according to claim 3, wherein the binder resin A contains 50.0% by mass or more and 90.0% by mass or less of a polyester portion capable of taking the crystal structure.   The said binder resin A contains the block polymer obtained by chemically combining the polyester site | part which can take the said crystal structure, and the site | part which cannot take a crystal structure, The Claim 3 or 4 characterized by the above-mentioned. Toner.   2. The resin B has a peak temperature TpB of a maximum endothermic peak at a first temperature increase of 55.0 ° C. or more and 80.0 ° C. or less as measured by a differential scanning calorimeter (DSC). The toner according to any one of Items 5 to 5.   The toner according to claim 1, wherein the resin B contains a resin having a polyester portion capable of taking a crystal structure.   The resin B is a copolymer obtained by copolymerizing a vinyl monomer a having a molecular structure with a polyester moiety capable of taking the crystal structure and another vinyl monomer b, and the copolymer The toner according to claim 7, wherein a ratio of the vinyl monomer a is 20.0 parts by mass or more and 50.0 parts by mass or less when the total amount of monomers used in the toner is 100 parts by mass.   The vinyl monomer b contains a vinyl monomer x, and the vinyl monomer x is a vinyl monomer having a glass transition temperature of 105 ° C. or more as a homopolymer, and the copolymer of the resin B The toner according to claim 8, wherein the ratio of the vinyl monomer x is 1.0 part by mass or more and 9.0 parts by mass or less with respect to 100 parts by mass of the total monomers used. The weight average molecular weight measured using gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble matter of the resin B is 20,000 or more and 100,000 or less, according to any one of claims 1 to 9. The toner according to one item. 11. The toner according to claim 6, wherein the value of TpA and the value of TpB satisfy a relationship of the following formula (3).
Formula (3) TpA ≧ TpB   12. The toner particle according to claim 1, wherein the toner particles contain 3.0 parts by mass or more and 15.0 parts by mass or less of the resin B with respect to 100.0 parts by mass of the binder resin A. The toner according to item.   13. The wax according to claim 1, wherein a peak temperature of a maximum endothermic peak at the first temperature rise is 60.0 ° C. or more and the TA or less as measured by a differential scanning calorimeter (DSC). The toner according to any one of the above.

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