JP2015055708A - Toner, developer, toner cartridge, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that suppresses occurrence of aggregation of toner in a developing unit while maintaining sharp meltability enabling achievement of both low-temperature fixability and heat-resistant storage property at high level, so as to solve transfer omission.SOLUTION: When a stiffening ratio and a thickening ratio, which are measured by a large amplitude oscillatory shear method, are S and T, respectively, S<-T and S≤0.5 when the temperature is 100°C and distortion amount is 100%, and S>-T and T≤-0.5 when the temperature is 70°C and distortion amount is 100%. When the temperature is decreased from 100°C or 70°C to 60°C and a distortion amount is 1%, a maximum elastic stress value (ES60) is ES60≥500 Pa.

Description

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

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

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

  As a technique that can solve these problems, it is known to use a crystalline resin as a binder resin for toner. Since the crystalline resin has a characteristic of softening rapidly from the crystallized state at the melting point, it is possible to greatly reduce the fixing temperature of the toner while ensuring heat-resistant storage stability below the melting point. That is, both low-temperature fixability and heat-resistant storage stability can be achieved with high quality. However, the crystalline resin having a melting point that exhibits low-temperature fixability is soft while being excellent in toughness, and is easily plastically deformed. For this reason, simply using a crystalline resin as a binder resin, the mechanical durability of the toner is very poor, such as toner deformation, aggregation, fixation in the image forming apparatus, toner contamination of members in the apparatus, etc. Various problems occur.

  For this reason, many toners using a crystalline resin and an amorphous resin in combination have been proposed as toners using a crystalline resin as a binder resin (see, for example, Patent Documents 1 to 5). These were excellent in compatibility between low-temperature fixability and heat-resistant storage stability as compared with conventional toners composed only of amorphous resins. However, when the crystalline resin is exposed on the toner surface, there is a problem that agglomeration of toner particles is generated due to agitation stress in the developing device and causes transfer omission. For this reason, the amount of addition of the crystalline resin is limited, and it has not been a technique that can fully utilize the advantages of the crystalline resin.

In addition, many toners using a resin in which a crystalline segment and an amorphous segment are chemically bonded are proposed. For example, a toner has been proposed in which a resin in which crystalline polyester and polyurethane are bonded is used as a binder resin (see, for example, Patent Documents 6 and 7). In addition, a toner using a resin in which a crystalline polyester and an amorphous vinyl polymer are combined has been proposed (see, for example, Patent Document 8). In addition, a toner using a resin in which a crystalline polyester and an amorphous polyester are combined as a binder resin has been proposed (see, for example, Patent Documents 9 to 11).
Furthermore, a technique (for example, see Patent Document 12) in which inorganic fine particle powder is added to a binder resin containing a crystalline resin as a main component, or a crystalline resin having a crosslinked structure with an unsaturated bond containing a sulfonic acid group was used. Techniques such as toner (see, for example, Patent Document 13) have been proposed.

  All of these proposed technologies were excellent in compatibility between low-temperature fixability and heat-resistant storage stability, but the softness derived from the crystalline segment was not fundamentally improved, and the toner Problems related to mechanical durability could not be solved.

A major problem with toners using crystalline resins is the problem of image abrasion resistance. When the toner is melted on the fixing medium at the time of heat fixing, it takes time for the crystalline resin in the toner to crystallize again, so that the hardness of the image surface cannot be recovered quickly. For this reason, there has been a problem that scars and changes in glossiness occur on the surface of the image due to contact and rubbing with a discharge roller or a conveying member in the discharge step after fixing.
In order to solve this problem, there has been proposed a technique for restraining the molecular motion of the crystalline segment by chemically bonding the crystalline segment and the amorphous segment and controlling the structure of each segment.
By using this technique, the problem when the mechanical stress is applied as described above can be solved, but there is a problem that an image sticking phenomenon (blocking) occurs when the images are stacked after fixing.

An object of the present invention is to solve the conventional problems and achieve the following objects.
That is, the present invention has a sharp melt property that can achieve both a low-temperature fixability and a heat-resistant storage stability at a high level, and is a problem specific to a toner using a crystalline resin. This suppresses the deterioration of the chargeability and fluidity caused by toner aggregation, carrier contamination, in-machine contamination, and external additive embedding, and the toner's elastic modulus quickly recovers after fixing, thereby improving the image hardness. An object of the present invention is to provide a toner capable of providing a high-quality image which is improved and excellent in abrasion resistance and does not cause blocking.

As a result of intensive studies to solve the above problems, the present inventors have found that the viscoelastic behavior when the mechanical stress of the toner after fixing and after the fixing is applied and the viscoelastic behavior when not applied. It has been found that the above problem can be solved by adjusting.
That is, the present invention relates to a toner having a configuration as described below.

Measured by the Large Amplitude Oscillatory Shear method, when Stiffening ratio is S and Thickening ratio is T,
S <−T and S ≦ 0.5 when the temperature is 100 ° C. and the strain is 100%.
When the temperature is 70 ° C. and the strain is 100%, S> −T and T ≦ −0.5
And
Furthermore, the maximum elastic stress value (ES60) when the strain is 1% when the temperature is lowered from 100 ° C or 70 ° C to 60 ° C is ES60 ≧ 500Pa.
Toner characterized by becoming.

  By providing the toner of the present invention with the above-described configuration, the toner can be prevented from agglomerating in the developing machine while maintaining sharp melt properties that can achieve both high-temperature fixability and heat-resistant storage stability at a high level. Can be eliminated. Further, deterioration of charging property and fluidity due to carrier contamination, in-machine contamination, and burying of external additives can be prevented. Furthermore, since the elastic modulus of the toner quickly recovers after fixing, the hardness of the image is improved, and a high-quality image having excellent abrasion resistance can be provided.

FIG. 3 is a view showing a phase image of a binder resin used in Example 1. It is a figure which shows the binarized image of the phase image of FIG. It is a figure which shows the micro diameter image from which it is judged as image noise or it is difficult to discriminate | determine whether it is image noise or a phase difference image. It is a figure which shows an example of the image forming apparatus used by this invention. It is a figure which shows an example of the image forming apparatus used by this invention. It is a figure which shows an example of the image forming apparatus used by this invention. It is a figure which shows the principal part of FIG.

The configuration of the present invention defines the viscoelastic behavior when the mechanical stress of the toner after fixing and after the fixing is applied, and the viscoelastic behavior when not applied.
In addition to a force that resists when a force is applied purely, there may be resistance to the strain and speed when changing the strain. It is considered that there is a resistance applied when such a force is applied at the time of fixing or at the time of contact with a paper discharge roller or a conveying member in a paper discharge process after fixing.
Physical property values representing such resistance include “stiffening ratio” representing resistance to strain and “Thickening ratio” representing resistance to speed.
If the value (S value) of the stiffening ratio (hereinafter also referred to as “S”) is greater than 0, the elasticity is increased, and if the S value is less than 0, the elasticity is decreased.
Further, if the Thickening ratio value (T value) is larger than 0, the viscosity becomes higher with respect to the speed, and if the T value is smaller than 0, the viscosity becomes lower with respect to the speed.

  The inventor has investigated how the toner behaves when stress is applied to the toner. As a result, it was found that the S value and the T value change depending on the toner configuration.

  Ideally, the toner characteristics at 100 ° C. near the fixing temperature are such that the toner is liable to be crushed when a force is applied during fixing. In this case, it is best that no resistance is applied, and it is preferable that both the S value and the T value are 0 or less. However, in the toner, this value has a high S value (that is, elasticity against strain). In many cases, the T value becomes low (that is, the viscosity becomes low with respect to speed). Even if the S value is high, if the T value is low, the fixing is easy, and if this value is reversed, the fixing is disadvantageous.

On the other hand, it is preferable that the S value is high in the vicinity of 70 ° C. when the image after fixing passes through the paper discharge process. Actually, the toners studied in the prior literature often have a high resistance, and it is considered that the problem in the paper discharge process has been cleared. On the other hand, since the force is not applied when the images are stacked after being discharged, such resistance is not applied, and the hardness of the pure image is important. For this reason, it is preferable that the elastic modulus is 1000 Pa or more when almost no strain is applied at a temperature around 60 ° C. when the paper is discharged. In this way, by controlling the viscoelastic characteristics in each temperature range, it is possible to eliminate all problems such as low-temperature fixing and image damage and blocking in the paper discharge process.
The toner having the above-described configuration can be obtained by using a block copolymer obtained by block polymerization of an amorphous resin and a crystalline resin as a binder resin for the toner.
Hereinafter, the portion of the amorphous resin constituting the block copolymer is referred to as “amorphous segment” or “amorphous portion”, and the portion of the crystalline resin is referred to as “crystalline segment” or “crystalline portion”. is there.

  The inventor selects an amorphous segment capable of constraining the molecular mobility of the crystalline segment, forms a microphase separation structure of the crystalline segment and the amorphous segment inside the toner, We controlled to refine the sea-island structure with crystalline segments as islands. Thus, below the melting point of the crystalline segment, it has excellent mechanical durability due to the restraint of the molecular mobility of the amorphous segment. When paper is used, the amorphous segment immediately suppresses excessive molecular motion of the crystalline segment, and the fine sea-island structure prevents the crystalline segment from being exposed to the image surface, enabling rapid image hardness recovery. A good toner was obtained.

It is more preferable to add a crystalline resin to the block copolymer composed of the crystalline segment and the amorphous segment because the crystalline resin functions to lower the T value at the time of fixing.
Furthermore, it is preferable to include an amorphous polyester resin having a large weight average molecular weight because the width of fixing can be maintained and the overlapping of images during stacking can be suppressed. The amorphous polyester resin is produced by a reaction between a non-linear reactive precursor having a branched structure imparted by a trivalent or higher functional group and a cross-linking agent capable of reacting with the reactive precursor. In the case of an amorphous polyester resin having a transition temperature of −60 ° C. or more and 0 ° C. or less, further low-temperature fixing, and further, the crystalline segment and the amorphous segment form a microphase separation structure. In the binarized image obtained by binarizing the observed phase image with an intermediate value between the maximum value and the minimum value of the phase difference in the phase image, the first phase difference image including a portion having a large phase difference, A second phase difference image having a small phase difference, wherein the first phase difference image is dispersed in the second phase difference image, and the first phase difference image is dispersed. Tona with a diameter of 100 nm or less It is obtained.

(Binder resin)
The binder resin is not particularly limited and may be appropriately selected depending on the purpose. For example, it contains at least a crystalline resin, and further contains other components such as an amorphous polyester resin as necessary. The binder resin to contain is mentioned.
As the binder resin, the toner main binder is preferably a block copolymer of an amorphous resin and a crystalline resin.

  The block copolymer is obtained by covalently bonding different types of polymer chains. Generally, many different types of polymer chains are incompatible with each other and do not mix like water and oil. In a simple mixed system, different polymer chains can move independently, so that macrophase separation occurs. However, in the case of a copolymer, macromolecules cannot be separated because different polymer chains are connected to each other. If the block copolymer is composed of two different polymer chains of A and B, both are connected, but they are aggregated with the same kind of polymer chains and try to be separated as much as possible. Alternatingly according to the size of the polymer chain, the part can be divided into a part with many A and a part with many B. For this reason, if the degree of phase mixing, composition and length (molecular weight and distribution) of A and B, and the blending ratio of both are changed, the form (structure) of phase separation changes. For example, A.I. K. Khandpur, S .; Forster, and F.M. S. Bates, Macromolecules, 28 (1995) 8996-8806. As illustrated in the above, periodic ordered mesostructures such as a Sphere structure, a Cylinder structure, a Gyroid structure, and a Lamella structure can be controlled.

  The toner having the physical property values defined in the present invention can be obtained by using a block copolymer comprising a crystalline segment (crystal part) and an amorphous segment (amorphous part) as a binder resin. If the above periodic ordered mesostructure can be controlled when crystallized from under the separated structure, the crystalline phase can be regularly arranged on the scale of several tens to several hundreds of nanometers by using the microphase separation structure of the melt as a template. Can be planned. Therefore, by utilizing these higher-order structures, in situations where fluidity is required, such as fixing, sufficient fluidity and deformability based on the solid-liquid phase transition phenomenon of the crystal part is provided, and the in-machine conveyance process after storage and fixing, etc. In cases where flow and deformation are not required, the mobility can be constrained by enclosing the crystal part in the structure. As a result, the object of the present invention can be achieved.

  The higher order structures such as the molecular structure, crystallinity, and microphase separation structure of the copolymer can be easily analyzed by a conventionally known method. Specifically, high-resolution NMR measurement (1H, 13C, etc.), differential scanning calorimeter (DSC) measurement, wide-angle X-ray diffraction measurement, (thermal decomposition) GC / MS measurement, LC / MS measurement, infrared absorption (IR) It can be confirmed by spectrum measurement, atomic force microscope observation, TEM observation or the like.

<Amorphous part>
The amorphous resin is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of excellent affinity with paper as a main recording medium and excellent heat-resistant storage stability of the toner, polyester. A resin is preferred.
The hydroxyl value of the resin can be appropriately selected according to the purpose, but is preferably 5 to 40 mgKOH / g. If the hydroxyl value is too low, the heat resistance of the toner may be poor and the durability against stress such as stirring in the developing device may be poor. May be inferior. A similar index includes a weight average molecular weight, which can be appropriately selected according to the purpose, but is preferably 3,000 to 30,000, more preferably 5,000 to 25,000. The weight average molecular weight of the amorphous resin can be measured by, for example, gel permeation chromatography (GPC).

  The glass transition temperature of the amorphous resin is preferably 50 ° C to 70 ° C. When the glass transition temperature is less than 50 ° C., it may lead to a decrease in heat-resistant storage stability and a decrease in durability against stress such as stirring in the developing device. May get worse. The glass transition temperature of the amorphous resin can be measured, for example, by differential scanning calorimetry (DSC method).

  The alcohol component used in the amorphous polyester resin is a divalent alcohol (diol), specifically, an alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene). Glycols, 1,4-butylene glycol and 1,6-hexanediol); alkylene ether glycols having 4 to 36 carbon atoms (such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol); C6-C36 alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); C2-C4 alkylene oxide of the above alicyclic diol [ethylene oxide (hereinafter abbreviated as EO)] ), Propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] addition products (number of added moles 1-30); carbon of bisphenols (such as bisphenol A, bisphenol F and bisphenol S) Examples include adducts having 2 to 4 alkylene oxides (such as EO, PO, and BO) (addition moles of 2 to 30).

  Further, in addition to the above divalent diol, an alcohol component having 3 or more valences (3 to 8 valences or more) may be contained, specifically, 3 to 8 valences having 3 to 36 carbon atoms or more. The above aliphatic polyhydric alcohols (alkane polyols and intramolecular or intermolecular dehydrates such as glycerin, triethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; Derivatives such as sucrose and methyl glucoside; etc.]; C 2-4 alkylene oxide (EO, PO, BO etc.) adducts of the above aliphatic polyhydric alcohols (addition moles 1-30); Trisphenols (Tris) C2-C4 alkylene oxide (EO, PO, BO, etc.) such as phenol PA Adduct (addition mole number 2-30); Novolak resin (phenol novolak, cresol novolak, etc .: average polymerization degree 3-60) C2-C4 alkylene oxide (EO, PO, BO etc.) addition product (addition mole) 2-30) etc. are mentioned.

As the carboxylic acid component used in the amorphous polyester resin, a divalent carboxylic acid (dicarboxylic acid), specifically, an alkanedicarboxylic acid having 4 to 36 carbon atoms (succinic acid, apidic acid, sebacic acid, etc.) And alkenyl succinic acid (such as dodecenyl succinic acid); alicyclic dicarboxylic acid having 4 to 36 carbon atoms [dimer acid (dimerized linoleic acid) and the like]; alkenedicarboxylic acid having 4 to 36 carbon atoms (maleic acid, fumaric acid, citracone) Acid and mesaconic acid); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid or derivatives thereof, and naphthalenedicarboxylic acid). Of these, alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable. In addition, as a polycarboxylic acid, you may use the acid anhydride of the above-mentioned thing, or a lower alkyl (C1-C4) ester (Methyl ester, ethyl ester, isopropyl ester, etc.).
In addition, ring-opening polymerization systems such as polylactic acid and polycarbonate diol can also be suitably used.
The molecular structure of the resin can be confirmed by GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid.

<Crystal part>
The crystalline resin can be appropriately selected according to the purpose, but is preferably a polyester resin from the viewpoint of sharp melting during fixing and sufficient flexibility and durability even when the molecular weight is lowered. Among the polyester resins, aliphatic polyester resins are particularly preferable because they have excellent sharp melt properties and high crystallinity. The aliphatic polyester resin is obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester and / or a derivative thereof. Also, a ring-opening polymerization system such as polycaprolactone can be suitably used.

  As melting | fusing point of the said crystalline resin, 50 to 75 degreeC is preferable. When the melting point is less than 50 ° C., the crystalline resin is likely to melt at a low temperature, and the heat-resistant storage stability of the toner may be reduced. When the melting point exceeds 75 ° C., the crystalline resin is heated by fixing. Insufficient melting may lower the low-temperature fixability of the toner.

  The hydroxyl value of the crystalline resin can be appropriately selected according to the purpose, but is preferably 5 to 40 mgKOH / g. If the hydroxyl value is too low, the heat resistance of the toner may be inferior in durability against stress such as stirring in the developing device. If the hydroxyl value is too high, the viscoelasticity at the time of melting of the toner will increase and low temperature fixing will occur. May be inferior. A similar index includes a weight average molecular weight, which can be appropriately selected according to the purpose, but is preferably 3,000 to 30,000, more preferably 5,000 to 25,000. The weight average molecular weight of the amorphous resin can be measured by, for example, gel permeation chromatography (GPC).

-Polyhydric alcohol-
There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, a linear saturated aliphatic diol is preferable, and a linear saturated aliphatic diol having 2 to 12 carbon atoms is more preferable. When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin may be lowered, and the melting point may be lowered. If the saturated aliphatic diol has more than 12 carbon atoms, it may be difficult to obtain the material. Therefore, the carbon number is more preferably 12 or less.

  Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, 18-octadecanediol, 1,14-eicosandecanediol, and the like. These may be used individually by 1 type and may use 2 or more types together.

Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10 are preferred because the crystalline polyester resin has high crystallinity and excellent sharp melt properties. Particularly preferred are -decanediol and 1,12-dodecanediol.
Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like. These may be used individually by 1 type and may use 2 or more types together.

-Multivalent carboxylic acid-
There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Examples thereof include aromatic dicarboxylic acids such as mesaconic acid, anhydrides thereof, or lower (C1 to C3) alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together.

Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, or anhydrides thereof, or these Lower (carbon number 1 to 3) alkyl ester, and the like. These may be used individually by 1 type and may use 2 or more types together.
In addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, the polyvalent carboxylic acid may contain a dicarboxylic acid having a sulfonic acid group, a dicarboxylic acid having a double bond, and the like. .

  The crystalline polyester resin is preferably obtained by condensation polymerization of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. . As a result, the resulting crystalline polyester resin has high crystallinity and excellent sharp melt properties, and therefore can exhibit excellent low-temperature fixability of toner.

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

<About block copolymer>
The block copolymerization method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include any of the following methods (1) to (3). From the viewpoint of the degree of freedom, (1) and (3) are preferable, and (1) is more preferable.
(1) An amorphous resin prepared in advance by a polymerization reaction and a crystalline resin prepared in advance by a polymerization reaction are dissolved or dispersed in a suitable solvent, and a hydroxyl group at the end of a polymer chain such as an isocyanate group, an epoxy group, or a carbodiimide group. Or a method of copolymerization by reacting with an extender having two or more functional groups that react with carboxylic acid.
(2) A method in which an amorphous resin prepared in advance by a polymerization reaction and a crystalline resin prepared in advance by a polymerization reaction are melt-kneaded and prepared by transesterification under reduced pressure.
(3) A method in which a hydroxyl group of a crystalline resin prepared in advance by a polymerization reaction is used as a polymerization initiation component, and an amorphous resin is subjected to ring-opening polymerization and copolymerization from a polymer chain end of the crystalline resin.

  In the preparation of the block copolymer, the ratio of the amorphous resin to the crystalline resin is more preferably in the range of 1.5 to 4.0 as amorphous part mass / crystal part mass. When the ratio is less than 1.5, the influence of the crystal part becomes too strong, and the microphase separation structure peculiar to the block copolymer is destroyed, often resulting in a whole surface lamellar structure, and fluidity such as fixing is required. In the case, it contributes effectively, but in situations where fluidity and deformability are not required, such as in-machine conveyance steps after storage and fixing, the mobility cannot be constrained and the purpose of the present application cannot be satisfied. On the other hand, if it exceeds 4.0, the influence of the amorphous part becomes too strong, and it contributes effectively in situations where fluidity and deformability are not required, such as in-machine conveyance processes after storage and fixing, but it does not flow, such as fixing. In the case where the property is necessary, sufficient fluidity and deformability cannot be secured, and the purpose of the present application cannot be satisfied.

Any conventionally known stretching material can be used, and one or more types may be used in combination depending on the purpose, but an isocyanate compound is preferred from the viewpoint of cost and reactivity, and particularly preferred is TDI. , MDI, HDI, hydrogenated MDI, and IPDI.
The amount of the extender used in preparing the copolymer is preferably in the range of 0.35 to 0.7 as the total number of moles of polyester polyol / total number of moles of isocyanate (OH / NCO). When OH / NCO is less than 0.35, the bonding between the amorphous resin and the crystalline resin is insufficient, the number of components present independently increases, and the stability of quality cannot be ensured, which is not preferable. When OH / NCO exceeds 0.7, the influence of the molecular weight of the copolymer and the interaction between urethane groups becomes too strong, and sufficient fluidity and deformability in situations where fluidity is required, such as fixing. Cannot be guaranteed, and the purpose of the present application cannot be satisfied.

  As a molecular weight of a copolymer, the range of 20,000-70,000 is preferable as a weight average molecular weight which can be measured by a gel permeation chromatography (GPC), for example. If the molecular weight is less than 20,000, the molecular weight of the system is low and sufficient viscoelasticity cannot be obtained, so the fluidity at the time of fixing is excellent, but in many cases the viscosity is too low leading to offset, and storage stability and abrasion resistance In the case of exceeding 70,000, the flow characteristics are very poor and the constant temperature fixability cannot be secured, which is not preferable.

  The higher order structures such as the molecular structure, crystallinity, and microphase separation structure of the copolymer can be easily analyzed by a conventionally known method. Specifically, high-resolution NMR measurement (1H, 13C, etc.), differential scanning calorimeter (DSC) measurement, wide-angle X-ray diffraction measurement, (thermal decomposition) GC / MS measurement, LC / MS measurement, infrared absorption (IR) It can be confirmed by spectrum measurement, atomic force microscope observation, TEM observation or the like.

<Externally added polyester resin>
A crystalline polyester resin or an amorphous polyester resin can be suitably used in combination with the block copolymer.
-Externally added crystalline polyester resin-
A crystalline polyester resin can be suitably used in combination with the aforementioned block copolymer.
As described above, when the block copolymer and the crystalline polyester resin are used in combination, the crystalline polyester resin functions to lower the T value during fixing.

-Externally added amorphous polyester resin-
As the amorphous polyester resin used in combination with the block copolymer, a modified polyester resin can be suitably used.
A modified polyester resin is an amorphous polyester resin that contains a functional group contained in a monomer unit of acid or alcohol and a bonding group other than an ester bond in the resin, or a resin component having a different structure in the resin. Refers to a polyester resin bonded by a covalent bond, an ionic bond or the like.

Examples of the modified polyester resin include those obtained by reacting the terminal of the polyester resin with a bond other than an ester bond. Specifically, a compound obtained by reacting an active hydrogen group-containing compound with a polyester resin having a functional group capable of reacting with the active hydrogen group of the compound to cause the polyester resin to undergo an extension reaction, a crosslinking reaction, or the like (urea-modified polyester resin) And urethane-modified polyester resin).
In addition, a reactive group such as a double bond is introduced into the main chain of the polyester resin, and radical polymerization is caused therefrom to introduce a graft component of a carbon-carbon bond to the side chain, or the double bonds are bridged. (Styrene modified polyester resin, acrylic modified polyester resin, etc.) are also included.

  In addition, a resin component having a different structure is copolymerized in the main chain of the polyester resin or reacted with a carboxyl group or a hydroxyl group at the terminal, for example, the terminal is modified with a carboxyl group, a hydroxyl group, an epoxy group, or a mercapto group Examples thereof include those copolymerized with a silicone resin (such as a silicone-modified polyester resin).

The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polyester resin having a functional group capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, when the polyester resin having a functional group capable of reacting with the active hydrogen group-containing compound is an isocyanate group-containing polyester prepolymer (A) described later, an elongation reaction with the isocyanate group-containing polyester prepolymer (A), Amines (B) are preferred because they can have a high molecular weight by a reaction such as a crosslinking reaction.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as said amines (B), According to the objective, it can select suitably. For example, diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6). It is done. These may be used alone or in combination of two or more.
Among these, the amines are particularly preferably diamine (B1), a mixture of diamine (B1) and a small amount of trivalent or higher polyamine (B2).

There is no restriction | limiting in particular as said diamine (B1), According to the objective, it can select suitably, For example, aromatic diamine, alicyclic diamine, aliphatic diamine etc. are mentioned. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
The trivalent or higher polyamine (B2) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.

The amino alcohol (B3) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.
The amino mercaptan (B4) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include minoethyl mercaptan and aminopropyl mercaptan.

The amino acid (B5) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.
There is no restriction | limiting in particular as what blocked the amino group of said (B1)-(B5) (B6), According to the objective, it can select suitably. Examples thereof include ketimine compounds and oxazolidone compounds obtained from any of the amines of (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

The polyester resin having a functional group capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “polyester prepolymer (A)”) includes at least a site capable of reacting with the active hydrogen group-containing compound. There is no restriction | limiting in particular if it is the polyester resin which has, It can select suitably according to the objective.
There is no restriction | limiting in particular as a functional group which can react with the said active hydrogen group in the said polyester prepolymer (A), It can select suitably from well-known substituents etc., For example, an isocyanate group, an epoxy group, carvone, etc. An acid, an acid chloride group, etc. are mentioned. These may be contained singly or in combination of two or more.
Among these, the functional group capable of reacting with the active hydrogen group-containing compound is particularly preferably an isocyanate group.

  There is no restriction | limiting in particular as a manufacturing method of the polyester prepolymer (A) which has the said isocyanate group, According to the objective, it can select suitably. For example, the polyol (A1) and the polycarboxylic acid (A2) are heated to 150 ° C. to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxy titanate or dibutyltin oxide, and the pressure is reduced as necessary. Generate. Water is distilled off to obtain a polyester having a hydroxyl group. Subsequently, it can obtain by making polyisocyanate (A3) react with polyester which has a hydroxyl group at 40 to 140 degreeC.

  There is no restriction | limiting in particular as said polyol (A1), According to the objective, it can select suitably, For example, the mixture of a diol, a trihydric or more polyol, a diol, and a trihydric or more polyol etc. are mentioned. These may be used alone or in combination of two or more. Among these, the polyol is preferably the diol alone or a mixture of the diol and a small amount of the trivalent or higher polyol.

  There is no restriction | limiting in particular as said diol, According to the objective, it can select suitably. For example, alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene) Glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; alkylene oxide of the bisphenol De (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. These may be used alone or in combination of two or more.

  Among these, the diol is an alkylene glycol having 2 to 12 carbon atoms, an alkylene oxide adduct of bisphenols (for example, bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct, bisphenol A propylene oxide 3). Mole adducts etc. are preferred.

  There is no restriction | limiting in particular as said polyol more than trivalence, According to the objective, it can select suitably. For example, polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (phenol novolak, cresol novolac, etc.); trivalent or higher polyphenols alkylene oxide addition Such as things. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as mixing mass ratio (diol: trihydric or more polyol) of the said diol and the said trihydric or more polyol in the mixture of the said diol and the said trihydric or more polyol, According to the objective suitably You can choose. The mixing mass ratio is preferably 100: 0.01 to 100: 10, and more preferably 100: 0.01 to 100: 1.

  There is no restriction | limiting in particular as said polycarboxylic acid (A2), According to the objective, it can select suitably, For example, alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); Alkenylene dicarboxylic acid (maleic acid, maleic acid) Fumaric acid, etc.); aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.). These may be used alone or in combination of two or more. Among these, the polycarboxylic acid (2) is preferably an alkenylene dicarboxylic acid having 4 to 20 carbon atoms and an aromatic dicarboxylic acid having 8 to 20 carbon atoms.

The trivalent or higher polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), etc. Is mentioned. These may be used alone or in combination of two or more.
In place of polycarboxylic acid, an anhydride or lower alkyl ester of polycarboxylic acid can also be used. There is no restriction | limiting in particular as said lower alkyl ester, According to the objective, it can select suitably, For example, methyl ester, ethyl ester, isopropyl ester etc. are mentioned.

  There is no restriction | limiting in particular as said polyisocyanate (A3), According to the objective, it can select suitably. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, those blocked with phenol derivatives, oximes, caprolactams, and the like.

There is no restriction | limiting in particular as said aliphatic polyisocyanate, According to the objective, it can select suitably. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate and the like. .
The alicyclic polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.

There is no restriction | limiting in particular as said aromatic diisocyanate, According to the objective, it can select suitably. For example, tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3-methyldiphenylmethane-4,4 ′ -Diisocyanate, diphenyl ether-4,4'-diisocyanate and the like.
The araliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α, α, α ′, α′-tetramethylxylylene diisocyanate.

There is no restriction | limiting in particular as said isocyanurates, According to the objective, it can select suitably, For example, a tris-isocyanate alkyl-isocyanurate, a triisocyanate cycloalkyl-isocyanurate, etc. are mentioned.
These may be used alone or in combination of two or more.
As an average number of the isocyanate groups contained per molecule of the polyester prepolymer (A) having the isocyanate group, 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable.

When the average number of the isocyanate groups is less than 1, the molecular weight of the resulting modified polyester resin becomes low, and the hot offset fixability and storage stability may be inferior.
The modified polyester resin includes, for example, a compound having an active hydrogen group such as the amines (B) and a polyester resin having a functional group capable of reacting with an active hydrogen group-containing compound such as the polyester prepolymer (A). It can be obtained by reacting in an aqueous medium.

When making the said polyester prepolymer (A) and the said amines (B) react, a solvent can also be used as needed.
There is no restriction | limiting in particular as said usable solvent, According to the objective, it can select suitably. For example, aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.), ethers (tetrahydrofuran, etc.) And those inert to the isocyanate (3). These may be used alone or in combination of two or more.

As a mixing ratio of the amines (B) and the polyester prepolymer (A) having an isocyanate group, the isocyanate group [NCO] in the polyester prepolymer (A) having the isocyanate group and the amines ( The mixing equivalent ratio ([NCO] / [NHx]) with the amino group [NHx] in B) is preferably 1/2 to 2/1, more preferably 1 / 1.5 to 1.5 / 1. 1/1/2 to 1.2 / 1 is particularly preferred.
When the mixing equivalent ratio ([NCO] / [NHx]) is more than 2 or less than 1/2, the molecular weight of the modified polyester resin is lowered, and the hot offset resistance may be lowered.

A reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, and the like in the active hydrogen group-containing compound and the polyester resin having a functional group capable of reacting with the active hydrogen group-containing compound.
The reaction terminator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) Etc. These may be used alone or in combination of two or more.
The modified polyester resin may contain a urethane bond as well as a urea bond.

A non-linear reactive precursor having a branched structure provided by a functional group having three or more valences and an amorphous polyester resin produced by the reaction of a cross-linking agent capable of reacting with the reactive precursor are non-linear. It consists of a reactive precursor a and a curing agent.
The reactive precursor a is a polyester having a reactive site such as isocyanate, epoxy, carbodiimide, etc. at the terminal, and is particularly preferably a terminal NCO compound of a polyester polyurethane.

As the polyhydric alcohol component in the polyester, any conventionally known polyhydric alcohol component may be used alone and / or mixed. An aliphatic diol such as 3-methyl-1,5-pentanediol or neopentyl glycol is preferred from the viewpoints of blocking resistance, image storage stability, and low-temperature fixability. As the acid component, any conventionally known one can be used alone and / or mixed, but terephthalic acid, isophthalic acid, phthalic anhydride, adipic acid, sebacic acid, dodecanedicarboxylic acid and the like are preferable from the viewpoint of cost and the like. .
As a non-linear component, that is, a component for taking a branched structure, a conventionally known polyfunctional component having a valence of 3 or more can be used. Acid is preferred.

As an isocyanate component, C6-C20 aromatic diisocyanate, C2-C18 aliphatic diisocyanate, C4-C15 alicyclic diisocyanate, C-carbon (excluding carbon in NCO group, the same applies hereinafter) 8-15 araliphatic diisocyanates and modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products, etc.) A mixture of two or more of these may be mentioned.
Moreover, you may use together polyisocyanate more than trivalence as needed.

  Specific examples of the aromatic diisocyanate (including triisocyanate or higher polyisocyanate) include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI). ), Crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or a mixture thereof; A mixture of diphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine] Phosgenation compound: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -Triphenylmethane triisocyanate, m- and p-isocyanatov Such as sulfonyl sulfonyl isocyanate.

  Specific examples of the aliphatic diisocyanate (including triisocyanate or higher polyisocyanate) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2, 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2 , 6-diisocyanatohexanoate and the like.

Specific examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.
Specific examples of the aromatic aliphatic diisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

Examples of the modified diisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), modified products of diisocyanates such as urethane modified TDI, and mixtures of two or more thereof [for example, modified MDI and urethane modified TDI (Combined use with an isocyanate-containing prepolymer)] is included.

Of these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI and water. Attached MDI and IPDI.
A conventionally known amine compound can be suitably used as the curing agent.

  Examples of diamines (including triamine or higher polyamines used as necessary) include aliphatic diamines (C2 to C18): [1] aliphatic diamines (C2 to C6 alkylenediamines (ethylenediamine, propylenediamine, trimethylene) Diamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) diamine (diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.)) [2] These alkyl (C1 to C4) or hydroxyalkyl (C2 to C4) substitutes [dialkyl (C1 to C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanol; Min, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, etc.]; [3] Alicyclic or heterocyclic-containing aliphatic diamines (alicyclic diamines (C4 to C15) [1,3 -Diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.], heterocyclic diamine (C4-C15) [piperazine, N-aminoethylpiperazine, 1, 4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] [4] Aromatic ring-containing aliphatic amines (C8-C15) (xylylenediamine, tetrachloro-p-ki) Silylenediamine, etc.).

As aromatic diamines (C6-C20),
[1]: unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine ), Diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylene diene Amines;

[2]: Aromatic diamine having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl], for example, 2,4- and 2,6-tolylenediamine, crude Tolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2 , 4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2 , 4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3, ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane 3,3′-diethyl-2,2′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminobenzophenone 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylsulfone, and the like, and isomers thereof A mixture of various proportions of

[3]: Aromatic diamine [methylene bis-o-chloroaniline, 4-chloro-] having a nucleus-substituted electron withdrawing group (halogen such as Cl, Br, I, F; alkoxy group such as methoxy and ethoxy; nitro group, etc.) o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5 -Nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo-diphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) pro Bread, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-amino) Phenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoaniline), 4,4′-methylenebis (2-bromoaniline), 4,4′-methylenebis ( 2-fluoroaniline), 4-aminophenyl-2-chloroaniline and the like];

[4]: Aromatic diamine having a secondary amino group [Partial or whole of —NH ₂ of the aromatic diamine of the above [1] to [3] is —NH—R ′ (R ′ is an alkyl group such as methyl, A lower alkyl group such as ethyl)] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.].
In addition to these, the diamine component can be obtained by condensation of polyamide polyamine [dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per mole of acid) polyamine (alkylenediamine, polyalkylenepolyamine etc.). Low molecular weight polyamide polyamine, etc.], polyether polyamine [hydride of cyanoethylated polyether polyol (polyalkylene glycol, etc.), etc.].

[Characteristics of toner and toner resin]
(Characteristics determined by Large Amplitude Oscillator Shear (LAOS) method)
In the present invention, it is necessary to have sufficient mobility when fluidity is required, such as fixing, and to be sufficiently restrained when fluidity is not required, such as a subsequent in-machine conveyance process. It is proposed that.
From the viewpoint of rheology, it is important to restrict the motility of the system in the cooling process after fixing. However, since the melt undergoes large strain and strain rate in the process of cooling and solidifying, it cannot be characterized only by the conventional equilibrium structure and linear viscoelasticity, but by nonlinear viscoelasticity under large deformation. It is necessary to discuss. Examples of methods for evaluating rheology under large deformation include a method using shear strain and a method using uniaxial elongation strain. In view of the target process, the former evaluation is necessary, and as the method, the Large Amplitude Oscillation Shear method (LAOS method) that can divide and discuss the stress value for strain into elastic stress and viscous stress is preferable. It is.
The “large amplitude oscillation method” in the present invention refers to the “Large Amplitude Oscillator Shear method” (LAOS method).

  As a result of the study, the inventors have found that the stiffening ratio and the thickening ratio at 100% strain obtained by performing the LAOS measurement at 100 ° C. can be used as values assuming a fixing process in solving the above-mentioned process problems, and It was found that Stiffening ratio and Thickening ratio at a strain of 100% at 70 ° C. when the temperature was lowered from 100 ° C. to 70 ° C. can be used as values assuming the conveying step immediately after fixing.

  In the present invention, it is preferable that Stiffening ratio S and Thickening ratio T assuming fixing are S <−T and S ≦ 0.5. Furthermore, the maximum elastic stress value (ES100) is preferably 3,000 Pa or less. When the pressure is 3,000 Pa or less, the essential feature for low-temperature fixing that the external force is quickly absorbed and is quickly and freely deformed according to the adherend shape is sufficiently exhibited.

  On the other hand, it is preferable that Stiffening ratio S and Thickening ratio T assuming a conveyance process immediately after fixing are S> −T and T ≦ −0.5. Further, the maximum elastic stress value (ES70) is preferably 5,000 Pa or more. By being 5,000 Pa or more, motility can be restrained quickly by self-aggregation after melting, and the material can sufficiently resist external forces (compression shearing, peeling, etc.) generated in the transport process.

<Large Amplitude Oscillatory Shear Flow Method (Measurement Method by LAOS Method)>
This was carried out using ARES-G2 manufactured by TA Instruments. A sample was prepared by measuring 0.2 g of toner powder into a pellet having a thickness of 2.0 ± 0.3 mm and 1.0 cmφ by applying a pressure of 25 MPa with a compression molding machine. For measurement, set the pellets on an aluminum disposable parallel plate of 8 mmφ, raise the temperature to 130 ° C. to plasticize, compress to a predetermined gap, and trim the melt that protrudes from the geometry with a brass spatula etc. I went there. The measurement gap was 2 mm, each frequency was 1 rad / s, and the amount of distortion was 1.0 to 200%. The measurement temperatures were 100 ° C., 70 ° C., and 60 ° C. After the measurement at 100 ° C. was completed, the sample was air-cooled to 70 ° C. and 60 ° C. for measurement. For the maximum elastic stress at 100 ° C. and 70 ° C., the value at the time of Hamonic number 2 at a strain of 200% was used, and for the elastic stress at 60 ° C., the value at the time of Hamonic number 2 at a strain of 1% was used.

(Characteristics required by tapping mode of atomic force microscope (AFM))
The binder resin for toner according to the present invention is a binary image obtained by binarizing a phase image observed by the tapping mode AFM with an intermediate value between the maximum value and the minimum value of the phase difference in the phase image. A first phase difference image having a large phase difference and a second phase difference image having a small phase difference, wherein the first phase difference image is dispersed in the second phase difference image; It is characterized by having a structured. It is preferable that the average of the maximum ferret diameter in the dispersed phase of the first phase difference image composed of a portion having a large phase difference is 10 nm or more and less than 100 nm.

In the present invention, in the binarized image of the phase image observed by the AFM of the binder resin, the first phase difference image has a structure dispersed in the second phase difference image. In the binarized image, the boundary between domains can be defined, and the Ferret diameter in the dispersed phase of the first phase difference image can be defined. If the first phase difference image in the binarized image has a minute particle size that is difficult to distinguish between image noise and phase difference image, or if a clear ferret diameter cannot be defined, it is "not a distributed structure" to decide. If the first phase difference image is buried in image noise and the boundary between domains cannot be defined, the ferret diameter cannot be defined.
Only when the domain shape is striped and the maximum ferret diameter is 300 nm or more, the minimum ferret diameter is used as the domain diameter instead of the maximum ferret diameter.

In order to improve the toughness of the binder resin, it is necessary to introduce a structure that relieves external deformation and pressure inside the resin. For this purpose, it is possible to introduce a softer structure. However, in this case, blocking in which toner particles are fused during storage, or damage and adhesion of an image due to the softness thereof is likely to occur. In order to achieve both toughness and relaxability, it was necessary to resolve the trade-off relationship between the two.
In the present invention, the binder resin can effectively act on the stress relaxation, and the first phase difference image composed of a portion having a large phase difference capable of improving toughness is represented by a second phase composed of a portion having a small phase difference. It was found that the trade-off relationship between improvement in resin toughness and relaxation can be eliminated by adopting a structure in which a phase difference image is dispersed with a fine structure.

(Phase image by tapping mode of atomic force microscope (AFM))
The internal dispersion state of the binder resin is confirmed by a phase image in a tapping mode using an atomic force microscope (AFM). The tapping mode in the atomic force microscope is a method described in Surface Science Letter, 290, 668 (1993), and the phase image is, for example, Polymer, 35, 5778 (1994), Macromolecules, 28, 6773 (1995). ) Etc., the shape of the sample surface is measured while vibrating the cantilever. At this time, due to the viscoelastic nature of the sample surface, a phase difference occurs between the drive that is the vibration source of the cantilever and the actual vibration. A phase image is obtained by mapping the phase difference. A soft part is observed with a large phase delay, and a hard part is observed with a small phase delay.
The binder resin according to the present invention is characterized in that a portion that is observed as an image having low softness, that is, a large phase difference, and a portion that is observed as an image that is hard and has a small phase difference are finely dispersed. At this time, the second phase difference image consisting of a hard and low phase difference portion is the outer phase, and the first phase difference image consisting of a soft high phase difference portion is finely dispersed in the inner phase. This is necessary in the present invention.

The sample for obtaining the phase image can be observed by using a Leica ultramicrotome ULTRACUT UCT, which is obtained by cutting a binder resin block under the following conditions to obtain a section.
・ Cutting thickness: 60 nm
・ Cutting speed: 0.4mm / sec
・ Use of diamond knife (Ultra Sonic 35 °)

As a typical apparatus for obtaining the AFM phase image, for example, MFP-3D manufactured by Asylum Technology Co., Ltd. can be used and observed using the OMCL-AC240TS-C3 as a cantilever under the following measurement conditions.
・ Target amplitide: 0.5V
-Target percent: -5%
・ Amplitude setpoint: 315 mV
・ Scan rate: 1Hz
・ Scan points: 256 × 256
・ Scan angle: 0 °

  As a specific method for measuring the average of the maximum ferret diameter of the first phase difference image (that is, the soft unit) composed of a portion having a large phase difference of the AFM phase image in the present invention, a phase image obtained by the tapping mode AFM is used. It is possible to create a binarized image that is binarized with an intermediate value between the maximum value of the phase difference and the minimum value of the phase difference. As described above, the binarized image is obtained by photographing a phase image so that a portion having a small phase difference has a dark color and a portion having a large phase difference has a light color contrast, and then the maximum value of the phase difference in the phase image is obtained. And binarization processing with the intermediate value between the minimum values of the phase differences as a boundary. In the binarized image, 30 points were selected in order from the ten largest images in the 300 nm square range from the first phase difference image having the largest maximum ferret diameter, and the average was taken as the average of the maximum ferret diameter. However, a minute diameter image (FIG. 3) that is clearly judged as image noise or that is difficult to distinguish between image noise and phase difference image is excluded from the calculation of the average diameter. Specifically, in the observed phase image, the first phase difference image having an area ratio of 1/100 or less existing on the same image is the average of the first phase difference image having the largest maximum ferret diameter. It shall not be used for diameter calculation. The maximum ferret diameter is the maximum distance between parallel lines when a phase difference image is sandwiched between two parallel lines.

  The average value of the maximum ferret diameter is preferably 10 nm or more and less than 100 nm. When the average value of the maximum ferret diameter is 100 nm or more, a strongly adherent unit is likely to be exposed by stress, and the toner filming property may be deteriorated. If the thickness is less than 10 nm, the degree of stress relaxation is significantly weakened, and the improvement effect on toughness may be insufficient. The average value of the maximum ferret diameter is more preferably 10 nm or more and 45 nm or less.

FIG. 1 shows a phase image of the binder resin 1 used in Example 1, which is a typical binder resin in the present invention, and shows a binarized image obtained by subjecting this phase image to the binarization process. It was shown in 2. In FIG. 2, the bright region is a first phase difference image (image with a large phase difference) composed of a portion having a large phase difference, and the dark region is a second phase difference image (a phase difference image) composed of a portion having a small phase difference. Corresponds to a small image).
Only when the domain shape is striped and the maximum ferret diameter is 300 nm or more, the minimum ferret diameter is used as the domain diameter instead of the maximum ferret diameter.

(Molecular weight of binder resin)
The Mw of the resin obtained by block copolymerization of the crystalline segment (A) and the amorphous segment (B) of the present invention is 20 from the viewpoint of achieving the above-mentioned characteristics and compatibility between low-temperature fixability and heat-resistant storage stability. , Preferably 1 to 150,000.
If it is less than 20,000, the heat-resistant storage stability of the toner tends to deteriorate, and the hot offset resistance tends to deteriorate. On the other hand, when it is larger than 150,000, the toner is not sufficiently melted at the time of fixing at a low temperature, and the image is liable to be peeled off.

  In the present invention, the tetrahydrofuran soluble content of the toner and the molecular weight distribution and weight average molecular weight (Mw) of the resin are measured using a gel permeation chromatography (GPC) measuring device (for example, HLC-8220 GPC (manufactured by Tosoh Corporation)). It can be measured. As the column, TSKgel SuperHZM-H 15 cm triplet (manufactured by Tosoh Corporation) was used. The resin to be measured was made into a 0.15 mass% solution in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate was used as a sample. 100 μl of the THF sample solution was injected into a measuring apparatus, and measurement was performed at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C.

The molecular weight was calculated using a calibration curve prepared with a monodisperse polystyrene standard sample. As the standard polystyrene sample, Showdex STANDARD series manufactured by Showa Denko KK and toluene were used. The following three kinds of monodisperse polystyrene standard sample THF solutions were prepared and measured under the above conditions, and a calibration curve was created using the peak top retention time as the light scattering molecular weight of the monodisperse polystyrene standard sample.
Solution A: S-7450 2.5mg, S-678 2.5mg, S-46.5 2.5mg, S-2.90 2.5mg, THF 50ml
Solution B: S-3730 2.5mg, S-257 2.5mg, S-19.8 2.5mg, S-0.580 2.5mg, THF 50ml
Solution C: S-1470 2.5mg, S-112 2.5mg, S-6.93 2.5mg, Toluene 2.5mg, THF 50ml
An RI (refractive index) detector was used as the detector.

(Toner production method)
The method for producing the toner of the present invention is not particularly limited, and examples thereof include known wet granulation methods such as dissolution suspension method and emulsion aggregation method, and pulverization methods. From the difficulty of molecular cutting by kneading and uniform kneading of high molecular weight resin and low molecular weight resin, the dissolution suspension method and emulsion aggregation method, which are production methods not involving kneading of the binder resin, are preferred, and the resin in the toner particles The dissolution suspension method is particularly preferred from the viewpoint of uniformity.

[Dissolution suspension method]
Production of toner by the dissolution suspension method is performed as follows.
First, a toner material liquid is prepared by dispersing or dissolving the above-described colorant, binder resin, mold release agent, and other toner materials in an organic solvent, and then the toner material liquid is aqueous based in the presence of a surfactant and resin fine particles. Particles can be obtained by emulsification in a medium.

(Organic solvent)
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. Particularly preferred are aromatic solvents such as toluene and xylene, halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride, and ethyl acetate. The amount of the organic solvent used is usually 0 to 300 parts, preferably 0 to 100 parts, and more preferably 25 to 70 parts with respect to 100 parts of the toner material.

(Aqueous medium)
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used with respect to 100 parts of the toner material liquid is usually 50 to 2000 parts, preferably 100 to 1000 parts. If the amount is less than 50 parts, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts, it is not economical.

(Surfactant, resin fine particles)
The reason why a dispersant such as a surfactant and resin fine particles is appropriately added to the aqueous medium is to improve the dispersion of the colorant, the hybrid resin, the release agent, and the like. As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt , Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries, Ltd.) Manufactured), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footgent F-300 (Neos), and the like.

(Resin fine particles)
As the resin fine particles, any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin. Examples thereof include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin, two or more of the above resins may be used in combination.
Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained. For example, vinyl resins are polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid-acrylic acid esters. Examples thereof include resins such as a polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer. The average particle size of the resin fine particles is 5 to 200 nm, preferably 20 to 300 nm. In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

(Dispersant)
As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

(Distribution method)
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

(Removal of organic solvent, washing, drying)
The organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation. A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are adhered to the base particles as external additives to obtain a toner. The charge control agent is injected and the inorganic fine particles are externally added by a known method using a mixer or the like.
From the viewpoint of particle size uniformity, the value of [volume average particle size / number average particle size] of the toner of the present invention is preferably 1.0 to 1.4, more preferably 1.0 to 1.3. Is more preferable. The volume average particle diameter of the toner varies depending on the application, but is generally preferably 0.1 to 16 μm. The upper limit is more preferably 11 μm, particularly preferably 9 μm, and the lower limit is further preferably 0.5 μm, particularly preferably 1 μm. The volume average particle size and the number average particle size can be measured simultaneously with Multisizer III (manufactured by Coulter).

<Particle size measurement>
The volume average particle diameter of the colored resin particles is determined by a Coulter counter method. Examples of the measuring device include Coulter Counter TA-II, Coulter Multisizer II, and Coulter Multisizer III (all manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and the number of toner particles or toner are measured with the measuring device using a 100 μm aperture as an aperture, Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter and number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Less than 40 μm; 25.40 to less than 32.00 μm; 13 channels less than 32.00 to 40.30 μm are used, and particles with a particle size of 2.00 to less than 40.30 μm are targeted.

[Emulsion aggregation method]
As a method for producing a toner using an emulsion aggregation method, at least a binder resin dispersion,
A toner slurry can be obtained by agglomeration and fusion with a colorant dispersion, a wax dispersion, etc., and can be recovered by washing and filtration according to a known method, followed by drying.

[Crushing method]
As a method for producing a toner using a pulverization method, according to a conventionally known means, at least a step of mechanically mixing a toner composition comprising a binder resin, a charge control agent of the present invention and a colorant, and melt-kneading And a pulverizing step, and a classification step. In addition, in the mechanical mixing step or the melt-kneading step, a toner other than the toner that becomes the product obtained in the pulverization or classification step may be reused.
The mechanical mixing process may be performed under normal conditions using a mixer having a stirring blade, and is not particularly limited. When this step is completed, the mixture is charged into a kneader and melt-kneaded.

  As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. Specifically, a KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), a TEM type extruder (manufactured by Toshiba Machine Co., Ltd.), a twin screw extruder (manufactured by Kay C.K.), and a PCM type twin screw extruder. (Ikegai Iron Works), Conyder (Bus), etc. The melt-kneading needs to be performed under conditions that do not break the molecular chain of the binder resin. If the melt kneading temperature is too lower than the softening point of the binder resin, the molecular chain is broken, and if it is too high, the dispersion of the charge control agent, colorant, etc. of the present invention does not proceed. It is preferable to set appropriately according to the softening point.

When the step of melt kneading is completed, the kneaded product is pulverized. In the pulverizing step, it is preferable to pulverize after coarse pulverization. Examples of such pulverization methods include a method of pulverizing by colliding with a collision plate in a jet stream, a method of pulverizing particles by colliding with each other in a jet stream, and pulverizing with a narrow gap between a mechanically rotating rotor and a stator. A method is mentioned.
After this step is completed, the pulverized product is classified in an air stream using centrifugal force or the like, whereby a toner having a predetermined particle diameter can be obtained.
Further, the toner is produced by a particle production method as disclosed in Japanese Patent No. 4531076, that is, after the material constituting the toner is dissolved in carbon dioxide in a liquid or supercritical state, the liquid or supercritical state of carbon dioxide is dissolved. It can also be produced by a particle production method for obtaining toner particles by removing carbon.

(Other toner materials)
―Colorant―
There is no restriction | limiting in particular as a coloring agent used for the toner of this invention, According to the objective, it can select suitably from a well-known coloring agent.
The color of the colorant of the toner is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner, Each color toner can be obtained by appropriately selecting the type of colorant, but is preferably a color toner.
Examples of black products include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45 and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like.
Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner may occur. The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. Such a resin is not particularly limited, but from the viewpoint of compatibility with the binder resin in the present invention, the binder resin of the present invention or a resin having a structure similar to the binder resin of the present invention should be used. Is preferred.

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

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

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

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50 to 100 degreeC is preferable and 60 to 90 degreeC is more preferable. If the melting point is less than 50 ° C., the heat resistant storage stability may be adversely affected. If the melting point exceeds 100 ° C., a cold offset may easily occur during fixing at a low temperature.
The melting point of the release agent can be measured using, for example, a differential scanning calorimeter (TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). That is, first, 5.0 mg of the mold release agent is put into an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, the temperature was raised from 0 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and then the temperature was lowered from 150 ° C. to 0 ° C. at a temperature lowering rate of 10 ° C./min. The temperature is raised to 150 ° C. in min and the DSC curve is measured. From the obtained DSC curve, using the analysis program in the DSC-60 system, the maximum peak temperature of the heat of fusion at the second temperature rise can be obtained as the melting point.

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

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 1 mass%-20 mass% are preferable, and 3 mass%-10 mass% are more preferable. . When the content is less than 1% by mass, the hot offset resistance tends to deteriorate, and when it exceeds 20% by mass, the heat resistant storage stability, chargeability, transferability, and stress resistance tend to deteriorate. It is not preferable.

―Charge control agent―
In addition, in order to impart an appropriate charging ability to the toner, a charge control agent can be contained in the toner as necessary.
Any known charge control agent can be used as the charge control agent. Since the color tone may change when a colored material is used, a colorless or nearly white material is preferable. For example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or Examples thereof include fluorine compounds, metal salts of salicylic acid, and metal salts of salicylic acid derivatives. These may be used individually by 1 type and may use 2 or more types together.

  The content of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited. 01 mass%-5 mass% are preferable, and 0.02 mass%-2 mass% are more preferable. When the addition amount exceeds 5% by mass, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is reduced, and the image The concentration may decrease. On the other hand, if it is less than 0.01% by mass, the charge rising property and the charge amount are not sufficient, and the toner image may be easily affected.

―External additive―
Various external additives can be added to the toner for purposes such as fluidity modification, charge amount adjustment, and electrical property adjustment. There is no restriction | limiting in particular as an external additive, According to the objective, it can select suitably from well-known things. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (eg, zinc stearate, aluminum stearate, etc.); metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoro Examples thereof include polymers. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the hydrophobized silica fine particles include HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Also manufactured by Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); Examples include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation). Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.); IT-S (produced by Ishihara Sangyo Co., Ltd.) and the like.

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

1-100 nm is preferable and, as for the average particle diameter of the primary particle of the said inorganic fine particle, 3-70 nm is more preferable. If the average particle size is less than 1 nm, the inorganic fine particles are embedded in the toner, and the function may not be effectively exhibited. If the average particle size exceeds 100 nm, the surface of the electrostatic latent image carrier may be damaged unevenly. May end up. As the external additive, inorganic fine particles or hydrophobized inorganic particles can be used in combination, but the hydrophobized primary particles have an average particle size of at least two types of inorganic fine particles of 20 nm or less, and 30 nm or more. More preferably, it contains at least one kind of inorganic fine particles. Moreover, it is preferable that the specific surface area by the BET method of the said inorganic fine particle is 20-500 m < ² > / g.
The amount of the external additive added is preferably 0.1 to 5% by mass and more preferably 0.3 to 3% by mass with respect to the toner.

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

-Fluidity improver-
When the surface treatment is performed using the fluidity improver, the hydrophobicity of the toner particle surface is improved, and it is possible to suppress a decrease in fluidity and charging characteristics even under high humidity.
Examples of the fluidity improver include, for example, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. Etc.

-Cleaning improver-
When the cleaning property improving agent is added to the toner, the transferred developer remaining on the photoreceptor or the primary transfer medium is easily removed.
Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid; resin particles obtained using soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles. . The resin particles preferably have a narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 μm to 1 μm.

-Magnetic material-
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, a white magnetic material is preferable in terms of color tone.

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

(Career)
There is no restriction | limiting in particular as a carrier, Although it can select suitably according to the objective, What has a core material and the resin layer (coating layer) which coat | covers this core material is preferable.
―Carrier core material―
The core material is not particularly limited as long as it has magnetic particles, and suitable examples include ferrite, magnetite, iron, and nickel. In addition, when considering adaptability to environmental aspects that have been remarkably advanced in recent years, if it is a ferrite, it is not a conventional copper-zinc ferrite, but, for example, manganese ferrite, manganese-magnesium ferrite, manganese-strontium ferrite, manganese- It is preferable to use magnesium-strontium ferrite, lithium ferrite, or the like.
―Coating layer―
The coating layer contains at least a binder resin, and may contain other components such as inorganic fine particles as necessary.

[Binder resin]
The binder resin for forming the carrier coating layer is not particularly limited and may be appropriately selected from known resins according to the purpose. For example, a crosslinkable copolymer containing polyolefin (eg, polyethylene, polypropylene, etc.) or a modified product thereof, styrene, acrylic resin, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc .; consisting of an organosiloxane bond Silicone resins or modified products thereof (for example, modified products by alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.); polyamide; polyester; polyurethane; polycarbonate; urea resin; melamine resin; benzoguanamine resin; Examples thereof include polyimide resins and derivatives thereof. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

  There is no restriction | limiting in particular as said silicone resin, According to the objective, it can select suitably from the silicone resin generally known. For example, a straight silicone resin composed only of an organosiloxane bond and a silicone resin modified with alkyd, polyester, epoxy, acrylic, urethane, etc. can be mentioned.

  Examples of the straight silicone resin include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2405, SR2406 (manufactured by Toray Dow Corning Silicone). Specific examples of the modified silicone resin include epoxy-modified product: ES-1001N, acrylic-modified silicone: KR-5208, polyester-modified product: KR-5203, alkyd-modified product: KR-206, and urethane-modified product: KR-. 305 (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified product: SR2115, alkyd-modified product: SR2110 (manufactured by Toray Dow Corning Silicone), and the like.

  The silicone resin can be used alone, but a crosslinking reactive component, a charge amount adjusting component, and the like can be used at the same time. Examples of the crosslinking reactive component include a silane coupling agent. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, aminosilane coupling agent, and the like.

[Fine particles]
The coating layer may contain fine particles as necessary, and the fine particles are not particularly limited and can be appropriately selected from conventionally known materials according to the purpose. For example, inorganic fine particles such as metal powder, tin oxide, zinc oxide, silica, titanium oxide, alumina, potassium titanate, barium titanate, aluminum borate, polyaniline, polyacetylene, polyparaphenylene, poly (para-phenylene sulfide) , Conductive polymers such as polypyrrole and parylene, and organic fine particles such as carbon black, and two or more of them may be used in combination.
Further, the surface of the fine particles may be subjected to a conductive treatment. As a method of such a conductive treatment, aluminum, zinc, copper, nickel, silver, or an alloy thereof, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin are formed on the surface of the fine particles. And indium oxide doped with antimony, tin oxide doped with antimony, zirconium oxide, and the like in the form of a solid solution or fusion. Among these, a method of conducting a conductive treatment using tin oxide, indium oxide, or indium oxide doped with tin is preferable.

The content of the coating layer in the carrier is preferably 5% by mass or more, and more preferably 5% by mass or more and 10% by mass or less.
The thickness of the coating layer is preferably 0.1 μm to 5 μm, and more preferably 0.3 μm to 2 μm.
Here, the thickness of the coating layer is, for example, 50 or more carrier cross sections using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) after creating a carrier cross section with FIB (focused ion beam). Can be calculated as an average value of the obtained film thicknesses.

―Method of forming carrier coating layer―
The method for forming the coating layer on the carrier is not particularly limited, and a conventionally known coating layer forming method can be used, and the above-described coating layer raw materials including the binder resin or the binder resin precursor are dissolved. The method of apply | coating a coating layer solution on the surface of a core material using the spraying method or the immersion method etc. is mentioned. It is preferable to promote the polymerization reaction of the binder resin or the binder resin precursor by applying the coating layer solution on the surface of the core material and heating the carrier on which the coating layer is formed. The heat treatment may be performed subsequently in the coating apparatus after the coating layer is formed, or may be performed by another heating means such as a normal electric furnace or a firing kiln after the coating layer is formed.
The heat treatment temperature varies depending on the constituent material of the coating layer to be used, and is not generally determined, but is preferably about 120 ° C. to 350 ° C., and particularly preferably not higher than the decomposition temperature of the constituent material of the coating layer. The decomposition temperature of the coating layer constituting material is preferably an upper limit temperature up to about 220 ° C., and the heat treatment time is preferably about 5 minutes to 120 minutes.

―Physical properties of the carrier―
The volume average particle diameter of the carrier is preferably in the range of 10 to 100 μm, and more preferably in the range of 20 to 65 μm.
If the volume average particle size of the carrier is less than 10 μm, carrier adhesion due to the decrease in uniformity of the core material particles may occur, and if it exceeds 100 μm, the reproducibility of image details is poor. It is not preferable because a fine image may not be obtained.
The method for measuring the volume average particle size is not particularly limited as long as it is a device capable of measuring the particle size distribution. Can do.

The volume resistivity of the carrier is preferably 9 [log (Ω · cm)] or more and 16 [log (Ω · cm)] or less, preferably 10 [log (Ω · cm)] or more and 14 [log (Ω · cm)]. cm)]] or less.
When the volume resistivity is less than 9 [log (Ω · cm)], carrier adhesion occurs in the non-image area, and when the volume resistivity is more than 16 [log (Ω · cm)], it is not preferable at the edge portion during development. The so-called edge effect, in which the image density is enhanced, is not preferable. The volume resistivity can be arbitrarily adjusted within this range by adjusting the film thickness of the carrier coating layer and the content of the conductive fine particles as necessary.

The volume resistivity is measured by filling a cell made of a fluororesin container containing electrodes 1a and 1b having a distance between electrodes of 0.2 cm and a surface area of 2.5 cm × 4 cm, and dropping height: Tapping is performed under the conditions of 1 cm, tapping speed: 30 times / min, and tapping frequency: 10 times. Next, a DC voltage of 1000 V was applied between both electrodes, and a resistance value r [Ω] after 30 seconds was measured with a high resistance meter 4329A (manufactured by Yokogawa Hewlett-Packard Co., Ltd .: High Resistance Meter). The volume resistivity R [log (Ω · cm)] can be calculated by calculating as 3).
R = Log [r × (2.5 cm × 4 cm) /0.2 cm] (3)

  When the developer is a two-component developer, the mixing ratio of the toner and the carrier in the two-component developer is preferably such that the mass ratio of the toner to the carrier is 2.0 to 12.0% by mass, More preferably, it is 2.5-10.0 mass%.

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

-Electrostatic latent image forming process and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. Although it can be selected as appropriate, the shape thereof is preferably a drum shape, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like. Is mentioned. Among these, amorphous silicon or the like is preferable in terms of long life.
The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.
The charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying a direct current and an alternating voltage.
Further, the charger is a charging roller disposed in a non-contact proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is carried by applying a direct current and an alternating voltage to the charging roller. Those that charge the body surface are preferred.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. Can do. Examples thereof include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using the developer of the present invention, and can be appropriately selected from known ones. For example, it is preferable to contain the developer of the present invention and to have at least a developing device capable of applying the developer to the electrostatic latent image in a contact or non-contact manner, and provided with the developer-containing container. A developing device or the like is more preferable.

The developing device may be a single color developing device or a multicolor developing device.For example, a stirrer for charging the developer by friction stirring and a rotatable magnet roller. What has is mentioned suitably.
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).
The developer accommodated in the developing device is the developer of the present invention.

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

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. The number of the transfer means may be one, or two or more.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

―Fixing process and fixing means―
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the developer of each color is transferred to the recording medium, or the developer of each color. On the other hand, it may be carried out at the same time in a state where these are laminated.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt.

  The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member It is preferably a unit that heats and fixes a recording medium on which an unfixed image is formed. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.

In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited, and may be appropriately selected from known cleaners as long as the toner remaining on the electrostatic latent image carrier can be removed. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner, and the like are preferable.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit. There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.
The control step is a step of controlling each step, and each step can be suitably performed by a control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

  FIG. 4 shows a first example of an image forming apparatus used in the present invention. The image forming apparatus 100A includes a photosensitive drum 10, a charging roller 20, an exposure device (not shown), a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a static elimination lamp 70. Prepare.

  The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged on the inner side, and can move in the direction of the arrow in the figure. A part of the three rollers 51 also functions as a transfer bias roller that can apply a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer belt 50. Further, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring the toner image to the transfer paper 95 is disposed to face the intermediate transfer belt 50. Further, around the intermediate transfer belt 50, a corona charging device 58 for applying a charge to the toner image transferred to the intermediate transfer belt 50 is connected to the photosensitive drum 10 with respect to the rotation direction of the intermediate transfer belt 50. It is disposed between the contact portion of the intermediate transfer belt 50 and the contact portion of the intermediate transfer belt 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Each color developing unit 45 includes a developer container 42, a developer supply roller 43, and a developing roller 44. The developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can move in the direction of the arrow in the figure. Further, a part of the developing belt 41 is in contact with the photosensitive drum 10.

  Next, a method for forming an image using the image forming apparatus 100A will be described. First, the charging roller 20 is used to uniformly charge the surface of the photosensitive drum 10, and then the exposure light L is exposed to the photosensitive drum 10 using an exposure device (not shown) to form an electrostatic latent image. Form. Next, the electrostatic latent image formed on the photosensitive drum 10 is developed with the toner supplied from the developing device 40 to form a toner image. Further, after the toner image formed on the photosensitive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, the transfer bias applied from the transfer roller 80 is used. Then, it is transferred (secondary transfer) onto the transfer paper 95. On the other hand, the photosensitive drum 10 on which the toner image is transferred to the intermediate transfer belt 50 is discharged by the discharging lamp 70 after the toner remaining on the surface is removed by the cleaning device 60.

  FIG. 5 shows a second example of the image forming apparatus used in the present invention. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are arranged directly facing each other around the photosensitive drum 10 without providing the developing belt 41. Other than that, the configuration is the same as that of the image forming apparatus 100A.

FIG. 6 shows a third example of the image forming apparatus used in the present invention. The image forming apparatus 100 </ b> C is a tandem type color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
In the embodiment of the present invention, the image forming apparatus used for performance evaluation is the one having the structure of the image forming apparatus 100C shown in FIG.

  The intermediate transfer belt 50 provided in the central portion of the copying apparatus main body 150 is an endless belt stretched around three support rollers 14, 15 and 16, and in the direction of the arrow (clockwise direction) in the figure. It can be rotated. In the vicinity of the support roller 15, a cleaning device 17 having a cleaning blade for removing the toner remaining on the intermediate transfer belt 50 on which the toner image is transferred to the recording medium is disposed. A tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are opposed and juxtaposed along the conveying direction while facing the intermediate transfer belt 50 stretched by the support roller 14 and the support roller 15. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. Further, the secondary transfer belt 24 is disposed on the side of the intermediate transfer belt 50 opposite to the side on which the tandem developing device 120 is disposed. The secondary transfer belt 24 is an endless belt stretched between a pair of rollers 23, and the recording medium conveyed on the secondary transfer belt 24 and the intermediate transfer belt 50 are between the rollers 16 and 23. Can touch. Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 is provided with a fixing belt 26 that is an endless belt stretched between a pair of rollers, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26. Is arranged. A sheet reversing device 28 for reversing the recording medium when an image is formed on both sides of the recording medium is disposed in the vicinity of the secondary transfer belt 24 and the fixing device 25.

  Next, a method for forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a color document is set on the contact glass 32 of the scanner 300 to automatically convey the document. The device 400 is closed. When a start switch (not shown) is pressed, when an original is set on the automatic document feeder 400, the original is conveyed and moved onto the contact glass 32, and then the original is set on the contact glass 32. In this case, the scanner 300 is immediately driven, and the first traveling body 33 including the light source and the second traveling body 34 including the mirror travel. At this time, the reflected light from the original surface of the light irradiated from the first traveling body 33 is reflected by the second traveling body 34 and then received by the reading sensor 36 via the imaging lens 35, whereby the original is received. It is read and image information of black, yellow, magenta and cyan is obtained.

The image information of each color of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit 18K, yellow image forming unit 18Y, magenta image forming unit 18M) in each color tandem developing device 120. , And cyan image forming means 18C) to form toner images of respective colors. That is, each image forming means 18 (black image forming means 18K, yellow image forming means 18Y, magenta image forming means 18M, and cyan image forming means 18C) in the tandem developing device 120 is as shown in FIG. And electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier, respectively. Body 10C), charging roller 160 for uniformly charging electrostatic latent image carrier 10, and exposure light L to electrostatic latent image carrier 10 based on the image information of each color, and electrostatic of each color An exposure device 21 that forms a latent image, a developing device 61 that develops an electrostatic latent image with a developer of each color to form a toner image of each color, and a transfer roller for transferring the toner image onto the intermediate transfer belt 50 62 and chestnut A photoconductor cleaning device 63 having a training blade, and a charge removing lamp 64.
The black image, the yellow image, the magenta image, and the cyan image formed by the tandem type developing device 120 for each color are placed on the intermediate transfer member 50 that is stretched around the support rollers 14, 15, and 16, and the static image for black. Black image formed on the electrostatic latent image carrier 10K, yellow image formed on the electrostatic latent image carrier 10Y for yellow, magenta image formed on the electrostatic latent image carrier 10M, and cyan The cyan image formed on the electrostatic latent image carrier 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out the recording medium from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller is rotated to feed out the recording medium on the manual feed tray 54, separated one by one by the separation roller 52, guided to the manual paper feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used with a bias applied in order to remove paper dust from the recording medium. Next, the registration roller 49 is rotated in synchronization with the composite color image (color transfer image) formed on the intermediate transfer belt 50, whereby a recording medium is interposed between the intermediate transfer belt 50 and the secondary transfer belt 24. Then, the composite color image is transferred onto the recording medium (secondary transfer) by the secondary transfer device 22, and the color image is transferred and formed on the recording medium. The toner remaining on the intermediate transfer belt 50 to which the composite color image has been transferred is removed by the intermediate transfer cleaning device 17.

The recording medium on which the composite color image is transferred is conveyed by the secondary transfer belt 24 and then the composite color image is fixed by the fixing device 25. Next, the conveyance path of the recording medium is switched by the switching claw 55, and the recording medium is stacked on the paper discharge tray 57 by the discharge roller 56. Alternatively, the conveyance path of the recording medium is switched by the switching claw 55, reversed by the sheet reversing device 28, guided again to the transfer position, and similarly, an image is formed on the back surface, and then discharged by the discharge roller 56. Stacked on the paper tray 57.
In the image forming apparatus 100C, the occurrence of image conveyance flaws that occur during recrystallization immediately after heat fixing in the present invention occurs when the recording medium passes through the discharge roller 56 or the conveyance roller disposed in the sheet reversing device 28. Occur.

The present invention relates to the following (1) electrophotographic toner, and includes the following (2) to (8) as embodiments.
(1) When the stiffness ratio measured by the large amplitude vibration method is S and the thickening ratio is T,
S <−T and S ≦ 0.5 when the temperature is 100 ° C. and the strain is 100%.
When the temperature is 70 ° C. and the strain is 100%, S> −T and T ≦ −0.5
And
Furthermore, the maximum elastic stress value (ES60) when the strain is 1% when the temperature is lowered from 100 ° C or 70 ° C to 60 ° C is ES60 ≧ 500Pa.
Toner characterized by becoming.
(2) The maximum elastic stress value (ES100) at 100 ° C. of the toner measured by the large amplitude vibration method is 3,000 Pa or less, and the maximum elastic stress value at 70 ° C. when the temperature is lowered from 100 ° C. to 70 ° C. ( The toner according to (1), wherein ES70) is 5,000 Pa or more.
(3) The toner contains a block copolymer having a segment (A) made of amorphous polyester and a segment (C) made of crystalline polyester as a binder resin (1) or ( The toner according to 2).
(4) The toner according to (3), wherein the binder resin further contains a crystalline resin.
(5) The toner according to (3) or (4), wherein the binder resin further contains a modified polyester resin.
(6) The binder resin is produced by a reaction of a non-linear reactive precursor having a branched structure provided by a functional group having a valence of 3 or more and a crosslinking agent capable of reacting with the reactive precursor. The toner according to any one of (3) to (5), comprising an amorphous polyester resin.
(7) In a binarized image obtained by binarizing the phase image observed by the toner tapping mode AFM with an intermediate value between the maximum value and the minimum value of the phase difference in the phase image, from a portion having a large phase difference A first phase difference image and a second phase difference image having a small phase difference, and the first phase difference image is dispersed in the second phase difference image. The toner according to any one of (1) to (6), wherein a dispersion diameter of the first retardation image is 100 nm or less.
(8) A developer containing the toner according to any one of (1) to (7).
(9) A toner cartridge filled with the toner according to any one of (1) to (7).
(10) An image forming apparatus using the toner according to any one of (1) to (7) as a toner

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited to a following example.
Moreover, in the following description, unless otherwise specified, parts indicate parts by mass.

(Production Example 1)
<Manufacture of amorphous resin A1>
A 5 L four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple is charged with propylene glycol as the diol and dimethyl terephthalate and dimethyl adipate at a molar ratio of 90/10. OH / COOH = 1.2, reacted with 300 ppm of titanium tetraisopropoxide while flowing methanol, and finally heated up to 230 ° C. until the resin acid value was 5 or less. Then, it was made to react at the reduced pressure of 20 mmHg-30mmHg for 4 hours, and the linear amorphous polyester resin was obtained. The obtained resin had an acid value (AV) of 1.08 mgKOH / g, a hydroxyl value (OHV) of 23.3 mgKOH / g, and a Tg of 59.2 ° C.

(Production Example 2)
<Production of amorphous resin A2>
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with propylene glycol as a diol and dimethyl terephthalate as a dicarboxylic acid at OH / COOH = 1.2, and 300 ppm of titanium tetraiso The reaction was carried out while flowing methanol together with propoxide, and finally the reaction was heated to 230 ° C. until the resin acid value was 5 or less. Then, it was made to react at the reduced pressure of 20 mmHg-30mmHg for 4 hours, and the linear amorphous polyester resin was obtained. The obtained resin had an acid value (AV) of 0.37 mg KOH / g, a hydroxyl value (OHV) of 25.3 mg KOH / g, and a Tg of 72.0 ° C.

(Production Example 3)
<Manufacture of amorphous resin A3>
A 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple is mixed with propylene glycol as a diol, dimethyl terephthalate and trimellitic anhydride as a polybasic acid in a molar ratio of 97.5 / 2. .5, charged with OH / COOH = 1.3, reacted with 300 ppm of titanium tetraisopropoxide while flowing methanol, and finally heated up to 230 ° C. until the resin acid value was 5 or less. I let you. Then, it was made to react at the reduced pressure of 20 mmHg-30mmHg for 4 hours, and the amorphous polyester resin with a branched structure was obtained. The obtained resin had an acid value (AV) of 0.94 mg KOH / g, a hydroxyl value (OHV) of 23.2 mg KOH / g, and a Tg of 48.6 ° C.

(Production Example 4)
<Production of crystalline resin C1>; BD / SA
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,4-butanediol as a diol, sebacic acid as a dicarboxylic acid, and a ratio of OH groups to COOH groups (OH / COOH) was adjusted to 1.1, and reacted with 300 ppm of titanium tetraisopropoxide while water was allowed to flow out. Finally, the temperature was raised to 230 ° C. until the resin acid value reached 5 KOH / g or less. Reacted. Then, it was made to react under reduced pressure of 10 mmHg or less for 6 hours, and [crystalline resin C1] which is crystalline polyester resin was obtained.
The obtained resin had an acid value (AV) of 0.38 mg KOH / g, a hydroxyl value (OHV) of 22.6 mg KOH / g, and a Tm of 63.8 ° C.
Table 1 summarizes the physical properties of the resins obtained in the above Production Examples 1 to 4.

(Production Example 5-Production Example 9)
<Production of block copolymers B1 to B5>
A 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was charged with 1400 g of [Amorphous Resin A1] and 600 g of [Crystalline Resin C1] at 60 ° C. for 2 hours. Vacuum drying was performed at 10 mmHg. After decompression of nitrogen, 2000 parts of ethyl acetate that had been dehydrated with molecular sieves 4A was added and dissolved under nitrogen flow until uniform. Next, 140 g of 4,4′-diphenylmethane diisocyanate was added to the system and stirred under visual observation until uniform. Thereafter, 100 ppm of tin 2-ethylhexanoate was added as a catalyst, the temperature was raised to 80 ° C., and the mixture was reacted for 5 hours under reflux. Next, ethyl acetate was distilled off under reduced pressure to obtain [Block Copolymer B1].
[Block copolymer B2] to [Block copolymer B5] in the same manner as in Production Example 95, except that the combination and input amount of amorphous resin A1 and crystalline resin C1 were changed as shown in Table 1. Got.
Table 2 shows the compositions and composition ratios of the obtained [Block Copolymer B2] to [Block Copolymer B5].

(Production Example 10)
<Manufacture of colorant master batch>
[Block copolymer B1] 100 parts, 100 parts of cyan pigment (CI Pigment blue 15: 3) and 30 parts of ion-exchanged water were mixed well, and an open roll kneader (NIDEX / Mitsui Mine ( Kneading). The kneading temperature started kneading from 90 ° C. and then gradually cooled to 50 ° C. to prepare [Colorant masterbatch P1] in which the ratio (mass ratio) of the resin to the pigment was 1: 1.
Further, [Colorant Masterbatch P2] is similarly applied except that [Block Copolymer B1] is changed to [Block Copolymer B2] to [Block Copolymer B5] or [Amorphous Resin A1]. [Colorant masterbatch P6] was produced.

(Production Example 11)
<Manufacture of wax dispersion>
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 20 parts of paraffin wax (HNP-9 (melting point: 75 ° C.), Nippon Seiwa Co., Ltd.) and 80 parts of ethyl acetate are placed and heated to 78 ° C. It melt | dissolved enough and it cooled to 30 degreeC in 1 hour, stirring. Next, wet pulverization was carried out with an ultra visco mill (manufactured by IMEX) under the conditions of a liquid feeding speed of 1.0 kg / hr, a disk peripheral speed of 10 m / sec, a 0.5 mm zirconia bead filling amount of 80% by volume, and a pass number of 6 times. Then, ethyl acetate was added to adjust the solid content concentration to produce a [wax dispersion] having a solid content concentration of 20%.

Example 1
-Production of Toner 1-
In a container equipped with a thermometer and a stirrer, 94 parts of [Block Copolymer B1] and 81 parts of ethyl acetate were placed and heated to the melting point of the resin or higher to dissolve well. Next, 25 parts of [Wax Dispersion] and 12 parts of [Colorant Masterbatch P1] were added, and the mixture was stirred at 50 ° C. with a TK homomixer (manufactured by Special Machine Co., Ltd.) at a rotation speed of 10,000 rpm. Was dissolved and dispersed in [Oil Phase 1]. The temperature of [Oil Phase 1] was kept at 50 ° C. in the container.
Next, in another container in which a stirrer and a thermometer are set, 75 parts of ion-exchanged water, organic resin fine particles for dispersion stabilization (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium, 3 parts of a 25% by weight dispersion of a salt copolymer) (manufactured by Sanyo Chemical Industries), 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (ELEMINOL MON-7, manufactured by Sanyo Chemical Industries) 16 parts and 5 parts of ethyl acetate were mixed and stirred at 40 ° C. to prepare an aqueous phase solution. Next, 50 parts of [Oil Phase 1] maintained at 50 ° C. was added and mixed at 45 ° C. to 48 ° C. with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at 12,000 rpm for 1 minute. An emulsified slurry 1] was obtained.
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 50 ° C. for 2 hours to obtain [Slurry 1].

After 100 parts of [Slurry 1] of the obtained toner base particles were filtered under reduced pressure, the following washing treatment was performed.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(2) 100 parts of a 10% by mass aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), and then filtered under reduced pressure.
(3) 100 parts of 10 mass% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (5 minutes at 6,000 rpm), and then filtered.
(4) Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (5 minutes at 6,000 rpm) and then filter twice, and filter [filter cake 1]. Obtained.

The obtained [Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, the mixture was sieved with a 75 μm mesh to produce [Toner Base Particle 1].
Next, 100 parts of [Mother toner particles 1] thus obtained were mixed with 1.0 part of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) and 0.3 part of titanium oxide (MT-150AI, manufactured by Teica). [Toner 1] was prepared by mixing using a Henschel mixer. The characteristic values of the obtained toner were evaluated, and the results are shown in Table 3.
The particle size distribution was measured using a Coulter Multisizer III.
The characteristic value by the LAOS method was measured using the ARES-G2 manufactured by TA Instruments, under the measurement conditions described above.
The dispersion diameter of the phase image was measured using MFP-3D manufactured by Asylum Technology, Inc., and using OMCL-AC240TS-C3 as a cantilever under the measurement conditions described above.

-Manufacture of carrier 1-
As a core material, 5,000 parts of Mn ferrite particles (weight average diameter: 35 μm) were used. Moreover, as a coating material, 300 parts of toluene, 300 parts of butyl cellosolve, an acrylic resin solution (composition ratio methacrylic acid: methyl methacrylate: 2-hydroxyethyl acrylate = 5: 9: 3, solid content 50 mass% toluene solution, Tg 38 ° C.) 60 parts of N-tetramethoxymethylbenzoguanamine resin solution (polymerization degree 1.5, solid content 77 mass% toluene solution) 15 weight and alumina particles (average primary particle size 0.30 μm) 15 weight were dispersed with a stirrer for 10 minutes. The prepared coating solution was used. The core material and the coating liquid were introduced into a coating apparatus for coating while forming a swirling flow provided with a rotary bottom plate disk and a stirring blade in a fluidized bed, and the coating liquid was applied onto the core material. The obtained coated material was baked in an electric furnace at 220 ° C. for 2 hours to obtain [Carrier 1].

-Production of Developer 1-
[Carrier 1] 7 parts of [Toner 1] prepared above with respect to 100 parts were mixed at 48 rpm using a type of tumbler mixer (manufactured by Willy et Bacofen (WAB)) in which the container was rolled and stirred. Were mixed uniformly for 5 minutes to obtain [Developer 1] as a two-component developer.
In addition, for the two-component developer produced above, an indirect transfer tandem image forming apparatus employing a contact charging method, a two-component development method, a secondary transfer method, a blade cleaning method, and an external heating roller fixing method (see FIG. The image was formed in the developing unit of the image forming apparatus A100C) shown in FIG. 6 to form an image, and the performance of the toner and developer was evaluated.

-Evaluation-
Hereinafter, the method for evaluating the quality of the toner and developer in the present invention will be described in detail.
(Evaluation method)
<< Fixability (Low-temperature fixability) >>
Using the tandem-type full-color image forming apparatus 100C shown in FIG. 6, the toner adhesion amount after transfer on the transfer paper (manufactured by Ricoh Business Expert Co., Ltd., <70>) is 0.85 ± 0.10 mg. A solid image (image size 3 cm × 8 cm) of / cm ^{2 on} the entire paper surface was formed, and fixing was performed by changing the temperature of the fixing belt. Using the drawing tester AD-401 (manufactured by Ueshima Seisakusho Co., Ltd.), the surface of the obtained fixed image is drawn with a ruby needle (tip radius 260 μmR to 320 μmR, tip angle 60 degrees), a load of 50 g, and a fiber (Hanicot # 440). (Manufactured by Hanilon Co., Ltd.), the drawing surface was rubbed strongly 5 times, and the fixing belt temperature at which the image was hardly scraped was determined as the minimum fixing temperature. Further, the solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction. The speed of passing through the nip portion of the fixing device is 280 mm / s. The lower the fixing minimum temperature, the better the low-temperature fixability.
〔Evaluation criteria〕
◎: 105 ° C or less ○: 105 ° C over 115 ° C or less △: 115 ° C over 130 ° C or less X: over 130 ° C

<< Fixability (Hot Offset Resistance / Fixing Width) >>
Using the tandem-type full-color image forming apparatus 100C shown in FIG. 6, the entire surface of the paper having a toner adhesion amount of 0.85 ± 0.10 mg / cm ² on the transfer paper (Ricoh Co., Ltd., type 6200). An image (image size 3 cm × 8 cm) is imaged, fixing is performed by changing the temperature of the fixing belt, the presence or absence of hot offset is visually evaluated, and the difference between the upper limit temperature at which hot offset does not occur and the lower limit fixing temperature are determined. The fixing width was used. Further, the solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction. The speed of passing through the nip portion of the fixing device is 280 mm / s. The wider the fixing width, the better the hot offset resistance, and about 50 ° C. is an average temperature range of the conventional full-color toner.
〔Evaluation criteria〕
◎: Over 100 ° C ○: Over 55 ° C over 100 ° C △: Over 30 ° C over 55 ° C ×: 30 ° C or below

<< Heat-resistant storage stability (Penetration) >>
Each toner was filled in a 50 mL glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the value of penetration is large, and in the case of less than 5 mm, there is a high possibility of problems in use.
In the present invention, the penetration is expressed by the penetration depth (mm).
〔Evaluation criteria〕
◎: Needle penetration 25 mm or more ○: Needle penetration 15 mm or more and less than 25 mm △: Needle penetration 5 mm or more and less than 15 mm ×: Needle penetration less than 5 mm

(Discharge resistance)
Developers (1) to (12) created from the obtained toners (1) to (12) are mounted on Imagio C2802, and 10 sheets of solid images (toner adhesion amount is 0.6 mg / cm ² ) on A4 paper Printed continuously. Images were visually observed and ranked as follows.
〔Evaluation criteria〕
(Double-circle): The state which a damage | wound or a gloss difference is not seen visually in all the images.
○: A state in which a slight gloss difference is visually observed in part of the image.
(Triangle | delta): The state in which the part with glossiness difference like a streak is visually observed in a part of image.
X: The toner is peeled off from the image and the paper can be seen.

<Image adhesion (stackability)>
30 sheets of unfixed image with a solid image on the A4 paper (toner adhesion amount of 0.85 mg / cm ² ) is continuously passed through the fixing machine, immediately overlaid, and 70 sheets of A4 paper are placed on top of it. I applied. The image state after leaving for 10 minutes was evaluated according to the following criteria.
A: The papers are not bonded. It peels off immediately.
○: Slightly bonded, but no traces left on the image.
X: When strongly adhered and forcibly removed, the toner on the image is peeled off and the paper is torn.

(Examples 2 to 5)
-Production of toners 2-5 and developers 2-5-
In the production of the toner of Example 1, instead of [Block Copolymer B1], [Block Copolymer B2] to [Block Copolymer B5] are respectively changed to [Colorant Master Batch P1] [ [Toner 2] to [Toner 5] and [Developer 2] to [Developer 5] in the same manner as in Example 1 except that the colorant master batch P2] to [Colorant master batch P5] were changed. The toner and the developer were evaluated for quality. The results are shown in Table 4.

(Example 6)
In the production of the toner of Example 1, 89 parts of [Block Copolymer B1], 5 parts of [Crystalline Resin C1] and 81 parts of Ethyl Acetate were added and heated to the melting point of the resin or higher and dissolved well to obtain an oil phase. [Toner 6] and [Developer 6] were prepared in the same manner as in Example 1 except that the toner and the developer were evaluated for quality. The results are shown in Table 4.

(Example 7)
In the production of the toner of Example 1, 84 parts of [Block Copolymer B1], 10 parts of [Crystalline Resin C1] and 81 parts of Ethyl Acetate are added and heated to the melting point of the resin or higher to dissolve well and the oil phase. [Toner 7] and [Developer 7] were prepared in the same manner as in Example 1 except that the toner and the developer were evaluated for quality. The results are shown in Table 4.

(Example 8)
-Synthesis of ketimine compounds-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1].
The amine value of [ketimine compound 1] was 418.

-Synthesis of (prepolymer 1) of urea-modified polyester resin-
712 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 285 parts of terephthalic acid, trimellitic anhydride 22 parts and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and then reacted for 5 hours under reduced pressure of 10 mmHg to 15 mmHg to obtain [Intermediate Polyester 1]. The glass transition point of [Intermediate polyester 1] was 57 ° C.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. [Prepolymer 1] was obtained.

  In the production of the toner of Example 1, 74 parts of [Block Copolymer B1], 5 parts of [Crystalline Resin C1] and 61 parts of Ethyl Acetate are added and heated to the melting point of the resin or higher to dissolve well. 25 parts of dispersion and 12 parts of [colorant master batch P1] are added and stirred at 50 ° C. with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotation speed of 10,000 rpm to be uniformly dissolved. Further, 15 parts of [Prepolymer 1] and 0.5 part of [ketimine compound] were dispersed to obtain [Oil Phase 8]. [Toner 8] and [Developer 8] were prepared in the same manner as in Example 1 except that the temperature of [Oil phase 1] was maintained at 50 ° C. in the container. Evaluation was performed.

Example 9
-Synthesis of Prepolymer 2-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe, 3-methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimellitic anhydride were added in a molar ratio of hydroxyl group to carboxyl group. A certain OH / COOH is 1.5, the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol, the composition of the dicarboxylic acid component is 40 mol% of isophthalic acid and 60 mol% of adipic acid, Titanium tetraisopropoxide (1,000 ppm with respect to the resin component) was added so that the amount of trimellitic anhydride in the monomer was 1 mol%. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Thereafter, the reaction was carried out under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate Polyester 2].
Next, [Intermediate polyester 2] and isophorone diisocyanate (IPDI) are in a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. The solution was added at 0, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain [Prepolymer 2].

  In the production of the toner of Example 1, 74 parts of [Block Copolymer B1], 5 parts of [Crystalline Resin C1] and 61 parts of Ethyl Acetate are added and heated to the melting point of the resin or higher to dissolve well. 25 parts of dispersion and 12 parts of [colorant master batch P1] are added and stirred at 50 ° C. with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotation speed of 10,000 rpm to be uniformly dissolved. Further, [Toner 9] and [Developer 9] were obtained in the same manner as in Example 1 except that 15 parts of [Prepolymer 2] and 0.5 part of [ketimine compound] were dispersed to obtain [Oil Phase 9]. The toner and the developer were evaluated for quality.

(Example 10)
[Toner 10] and [Developer 10] were prepared in the same manner as in Example 9 except that [Block Copolymer B1] was changed to [Block Copolymer B4] in the production of the toner of Example 9. The quality of the toner and developer was evaluated.

(Comparative Example 1)
In the production of the toner of Example 7, except that [Block Copolymer B1] is replaced with [Block Copolymer B5] and [Colorant Masterbatch P1] is replaced with [Colorant Masterbatch P6]. [Toner 11] and [Developer 11] were prepared in the same manner as in Example 7, and the quality of the toner and developer was evaluated. The results are shown in Table 4.

(Comparative Example 2)
In the production of the toner of Example 7, except that [Block Copolymer B1] is replaced with [Amorphous Resin A1] and [Colorant Masterbatch P1] is replaced with [Colorant Masterbatch P6]. [Toner 12] and [Developer 12] were prepared in the same manner as in Example 7, and the quality of the toner and developer was evaluated. The results are shown in Table 4.

10 Electrostatic latent image carrier (photosensitive drum)
10K Black electrostatic latent image carrier 10Y Yellow electrostatic latent image carrier 10M Magenta electrostatic latent image carrier 10C Cyan electrostatic latent image carrier 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer Supply roller 44K Developing roller 44Y Developing roller 44M Developing row 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer belt 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona Charging device 60 Cleaning device 61 Developing device 62 Transfer roller 63 Photoconductor cleaning device 64 Static elimination lamp 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A, 100B, 100C Image forming device 120 Tandem type developer 130 Document table 142 Paper feed Roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying device main body 160 Charging device 200 Paper feed tray Le 300 Scanner 400 automatic document feeder (ADF)

Japanese Patent No. 3949553 Japanese Patent No. 4155108 JP 2006-071906 A JP 2006-251564 A JP 2007-286144 A Japanese Patent Publication No. 4-024702 JP-B-4-024703 JP-A 63-027855 Japanese Patent No. 4563546 Japanese Patent No. 4218303 JP2012-27212A Japanese Patent No. 3360527 Japanese Patent No. 3910338

Claims (10)

Measured by the large amplitude vibration method, when the stiffness ratio is S and the thickness ratio is T,
S <−T and S ≦ 0.5 when the temperature is 100 ° C. and the strain is 100%.
When the temperature is 70 ° C. and the strain is 100%, S> −T and T ≦ −0.5
And
Furthermore, the maximum elastic stress value (ES60) when the strain is 1% when the temperature is lowered from 100 ° C or 70 ° C to 60 ° C is ES60 ≧ 500Pa.
Toner characterized by becoming.   The maximum elastic stress value (ES100) at 100 ° C. of the toner measured by the large amplitude vibration method is 3,000 Pa or less, and the maximum elastic stress value (ES70) at 70 ° C. when the temperature is lowered from 100 ° C. to 70 ° C. The toner according to claim 1, wherein the toner is 5,000 Pa or more.   3. The toner according to claim 1, wherein the toner contains a block copolymer having a segment (A) made of amorphous polyester and a segment (C) made of crystalline polyester as a binder resin. toner.   The toner according to claim 3, further comprising a crystalline resin as the binder resin.   The toner according to claim 3, further comprising a modified polyester resin as the binder resin.   As the binder resin, a non-linear reactive precursor having a branched structure imparted by a functional group having a valence of 3 or more and an amorphous product formed by the reaction of a crosslinking agent capable of reacting with the reactive precursor. The toner according to claim 3, comprising a polyester resin.   A binarized image obtained by binarizing the phase image observed by the toner tapping mode AFM with an intermediate value between the maximum value and the minimum value of the phase difference in the phase image is a first image having a portion having a large phase difference. And a second phase difference image composed of a portion having a small phase difference, wherein the first phase difference image is dispersed in the second phase difference image, The toner according to claim 1, wherein the dispersion diameter of one retardation image is 100 nm or less.   A developer comprising the toner according to claim 1.   A toner cartridge filled with the toner according to claim 1.   An image forming apparatus using the toner according to claim 1 as a toner.