JP2014048638A - Toner, developer, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has excellent low-temperature fixability and heat-resistance storage stability, and has sufficient strength against dynamic stress.SOLUTION: A toner contains a crystalline resin; and the crystalline resin contains a crystalline resin having at least any one of a urethane bond and a urea bond, and a crystalline polyester unit. The tetrahydrofuran solubles of the toner includes 5.0% or more of a compound with the molecular weight of 100,000 or more at the peak area, in the molecular weight distribution measured by gel permeation chromatography; and when the tetrahydrofuran solubles of the toner is decomposed in a 0.1 N KOH methanol solution, the rate of decomposition residue insoluble to methanol is 5.0 mass% or more.

Description

  The present invention relates to a toner, a developer, 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 recording medium such as paper and then fixed on the recording medium such as paper. In the fixing process for fixing a toner image on a recording medium, a heat fixing method such as a heating roller fixing method or a heating belt fixing method is widely used because of its energy efficiency.

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

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

As a toner using a crystalline resin, for example, a toner using a crystalline resin obtained by extending crystalline polyester with diisocyanate as a binder resin has been proposed (see, for example, Patent Documents 1 and 2).
In addition, a toner using a crystalline resin having a crosslinked structure with an unsaturated bond containing a sulfonic acid group has been proposed (see, for example, Patent Document 3).
In addition, a resin particle technique has been proposed that defines the ratio between the softening temperature and the melting heat peak temperature and the viscoelastic properties and is excellent in low-temperature fixability and heat-resistant storage stability (see, for example, Patent Document 4).
Further, when a toner containing a block polymer having a crystal structure as a main component of a binder resin is produced by a dissolution suspension method, after removing the organic solvent, the toner is heated at a specific temperature in consideration of the thermal characteristics of the block polymer. A toner manufacturing method that performs heat treatment has been proposed (see, for example, Patent Document 5).

  However, including these proposed technologies, conventional toners using crystalline resins as binder resins have excellent low-temperature fixability and heat-resistant storage stability, but have low toner strength against mechanical stress. There is a problem in that toner agglomerates are generated due to a stirring stress or the like, and as a result, a print image is lost or an image is smeared and the print quality is remarkably impaired.

  Therefore, the present situation is that there is a demand for a toner having excellent low-temperature fixability and heat-resistant storage stability and sufficient strength against mechanical stress.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a toner having excellent low-temperature fixability and heat-resistant storage stability and sufficient strength against mechanical stress.

Means for solving the problems are as follows. That is,
The toner of the present invention is a toner containing a crystalline resin,
The crystalline resin contains a crystalline resin having at least one of a urethane bond and a urea bond, and a crystalline polyester unit;
In the molecular weight distribution measured by gel permeation chromatography, the tetrahydrofuran-soluble content of the toner contains a component having a molecular weight of 100,000 or more in a peak area of 5.0% or more,
The ratio of the decomposition residue insoluble in methanol when the tetrahydrofuran-soluble component of the toner is decomposed in a 0.1N KOH methanol solution is 5.0% by mass or more.

  According to the present invention, the conventional problems can be solved, and a toner having excellent low-temperature fixability and heat-resistant storage stability and sufficient strength against mechanical stress can be provided.

FIG. 1A is a diagram showing an example of a diffraction spectrum obtained by X-ray diffraction measurement. FIG. 1B is a diagram showing an example of a diffraction spectrum obtained by X-ray diffraction measurement. FIG. 2 shows an example of a ¹³ C NMR spectrum confirming the presence of a urea bond. FIG. 3 is a schematic configuration diagram showing an example of the image forming apparatus of the present invention. FIG. 4 is a partially enlarged view of FIG. FIG. 5 is an integral molecular weight distribution curve in the GPC measurement of the toner in Example 1.

(toner)
The toner of the present invention contains at least a crystalline resin, and further contains other components as necessary.
The crystalline resin contains a crystalline resin having at least one of a urethane bond and a urea bond and a crystalline polyester unit.
The tetrahydrofuran-soluble component of the toner contains 5.0% or more of a peak area of components having a molecular weight of 100,000 or more in the molecular weight distribution measured by gel permeation chromatography.
The ratio of the decomposition residue insoluble in methanol when the tetrahydrofuran-soluble content of the toner is decomposed in a 0.1N KOH methanol solution is 5.0% by mass or more.

  In order to provide a toner having excellent low-temperature fixability and heat-resistant storage stability and having sufficient strength against mechanical stress, the present inventors have conducted intensive studies and found that at least urethane bonds and urea bonds as binder resins. In a toner containing a crystalline resin having any of the above and a crystalline polyester unit (particularly, a toner containing a crystalline resin as a main component), the tetrahydrofuran soluble content of the toner is measured by gel permeation chromatography. In which a component having a molecular weight of 100,000 or more is contained in a peak area of 5.0% or more and a tetrahydrofuran-soluble component of the toner is decomposed in a 0.1N KOH methanol solution in a methanol-insoluble decomposition residue. Only when the ratio is 5.0% by mass or more can the toner be subjected to mechanical stress. While having that intensity sufficiently, it found that it is possible to provide a toner excellent in heat storage stability and low-temperature fixing property.

  The reason is considered as follows. First, by introducing urethane bond sites and urea bond sites with large cohesive energy into the polymer skeleton, which is a binder resin, a portion that can be physically cross-linked is created in the polymer chain, and as a result, the mechanical strength of the resin is improved. Thus, toner aggregation can be suppressed. However, since a structure different from the crystal structure forming unit is introduced into the resin having crystallinity, the crystal structure of the entire resin becomes non-uniform, so the temperature is lower than the melting point originally possessed. As a result, the resin is softened, resulting in a decrease in heat resistant storage stability. A method for preventing softening of the resin at a temperature lower than the original melting point is to increase the order of the molecular structure of the polymer. In other words, the crystalline structure of the crystalline resin can be obtained by introducing a urethane unit or a urea binding site into the resin as a polyurethane unit or a polyurea unit in a block having a certain size, instead of being scattered in the molecule. Since the portion can be ordered and a crystal structure can be formed, a toner having high mechanical strength can be obtained while maintaining the original melting point. However, since the number of physical cross-linking points is reduced as compared with a state where urethane bond sites or urea bond sites are scattered, the mechanical strength is lowered and the strength against the mechanical stress of the toner becomes insufficient. Therefore, the presence of a high molecular weight component, specifically, a component having a molecular weight in terms of polystyrene of 100,000 or more in gel permeation chromatography (GPC) of a certain amount or more increases mechanical strength and has sufficient toner strength. In addition, it is possible to obtain a toner excellent in low-temperature fixability and heat-resistant storage stability.

  The presence of polyurethane units and polyurea units in the crystalline resin in the toner can be known from the amount of decomposition residue insoluble in methanol when the tetrahydrofuran solubles of the toner are decomposed in a 0.1N KOH methanol solution. it can. In an alkaline environment, the polyester unit breaks the ester bond and decomposes to the monomer unit, but the degradation of the polyurethane unit and the polyurea unit does not proceed or is extremely slow. Therefore, if the unit is somewhat large, it does not dissolve in the solvent (methanol) and remains as a decomposition residue. The ratio of the decomposition residue can be defined as a numerical value obtained by dividing the decomposition residue by the original sample amount subjected to decomposition. The component of the decomposition residue can be confirmed by a method such as an infrared absorption spectrum (IR) pattern or a pyrolysis gas chromatogram mass spectrometer (py-GCMS).

<Binder resin>
The toner contains a crystalline resin as a binder resin.
The binder resin contains at least a crystalline resin, and further contains other components such as an amorphous resin as necessary.

<< Crystalline resin >>
The crystalline resin contains at least a crystalline resin having at least one of a urethane bond and a urea bond and a crystalline polyester unit, and further contains other components as necessary.

The crystalline resin in the present invention is a resin having a portion having a crystal structure, and has a diffraction peak derived from the crystal structure in a diffraction spectrum obtained by an X-ray diffractometer. The crystalline resin is, for example, a ratio of a softening temperature measured by a Kaohashi flow tester and a maximum peak temperature of heat of fusion measured by a differential scanning calorimeter (DSC) (softening temperature / maximum peak of heat of fusion). Temperature) is 0.8 to 1.6, and shows a property of being softened sharply by heat.
The non-crystalline resin in the present invention is a resin having no crystal structure, and does not have a diffraction peak derived from the crystal structure in a diffraction spectrum obtained by an X-ray diffractometer. The amorphous resin has, for example, a ratio of softening temperature to the maximum peak temperature of the heat of fusion (softening temperature / maximum peak temperature of the heat of fusion) greater than 1.6 and exhibits a property of being softened gently by heat.

  The softening temperature of the resin can be measured using a Koka flow tester (for example, CFT-500D (manufactured by Shimadzu Corporation)). While heating 1 g of resin as a sample at a heating rate of 3 ° C./min, a load of 2.94 MPa was applied by a plunger, extruded from a nozzle with a diameter of 0.5 mm and a length of 1 mm, and the plunger drop of the flow tester against the temperature The amount is plotted, and the temperature at which half of the sample flows out is defined as the softening temperature.

  The maximum peak temperature of the heat of fusion of the resin can be measured using a differential scanning calorimeter (DSC) (for example, a differential scanning calorimeter Q2000 (manufactured by TA Instruments)). As a pretreatment, a sample to be used for measurement of the maximum peak temperature of heat of fusion is melted at 130 ° C., then lowered from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./minute, and then from 70 ° C. to 10 ° C. The temperature is lowered at a rate of 0.5 ° C./min. Here, by DSC, the temperature is increased at a rate of temperature increase of 10 ° C./min to measure the endothermic change, and a graph of “endothermic amount” and “temperature” is drawn. The endothermic peak temperature at 100 ° C. is defined as “Ta *”. When there are a plurality of endothermic peaks, the temperature of the peak with the largest endothermic amount is Ta *. Thereafter, the sample is stored at (Ta * −10) ° C. for 6 hours, and further stored at (Ta * −15) ° C. for 6 hours. Next, the sample was cooled to 0 ° C. by DSC at a temperature decrease rate of 10 ° C./min, and then the temperature was increased at a temperature increase rate of 10 ° C./min to measure the endothermic change. The temperature corresponding to the maximum peak of heat quantity is defined as the maximum peak temperature of heat of fusion.

-Crystalline resin having at least one of urethane bond and urea bond and crystalline polyester unit-
There is no restriction | limiting in particular as crystalline resin which has at least any one of the said urethane bond and a urea bond, and a crystalline polyester unit, According to the objective, it can select suitably.

A method for obtaining a crystalline resin having at least one of the urethane bond and the urea bond and a crystalline polyester unit is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyurethane unit or a polyurea is previously prepared. A method (prepolymer method) obtained by preparing a prepolymer comprising units and bonding it to a separately prepared crystalline polyester unit having a hydroxyl group at the terminal, a crystalline polyester unit having a hydroxyl group at the terminal and a low molecular weight polyisocyanate Examples thereof include a method (one-shot method) obtained by mixing and reacting with a low molecular weight polyol or polyamine. Among these, the prepolymer method is preferable. In the one-shot method, the formation of the polyurethane unit or the polyurea unit is usually uneven, and a large unit cannot be formed and the crystallinity of the crystalline polyester unit tends to be hindered. At least one of the unit and the polyurea unit can be sufficiently formed. For example, by using a polyamine whose reaction with isocyanate is faster than a crystalline polyester unit having a hydroxyl group at the terminal, a polyurea unit is formed preferentially at the beginning of the reaction, and then the bonding between the crystalline polyester unit and the polyurea unit is performed. By proceeding with the reaction, a crystalline resin having at least one of the urethane bond and urea bond and a crystalline polyester unit having a somewhat large polyurea unit and a crystalline urea unit can be obtained even by the one-shot method.
In the prepolymer method, a polyurethane urea unit in which a polyurethane unit and a polyurea unit are mixed may be used as a prepolymer.

--- Crystalline polyester unit--
The crystalline polyester unit is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polycondensed polyester unit synthesized from a polyol and a polycarboxylic acid, a lactone ring-opening polymer, An acid etc. are mentioned. Among these, a polycondensation polyester unit of diol and dicarboxylic acid is preferable from the viewpoint of crystallinity.

--- Polyol ---
Examples of the polyol include diols, trivalent to octavalent or higher polyols.

  The diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic diols such as linear aliphatic diols and branched aliphatic diols, and alkylene ether glycols having 4 to 36 carbon atoms. , An alicyclic diol having 4 to 36 carbon atoms, an alkylene oxide of the alicyclic diol (hereinafter, “alkylene oxide” may be abbreviated as “AO”), an AO adduct of bisphenols, a polylactone diol, Examples thereof include polybutadiene diol, diol having a carboxyl group, diol having a sulfonic acid group or sulfamic acid group, and a diol having another functional group such as a salt thereof. Among these, an aliphatic diol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic diol having 2 to 36 chain carbon atoms is more preferable. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content with respect to the whole diol of the said linear aliphatic diol, Although it can select suitably according to the objective, 80 mol% or more is preferable and 90 mol% or more is more preferable. When the content is 80 mol% or more, the crystallinity of the resin is improved, the compatibility between the low temperature fixability and the heat resistant storage stability is good, and the resin hardness tends to be improved.

  The linear aliphatic diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentane. Diol, 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, 1,20-eicosanediol and the like. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability. Among these, a linear aliphatic diol having 2 to 36 chain carbon atoms is preferable.

  The branched aliphatic diol is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a branched aliphatic diol having 2 to 36 chain carbon atoms. Examples of the branched aliphatic diol include 1,2-propylene glycol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, and the like.

  The alkylene ether glycol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene Ether glycol etc. are mentioned.

  The alicyclic diol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

  The alkylene oxide of the alicyclic diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene oxide (hereinafter sometimes abbreviated as EO), propylene oxide (hereinafter referred to as PO and PO). And an adduct such as butylene oxide (hereinafter sometimes abbreviated as BO) (additional mole number: 1 to 30).

  The AO adduct of the bisphenol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an AO (EO, PO, BO, etc.) adduct (eg, bisphenol A, bisphenol F, bisphenol S) ( Addition mole number 2-30) etc. are mentioned.

  There is no restriction | limiting in particular as said polylactone diol, According to the objective, it can select suitably, For example, poly-epsilon-caprolactone diol etc. are mentioned.

  There is no restriction | limiting in particular as diol which has the said carboxyl group, According to the objective, it can select suitably, For example, dialalkylol alkanoic acid etc. are mentioned. As carbon number of the said dialkyrol alkanoic acid, 6-24 etc. are mentioned, for example. Examples of the dialkyrol alkanoic acid having 6 to 24 carbon atoms include 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, 2,2- Examples include dimethylol octanoic acid.

The diol having a sulfonic acid group or a sulfamic acid group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include sulfamic acid diol, N, N-bis (2-hydroxyalkyl) sulfamic acid ( Examples include AO adducts having 1 to 6 carbon atoms of an alkyl group (AO includes 1 to 6 moles of AO added such as EO or PO), bis (2-hydroxyethyl) phosphate, and the like.
Examples of the sulfamic acid diol include N, N-bis (2-hydroxyethyl) sulfamic acid, N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, and the like.

  There is no restriction | limiting in particular as a neutralization base of the diol which has these neutralization bases, According to the objective, it can select suitably, For example, C3-C30 tertiary amine (triethylamine etc.), an alkali metal ( Sodium salt).

  Among these, an aliphatic diol having 2 to 12 carbon atoms, a diol having a carboxyl group, an AO adduct of bisphenols, and a combination thereof are preferable.

Moreover, there is no restriction | limiting in particular as said trivalent-octavalent or more polyol used as needed, According to the objective, it can select suitably, For example, C3-C36 trivalent-8 Or higher polyhydric aliphatic alcohols; AO adducts of trisphenols (addition moles 2-30); AO adducts of novolak resins (addition moles 2-30); hydroxyethyl (meth) acrylate and others And acrylic polyols such as copolymers with vinyl monomers.
Examples of the trivalent to octavalent or higher polyhydric aliphatic alcohol having 3 to 36 carbon atoms include, for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin. It is done.
Among these, trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts are preferred, and novolak resin AO adducts are more preferred.

--- Polycarboxylic acid ---
Examples of the polycarboxylic acid include dicarboxylic acids, trivalent to hexavalent or higher polycarboxylic acids.

  The dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic dicarboxylic acids such as linear aliphatic dicarboxylic acids and branched aliphatic dicarboxylic acids; aromatic dicarboxylic acids and the like. Is mentioned. Among these, linear aliphatic dicarboxylic acid is preferable.

There is no restriction | limiting in particular as said aliphatic dicarboxylic acid, According to the objective, it can select suitably, For example, alkane dicarboxylic acid, alkenyl succinic acid, alkene dicarboxylic acid, alicyclic dicarboxylic acid etc. are mentioned.
Examples of the alkanedicarboxylic acid include alkanedicarboxylic acid having 4 to 36 carbon atoms. Examples of the alkanedicarboxylic acid having 4 to 36 carbon atoms include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, and decylsuccinic acid.
Examples of the alkenyl succinic acid include dodecenyl succinic acid, pentadecenyl succinic acid, and octadecenyl succinic acid.
Examples of the alkene dicarboxylic acid include alkene dicarboxylic acids having 4 to 36 carbon atoms. Examples of the alkene dicarboxylic acid having 4 to 36 carbon atoms include maleic acid, fumaric acid, and citraconic acid.
As said alicyclic dicarboxylic acid, a C6-C40 alicyclic dicarboxylic acid etc. are mentioned, for example. Examples of the alicyclic dicarboxylic acid having 6 to 40 carbon atoms include dimer acid (dimerized linoleic acid).

  There is no restriction | limiting in particular as said aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, C8-36 aromatic dicarboxylic acid etc. are mentioned. Examples of the aromatic dicarboxylic acid having 8 to 36 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. It is done.

  Examples of the trivalent to hexavalent or higher polycarboxylic acid used as necessary include aromatic polycarboxylic acids having 9 to 20 carbon atoms. Examples of the aromatic polycarboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

  In addition, as the dicarboxylic acid or the trivalent to hexavalent or higher polycarboxylic acid, the above acid anhydrides or alkyl esters having 1 to 4 carbon atoms may be used. Examples of the alkyl ester having 1 to 4 carbon atoms include methyl ester, ethyl ester, and isopropyl ester.

  Among the dicarboxylic acids, the aliphatic dicarboxylic acid is preferably used alone, and adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, or isophthalic acid is more preferably used alone. Also preferred are those obtained by copolymerizing the aromatic dicarboxylic acid together with the aliphatic dicarboxylic acid. As the aromatic dicarboxylic acid to be copolymerized, terephthalic acid, isophthalic acid, t-butylisophthalic acid, and alkyl esters of these aromatic dicarboxylic acids are preferable. Examples of the alkyl ester include methyl ester, ethyl ester, isopropyl ester, and the like. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

--- Lactone ring-opening polymer ---
The lactone ring-opening polymer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 3 carbon atoms such as β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Lactone ring-opening polymer obtained by ring-opening polymerization of lactones such as -12 monolactones (one ester group in the ring) using a catalyst such as a metal oxide or an organometallic compound; glycol as an initiator Examples thereof include a lactone ring-opening polymer having a hydroxyl group at the terminal, obtained by ring-opening polymerization of the monolactone having 3 to 12 carbon atoms using ethylene glycol, diethylene glycol or the like.

  There is no restriction | limiting in particular as said C3-C12 monolactone, Although it can select suitably according to the objective, (epsilon) -caprolactone is preferable from a crystalline viewpoint.

  In addition, as the lactone ring-opening polymer, a commercially available product may be used. Examples of the commercially available product include highly crystalline polycaprolactones such as H1P, H4, H5, and H7 of the PLACEL series manufactured by Daicel Corporation. Can be mentioned.

--- Polyhydroxycarboxylic acid ---
There is no restriction | limiting in particular as the preparation method of the said polyhydroxycarboxylic acid, According to the objective, it can select suitably, For example, hydroxycarboxylic acids, such as glycolic acid and lactic acid (L-form, D-form, a racemate, etc.), are directly used. Dehydration condensation method: cyclic ester having 4 to 12 carbon atoms corresponding to a dehydration condensate of two or three molecules of hydroxycarboxylic acid such as glycolide or lactide (L-form, D-form, meso-form, etc.) Examples of the method include ring-opening polymerization of 2 to 3 ester groups using a catalyst such as a metal oxide or an organometallic compound. The method of ring-opening polymerization is preferable from the viewpoint of adjusting the molecular weight.
Among the cyclic esters, L-lactide and D-lactide are preferable from the viewpoint of crystallinity. These polyhydroxycarboxylic acids may be modified so that the terminal is a hydroxyl group or a carboxyl group.

--Polyurethane unit--
Examples of the polyurethane unit include a polyurethane unit synthesized from a polyol such as a diol, a trivalent to octavalent or higher polyol, and a polyisocyanate such as a diisocyanate or a trivalent or higher polyisocyanate. Among these, a polyurethane unit synthesized from the diol and the diisocyanate is preferable.
As said polyol, the thing similar to the said polyol quoted in the said polyester unit is mentioned.

--- Polyisocyanate ---
Examples of the polyisocyanate include diisocyanate, trivalent or higher polyisocyanate, and the like.

  There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably, For example, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate etc. are mentioned. Among these, the carbon number excluding carbon in the NCO group is 6-20 aromatic diisocyanate, 2-18 aliphatic diisocyanate, 4-15 alicyclic diisocyanate, 8-15 araliphatic diisocyanate, these A modified product of diisocyanate, and a mixture of two or more of these are preferred.

Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), crude TDI, 2, 4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenylmethane diisocyanate (MDI), crude MDI, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, mp-isocyanate And natophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate, and the like.
Examples of the crude MDI include phosgenates of crude diaminophenylmethane, polyallyl polyisocyanate (PAPI), and the like. Examples of the crude diaminophenylmethane include a condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof, a mixture of diaminodiphenylmethane and a small amount (for example, 5% by mass to 20% by mass) of a trifunctional or higher polyamine. Is mentioned.

  Examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc. Can be mentioned.

  Examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanate). Natoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-2,6-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.

  Examples of the araliphatic diisocyanate include m-xylylene diisocyanate (XDI), p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like. .

  Examples of the modified diisocyanate include urethane group-containing modified products, carbodiimide group-containing modified products, allophanate group-containing modified products, urea group-containing modified products, burette group-containing modified products, uretdione group-containing modified products, and uretoimine group-containing products. Examples include modified products, isocyanurate group-containing modified products, and oxazolidone group-containing modified products. Specific examples include modified diisocyanates such as modified MDI and urethane-modified TDI, and mixtures of two or more of these. Examples of the modified MDI include urethane-modified MDI, carbodiimide-modified MDI, and trihydrocarbyl phosphate-modified MDI. Examples of the mixture include a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer).

  Among these, aromatic diisocyanate having 6 to 15 carbon atoms excluding carbon in the NCO group, 4 to 12 aliphatic diisocyanate, and 4 to 15 alicyclic diisocyanate are preferable, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and isophorone diisocyanate are more preferable.

--Polyurea unit--
Examples of the polyurea unit include a polyurea unit synthesized from a polyamine such as a diamine or a trivalent or higher polyamine, and a polyisocyanate such as a diisocyanate or a trivalent or higher polyisocyanate.

--- Polyamine ---
There is no restriction | limiting in particular as said polyamine, According to the objective, it can select suitably, For example, aliphatic diamine, aromatic diamine, etc. are mentioned. Among these, an aliphatic diamine having 2 to 18 carbon atoms and an aromatic diamine having 6 to 20 carbon atoms are preferable. Further, if necessary, a trivalent or higher valent amine may be used.

Examples of the aliphatic diamine having 2 to 18 carbon atoms include, for example, alkylene diamine having 2 to 6 carbon atoms, polyalkylene diamine having 4 to 18 carbon atoms, alkyl having 1 to 4 carbon atoms, or 2 to 4 carbon atoms. Examples include hydroxyalkyl-substituted products, alicyclic or heterocyclic-containing aliphatic diamines, and aromatic ring-containing aliphatic amines having 8 to 15 carbon atoms.
Examples of the alkylene diamine having 2 to 6 carbon atoms include ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the polyalkylenediamine having 4 to 18 carbon atoms include diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
Examples of the alkyl having 1 to 4 carbon atoms or the substituted hydroxyalkyl having 2 to 4 carbon atoms include dialkylaminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexa. Examples include methylenediamine and methyliminobispropylamine.
Examples of the alicyclic or heterocyclic ring-containing aliphatic diamines include alicyclic diamines having 4 to 15 carbon atoms and heterocyclic diamines having 4 to 15 carbon atoms. Examples of the alicyclic diamine having 4 to 15 carbon atoms include 1,3-diaminocyclohexane, isophorone diamine, mensen diamine, and 4,4′-methylene dicyclohexane diamine (hydrogenated methylene dianiline). . Examples of the heterocyclic diamine having 4 to 15 carbon atoms include piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, 3 , 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.
Examples of the aromatic ring-containing aliphatic amine having 8 to 15 carbon atoms include xylylenediamine and tetrachloro-p-xylylenediamine.

Examples of the aromatic diamine having 6 to 20 carbon atoms include, for example, unsubstituted aromatic diamine, aromatic diamine having a nucleus-substituted alkyl group having 1 to 4 carbon atoms, a mixture of these isomers in various proportions, and nuclear substitution. An aromatic diamine having an electron withdrawing group, an aromatic diamine having a secondary amino group, and the like can be given.
Examples of the unsubstituted aromatic diamine include 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4′-diphenylmethanediamine, 4,4′-diphenylmethanediamine, and crude diphenylmethane. Diamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 "-triamine, naphthylenediamine and the like can be mentioned.
Examples of the aromatic diamine having a nucleus-substituted alkyl group having 1 to 4 carbon atoms include 2,4-tolylenediamine, 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, 3,3 ′, 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 Examples include '-diaminodiphenyl ether, 3,3', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone.
Examples of the nucleus-substituted electron withdrawing group of the aromatic diamine having the nucleus-substituted electron withdrawing group include a halogen, an alkoxy group, and a nitro group. Examples of the halogen include Cl, Br, I, and F. Examples of the alkoxy group include methoxy and ethoxy. Examples of the aromatic diamine having a nucleus-substituted electron withdrawing group include methylene bis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, and 3-amino-4-chloro. Aniline, 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) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methyl) Xylphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) 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.
Examples of the aromatic diamine having a secondary amino group include, for example, the unsubstituted aromatic diamine, the aromatic diamine having a C1-C4 nucleus-substituted alkyl group, and mixtures of various ratios of these isomers. And a part of or all of the primary amino group of the aromatic diamine having a nucleus-substituted electron withdrawing group replaced with a secondary amino group by a lower alkyl group such as methyl or ethyl.

Examples of the trivalent or higher amine include polyamide polyamine and polyether polyamine.
Examples of the polyamide polyamine include a low molecular weight polyamide polyamine obtained by condensation of dicarboxylic acid and excess polyamine (more than 2 moles per mole of acid). Examples of the dicarboxylic acid include dimer acid. Examples of the polyamine include alkylene diamine and polyalkylene polyamine.
Examples of the polyether polyamine include a hydride of a cyanoethylated polyether polyol. Examples of the polyether polyol include polyalkylene glycol.

  According to Solidity Parameter Values (Polymer handbook 4th Ed), the cohesive energy of urea bonds is 50,230 [J / mol], which is about twice the cohesive energy of urethane bonds (26,370 [J / mol]). Therefore, even if the amount is small, it is possible to expect the toughness of the toner and the effect of improving the offset resistance at the time of fixing.

  The crystalline resin having at least one of the urethane bond and the urea bond and the crystalline polyester unit preferably contains a crystalline resin having at least one of the polyurethane unit and the polyurea unit and the crystalline polyester unit. It is more preferable to contain a crystalline resin having a polyurethane unit and a crystalline polyester unit.

  The crystalline resin having at least one of the urethane bond and the urea bond and the crystalline polyester unit includes a first crystalline resin and a second crystalline having a weight average molecular weight larger than that of the first crystalline resin. It is preferable to contain a resin.

The weight average molecular weight of the first crystalline resin is preferably 10,000 to 40,000, more preferably 15,000 to 35,000, from the viewpoint of compatibility between low-temperature fixability and heat-resistant storage stability. 30,000 to 30,000 is particularly preferred. When the weight average molecular weight is less than 10,000, the heat-resistant storage stability of the toner may be lowered, and when it exceeds 40,000, the low-temperature fixability of the toner may be lowered.
The weight average molecular weight of the second crystalline resin is preferably 40,000 to 300,000, more preferably 50,000 to 150,000, from the viewpoint of achieving both low temperature fixability and hot offset resistance. If the weight average molecular weight is less than 40,000, the hot offset resistance of the toner may be lowered. If it exceeds 300,000, the toner is not sufficiently melted particularly at the time of fixing at a low temperature. Peeling easily occurs and the low-temperature fixability of the toner may be reduced.
The difference (Mw2-Mw1) between the weight average molecular weight (Mw1) of the first crystalline resin and the weight average molecular weight (Mw2) of the second crystalline resin is not particularly limited, and is appropriately determined according to the purpose. Although it can be selected, it is preferably 5,000 or more, more preferably 10,000 or more. If the difference is less than 5,000, the toner fixing width may be narrowed.

  The mass ratio between the first crystalline resin (1) and the second crystalline resin bond (2) is not particularly limited and may be appropriately selected depending on the purpose. / (2) = 5/95 to 60/40 is preferable, 8/92 to 50/50 is more preferable, 12/88 to 35/65 is still more preferable, and 15/85 to 25/75 is particularly preferable. If the ratio (1) is larger than this range, the hot offset resistance of the toner may be lowered, and if the ratio (2) is larger than this range, the low-temperature fixability of the toner may be lowered. .

  The toner is a toner obtained by stretching a crystalline polyester resin having an isocyanate group in an aqueous medium, and the crystalline resin having at least one of a urethane bond and a urea bond, and a crystalline polyester unit, It is preferable to contain a resin obtained by extending the crystalline polyester resin having an isocyanate group. Examples of the elongation method include a method of reacting a compound having a functional group that reacts with an isocyanate group and an isocyanate group of a crystalline polyester resin having an isocyanate group at the terminal. Examples of the compound having a functional group that reacts with the isocyanate group include water and the aforementioned polyamine. The elongation is performed in an aqueous medium when the toner is produced.

  The crystalline resin having at least one of the urethane bond and the urea bond and the crystalline polyester unit is a first crystalline resin and a second crystalline having a weight average molecular weight larger than that of the first crystalline resin. When the resin is contained, the second crystalline resin is preferably a resin obtained by extending the crystalline polyester resin having an isocyanate group.

  In the case of using a crystalline resin whose molecular weight distribution is controlled at the time of polymerization, as a method for obtaining such a resin, for example, in the case of a polymerization form such as polycondensation, polyaddition, and addition condensation, a bifunctional monomer is used. In addition, the molecular weight distribution can be broadened by adding a small amount of monomers having different numbers of functional groups. Monomers with different numbers of functional groups include tri- or higher-functional monomers and mono-functional monomers. However, when tri- or higher-functional monomers are used, a branched structure is generated. May be difficult to form. If a monofunctional monomer is used, the polymerization reaction is stopped by the monofunctional monomer, thereby producing a low molecular weight resin in the case of using two or more types of resins, while a part of the polymerization reaction proceeds and a high molecular weight component. It becomes.

Examples of the monofunctional monomer include monool, monocarboxylic acid, and monoamine.
Examples of the monool include methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, t-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecanol, lauryl alcohol, myristyl. Alcohol, palmityl alcohol, stearyl alcohol, docosanol, eicosanol, phenol, substituted phenol, 1-naphthol, 2-naphthol, benzyl alcohol, substituted benzyl alcohol, cyclopentanol, cyclohexanol, adamantanol, cholesterol, cholesterol And the like.
Examples of the monocarboxylic acid include formic acid, acetic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, 2-ethylhexanoic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearin. Examples include acids, oleic acid, linoleic acid, behenic acid, serotic acid, montanic acid, triacontanoic acid, benzoic acid, substituted benzoic acid, benzylic acid, and substituted benzylic acid.
Examples of the monoamine include alkyl amines, aromatic amines, and amino acids. Examples of the alkylamine include methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, octylamine, 2-ethylhexylamine, decylamine, laurylamine, myristylamine, Examples include mytylamine, stearylamine, and behenylamine. Examples of the aromatic amine include aniline, benzylamine, o-anisidine, m-anisidine, p-anisidine, o-toluidine, m-toluidine, p-toluidine and the like. Examples of the amino acids include glycine, α-alanine, β-alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, Examples include tyrosine and valine.

<< Amorphous Resin >>
The non-crystalline resin is not particularly limited as long as it is non-crystalline, and can be appropriately selected according to the purpose. For example, styrene such as polystyrene and polyvinyltoluene or a homopolymer of a substituted product thereof; styrene -Methyl acrylate copolymer, styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Styrene copolymers such as polymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-maleic acid ester copolymers; polythyme methacrylate resins, polybutyl methacrylate resins, polyvinyl acetate resins , Polyethylene resin, polyester resin, polyurethane resin, epoxy Shi resins, polyvinyl butyral resins, polyacrylic acid resins, rosin resins, modified rosin resins, such as modified these resins so as to have a functional group reactive with an active hydrogen group. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said amorphous resin in the said binder resin, According to the objective, it can select suitably.

  The content of the crystalline resin with respect to the binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, the compatibility of excellent low-temperature fixability and heat-resistant storage stability with the crystalline resin is not limited. Is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 80% by mass or more, and particularly preferably 95% by mass or more. When the content is less than 50% by mass, the heat steepness of the binder resin cannot be expressed on the viscoelastic properties of the toner, and it may be difficult to achieve both low-temperature fixability and heat-resistant storage stability.

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

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

  There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toners, and 3 mass parts-10 parts. Part by mass is more preferable. When the content is less than 1 part by mass, the coloring power of the toner may be reduced. When the content exceeds 15 parts by mass, poor pigment dispersion occurs in the toner, and the coloring power is reduced. The characteristics may be degraded.

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

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

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

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

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

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 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). First, 5.0 mg of the mold release agent is put in 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 lowered, and if it exceeds 100 mPa · sec, the hot offset resistance and the releasability at low temperature may be deteriorated.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 1 mass part-20 mass parts are preferable with respect to 100 mass parts of said toner, 3 mass parts- 10 parts by mass is more preferable. When the content is less than 1 part by mass, the hot offset resistance may be deteriorated. When the content is more than 20 parts by mass, the heat resistant storage stability, chargeability, transferability, and stress resistance may be deteriorated. is there.

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

  There is no restriction | limiting in particular as content of the said charge control agent, Although it can select suitably according to the objective, 0.01 mass part-5 mass parts are preferable with respect to 100 mass parts of said toner. 02 parts by mass to 2 parts by mass is more preferable. When the content is less than 0.01 parts by mass, the charge rising property and the charge amount are not sufficient, and the toner image may be deteriorated. When the content exceeds 5 parts by mass, the chargeability of the toner is too high, and the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density. .

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

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

  There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.1 mass part-5 mass parts are preferable with respect to 100 mass parts of the said toner. 3 mass parts-3 mass parts are more preferable.

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

<Weight average molecular weight>
The weight average molecular weight of the tetrahydrofuran (THF) soluble component of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20,000 to 60,000, and 25,000 to 55,000. 000 is more preferable, and 30,000 to 50,000 is particularly preferable. When the weight average molecular weight is less than 20,000, the internal cohesive force at the time of melting the toner becomes too low, no matter how much high molecular weight components are present, causing hot offset and paper wrapping around the fixing member. If it exceeds 60,000, the entire binder resin is too high in molecular weight, so that the fixing property is deteriorated, the gloss is lowered, and the image after fixing may be easily lost due to external stress. .

<Amount of high molecular weight component>
The THF-soluble component of the toner contains 5.0% or more, preferably 7.0% or more of a component having a molecular weight of 100,000 or more in the molecular weight distribution measured by gel permeation chromatography, and preferably 10.0% or more. It is more preferable that it contains more than%. There is no restriction | limiting in particular as an upper limit, Although it can select suitably according to the objective, 25.0% or less is preferable.
From the viewpoint of toner durability, the THF soluble content of the toner preferably contains 1.0% or more of a component having a molecular weight of 250,000 or more in the molecular weight distribution measured by gel permeation chromatography.
The ratio of components having a molecular weight of 100,000 or more can be examined from the intersection of the molecular weight 100,000 and the curve in the integral molecular weight distribution curve.
The ratio of components having a molecular weight of 250,000 or more can be examined from the intersection of the molecular weight 250,000 and the curve in the integral molecular weight distribution curve.

Here, the weight average molecular weight and the molecular weight distribution of the tetrahydrofuran (THF) soluble component are measured using, for example, a gel permeation chromatography (GPC) measuring device (for example, HLC-8220 GPC (manufactured by Tosoh Corporation)). it can. As a column, TSKgel SuperHZM-H 15 cm triple (made by Tosoh Corporation) is used. 30 mg of toner or resin is added to 20 mL of tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.), stirred for 1 hour, and filtered with a 0.2 μm filter as a sample. 100 μL of the THF sample solution is injected into the measuring apparatus, and the measurement is performed at a flow rate of 0.35 mL / min in an environment at a temperature of 40 ° C.
The molecular weight of the sample is calculated using a calibration curve created from a monodisperse polystyrene standard sample. As the monodisperse polystyrene standard sample, for example, Showdex STANDARD series manufactured by Showa Denko KK and toluene are used. The following three types of monodisperse polystyrene standard sample THF solutions are prepared and measured under the above conditions, and a calibration curve is prepared using the peak top retention time as the light scattering molecular weight of the monodisperse polystyrene standard sample. An RI (refractive index) detector is used as the detector.
Solution A: S-7450 2.5 mg, S-678 2.5 mg, S-46.5 2.5 mg, S-2.90 2.5 mg, THF 50 mL
Solution B: S-3730 2.5 mg, S-257 2.5 mg, S-19.8 2.5 mg, S-0.580 2.5 mg, THF 50 mL
Solution C: S-1470 2.5 mg, S-112 2.5 mg, S-6.93 2.5 mg, Toluene 2.5 mg, THF 50 mL

  Tetrahydrofuran (THF) soluble content in the following measurement of decomposition residue, measurement of N element amount, measurement of urethane bond, and measurement of urea bond is, for example, 30 mg of toner in tetrahydrofuran (THF) (containing stabilizer, Wako Pure Chemical) (Made by Co., Ltd.) It can be obtained by adding to 20 mL, stirring for 1 hour, and filtering with a 0.2 μm filter.

<Decomposition residue>
The ratio of the decomposition residue insoluble in methanol when the tetrahydrofuran soluble part of the toner is decomposed in a 0.1N KOH methanol solution is 5.0% by mass or more, and preferably 10.0% by mass or more. There is no restriction | limiting in particular as an upper limit, Although it can select suitably according to the objective, 20.0 mass% or less is preferable. When the decomposition residue is less than 5.0% by mass, the durability of the toner becomes insufficient.

The decomposition residue can be measured by the following method.
1 g of the THF soluble part of the toner is weighed, 100 mL of 0.1 N potassium hydroxide methanol solution is added, and a decomposition reaction is carried out at 50 ° C. for 24 hours with gentle stirring. Thereafter, the mixture is cooled to room temperature, and the decomposition residue is washed with 20 mL of room temperature methanol, then washed with 20 mL of ion-exchanged water three times, and dried in vacuo at 50 ° C. for 12 hours to obtain a decomposition residue.
By weighing the obtained decomposition residue and dividing by the sample amount before the decomposition reaction, the decomposition residue ratio (decomposition residue ratio (mass%)) can be calculated.

<N element amount>
The amount of N element when performing CHN analysis on the THF soluble content of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.3% by mass to 2.0% by mass. Preferably, 0.9 mass%-2.0 mass% is more preferable. If the amount of N element is less than 0.3% by mass, there is a problem of high temperature offset due to aggregation or member contamination in the image forming apparatus due to a decrease in toner toughness, or a decrease in viscoelasticity when the toner is melted. If it exceeds 2.0% by mass, the viscoelasticity in the melted state of the toner becomes too high, which may cause deterioration of fixing property, reduction of gloss, deterioration of charging property, etc. is there.
The N element amount is the amount of N element derived from a urethane bond and a urea bond in the resin.

The amount of N element is CHN simultaneously using, for example, a vario MICRO cube (manufactured by Elemental) under the conditions of a combustion furnace at 950 ° C., a reduction furnace at 550 ° C., a helium flow rate of 200 mL / min, and an oxygen flow rate of 25 mL / min to 30 mL / min. It can measure and can obtain | require from the average value of the value measured twice. In addition, when N element amount is less than 0.5 mass% by this measuring method, it measures by trace nitrogen analyzer ND-100 type (made by Mitsubishi Chemical Corporation) further. Electric furnace temperature (horizontal reactor) pyrolysis portion 800 ° C, catalyst portion 900 ° C, measurement conditions are main O ₂ flow rate 300 mL / min, O ₂ flow rate 300 mL / min, Ar flow rate 400 mL / min, sensitivity Low, pyridine Quantify the calibration curve created with the standard solution.

<Crystal structure amount [C / (A + C)]>
In the diffraction spectrum of the toner obtained by X-ray diffraction measurement of the toner, the integrated intensity (C) of the spectrum derived from the crystal structure of the binder resin and the integrated intensity (A) of the spectrum derived from the amorphous structure The ratio of C to the total [C / (A + C)] is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.15 or more, and more preferably 0.20 or more. There is no restriction | limiting in particular as an upper limit, Although it can select suitably according to the objective, 0.50 or less is preferable and 0.30 or less is more preferable. When the ratio [C / (A + C)] is less than 0.15, the properties as a crystalline resin are reduced, and it may be difficult to achieve both low-temperature fixability and heat-resistant storage stability. When the ratio [C / (A + C)] is within the more preferable range, it is advantageous in terms of both low-temperature fixability and heat-resistant storage stability.

  The ratio [C / (A + C)] is an index indicating the amount of crystallization sites in the binder resin, and is the main diffraction peak derived from the crystal structure of the binder resin in the diffraction spectrum obtained by X-ray diffraction measurement. And the area ratio of the halo derived from the amorphous structure.

The X-ray diffraction measurement can be performed using a two-dimensional detector-mounted X-ray diffraction apparatus (D8 DISCOVER with GADDS / Bruker).
The capillary used for the measurement uses a mark tube (Lindenman glass) diameter of 0.70 mm. The sample is measured up to the top of the capillary tube. Further, tapping is performed when filling the sample, and the number of tapping is 100 times. Detailed measurement conditions are shown below.
Tube current: 40 mA
Tube voltage: 40 kV
Goniometer 2θ axis: 20.0000 °
Goniometer Ω axis: 0.0000 °
Goniometer φ axis: 0.0000 °
Detector distance: 15cm (wide angle measurement)
Measurement range: 3.2 ≦ 2θ (°) ≦ 37.2
Measurement time: 600 sec
A collimator having a pinhole with a diameter of 1 mm is used for the incident optical system. The obtained two-dimensional data is integrated with the attached software (chi axis is 3.2 ° to 37.2 °) and converted to one-dimensional data of diffraction intensity and 2θ.
A method for calculating the ratio [C / (A + C)] based on the obtained X-ray diffraction measurement result will be described below. Examples of diffraction spectra obtained by X-ray diffraction measurement are shown in FIGS. 1A and 1B. The horizontal axis is 2θ, the vertical axis is the X-ray diffraction intensity, and both are linear axes. In the X-ray diffraction spectrum in FIG. 1A, there are main peaks (P1, P2) at 2θ = 21.3 ° and 24.2 °, and halo (h) is observed in a wide range including these two peaks. Here, the main peak is derived from the crystal structure of the binder resin, and the halo is derived from the amorphous structure.
These two main peaks and halos are Gaussian functions,
f _p1 (2θ) = a _p1 exp {− (2θ−b _p1 ) ² / (2c _p1 ² )} (formula A (1))
f _p2 (2θ) = a _p2 exp {− (2θ−b _p2 ) ² / (2c _p2 ² )} (formula A (2))
f _h (2θ) = a _h exp {− (2θ−b _h ) ² / (2c _h ² )} (Formula A (3))
(F _p1 (2θ), f _p2 (2θ), and f _h (2θ) represent functions corresponding to the main peaks P1, P2, and halo, respectively), and the sum of these three functions f (2θ) = f _p1 (2θ) + f _p2 (2θ) + f _h (2θ) (formula A (4))
Is the fitting function (illustrated in FIG. 1B) of the entire X-ray diffraction spectrum, and fitting by the least square method is performed.
Fitting variables _are nine of _{a p1, b p1, c p1} , a p2, b p2, c p2, a h, b h, c h. As initial values of the fitting of each variable, b _p1 , b _p2 , and b _h are X-ray diffraction peak positions (in the example of FIG. 1A, b _p1 = 21.3, b _p2 = 24.2, b _h = 22 .5) is appropriately input to other variables, and values obtained by matching the two main peaks and the halo with the X-ray diffraction spectrum as much as possible are set. The fitting can be performed, for example, using a Microsoft 2003 Excel 2003 solver.
The integrated area (S) for each of the Gaussian functions f _p1 (2θ), f _p2 (2θ) corresponding to the two main peaks (P1, P2) after fitting, and the Gaussian function f _h (2θ) corresponding to the halo. _{From P1} , S _p2 , S _h ), when (S _p1 + S _p2 ) is (C) and (S _h ) is (A), a ratio [C / (A + C) which is an index indicating the amount of crystallization sites ] Can be calculated.

<Mixed solution insoluble matter>
The insoluble content of the toner in a mixed solution of tetrahydrofuran and ethyl acetate [tetrahydrofuran / ethyl acetate = 50/50 (mass ratio)] is not particularly limited and may be appropriately selected depending on the intended purpose. 0 mass% or more is preferable and 10.0 mass% or more is more preferable. There is no restriction | limiting in particular as an upper limit, Although it can select suitably according to the objective, 25.0 mass% or less is preferable and 20.0 mass% or less is more preferable. When the insoluble content is less than 5.0% by mass, the heat-resistant storage stability may be deteriorated, or offset may occur during fixing, particularly at high temperature. When the insoluble content is within the more preferable range, it is advantageous in terms of both low-temperature fixability and heat-resistant storage stability.
Note that a mixed solution of tetrahydrofuran and ethyl acetate [tetrahydrofuran / ethyl acetate = 50/50 (mass ratio)] hardly dissolves a high molecular weight component (molecular weight of about 20,000 or more) in the toner, and has a low molecular weight less than that. Since the components are easily dissolved, a sample with an increased concentration of the high molecular weight resin component can be prepared by treating the toner with the above mixed solution.

  The insoluble matter is obtained by adding 0.4 g of toner to 40 g of a mixed solution of tetrahydrofuran (THF) and ethyl acetate (mixing ratio is 50:50 by mass ratio) and shaking and mixing for 20 minutes, and then a centrifuge. The solution obtained by precipitating insoluble components and removing the supernatant liquid can be obtained by vacuum drying.

<Ratio of endothermic amount [ΔH (H) / ΔH (T)]>
The endothermic amount [ΔH (T), (J / g)] in differential scanning calorimetry of the toner and the mixed solution of tetrahydrofuran and ethyl acetate of the toner [tetrahydrofuran / ethyl acetate = 50/50 (mass ratio)]. The ratio [ΔH (H) / ΔH (T)] to the endothermic amount [ΔH (H), (J / g)] in the differential scanning calorimetry of the insoluble matter is not particularly limited and is appropriately selected according to the purpose. However, 0.15 or more is preferable and 0.20 to 1.25 is more preferable.
The endothermic amount can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). A sample to be used for measurement of the maximum peak temperature of heat of fusion was heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./minute, then cooled to 0 ° C. at a cooling rate of 10 ° C./minute, and then again the heating rate The temperature is increased at 10 ° C./min, the endothermic change is measured, a graph of heat flow and temperature is drawn, and the endothermic amount at the second temperature increase is evaluated.

The ratio [ΔH (H) / ΔH (T)] indicates the ratio between the crystalline structure of the high molecular weight component and the crystalline structure of the entire binder resin.
The high molecular weight component preferably has a resin structure close to that of the entire binder resin. If the binder resin has crystallinity, the high molecular weight component also preferably has crystallinity. On the other hand, when the high molecular weight component is significantly different in structure from the other resin components, the high molecular weight component easily separates into a sea-island state, so it cannot be expected to contribute to the improvement of the viscoelasticity and cohesion of the entire toner. Sometimes.
When the ratio [ΔH (H) / ΔH (T)] is within the more preferable range, the low molecular weight component and the high molecular weight component of the resin in the toner can exist more uniformly, and the variation in the toner particles is small. Therefore, it is advantageous in terms of charging uniformity.

<Maximum peak temperature of heat of fusion and heat of fusion>
The maximum peak temperature and heat of fusion at the second temperature increase in the differential scanning calorimetry of the toner are not particularly limited and may be appropriately selected depending on the intended purpose. In terms of higher level and excellent hot offset resistance, the maximum peak temperature of the heat of fusion at the second temperature increase is 50 ° C. to 70 ° C., and the heat of fusion at the second temperature increase is 30 J. / G to 75 J / g is preferable.
When the maximum peak temperature of the heat of fusion is less than 50 ° C., toner blocking may easily occur in a high temperature environment, and when it exceeds 70 ° C., low temperature fixability may be difficult to develop.
The maximum peak temperature of the heat of fusion is more preferably 55 ° C to 68 ° C, and particularly preferably 58 ° C to 65 ° C.
When the heat of fusion is less than 30 J / g, the number of sites having a crystal structure in the toner is reduced, sharp melt properties are lowered, and it may be difficult to obtain a balance between low-temperature fixability and heat-resistant storage stability. If it exceeds 75 J / g, the energy required to melt and fix the toner becomes large, and the fixability may deteriorate depending on the fixing device.
The amount of heat of fusion is more preferably 45 J / g to 70 J / g, and particularly preferably 50 J / g to 60 J / g.

  The maximum peak temperature of the heat of fusion and the heat of fusion can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). A sample to be used for measurement of the maximum peak temperature of heat of fusion was heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./minute, then cooled to 0 ° C. at a cooling rate of 10 ° C./minute, and then again the heating rate The temperature is increased at 10 ° C./min and the change in absorption and exotherm is measured, a graph of heat flow and temperature is drawn, and the temperature corresponding to the maximum peak of the heat flow is set as the maximum peak temperature of the second heat of melting. Further, the endothermic amount of the endothermic peak having the maximum peak temperature at this time is defined as the second heat of fusion.

<Maximum endothermic peak temperature (T1) and maximum exothermic peak temperature (T2)>
The relationship between the maximum endothermic peak temperature (T1) at the second temperature increase in the range of 0 ° C. to 150 ° C. and the maximum exothermic peak temperature (T2) at the first temperature decrease in the differential scanning calorimetry of the toner is not particularly limited. However, satisfying the following formula (1) and formula (2) satisfies the following formula (1) and formula (2), while maintaining excellent heat-resistant storage stability and low-temperature fixability, and blocking and conveying toner images: It is preferable at the point which suppresses a damage | wound.
T1-T2 ≦ 30 ° C. Formula (1)
T2 ≧ 30 ° C. Formula (2)
However, the temperature increase rate from 0 ° C. to 150 ° C. at the time of temperature increase in the differential scanning calorimetry is 10 ° C./min, and the temperature decrease rate from 100 ° C. to 0 ° C. at the time of temperature decrease is 10 ° C./min. is there.

As said (T1-T2), 25 degrees C or less is more preferable, and 20 degrees C or less is especially preferable. When (T1-T2) exceeds 30 ° C., the difference between the fixing temperature and the temperature at which the toner image is solidified is large, and the effect of suppressing toner image blocking and conveyance flaws may not be obtained.
As said T2, 30 to 55 degreeC is more preferable, 35 to 55 degreeC is still more preferable, and 40 to 55 degreeC is especially preferable. Although T2 is preferably as high as possible, T2 is a crystallization temperature, and therefore it is impossible to take a temperature higher than T1 that is the melting point. If the T2 is less than 30 ° C., the speed at which the fixed image is solidified by cooling is slow, and the toner image (printed matter) may be blocked and transport scratches may occur.
As said T1, 50 to 70 degreeC is preferable, 53 to 65 degreeC is more preferable, and 58 to 62 degreeC is especially preferable. When the T1 is 50 ° C. to 70 ° C., the minimum heat-resistant storage stability required for the toner can be ensured, and a toner having excellent low-temperature fixability that is not conventionally obtained can be obtained. When T1 is less than 50 ° C., the low-temperature fixability is improved, but heat-resistant storage stability may be deteriorated. When T1 is higher than 70 ° C., the heat-resistant storage stability is improved, but low-temperature fixability may be deteriorated. .

  The T1 and T2 can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). A sample to be measured was heated from 0 ° C. to 100 ° C. at a temperature rising rate of 10 ° C./min, then cooled to 0 ° C. at a temperature decreasing rate of 10 ° C./min, and then heated again at a temperature rising rate of 10 ° C./min. To do. Then, the heat absorption change at the second temperature increase and the first temperature decrease is measured, and a graph of “amount of heat absorption” and “temperature” is drawn. The temperature corresponding to the maximum peak of the endothermic amount at the second temperature increase is defined as the maximum endothermic peak temperature (T1) at the second temperature increase. Further, the temperature corresponding to the maximum peak of the calorific value at the first temperature drop is defined as the maximum exothermic peak temperature (T2) at the first temperature drop.

<Urea bond>
Even if the urea bond is small, it can be expected that the toner has high toughness and the effect of improving the offset resistance at the time of fixing. Therefore, it is preferable that the THF-soluble component of the toner has a urea bond.
The presence of the urea bond in the THF soluble part of the toner can be confirmed by ¹³ C NMR. Specifically, the analysis is performed as follows. 2 g of the sample to be analyzed is immersed in 200 mL of a potassium hydroxide methanol solution having a concentration of 0.1 mol / L and placed at 50 ° C. for 24 hours. Then, the solution is removed, and the residue is further neutralized with ion-exchanged water. Wash until dry and dry the remaining solid. The sample after drying was added to a mixed solvent (volume ratio 9: 1) of dimethylacetamide (DMAc) and deuterated dimethylsulfoxide (DMSO-d ₆ ) at a concentration of 100 mg / 0.5 mL, and the mixture was stirred at 70 ° C. for 12 hours. After dissolving for ˜24 hours, the temperature is set to 50 ° C., and ¹³ C NMR measurement is performed. The measurement frequency is, for example, 125.77 MHz, 1H 60 ° pulse is 5.5 μs, and the reference material is 0.0 ppm tetramethylsilane (TMS).
Presence of urea binding in the sample is confirmed by checking whether a signal is seen in the chemical shift of the signal derived from the carbonyl carbon of the urea binding site of the polyurea used as a sample. The chemical shift of carbonyl carbon is generally seen at 150 ppm to 160 ppm. As an example of polyurea, FIG. 2 shows a ¹³ C NMR spectrum near the carbonyl carbon of polyurea, which is a reaction product of 4,4′-diphenylmethane diisocyanate (MDI) and water. A signal derived from carbonyl carbon is seen at 153.27 ppm.

<Urethane bond>
The THF soluble content of the toner preferably has a urethane bond. The urethane bond can be confirmed in the same manner as the urea bond confirmation method using ¹³ C NMR in addition to the analysis of the monomer constituting the resin using an infrared absorption spectrum or a pyrolysis gas chromatogram-mass spectrometer.

<Toner production method>
There is no restriction | limiting in particular as a manufacturing method of the said toner, According to the objective, it can select suitably, For example, what is called a chemical construction method etc. which granulate a toner particle in an aqueous medium and a granulation method etc. are mentioned. Among these, the chemical method is a production method that does not involve the kneading of the binder resin from the viewpoint that molecular cutting by kneading does not occur and kneading of a high molecular weight resin and a low molecular weight resin, which are difficult to uniformly knead, can be avoided. preferable.

  Examples of the chemical method include a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, a dispersion polymerization method, etc., in which a monomer is used as a starting material; a resin or a resin precursor is dissolved in an organic solvent and the like in an aqueous medium. In the dissolution suspension method, an oil phase composition containing a resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group is dissolved in an aqueous medium. A method of emulsifying or dispersing and reacting an active hydrogen group-containing compound and the reactive group-containing prepolymer in the aqueous medium (production method (I)); a solution comprising a resin or resin precursor and an appropriate emulsifier Phase inversion emulsification method in which water is added to phase inversion; agglomeration method in which resin particles obtained by these methods are agglomerated in a dispersed state in an aqueous medium and granulated into particles of a desired size by heating and melting, etc. Is mentioned . Among these, the toner obtained by the dissolution suspension method, the production method (I), and the aggregation method is preferable from the viewpoint of granulation properties (particle size distribution control, particle shape control, etc.) by the crystalline resin, and the production method described above. The toner obtained in (I) is more preferable.

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

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

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

<< Chemical method >>
The chemical method is not particularly limited and may be appropriately selected depending on the intended purpose. However, at least the toner material liquid containing the binder resin is dispersed or emulsified in an aqueous medium, and the toner base particles. The method of granulating is preferable.
Further, as the chemical method, an oil phase (toner material liquid) obtained by dissolving or dispersing a toner material containing at least one of the binder resin and the binder resin precursor in an organic solvent is used as an aqueous medium. A method of granulating the toner base particles by dispersing or emulsifying in the toner is preferable. In this case, the binder resin precursor (resin precursor having a functional group capable of reacting with active hydrogen groups) and the active hydrogen group-containing compound react in an aqueous medium.
Examples of the active hydrogen group-containing compound include water and polyamine. The polyamine also includes an amine compound (ketimine compound) blocked with a ketone. As said polyamine, the above-mentioned thing illustrated by description of the said polyurea unit is mentioned, for example.
Examples of the binder resin precursor include a crystalline polyester resin having an isocyanate group at the terminal.
In the dissolution suspension method and the ester elongation method, the crystalline resin can be easily granulated.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The content of the toner when the developer is a two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, but is 2.0 mass relative to 100 mass parts of the carrier. Parts to 12.0 parts by mass are preferable, and 2.5 parts to 10.0 parts by mass are more preferable.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention has at least an electrostatic latent image carrier (hereinafter sometimes referred to as a “photosensitive member”), an electrostatic latent image forming unit, and a developing unit, and if necessary. And have other means.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photosensitive members such as amorphous silicon and selenium. And organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

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

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

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

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

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

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

<Developing means and development process>
The developing means is not particularly limited as long as it is a means including a toner that develops the latent electrostatic image formed on the latent electrostatic image bearing member to form a visible image. It can be selected appropriately.
The development step is not particularly limited as long as it is a step of developing the latent electrostatic image formed on the latent electrostatic image bearing member with a toner to form a visible image, depending on the purpose. For example, it can be carried out by the developing means.

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

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

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

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

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

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

<< Cleaning means and cleaning process >>
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoconductor, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, Examples thereof include a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, the cleaning step can be performed by the cleaning unit.

<< Static elimination means and static elimination process >>
The neutralizing means is not particularly limited as long as it is a means for neutralizing by applying a neutralizing bias to the photosensitive member, and can be appropriately selected according to the purpose. Examples thereof include a neutralizing lamp.
The neutralization step is not particularly limited as long as it is a step of neutralizing by applying a neutralization bias to the photoconductor, and can be appropriately selected according to the purpose. For example, it can be performed by the neutralization unit. .

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

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

An example of the image forming apparatus of the present invention will be described with reference to the drawings.
The image forming apparatus shown in FIG. 3 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 3. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. In the vicinity of the tandem developing device 120, an exposure device 21 as the exposure member is disposed. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. In the vicinity of the secondary transfer device 22, a fixing device 25 as the fixing means is arranged. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image bearing member 10 is uniformly charged, and the electrostatic latent image bearing member is exposed in an image corresponding to each color image based on each color image information (FIG. 4). L), and an exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image for each color toner (black toner, yellow toner, magenta toner). And cyan tona ), A developing device 61 as the developing means for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, The static eliminator 64 is provided, and each monochrome image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

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

(Various measurements)
Various measurement methods in the examples are shown below. The results are shown in Tables 2-1 and 2-2.

<Molecular weight>
The molecular weight [number average molecular weight (Mn), weight average molecular weight (Mw), peak top molecular weight (Mpt) and molecular weight distribution] of the toner is a gel permeation chromatography (GPC) measuring device (HLC-8220GPC (manufactured by Tosoh Corporation)). It measured using. As a column, TSKgel SuperHZM-H 15 cm triple (made by Tosoh Corporation) was used. 30 mg of toner was added to 20 mL of tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.), stirred for 1 hour, and then filtered through a 0.2 μm filter. 100 μL of the sample was injected into the 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 of the sample was calculated using a calibration curve prepared from a monodisperse polystyrene standard sample. As the monodisperse polystyrene standard sample, Showdex STANDARD series manufactured by Showa Denko KK and toluene were used. The following three types of monodisperse polystyrene standard sample THF solutions were prepared and measured under the above conditions, and a calibration curve was prepared using the peak top retention time as the light scattering molecular weight of the monodisperse polystyrene standard sample. An RI (refractive index) detector was used as the detector.
Solution A: S-7450 2.5 mg, S-678 2.5 mg, S-46.5 2.5 mg, S-2.90 2.5 mg, THF 50 mL
Solution B: S-3730 2.5 mg, S-257 2.5 mg, S-19.8 2.5 mg, S-0.580 2.5 mg, THF 50 mL
Solution C: S-1470 2.5 mg, S-112 2.5 mg, S-6.93 2.5 mg, Toluene 2.5 mg, THF 50 mL
The proportion of components having a molecular weight of 100,000 or more was examined from the intersection of the molecular weight 100,000 and the curve in the obtained integral molecular weight distribution curve.
The proportion of components having a molecular weight of 250,000 or more was examined from the intersection of the molecular weight 250,000 and the curve in the obtained integral molecular weight distribution curve.
For reference, the integral molecular weight distribution curve of the toner obtained in Example 1 below is shown in FIG.

  Tetrahydrofuran (THF) soluble content in the following measurement of decomposition residue, measurement of N element amount, measurement of urethane bond, and measurement of urea bond was 30 mg of toner in tetrahydrofuran (THF) (containing stabilizer, Wako Pure Chemical Industries, Ltd.) The product was added to 20 mL, stirred for 1 hour, and then filtered through a 0.2 μm filter.

<Decomposition residue>
The decomposition residue was measured by the following method.
1 g of THF soluble matter obtained by the above-mentioned method was weighed, 100 mL of 0.1 N potassium hydroxide methanol solution was added, and a decomposition reaction was carried out at 50 ° C. for 24 hours with gentle stirring. Thereafter, the reaction mixture was cooled to room temperature, and the decomposition residue was washed with 20 mL of room temperature methanol, then washed with 20 mL of ion-exchanged water three times, and vacuum dried at 50 ° C. for 12 hours to obtain a decomposition residue.
The obtained decomposition residue was weighed and divided by the amount of the sample before the decomposition reaction to calculate the decomposition residue ratio (decomposition residue ratio (mass%)).

<N element amount>
The amount of N element was determined by the following method.
As the measurement sample, the THF-soluble component of the toner obtained by the above-described preparation method was used.
Using a vario MICRO cube (manufactured by Elementar), CHN was measured twice under the conditions of a combustion furnace at 950 ° C., a reduction furnace at 550 ° C., a helium flow rate of 200 mL / min, and an oxygen flow rate of 25 mL / min to 30 mL / min. The amount of N element was determined from the average value. In addition, when N element amount was less than 0.5 mass% by this measuring method, it measured by trace nitrogen analyzer ND-100 type (made by Mitsubishi Chemical Corporation) further. Electric furnace temperature (horizontal reactor) pyrolysis portion 800 ° C, catalyst portion 900 ° C, measurement conditions are main O ₂ flow rate 300 mL / min, O ₂ flow rate 300 mL / min, Ar flow rate 400 mL / min, sensitivity Low, pyridine Both calibration curves prepared with the standard solution were quantified.

<Crystal structure amount [C / (A + C)]>
The crystal structure amount [C / (A + C)] was measured by X-ray diffraction measurement. The method is shown below.
X-ray diffraction measurement was performed using a two-dimensional detector-mounted X-ray diffractometer (D8 DISCOVER with GADDS / Bruker).
The capillary used for the measurement was a mark tube (Lindenman glass) having a diameter of 0.70 mm. The sample was packed up to the top of the capillary tube and measured. Further, tapping was performed when filling the sample, and the number of tapping was 100 times. Detailed measurement conditions are shown below.
Tube current: 40 mA
Tube voltage: 40 kV
Goniometer 2θ axis: 20.0000 °
Goniometer Ω axis: 0.0000 °
Goniometer φ axis: 0.0000 °
Detector distance: 15cm (wide angle measurement)
Measurement range: 3.2 ≦ 2θ (°) ≦ 37.2
Measurement time: 600 sec
For the incident optical system, a collimator having a pinhole with a diameter of 1 mm was used. The obtained two-dimensional data was integrated with the attached software (chi axis is 3.2 ° to 37.2 °) and converted into one-dimensional data of diffraction intensity and 2θ.
A method for calculating the ratio [C / (A + C)] based on the obtained X-ray diffraction measurement result will be described below. Examples of diffraction spectra obtained by X-ray diffraction measurement are shown in FIGS. 1A and 1B. The horizontal axis is 2θ, the vertical axis is the X-ray diffraction intensity, and both are linear axes. In the X-ray diffraction spectrum in FIG. 1A, there are main peaks (P1, P2) at 2θ = 21.3 ° and 24.2 °, and halo (h) is observed in a wide range including these two peaks. Here, the main peak is derived from the crystal structure of the binder resin, and the halo is derived from the amorphous structure.
These two main peaks and halos are Gaussian functions,
f _p1 (2θ) = a _p1 exp {− (2θ−b _p1 ) ² / (2c _p1 ² )} (formula A (1))
f _p2 (2θ) = a _p2 exp {− (2θ−b _p2 ) ² / (2c _p2 ² )} (formula A (2))
f _h (2θ) = a _h exp {− (2θ−b _h ) ² / (2c _h ² )} (Formula A (3))
(F _p1 (2θ), f _p2 (2θ), and f _h (2θ) represent functions corresponding to the main peaks P1, P2, and halo, respectively), and the sum of these three functions f (2θ) = f _p1 (2θ) + f _p2 (2θ) + f _h (2θ) (formula A (4))
Is the fitting function (illustrated in FIG. 1B) of the entire X-ray diffraction spectrum, and fitting by the least square method is performed.
Fitting variables _are nine of _{a p1, b p1, c p1} , a p2, b p2, c p2, a h, b h, c h. As initial values of the fitting of each variable, b _p1 , b _p2 , and b _h are X-ray diffraction peak positions (in the example of FIG. 1A, b _p1 = 21.3, b _p2 = 24.2, b _h = 22 .5) is appropriately input for other variables, and values obtained by matching the two main peaks and the halo with the X-ray diffraction spectrum as much as possible are set. For the fitting, a Microsoft Excel 2003 solver was used.
The integrated area (S) for each of the Gaussian functions f _p1 (2θ), f _p2 (2θ) corresponding to the two main peaks (P1, P2) after fitting, and the Gaussian function f _h (2θ) corresponding to the halo. _{From P1} , S _p2 , S _h ), when (S _p1 + S _p2 ) is (C) and (S _h ) is (A), a ratio [C / (A + C) which is an index indicating the amount of crystallization sites ] Can be calculated.

<Urea bond and urethane bond>
The presence of a urea bond in the THF soluble part of the toner was confirmed by ¹³ C NMR. Specifically, the analysis is performed as follows.
After 2 g of the sample to be analyzed (toner soluble in toner) was immersed in 200 mL of a potassium hydroxide methanol solution having a concentration of 0.1 mol / L and placed at 50 ° C. for 24 hours, the solution was removed and the residue was further removed. Washing with ion-exchanged water until the pH became neutral, the remaining solid was dried. The sample after drying was added to a mixed solvent (volume ratio 9: 1) of dimethylacetamide (DMAc) and deuterated dimethylsulfoxide (DMSO-d ₆ ) at a concentration of 100 mg / 0.5 mL, and the mixture was stirred at 70 ° C. for 12 hours. After dissolving for ˜24 hours, the temperature was set to 50 ° C., and ¹³ C NMR measurement was performed. The measurement frequency was 125.77 MHz, 1H 60 ° pulse was 5.5 μs, and the reference material was 0.0 ppm tetramethylsilane (TMS).
Presence of urea binding in the sample was confirmed by whether or not a signal was observed in the chemical shift of the signal derived from the carbonyl carbon at the urea binding site of the polyurea used as a sample. The chemical shift of carbonyl carbon is generally seen at 150 ppm to 160 ppm. As an example of polyurea, FIG. 2 shows a ¹³ C NMR spectrum near the carbonyl carbon of polyurea, which is a reaction product of 4,4′-diphenylmethane diisocyanate (MDI) and water. A signal derived from carbonyl carbon is seen at 153.27 ppm.
Confirmation of the presence of urethane bonds in the THF soluble part of the toner was also carried out in the same manner.

<Mixed solution insoluble matter>
Insoluble matter in the mixed solution was obtained by adding 0.4 g of toner to 40 g of a mixed solution of tetrahydrofuran (THF) and ethyl acetate (mixing ratio is 50:50 by mass ratio) and shaking and mixing for 20 minutes, followed by centrifugation. It was obtained by vacuum-drying what removed the supernatant liquid by settling insoluble components with a machine.
The obtained mixed solution insoluble content was divided by 0.4 g of toner and multiplied by 100 to calculate the mixed solution insoluble content (mass%).

<Ratio [ΔH (H) / ΔH (T)]>
The ratio [ΔH (H) / ΔH (T)] is the differential scanning calorimetry of the heat absorption amount [ΔH (T), (J / g)] in the differential scanning calorimetry of the toner and the mixed solvent insoluble component of the toner. It was calculated | required from the amount of heat absorption in ([Delta] H (H), (J / g)).
The measurement conditions in differential scanning calorimetry are as follows.
The endothermic amount was measured using a differential scanning calorimeter (DSC) (TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). A sample to be used for measurement of the maximum peak temperature of heat of fusion was heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./minute, then cooled to 0 ° C. at a cooling rate of 10 ° C./minute, and then again the heating rate The temperature was increased at 10 ° C./min and the endothermic change was measured, a graph of heat flow and temperature was drawn, and the endothermic amount at the second temperature increase was evaluated.

<Maximum peak temperature of heat of fusion and heat of fusion>
The maximum peak temperature of heat of fusion and the heat of fusion were measured using a differential scanning calorimeter (DSC) (TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). A sample to be used for measurement of the maximum peak temperature of heat of fusion was heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./minute, then cooled to 0 ° C. at a cooling rate of 10 ° C./minute, and then again the heating rate Measure the endothermic change by increasing the temperature at 10 ° C / min, draw a graph of "endothermic amount" and "temperature", and set the temperature corresponding to the maximum peak of the endothermic amount to the second heat of fusion The maximum peak temperature of In addition, the endothermic amount of the endothermic peak having the maximum peak temperature at this time was defined as the second heat of fusion.

<T1 and T2>
The maximum endothermic peak temperature (T1) at the second temperature increase and the maximum exothermic peak temperature (T2) at the first temperature decrease in the differential scanning calorimetry range were measured by the following methods.
It measured using the differential scanning calorimeter (DSC) (TA-60WS and DSC-60 (made by Shimadzu Corporation)). The sample to be measured was heated from 0 ° C. to 100 ° C. at a temperature rising rate of 10 ° C./min, then cooled to 0 ° C. at a temperature decreasing rate of 10 ° C./min, and then again at a temperature rising rate of 10 ° C./min. The temperature was raised to. Then, the endothermic change at the second temperature increase and the first temperature decrease was measured, and a graph of heat flow and temperature was drawn. The temperature corresponding to the maximum endothermic peak at the second temperature increase was defined as the maximum endothermic peak temperature (T1) at the second temperature increase. Further, the temperature corresponding to the maximum peak of the calorific value at the first temperature drop was defined as the maximum exothermic peak temperature (T2) at the first temperature drop.

(Production Example 1-1)
<Synthesis of crystalline polyester unit 1>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 249 parts of 1,6-hexanediol, 394 parts of sebacic acid, and 0.8 part of dibutyltin oxide were charged, and the mixture was heated at 180 ° C. for 6 hours under normal pressure. Reacted.
Next, the reaction was performed for 4 hours under a reduced pressure of 10 mmHg to 15 mmHg to synthesize [crystalline polyester unit 1].
The obtained [Crystalline Polyester Unit 1] had a number average molecular weight of 4,000, a weight average molecular weight of 9,100, and a melting point of 66 ° C.

(Production Example 1-2)
<Synthesis of crystalline polyester unit 2>
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube are charged 230 parts of 1,6-hexanediol, 23 parts of 1,4-butanediol, 390 parts of sebacic acid, and 0.8 part of dibutyltin oxide. The mixture was reacted at 180 ° C. for 6 hours under normal pressure.
Next, the reaction was performed for 4 hours under a reduced pressure of 10 mmHg to 15 mmHg to synthesize [crystalline polyester unit 2].
The obtained [Crystalline Polyester Unit 2] had a number average molecular weight of 2,500, a weight average molecular weight of 7,600, and a melting point of 57 ° C.

(Production Example 1-3)
<Synthesis of crystalline polyester unit 3>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 316 parts of 1,10-decandiol, 19 parts of 1-docosanol, 271 parts of adipic acid and 0.8 part of dibutyltin oxide were charged under normal pressure. And reacted at 180 ° C. for 6 hours.
Next, the reaction was performed for 4 hours under a reduced pressure of 10 mmHg to 15 mmHg to synthesize [Crystalline Polyester Unit 3].
The obtained [Crystalline Polyester Unit 3] had a number average molecular weight of 4,900, a weight average molecular weight of 24,200, and a melting point of 63 ° C.

(Production Example 2-1)
<Synthesis of polyurethane prepolymer 1>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 235 parts of bisphenol A propylene oxide 2-mol adduct, 10 parts of propylene glycol, 254 parts of 4,4′-diphenylmethane diisocyanate, and 600 parts of ethyl acetate were added. [Polyurethane Prepolymer 1] was synthesized by charging and reacting at 80 ° C. for 3 hours under normal pressure.
The obtained [Polyurethane Prepolymer 1] had a number average molecular weight of 2,600.

(Production Example 2-2)
<Synthesis of polyurethane urea prepolymer 2>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 234 parts of bisphenol A propylene oxide 2 mol adduct, 7 parts of propylene glycol, 2 parts of ion-exchanged water, 265 parts of 4,4′-diphenylmethane diisocyanate, Then, 600 parts of ethyl acetate was added and reacted at 80 ° C. for 3 hours under normal pressure to synthesize [Polyurethane urea prepolymer 2].
The obtained [Polyurethane urea prepolymer 2] had a number average molecular weight of 2,900.

(Production Example 2-3)
<Synthesis of polyurethane prepolymer 3>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 80 parts of bisphenol A ethylene oxide 2-mole adduct, 175 parts of bisphenol A propylene oxide 2-mole adduct, 11 parts of propylene glycol, 248 parts of isophorone diisocyanate, Then, 600 parts of methyl ethyl ketone was charged and reacted at 80 ° C. for 3 hours under normal pressure to synthesize [Polyurethane Prepolymer 3].
The obtained [Polyurethane Prepolymer 3] had a number average molecular weight of 2,700.

(Production Example 3-1)
<Synthesis of Resin A-1>
430 parts of [Crystalline Polyester Unit 1], 176 parts of [Polyurethane Prepolymer 1], and 400 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and 80 ° C. under normal pressure. Then, the solvent was removed to obtain [Resin A-1] consisting of a crystalline polyester unit and a polyurethane prepolymer unit.
The obtained [Resin A-1] had a number average molecular weight of 10,100, a weight average molecular weight of 31,000, a nitrogen atom concentration of 1.7% by mass, and a melting point of 65 ° C.

(Production Example 3-2)
<Synthesis of Resin A-2>
352 parts of [Crystalline Polyester Unit 2], 198 parts of [Polyurethane Prepolymer 1], and 420 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, at 80 ° C. under normal pressure. Then, the solvent was removed to obtain [Resin A-2] consisting of a crystalline polyester unit and a polyurethane prepolymer unit.
The obtained [Resin A-2] had a number average molecular weight of 8,100, a weight average molecular weight of 22,000, a nitrogen atom concentration of 2.1% by mass, and a melting point of 56 ° C.

(Production Example 3-3)
<Synthesis of Resin A-3>
480 parts of [Crystalline Polyester Unit 3], 59 parts of [Polyurethane Prepolymer 3], and 531 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, at 80 ° C. under normal pressure. Then, the solvent was removed to obtain [Resin A-3] consisting of a crystalline polyester unit and a polyurethane prepolymer unit.
The obtained [Resin A-3] had a number average molecular weight of 5,600, a weight average molecular weight of 40,600, a nitrogen atom concentration of 0.6% by mass, and a melting point of 63 ° C.

(Production Example 3-4)
<Synthesis of Resin A-4>
480 parts of [Crystalline Polyester Unit 3], 61 parts of [Polyurethane Urea Prepolymer 2], and 540 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. After reacting at 5 ° C. for 5 hours, the solvent was removed to obtain [Resin A-4] consisting of a crystalline polyester unit and a polyurethane urea prepolymer unit.
The obtained [Resin A-4] had a number average molecular weight of 5,900, a weight average molecular weight of 41,100, a nitrogen atom concentration of 0.6% by mass, and a melting point of 63 ° C.

(Production Example 3-5)
<Synthesis of Resin A-5>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 430 parts of [Crystalline Polyester Unit 1], 83 parts of bisphenol A propylene oxide 2-mol adduct, 3.5 parts of propylene glycol, 4, 4 ′ -90 parts of diphenylmethane diisocyanate and 400 parts of ethyl acetate were charged, reacted at 80 ° C under normal pressure for 8 hours, and then the solvent was removed to obtain [Resin A-5] consisting of a crystalline polyester unit and a polyurethane part. .
The obtained [Resin A-5] had a number average molecular weight of 9,200, a weight average molecular weight of 31,100, a nitrogen atom concentration of 1.7% by mass, and a melting point of 61 ° C.

(Production Example 4-1)
<Synthesis of Resin B-1>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 391 parts of [Crystalline Polyester Unit 1], 47 parts of 4,4′-diphenylmethylene diisocyanate, and 438 parts of ethyl acetate were charged under normal pressure. It was made to react at 82 degreeC for 5 hours, and [resin B-1] (resin content 50%) which is a polyester prepolymer was obtained.

(Production Example 4-2)
<Synthesis of Resin B-2>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 684 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours under normal pressure, and further reacted for 5 hours under reduced pressure of 10 mmHg to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 49 mgKOH / g.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate, and 499 parts of ethyl acetate were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 95 ° C. for 6 hours. [Resin B-2] (resin content: 50%) was obtained as a polyester prepolymer.

(Production Example 5)
<Production of Colorant Dispersion 1>
In a beaker, 20 parts of copper phthalocyanine (manufactured by Dainichi Seika Kogyo Co., Ltd.), 4 parts of a colorant dispersant (Solspers 28000, manufactured by Avicia Co., Ltd.) and 76 parts of ethyl acetate were stirred and dispersed uniformly. Copper phthalocyanine was finely dispersed by a bead mill to obtain [Colorant Dispersion Liquid 1]. The volume average particle size of [Colorant Dispersion Liquid 1] measured with a particle size measuring device LA-920 manufactured by Horiba Ltd. was 0.3 μm.

(Production Example 6)
<Manufacture of mold release agent dispersion 1>
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 15 parts of paraffin wax (HNP-9, manufactured by Nippon Seiki Co., Ltd.) and 85 parts of ethyl acetate are placed and heated to 78 ° C. to sufficiently dissolve. After cooling to 30 ° C. in 1 hour with stirring, the solution was further fed with an ultra visco mill (manufactured by IMEX Co., Ltd.) at a liquid feeding speed of 1.0 kg / hr, a disk peripheral speed: 10 m / sec, and a diameter of 0.5 mm zirconia Wet pulverization was performed under the conditions of 80% by volume of beads and 6 passes. Finally, ethyl acetate was added and adjusted so that the solid content concentration was 15% to obtain [Releasing Agent Dispersion Liquid 1].

Example 1
[Resin A-1] 84 parts, [Resin B-1] (resin content 50%) 32 parts, [Releasing agent dispersion 1] 14 parts, [Colorant dispersion 1] 10 parts, and acetic acid in a beaker After 84 parts of ethyl was added and the resin was dissolved while stirring at 50 ° C., the mixture was stirred at 8,000 rpm with a TK homomixer and dispersed uniformly to obtain [Toner Material Liquid 1].

In another beaker, 99 parts of ion-exchanged water and 25% aqueous dispersion of organic resin fine particles for dispersion stabilization (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) 6 parts, 1 part of sodium carboxymethylcellulose, and 10 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, Ltd., “Eleminol MON-7”) were uniformly dissolved.
Next, while stirring the TK homomixer at 10,000 rpm at 50 ° C., 75 parts of [Toner material liquid 1] was put into the other beaker and stirred for 2 minutes.
Next, this mixed solution was transferred to a stir bar and a Kolben equipped with a thermometer, and ethyl acetate was distilled off at 55 ° C. until the concentration became 0.5% or less to obtain [Aqueous resin dispersion 1 of resin particles]. It was.

  Next, as a pre-cleaning step, [Aqueous resin dispersion 1 of resin particles] was cooled to room temperature, filtered, and 300 parts of ion-exchanged water was added to the obtained filter cake, and a TK homomixer was used. The mixture was mixed at 12,000 rpm for 10 minutes and then filtered twice to obtain a filter cake.

Next, 300 parts of ion-exchanged water is added to the obtained filter cake, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered three times. 300 parts of 1% hydrochloric acid was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered.
Finally, 300 parts of ion-exchanged water was added to the obtained filter cake, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer, the operation of filtering was performed twice to obtain a filter cake.
The obtained cake was crushed and then dried at 40 ° C. for 22 hours to obtain [Resin Particle 1] having a volume average particle size of 5.6 μm.

  Using 100 parts of the obtained [resin particles 1] and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) was used. After 5 cycles of mixing at 30 m / second for 30 seconds and resting for 1 minute, a sieve having a mesh size of 35 μm was sieved to prepare toner 1.

  The decomposition residue rate of the THF soluble matter of Toner 1 was 17.1% by mass. Moreover, when this decomposition | disassembly residue was analyzed by py-GCMS, the main component was bisphenol A propylene oxide 2 mol addition product, propylene glycol, and 4,4'- diphenylmethane diisocyanate. The IR spectrum of the decomposition residue was presumed to be mainly composed of a polyurethane composed of bisphenol A propylene oxide 2-mole adduct, propylene glycol, and 4,4'-diphenylmethane diisocyanate.

<Evaluation>
The obtained toner was subjected to the following evaluation. The results are shown in Table 3.

<< Low-temperature fixability >>
A solid image having a width of 50 mm was formed on a T-th sheet of copy printing paper <55> (manufactured by Ricoh Co., Ltd.) as a thin paper so that the toner adhesion amount was 0.85 ± 0.1 mg / cm ² . Specifically, using an apparatus in which the fixing unit of a color laser printer IPSiO SP C420 (manufactured by Ricoh Co., Ltd.) is modified, an image created at a linear velocity of 300 mm / min while controlling the temperature of the fixing member by external control is passed. Paper.
Next, with respect to the image after fixing, a drawing tester AD-401 manufactured by Ueshima Seisakusho was used, and in contact with the colored portion of the fixed image under the conditions of a sapphire needle (radius 125 μm), a needle rotation diameter of 8 mm, and a load of 1 g. The running surface of the sapphire needle tip was observed visually, and the lowest temperature at which no scratches were seen was defined as the minimum fixing temperature.

<< Toner Durability >>
Set the toner in the device modified so that the process speed of the color laser printer IPSiO SP C420 (manufactured by Ricoh Co., Ltd.) can be controlled from the outside, and set the output speed of the paper to 600 mm / min. 1,000 sheets of blank paper were printed. Thereafter, the developer was collected, the toner in the developer was observed with a scanning electron microscope, and the degree of toner deterioration was evaluated according to the following evaluation criteria. Note that “Δ” is an acceptable level, and “Δx” and “x” are problematic levels.
〔Evaluation criteria〕
A: No aggregation of toner is observed.
◯: A very small amount of 2 to 3 toner aggregates is observed, but no melting between the aggregates is observed.
Δ: A plurality of aggregated toners can be seen, but no melting between the aggregates is observed.
Δ: A plurality of toner aggregates are observed, and the aggregates are slightly melted and bonded.
X: The toner is agglomerated, and the agglomerates are clearly melted and bonded.

<< Heat resistant storage stability >>
A glass container was filled with toner and left in a constant temperature bath at 55 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration was measured by a penetration test (JIS K2235-1991). A toner having a larger penetration value indicates better storage stability against heat. If the penetration value is less than 15 mm, there is a high possibility of problems in use. The penetration was evaluated according to the following evaluation criteria. The criteria for determining the heat resistant storage stability are as follows.
◎: Penetration ○: 25 mm or more and less than penetration Δ: 20 mm or more and less than 25 mm Δ ×: 15 mm or more and less than 20 mm ×: Less than 15 mm

(Example 2)
A toner was produced in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 2] in Example 1. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 2>
[Resin A-1] 89 parts, [Resin B-1] (resin content 50%) 22 parts, [Releasing agent dispersion 1] 14 parts, [Colorant dispersion 1] 10 parts, and acetic acid in a beaker After 89 parts of ethyl was added and the resin was dissolved while stirring at 50 ° C., the mixture was stirred at 8,000 rpm with a TK homomixer and dispersed uniformly to obtain [Toner Material Liquid 2].

(Example 3)
A toner was manufactured in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 3] in Example 1. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of toner material liquid 3>
[Resin A-1] 94 parts, [Resin B-1] (resin content 50%) 12 parts, [Releasing agent dispersion 1] 14 parts, [Colorant dispersion 1] 10 parts, and acetic acid in a beaker After 94 parts of ethyl was added and the resin was dissolved while stirring at 50 ° C., the mixture was stirred at 8,000 rpm with a TK homomixer and dispersed uniformly to obtain [Toner Material Liquid 3].

Example 4
A toner was manufactured in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 4] below in Example 1. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 4>
In a beaker, 75 parts of [resin A-1], 50 parts of [resin B-1] (resin content 50%), 14 parts of [release agent dispersion 1], 10 parts of [colorant dispersion 1], and acetic acid 75 parts of ethyl was added and the resin was dissolved while stirring at 50 ° C., and then stirred at 8,000 rpm with a TK homomixer and dispersed uniformly to obtain [Toner Material Liquid 4].

(Example 5)
A toner was manufactured in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 5] in Example 1. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 5>
[Resin A-1] 97 parts, [Resin B-1] (resin content 50%) 6 parts, [Releasing agent dispersion 1] 14 parts, [Colorant dispersion 1] 10 parts, and acetic acid in a beaker 97 parts of ethyl was added and the resin was dissolved while stirring at 50 ° C., and then stirred at 8,000 rpm with a TK homomixer and dispersed uniformly to obtain [Toner Material Liquid 5].

(Example 6)
In Example 1, a toner was produced in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 6] described below. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 6>
[Resin A-2] 68 parts, [Resin B-1] (resin content 50%) 64 parts, [Releasing agent dispersion 1] 14 parts, [Colorant dispersion 1] 10 parts, and acetic acid in a beaker 68 parts of ethyl was added, and the resin was dissolved while stirring at 50 ° C., and then stirred at 8,000 rpm with a TK homomixer and dispersed uniformly to obtain [Toner Material Liquid 6].

(Example 7)
A toner was manufactured in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 7] in Example 1. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of toner material liquid 7>
In a beaker, 100 parts of [Resin A-3], 14 parts of [Releasing Agent Dispersion 1], 10 parts of [Colorant Dispersion 1], and 120 parts of ethyl acetate are added and the resin is stirred at 50 ° C. After dissolution, the mixture was stirred at 8,000 rpm with a TK homomixer and dispersed uniformly to obtain [Toner Material Liquid 7].

(Example 8)
In Example 1, a toner was produced in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 8] described below. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 8>
In a beaker, 100 parts of [Resin A-4], 14 parts of [Releasing Agent Dispersion 1], 10 parts of [Colorant Dispersion 1], and 120 parts of ethyl acetate are added and the resin is stirred at 50 ° C. After dissolution, the mixture was stirred at 8,000 rpm with a TK homomixer and dispersed uniformly to obtain [Toner Material Liquid 8].

Example 9
In Example 1, a toner was produced in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 9] below. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 9>
[Resin A-1] 84 parts, [Resin B-1] (resin content: 50%) 4 parts, [Resin B-2] 28 parts, [Releasing Agent Dispersion 1] 14 parts, [Colorant] Dispersion 1] 10 parts and 84 parts of ethyl acetate were added, and the resin was dissolved while stirring at 50 ° C., then stirred at 8,000 rpm with a TK homomixer, and uniformly dispersed [toner material liquid 9] was obtained.

(Example 10)
A toner was manufactured in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 10] in Example 1. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 10>
[Resin A-1] 23 parts, [Resin A-5] 61 parts, [Resin B-1] (resin content 50%) 32 parts, [Releasing agent dispersion 1] 14 parts, [Colorant] Dispersion 1] 10 parts and 84 parts of ethyl acetate were added, and the resin was dissolved while stirring at 50 ° C., then stirred at 8,000 rpm with a TK homomixer, and uniformly dispersed [toner material liquid 10] was obtained.

(Example 11)
In Example 1, a toner was produced in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 11] described below. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 11>
[Resin A-1] 84 parts, [Resin B-1] (resin content 50%) 32 parts, [Releasing agent dispersion 1] 14 parts, [Colorant dispersion 1] 10 parts, Nucleation 0.06 parts of an agent (manufactured by ADEKA, Adeka Stub NA-11, melting point 400 ° C.) and 84 parts of ethyl acetate were added, and the resin was dissolved while stirring at 50 ° C., and then 8,000 rpm with a TK homomixer. The mixture was stirred and dispersed uniformly to obtain [Toner Material Liquid 11].

(Comparative Example 1)
A toner was manufactured in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 12] in Example 1. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 12>
[Resin A-1] 99 parts, [Resin B-1] (resin content 50%) 2 parts, [Releasing agent dispersion 1] 14 parts, [Colorant dispersion 1] 10 parts, and acetic acid in a beaker 99 parts of ethyl was added, and the resin was dissolved while stirring at 50 ° C., then, stirred at 8,000 rpm with a TK homomixer and uniformly dispersed to obtain [Toner Material Liquid 12].

(Comparative Example 2)
A toner was manufactured in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 13] in Example 1. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 13>
[Resin A-5] 84 parts, [Resin B-1] (resin content 50%) 32 parts, [Releasing agent dispersion 1] 14 parts, [Colorant dispersion 1] 10 parts, and acetic acid in a beaker 84 parts of ethyl was added and the resin was dissolved while stirring at 50 ° C., and then stirred at 8,000 rpm with a TK homomixer and dispersed uniformly to obtain [Toner Material Liquid 13].

(Comparative Example 3)
In Example 1, a toner was produced in the same manner as in Example 1 except that [Toner material liquid 1] was changed to [Toner material liquid 14] described below. The obtained toner was subjected to the same evaluation as in Example 1. The results are shown in Table 3.

<Preparation of Toner Material Liquid 14>
[Resin A-1] 15 parts, [Resin A-5] 69 parts, [Resin B-1] (resin content 50%) 32 parts, [Releasing agent dispersion 1] 14 parts, [Colorant] Dispersion 1] 10 parts and 84 parts of ethyl acetate were added, and the resin was dissolved while stirring at 50 ° C., then stirred at 8,000 rpm with a TK homomixer, and uniformly dispersed [toner material liquid 14].

  The mass ratios of the resins in the toner material liquids used in the above examples and comparative examples are summarized in Table 1 below.

  The results of evaluating the characteristics of the toners obtained in the above Examples and Comparative Examples are shown in Tables 2-1 to 2-2.

As an aspect of this invention, it is as follows, for example.
<1> A toner containing a crystalline resin,
The crystalline resin contains a crystalline resin having at least one of a urethane bond and a urea bond, and a crystalline polyester unit;
In the molecular weight distribution measured by gel permeation chromatography, the tetrahydrofuran-soluble content of the toner contains a component having a molecular weight of 100,000 or more in a peak area of 5.0% or more,
The toner is characterized in that the ratio of the decomposition residue insoluble in methanol when the tetrahydrofuran soluble part of the toner is decomposed in a 0.1N KOH methanol solution is 5.0% by mass or more.
<2> The toner according to <1>, wherein a ratio of a decomposition residue insoluble in methanol when the tetrahydrofuran soluble part of the toner is decomposed with a 0.1N KOH methanol solution is 10.0% by mass or more. .
<3> The above-mentioned <1> to <2>, wherein the tetrahydrofuran soluble content of the toner includes a component having a molecular weight of 250,000 or more in a molecular weight distribution measured by gel permeation chromatography at a peak area of 1.0% or more. The toner according to any one of the above.
<4> The above crystalline resin having at least one of a urethane bond and a urea bond and a crystalline polyester unit contains a crystalline resin having at least one of a polyurethane unit and a polyurea unit and a crystalline polyester unit. The toner according to any one of <1> to <3>.
<5> The toner according to any one of <1> to <4>, wherein the amount of N element when the CHN analysis of the tetrahydrofuran soluble part of the toner is performed is 0.9 mass% to 2.0 mass%. It is.
<6> In the diffraction spectrum obtained by the X-ray diffraction measurement of the toner, the sum of the integrated intensity (C) of the spectrum derived from the crystal structure of the binder resin and the integrated intensity (A) of the spectrum derived from the amorphous structure The toner according to any one of <1> to <5>, wherein a ratio of C to C [C / (A + C)] is 0.15 or more.
<7> Endothermic amount [ΔH (T), (J / g)] in differential scanning calorimetry of toner and a mixed solution of tetrahydrofuran and ethyl acetate of the toner [tetrahydrofuran / ethyl acetate = 50/50 (mass ratio) The ratio [ΔH (H) / ΔH (T)] to the endothermic amount [ΔH (H), (J / g)] in the differential scanning calorimetry of the insoluble matter relative to] is 0.20 to 1.25 The toner according to any one of <1> to <6>.
<8> A toner obtained by stretching a crystalline polyester resin having an isocyanate group in an aqueous medium,
<1> to <7>, wherein the crystalline resin having at least one of a urethane bond and a urea bond and a crystalline polyester unit contains a resin obtained by extending the crystalline polyester resin having an isocyanate group. The toner according to any one of the above.
<9> The maximum endothermic peak temperature (T1) of the second temperature increase in the range of 0 ° C. to 150 ° C. in the differential scanning calorimetry of the toner and the maximum exothermic peak temperature (T2) of the first temperature decrease are represented by the following formula (1 ) And the formula (2), the toner according to any one of <1> to <8>.
T1-T2 ≦ 30 ° C. Formula (1)
T2 ≧ 30 ° C. Formula (2)
However, the temperature increase rate from 0 ° C. to 150 ° C. at the time of temperature increase in the differential scanning calorimetry is 10 ° C./min, and the temperature decrease rate from 100 ° C. to 0 ° C. at the time of temperature decrease is 10 ° C./min. is there.
<10> The maximum peak temperature of the second heat of fusion in the differential scanning calorimetry of the toner is 50 ° C. to 70 ° C., and the heat of fusion of the second temperature rise is 30 J / g to 75 J / g. The toner according to any one of <1> to <9>.
<11> A crystalline resin having at least one of a urethane bond and a urea bond and a crystalline polyester unit is a first crystalline resin and a second polymer having a weight average molecular weight larger than that of the first crystalline resin. The toner according to any one of <1> to <10>, which contains a crystalline resin.
<12> Any one of <1> to <11>, wherein an insoluble content of the toner in a mixed solution of tetrahydrofuran and ethyl acetate [tetrahydrofuran / ethyl acetate = 50/50 (mass ratio)] is 10.0% by mass or more. The toner according to claim 1.
<13> A developer containing the toner according to any one of <1> to <12>.
<14> an electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising toner for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image;
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <12>.

10. Electrostatic latent image carrier 61 Developing device

Japanese Patent Publication No. 4-024702 JP-B-4-024703 Japanese Patent No. 3910338 JP 2010-0777419 A JP 2012-118466 A

Claims (14)

A toner containing a crystalline resin,
The crystalline resin contains a crystalline resin having at least one of a urethane bond and a urea bond, and a crystalline polyester unit;
In the molecular weight distribution measured by gel permeation chromatography, the tetrahydrofuran-soluble content of the toner contains a component having a molecular weight of 100,000 or more in a peak area of 5.0% or more,
A toner characterized in that a ratio of a decomposition residue insoluble in methanol when a tetrahydrofuran soluble part of the toner is decomposed in a 0.1N KOH methanol solution is 5.0% by mass or more.   2. The toner according to claim 1, wherein when the tetrahydrofuran soluble content of the toner is decomposed with a 0.1 N KOH methanol solution, the ratio of decomposition residue insoluble in methanol is 10.0% by mass or more.   3. The toner according to claim 1, wherein the tetrahydrofuran-soluble component of the toner contains 1.0% or more in terms of peak area of a component having a molecular weight of 250,000 or more in a molecular weight distribution measured by gel permeation chromatography. .   The crystalline resin having at least one of a urethane bond and a urea bond and a crystalline polyester unit contains a crystalline resin having at least one of a polyurethane unit and a polyurea unit and a crystalline polyester unit. The toner according to any one of the above.   The toner according to any one of claims 1 to 4, wherein the amount of N element when CHN analysis of the tetrahydrofuran-soluble content of the toner is 0.9 mass% to 2.0 mass%.   In the diffraction spectrum obtained by the X-ray diffraction measurement of the toner, the C relative to the sum of the integrated intensity (C) of the spectrum derived from the crystal structure of the binder resin and the integrated intensity (A) of the spectrum derived from the amorphous structure. The toner according to claim 1, wherein the ratio [C / (A + C)] is 0.15 or more.   Insoluble in endothermic amount [ΔH (T), (J / g)] in differential scanning calorimetry of toner and a mixed solution of tetrahydrofuran and ethyl acetate in said toner [tetrahydrofuran / ethyl acetate = 50/50 (mass ratio)] The ratio [ΔH (H) / ΔH (T)] to the endothermic amount [ΔH (H), (J / g)] in differential scanning calorimetry of the minute is 0.20 to 1.25. The toner according to any one of 6. A toner obtained by stretching a crystalline polyester resin having an isocyanate group in an aqueous medium,
The crystalline resin having at least one of a urethane bond and a urea bond and a crystalline polyester unit contains a resin obtained by extending the crystalline polyester resin having an isocyanate group. The toner described. In the differential scanning calorimetry of the toner, the maximum endothermic peak temperature (T1) at the second temperature increase in the range of 0 ° C. to 150 ° C. and the maximum exothermic peak temperature (T2) at the first temperature decrease are represented by the following formulas (1) and (1). The toner according to claim 1, wherein the toner satisfies (2).
T1-T2 ≦ 30 ° C. Formula (1)
T2 ≧ 30 ° C. Formula (2)
However, the temperature increase rate from 0 ° C. to 150 ° C. at the time of temperature increase in the differential scanning calorimetry is 10 ° C./min, and the temperature decrease rate from 100 ° C. to 0 ° C. at the time of temperature decrease is 10 ° C./min. is there.   2. The maximum peak temperature of heat of fusion at the second temperature increase in differential scanning calorimetry of the toner is 50 ° C. to 70 ° C., and the heat of fusion at the second temperature increase is 30 J / g to 75 J / g. 10. The toner according to any one of 9 to 9.   A crystalline resin having at least one of a urethane bond and a urea bond and a crystalline polyester unit is a first crystalline resin and a second crystalline resin having a weight average molecular weight larger than that of the first crystalline resin The toner according to claim 1, comprising:   The toner according to claim 1, wherein an insoluble content of the toner in a mixed solution of tetrahydrofuran and ethyl acetate [tetrahydrofuran / ethyl acetate = 50/50 (mass ratio)] is 10.0% by mass or more.   A developer comprising the toner according to claim 1. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising toner for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image;
An image forming apparatus, wherein the toner is the toner according to claim 1.