JP2018180515A - Toner, developer, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that is excellent in low-temperature fixability, high-temperature offset resistance, heat-resistant storage property, and image glossiness, and with which a good image can be formed irrespective of the type of paper.SOLUTION: A toner contains a polyester resin. The glass transition temperature of the toner during the first temperature increase in differential scanning calorimetry (DSC) (Tg1st) is 45°C to 65°C; the glass transition temperature of a component of the toner insoluble in tetrahydrofuran (THF) during the first temperature increase in DSC (Tg1st) is observed at two points of Tga1st and Tgb1st; Tga1st is within a range of -45°C to 5°C, and Tgb1st is within a range of 45°C to 70°C; the glass transition temperature of the component of the toner insoluble in THF during the second temperature increase in DSC (Tg2nd) is 40°C to 65°C.SELECTED DRAWING: Figure 2

Description

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

  In recent years, toners can withstand reduction in particle size and high temperature offset for high quality output images, low temperature fixability for energy saving, and high temperature and humidity during storage and transportation after manufacturing Heat resistant storage stability is required. In particular, since the power consumption at the time of fixing occupies most of the power consumption in the image forming process, the improvement of the low temperature fixability is very important.

  Heretofore, toners produced by a kneading and pulverizing method have been used. However, it is difficult to reduce the particle size of the toner produced by the kneading and pulverizing method, and since the shape is indeterminate and the particle size distribution is broad, the quality of the output image is not sufficient. There were problems such as high prices. In addition, when a wax (release agent) is added to improve the fixing property, the toner produced by the kneading and pulverizing method is broken at the interface of the wax during grinding, and a large amount of wax is present on the toner surface. It will Therefore, while the mold release effect is obtained, the toner adhesion (filming) to the carrier, the photosensitive member and the blade is likely to occur, and there is a problem that the overall performance is not satisfactory.

  Therefore, in order to overcome the problems of the above-mentioned kneading and pulverizing method, a method of producing a toner by a polymerization method has been proposed. The toner manufactured by the polymerization method can be easily reduced in particle size, the particle size distribution is sharper than that of the toner manufactured by the kneading and pulverizing method, and further, the inclusion of the releasing agent is also possible. As a method of producing a toner by a polymerization method, a method of producing a toner from a stretching reaction product of a urethane-modified polyester as a toner binder is disclosed for the purpose of improving low temperature fixability and improving high temperature offset resistance. (See, for example, Patent Document 1).

In addition, a method of producing a toner is disclosed which is excellent in powder flowability and transferability in the case of using a small particle size toner, and which is excellent in any of heat resistance storage stability, low temperature fixability and high temperature offset resistance (for example, , Patent Documents 2 and 3). Also, a method of producing a toner having a ripening step for producing a toner binder having a stable molecular weight distribution and achieving both low temperature fixability and high temperature offset resistance is disclosed (see, for example, Patent Documents 4 and 5).
However, the above techniques do not meet the high level of low temperature fixability required in recent years.

Therefore, in order to obtain a high level of low-temperature fixability, a toner is proposed which contains a resin containing a crystalline polyester resin and a releasing agent, and the resin and wax are incompatible with each other and have a sea-island phase separation structure. (See, for example, Patent Document 6). Further, a toner containing a crystalline polyester resin, a releasing agent and a graft polymer has been proposed (see, for example, Patent Document 7).
Further, toners which contain predetermined amorphous polyester resins A and B and crystalline polyester resin C and which are excellent in low-temperature fixing, heat-resistant storage stability, and high-temperature high-humidity storage property have been proposed (for example, Patent Documents 8 to 8). 10).

  These proposed techniques can achieve low temperature fixing because crystalline polyester resins melt more rapidly than amorphous polyester resins. However, in the case of a toner containing a crystalline polyester resin, there is also a problem that toner aggregates are generated in a high temperature and high humidity environment. Also, in recent years, the toner is fixed on the paper surface, and when stacked on the paper discharge tray, the problem that the toner and paper adhere to each other due to the pressure due to the weight of the paper and the residual heat at fixing (paper discharge blocking) There is a problem such as an image defect (bottledness) due to toner deterioration caused by toner stress inside.

  Furthermore, with toners used in ultra-high-speed printing systems in recent years, even when exposed to severe use conditions such as fluctuations in the operating environment temperature and humidity of the image forming apparatus, continuous output of a large number of images, output images of constant image quality There is a need to be compatible with paper types because of the continuing use of various types of paper.

  An object of the present invention is to provide a toner which is excellent in low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and image gloss, and can form a good image regardless of the paper type.

  In order to solve the above problems, the present invention is a toner containing a polyester resin, wherein the glass transition temperature (Tg1st) at the first temperature rise of differential scanning calorimetry (DSC) of the toner is 45 ° C. to 65 ° C. As a component insoluble in tetrahydrofuran (THF) of the toner, the glass transition temperature (Tg1st) at the first temperature elevation of DSC is observed at two points of Tga1st and Tgb1st, and Tga1st is in the range of −45 ° C. to 5 ° C. Tgb1st is in the range of 45 ° C. to 70 ° C., and the glass transition temperature (Tg2nd) at the second temperature increase of DSC of the component soluble in THF of the toner is 40 ° C. to 65 ° C. Do.

  According to the present invention, it is possible to provide a toner which is excellent in low-temperature fixability, high-temperature offset resistance, heat resistant storage stability, and image gloss, and can form a good image regardless of the paper type.

It is a figure for demonstrating how to obtain | require Tg in a DSC curve. FIG. 1 is a schematic view showing an example of an image forming apparatus according to the present invention. It is the schematic which shows an example of a process cartridge.

  Hereinafter, the toner, the developer and the image forming apparatus according to the present invention will be described with reference to the drawings. In addition, this invention is not limited to embodiment shown below, It can change in the range which those skilled in the art could concidentize, such as other embodiment, addition, correction, deletion, and any aspect Even within the scope of the present invention, as long as the functions and effects of the present invention can be achieved.

(toner)
The present invention relates to a toner containing a polyester resin, wherein the glass transition temperature (Tg1st) at the first temperature elevation of differential scanning calorimetry (DSC) of the toner is 45 ° C. to 65 ° C. As a component insoluble in THF), the glass transition temperature (Tg1st) at the first temperature elevation of DSC is observed at two points of Tga1st and Tgb1st, Tga1st is in the range of −45 ° C. to 5 ° C., and Tgb1st is 45 ° C. to The temperature is in the range of 70 ° C., and the glass transition temperature (Tg2nd) at the second temperature rising of DSC of the component soluble in THF of the toner is 40 ° C. to 65 ° C.

  The component insoluble in THF is preferably a polyester resin, and components resulting from the two glass transition temperatures Tga1st and Tgb1st at the first temperature rise of DSC are respectively a polyester resin component A and a polyester resin component B. In this case, the component insoluble in THF of the toner is the polyester resin component A whose glass transition temperature (Tg2nd) at the second temperature rise of DSC is -50 ° C. to 0 ° C., and the glass transition temperature at the second temperature rise of DSC. It is preferable that (Tg2nd) contains the polyester resin component B used as 45 degreeC-65 degreeC. Thus, the fact that the component insoluble in THF exhibits two glass transition temperatures originates in two different polyesters (prepolymers) having different physical properties.

  Further, it is preferable that the glass transition temperature (Tg2nd ') at the second temperature increase of DSC of the component insoluble in THF of the toner is 0 ° C to 50 ° C.

  The component soluble in THF is preferably a polyester resin, and the component resulting from the glass transition temperature (Tg2nd) at the second temperature rise of DSC of the component soluble in THF of the toner is polyester resin component C. . In this case, it is preferable that the component soluble in THF of the toner contains the polyester resin component C which has a glass transition temperature (Tg2nd) of 40 to 65 ° C. at the second temperature rise of DSC.

  In the following, when the glass transition temperatures Tg of polyester resin components A, B, and C are used, the glass transition temperature Tg2nd at the second temperature rise is indicated unless otherwise noted.

  The THF-insoluble polyester resin component A and the polyester resin component B are components mainly derived from a large amorphous polyester resin having a weight average molecular weight (Mw) of 100,000 to 200,000, and are soluble in the THF The polyester resin component C is a component derived mainly from an amorphous polyester resin having a weight average molecular weight (Mw) of 3,000 to 10,000.

  The polyester resin component A imparts plasticity to the toner. The polyester resin component A which is insoluble in tetrahydrofuran (THF) in the toner of the present invention has a branched structure in the molecular skeleton while lowering the Tg and the melt viscosity to secure the low temperature fixability, and the molecular chain is three-dimensional It has a rubbery property that it deforms at low temperature but does not flow.

  The prior art (for example, Patent Document 8) has solved the problem by optimizing the ratio of the polyester resin component A and the polyester resin component C. However, if the amount of the polyester resin component A is too much, the Tg is lowered, and the preservability can not be ensured. In addition, the stress resistance of the toner is deteriorated, and a fluidizing agent or the like on the surface of the toner is buried by thermal and mechanical stress received by stirring in the developing device, and adhesion of the toner particles is increased. As a result, in the transfer process, there is a concern that problems such as image blurring may occur. On the other hand, when the amount of the polyester resin component A is too small, imparting of the plasticity is insufficient and the low temperature fixability can not be satisfied. Further, there is a concern that the required elasticity is not imparted, the high temperature offset is deteriorated, the fixable region becomes narrow, and the image glossiness becomes too high.

  In the present invention, by using the polyester resin component B in which Tg is equal to that of toner and imparts elasticity, elasticity can be imparted while securing Tg, and an offset region can be secured, and image ruby is also possible. It is possible to control the image gloss in an appropriate area in a good area. However, although the cause is not clear, it has been found that when mixed at an arbitrary ratio, the resin separates, causing poor pigment dispersion and reducing the degree of coloring. By determining the polyester resin components A, B and C so that the component ratio becomes appropriate, it has been found that the fixing area and the storage stability can be secured without a decrease in coloring degree, and a more excellent toner can be obtained.

Further, the glass transition temperature (Tg1st) at the first temperature elevation in differential scanning calorimetry (DSC) of the toner and the glass transition point (Tg2nd) at the second temperature elevation are as follows:
Tg1st-Tg2nd ≧ 10 [° C.]
It is preferable to satisfy In order to set Tg1st-Tg2nd to 10 ° C. or more, specifically, a crystalline resin can be used as a binder resin, or can be partially contained. The fact that Tg1st-Tg2nd is 10 ° C. or higher means that the crystalline resin and the binder resin other than the crystalline resin are compatible with each other to lower the glass transition temperature of the binder resin. Excellent low temperature fixability can be achieved.

<Polyester resin component A insoluble in tetrahydrofuran (THF)>
The polyester resin component A preferably contains a polyhydric alcohol component and a polyvalent carboxylic acid component as constituent components, and the polyhydric alcohol component is preferably a diol component.

As said diol component, a C3-C10 aliphatic diol is mentioned, for example.
Examples of the aliphatic diol having 3 to 10 carbon atoms include 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, and 1,5. -Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol and the like.
It is preferable to contain 50 mol% or more of C3-C10 aliphatic diol, and it is more preferable to contain 80 mol% or more.

  Further, as the diol component of the polyester resin component A, the carbon number of the portion to be the main chain is an odd number of 3 to 9, and it is preferable to have an alkyl group in the side chain, and in particular, it is represented by the following general formula (1) The structure of the

HO-(CR ₁ R ₂ ) _n -OH ... General formula (1)

In said formula, R < ₁ > and R < ₂ > respectively independently represent a hydrogen atom or a C1-C3 alkyl group. n represents an odd number of 3 to 9. In n repeating units, R ₁ and R ₂ may be the same or different.

  Moreover, it is preferable that the polyester resin component A contains a crosslinking component. As a crosslinking component, it is preferable to contain a trivalent or higher aliphatic alcohol component, and it is more preferable to contain a trivalent or tetravalent aliphatic alcohol component from the viewpoint of the gloss of the fixed image and the image density. The trivalent or tetravalent aliphatic alcohol component is preferably a trivalent or tetravalent aliphatic polyhydric alcohol component having 3 to 10 carbon atoms. The crosslinking component may be only the trivalent or higher aliphatic alcohol.

  The trivalent or higher aliphatic alcohol can be appropriately selected depending on the purpose, and examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and dipentaerythritol. One of these trivalent or higher aliphatic alcohols may be used alone, or two or more thereof may be used in combination.

  As the crosslinking component of the polyester resin component A, trivalent or higher carboxylic acid, epoxy compound and the like can be used, but from the viewpoint that unevenness hardly occurs and sufficient gloss and image density can be obtained, the crosslinking component is trivalent or more More preferably, it contains an aliphatic alcohol.

  There is no restriction | limiting in particular in the ratio of the crosslinking component in the component of polyester resin component A, Although it can select suitably according to the objective, 0.5-5 mass% is preferable, 1-3 mass% is more preferable .

  There are no particular limitations on the proportion of trivalent or higher aliphatic alcohol in the polyhydric alcohol component that is a component of the polyester resin component A, and it can be appropriately selected according to the purpose, but 50 to 100 mass% is preferable. And 90 to 100% by mass are more preferable.

The dicarboxylic acid component of the polyester resin component A contains an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and preferably contains 50 mol% or more.
Examples of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.

  The polyester resin component A preferably has a urethane bond and / or a urea bond from the viewpoint of more excellent adhesion to a recording medium such as paper. As a result, the urethane bond or the urea bond behaves like a pseudo-crosslinking point, the rubber-like properties of the polyester resin component A become strong, and the heat resistant storage stability of the toner and the high temperature offset resistance are more excellent.

  There is no restriction | limiting in particular in the molecular weight of polyester resin component A, According to the objective, it can select suitably. However, if the molecular weight is too low, the toner may have poor heat resistance storage stability and durability to stress such as agitation in a developing machine. If the molecular weight is too high, the viscoelasticity of the toner upon melting will be high and low temperature fixability It may be inferior to Therefore, in GPC (gel permeation chromatography) measurement, it is preferable that a weight average molecular weight (Mw) is 100,000-200,000.

  The Tg of the polyester resin component A is preferably -50 ° C to 0 ° C, and more preferably -40 ° C to -20 ° C. When the Tg is -50 [deg.] C. or more, the heat resistant storage stability of the toner and the durability to stress such as agitation in a developing machine are improved, and the filming resistance is also improved. On the other hand, when the Tg is 0 ° C. or less, deformation due to heating and pressure at the time of fixing of the toner becomes good, and the low temperature fixing property is improved.

<Polyester resin component B insoluble in tetrahydrofuran (THF)>
The polyester resin component B preferably contains a polyhydric alcohol component and a polyhydric carboxylic acid component. Moreover, it is preferable that it is a modified polyester containing ester unit and bonding units other than this ester bond, and it is preferable that a binder resin precursor is a resin precursor which can produce | generate said modified polyester.

  As the polyhydric alcohol component, alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like); alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A and the like); bisphenols (bisphenol A, bisphenol F, Bisphenol S, etc .; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts, and the like, may be used in combination of two or more. Among them, alkylene glycol and alkylene oxide adducts of bisphenols having 2 to 12 carbon atoms (for example, 2 mol adduct of bisphenol A ethylene oxide, 2 mol adduct of bisphenol A propylene oxide, 3 mol adduct of bisphenol A propylene oxide, etc.) Is preferred.

  Also, as a trivalent or higher polyol, polyhydric aliphatic alcohol (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (phenol novolac, cresol novolac, etc.); trivalent or higher And the alkylene oxide adducts of polyphenols, etc. may be mentioned, and two or more may be used in combination.

  Examples of the divalent carboxylic acid component include alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid) Etc. may be mentioned, and two or more may be used in combination. Among them, alkenyl dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.

  Examples of trivalent or higher polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and two or more of them may be used in combination.

In addition, you may use the anhydride or lower alkyl ester (a methyl ester, an ethyl ester, isopropyl ester etc.) of polycarboxylic acid instead of a polycarboxylic acid.
The polyester resin component B preferably has a urethane bond and / or a urea bond, from the viewpoint of more excellent adhesion to a recording medium such as paper. As a result, the urethane bond or the urea bond behaves like a pseudo-crosslinking point, the rubber-like property of the polyester resin component B becomes strong, and the heat resistant storage stability of the toner and the high temperature offset resistance are more excellent.

  45 degreeC-65 degreeC is preferable, and, as for Tg of the polyester resin component B, 50 degreeC-60 degreeC is more preferable. When the Tg is 45 ° C. or higher, the heat resistant storage stability of the toner, and the durability to stress such as agitation in a developing machine are improved, and the filming resistance is improved. On the other hand, when the Tg is 65 ° C. or less, deformation due to heating and pressure at the time of fixing of the toner becomes good, and the low temperature fixing property is improved.

<Polyester resin component C soluble in tetrahydrofuran (THF)>
The polyester resin component C preferably contains a diol component and a dicarboxylic acid component as constituent components, and preferably contains 40 mol% or more of an alkylene glycol. The polyester resin component C may or may not contain a crosslinking component as a component.

As polyester resin component C, linear polyester resin is preferable.
Moreover, as polyester resin component C, non-modified polyester resin is preferable. The unmodified polyester resin is a polyester resin obtained by using a polyhydric alcohol and a polyvalent carboxylic acid such as polyvalent carboxylic acid, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid ester, or a derivative thereof, It is not modified by an isocyanate compound or the like.

As said polyhydric alcohol, diol etc. are mentioned, for example.
Examples of the diol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Alkylene (2 to 3 carbon atoms) oxide (average addition mole number 1 to 10) adduct of bisphenol A such as; ethylene glycol, propylene glycol; hydrogenated bisphenol A, hydrogenated bisphenol A alkylene (2 to 3 carbon atoms) Oxide (average added mole number 1 to 10) adducts and the like can be mentioned.
One of these may be used alone, or two or more may be used in combination.

As said polyvalent carboxylic acid, dicarboxylic acid etc. are mentioned, for example.
Examples of the dicarboxylic acids include alkyl groups having 1 to 20 carbon atoms such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, dodecenyl succinic acid, octyl succinic acid, etc. or alkenyl having 2 to 20 carbon atoms. Group-substituted succinic acid and the like. In particular, it is preferable to contain 50 mol% or more of terephthalic acid.
One of these may be used alone, or two or more may be used in combination.

  In addition, the polyester resin component C may contain a trivalent or higher carboxylic acid and / or a trivalent or higher alcohol at the terminal of the resin chain in order to adjust the acid value and the hydroxyl value.

As said trivalent or more carboxylic acid, trimellitic acid, pyromellitic acid, or those acid anhydrides etc. are mentioned, for example.
Examples of the trihydric or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.

  Moreover, it is preferable that the polyester resin component C contains a crosslinking component. It is preferable to contain a trivalent or higher aliphatic alcohol as the crosslinking component, and it is more preferable to contain a trivalent or tetravalent aliphatic alcohol in terms of the gloss of the fixed image and the image density. The trivalent or tetravalent aliphatic alcohol is preferably a trivalent or tetravalent aliphatic polyhydric alcohol component having 3 to 10 carbon atoms. The crosslinking component may be only the trivalent or higher aliphatic alcohol.

  The trivalent or higher aliphatic alcohol can be appropriately selected depending on the purpose, and examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and dipentaerythritol. One of these trivalent or higher aliphatic alcohols may be used alone, or two or more thereof may be used in combination.

  As the crosslinking component of the polyester resin component C, trivalent or higher carboxylic acid, epoxy compound and the like can be used, but from the viewpoint that unevenness is hard to occur and sufficient gloss and image density can be obtained More preferably, it contains an aliphatic alcohol.

  There is no restriction | limiting in particular in the molecular weight of the polyester resin component C, According to the objective, it can select suitably. However, if the molecular weight is too low, the toner may have poor heat resistance storage stability and durability to stress such as agitation in a developing machine. If the molecular weight is too high, the viscoelasticity of the toner upon melting will be high and low temperature fixability It may be inferior to If the amount of components having a molecular weight of 600 or less is too large, the toner may be inferior in heat resistance storage stability and durability to stress such as stirring in a developing machine. If the amount of components having a molecular weight of 600 or less is too small, low temperature fixability may be poor. There is.

  Therefore, in GPC (gel permeation chromatography) measurement, the weight average molecular weight (Mw) is preferably 3,000 to 10,000, and the number average molecular weight (Mn) is 1,000 to 4,000. preferable. Further, Mw / Mn is preferably 1.0 to 4.0. The weight average molecular weight (Mw) is more preferably 4,000 to 7,000, the number average molecular weight (Mn) is more preferably 1,500 to 3,000, and the Mw / Mn is preferably 1. 0-3.5 are more preferable.

  Moreover, 2-10 mass% is preferable, and the component whose molecular weight of THF soluble part is 600 or less is preferable, The polyester resin component C may be extracted with methanol, the component of molecular weight 600 or less may be removed, and it may refine | purify.

  There is no restriction | limiting in particular in the acid value of the polyester resin component C, Although it can select suitably according to the objective, 1-50 mgKOH / g is preferable and 5-30 mgKOH / g is more preferable. When the acid value is 1 mg KOH / g or more, the toner tends to be negatively chargeable, and further, the affinity between the paper and the toner is improved at the time of fixing on paper, and the low temperature fixing ability can be improved. On the other hand, when the acid value exceeds 50 mg KOH / g, the charge stability, particularly the charge stability against environmental fluctuations may be reduced.

  The hydroxyl value of the polyester resin component C is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 5 mg KOH / g or more.

  40 degreeC-65 degreeC is preferable, as for Tg of the polyester resin component C, 45 degreeC-65 degreeC is more preferable, and 50 degreeC-60 degreeC is further more preferable. When the Tg is 40 ° C. or higher, the heat resistant storage stability of the toner, and the durability to stress such as agitation in a developing machine are improved, and the filming resistance is improved. On the other hand, when the Tg is 65 ° C. or less, deformation due to heating and pressure at the time of fixing of the toner becomes good, and the low temperature fixing property is improved.

  The content of the polyester resin component C is preferably 80 to 90 parts by mass, and more preferably 80 parts by mass with respect to 100 parts by mass of the toner. In the case of a three-component system such as polyester resin component A, polyester resin component B, and polyester resin component C as in the present invention, the cause is not clear, but if the content of polyester resin component C is less than 80 parts by mass, The polyester resin component A and the polyester resin component B may be separated, the dispersibility of the pigment in the toner may be deteriorated, and the degree of coloring of the toner may be lowered.

<Polyester resin having a urethane bond and / or a urea bond>
There is no restriction | limiting in particular in the polyester resin which has the said urethane bond and / or urea bond, According to the objective, it can select suitably. Examples thereof include reaction products of a polyester resin having an active hydrogen group and a polyisocyanate. This reaction product is preferably used as a reaction precursor (hereinafter sometimes referred to as "prepolymer") to be reacted with a curing agent described later.
Examples of the polyester resin having an active hydrogen group include polyester resins having a hydroxyl group.

-Polyisocyanate-
There is no restriction | limiting in particular in the said polyisocyanate, According to the objective, it can select suitably, For example, diisocyanate, trivalent or more isocyanate etc. are mentioned.
Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those obtained by blocking them with a phenol derivative, oxime, caprolactam or the like.

Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethine diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylene diisocyanate. Methyl hexane diisocyanate etc. are mentioned.
Examples of the alicyclic diisocyanate include isophorone diisocyanate, cyclohexylmethane diisocyanate and the like.

  Examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4'-diisocyanatodiphenyl, and 4,4'-diisocyanato-3,3'-dimethyldiphenyl. 4,4'-diisocyanato-3-methyldiphenylmethane, 4,4'-diisocyanato-diphenyl ether and the like.

  As said aromatic aliphatic diisocyanate, (alpha), (alpha), (alpha) ', (alpha)'-tetramethyl xylylene diisocyanate etc. are mentioned, for example.

Examples of the isocyanurate include tris (isocyanatoalkyl) isocyanurate, tris (isocyanatocycloalkyl) isocyanurate and the like.
These polyisocyanates may be used alone or in combination of two or more.

-Curing agent-
The curing agent is not particularly limited as long as it reacts with the prepolymer, and may be appropriately selected depending on the purpose. Examples thereof include active hydrogen group-containing compounds.

--Active hydrogen group containing compound--
There is no restriction | limiting in particular in the active hydrogen group in the said active hydrogen group containing compound, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. Can be mentioned. One of these may be used alone, or two or more may be used in combination.

As the active hydrogen group-containing compound, amines are preferable in that they can form a urea bond.
Examples of the amines include diamines, trivalent or higher amines, aminoalcohols, aminomercaptans, amino acids, and blocked amino groups thereof. One of these may be used alone, or two or more may be used in combination.
Among these, diamine or a mixture of diamine and a small amount of trivalent or higher amine is preferable.

  As said diamine, an aromatic diamine, an alicyclic diamine, an aliphatic diamine etc. are mentioned, for example. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane and the like. Examples of the alicyclic diamine include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminocyclohexane, isophorone diamine and the like. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, hexamethylene diamine and the like.

  Examples of the trivalent or higher amines include diethylenetriamine and triethylenetetramine.

  Examples of the amino alcohol include ethanolamine and hydroxyethyl aniline.

Examples of the aminomercaptan include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acids include aminopropionic acid and aminocaproic acid.
As what blocked the said amino group, the ketimine compound obtained by blocking an amino group with ketones, such as acetone, methyl ethyl ketone, a methyl isobutyl ketone, an oxazoline compound etc. are mentioned, for example.

The molecular structures of the polyester resin components A, B, C, etc. can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement in solution or solid. Conveniently the infrared absorption spectrum, and a method of detecting the one having no absorption based on 965 ± 10 cm ^-1 and 990 of olefins ± 10cm ^-1 δCH (out-of-plane bending vibration) as the polyester resin.

<Crystalline polyester resin D>
A crystalline polyester resin D (hereinafter referred to as a crystalline polyester resin) will be mentioned and described as the crystalline resin. The crystalline polyester resin exhibits heat melting characteristics showing a sharp viscosity decrease near the fixing start temperature because it has high crystallinity. By using a crystalline polyester resin having such properties together with the polyester resin, the heat-resistant storage stability is good until just before the melting start temperature, and the viscosity decreases rapidly due to the melting of the crystalline polyester resin at the melting start temperature ( Can cause sharp melt). Then, the crystalline polyester resin is compatible with the polyester resin, and the viscosity is rapidly lowered together with the polyester resin to fix the toner. Thus, a toner having both good heat-resistant storage stability and low-temperature fixability can be obtained. In addition, good results are also shown for the release width (the difference between the lower limit fixing temperature and the high-temperature offset occurrence temperature).

The crystalline polyester resin is obtained using a polyhydric alcohol and a polyvalent carboxylic acid such as polyvalent carboxylic acid, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid ester, or a derivative thereof.
In the present invention, as described above, the crystalline polyester resin comprises a polyhydric alcohol and a polyvalent carboxylic acid such as polyvalent carboxylic acid, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid ester or a derivative thereof. The resin obtained by modifying the polyester resin, for example, the prepolymer, and the resin obtained by crosslinking and / or elongating the prepolymer do not belong to the crystalline polyester resin.

The presence or absence of crystallinity of the crystalline polyester resin in the present invention can be confirmed by a crystallographic X-ray diffractometer (for example, X'Pert Pro MRD Phillips). The measurement method is described below.
First, a target sample is ground with a mortar to prepare a sample powder, and the obtained sample powder is uniformly applied to a sample holder. Thereafter, the sample holder is set in the diffractometer, measurement is performed, and a diffraction spectrum is obtained. Among the peaks obtained in the range of 20 ° <2θ <25 °, it is judged that the obtained diffraction peak has crystallinity when the peak half width of the peak having the largest peak intensity is 2.0 or less.
In the present invention, a polyester resin which does not exhibit the above-mentioned state with respect to a crystalline polyester resin is referred to as an amorphous polyester resin.

Below, an example of the measurement conditions of X-ray diffraction is described.
〔Measurement condition〕
Tension kV: 45 kV
Current: 40mA
MPSS
Upper
Gonio
Scanmode: continuos
Start angle: 3 °
End angle: 35 °
Angle Step: 0.02 °
Lucident beam optics
Divergence slit: Div slit 1/2
Difflection beam optics
Anti scatter slit: As Fixed 1/2
Receiving slit: Prog rec slit

-Polyhydric alcohol-
There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, diol and alcohol with a trivalent or more are mentioned.

  As said diol, a saturated aliphatic diol etc. are mentioned, for example. Examples of the saturated aliphatic diols include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated fats having 2 or more and 12 or less carbon atoms Family diols are more preferred. When the saturated aliphatic diol is a branched type, the crystallinity of the crystalline polyester resin may be reduced, and the melting point may be reduced. In addition, when the carbon number of the saturated aliphatic diol exceeds 12, it becomes difficult to obtain a practical material. The carbon number is more preferably 12 or less.

  Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and the like. 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 18-octadecanediol, 1, 20-eicosan diol etc. are mentioned. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10 in view of high crystallinity of the crystalline polyester resin and excellent sharp melt properties. Decanediol and 1,12-dodecanediol are preferred.

  Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used alone or in combination of two or more.

-Polyvalent carboxylic acid-
There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.

  Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, speric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, and the like. Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and further, anhydrides thereof and lower (1 to 3 carbon atoms) alkyl esters thereof can also be mentioned.

Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid,
1, 2, 5- benzene tricarboxylic acid, 1, 2, 4- naphthalene tricarboxylic acid etc., these anhydrides, these lower (C1-C3) alkyl ester, etc. are mentioned.

  In addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, a dicarboxylic acid having a sulfonic acid group may be contained as the polyvalent carboxylic acid. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained. These may be used alone or in combination of two or more.

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

  There is no restriction | limiting in particular as melting | fusing point of the said crystalline polyester resin, Although it can select suitably according to the objective, It is preferable that they are 60 degreeC or more and 80 degrees C or less. When the melting point is less than 60 ° C., the crystalline polyester resin is easily melted at a low temperature, and the heat resistant storage stability of the toner may decrease. When the melting point exceeds 80 ° C., the crystalline polyester resin is Insufficient melting may lower the low temperature fixability.

  There is no restriction | limiting in particular as a molecular weight of the said crystalline polyester resin, According to the objective, it can select suitably. The soluble component of the ortho-dichlorobenzene of the crystalline polyester resin is GPC from the viewpoint that the sharp heat-resistant, low-molecular weight distribution is excellent in low-temperature fixability, and the heat-resistant storage stability is lowered when there are many components with low molecular weight. In measurement, it is preferable that they are a weight average molecular weight (Mw) 3,000-30,000, a number average molecular weight (Mn) 1,000-10,000, and Mw / Mn 1.0-10. Furthermore, it is preferable that they are a weight average molecular weight (Mw) 5,000-15,000, a number average molecular weight (Mn) 2,000-10,000, and Mw / Mn 1.0-5.0.

  There is no restriction | limiting in particular as an acid value of the said crystalline polyester resin, Although it can select suitably according to the objective, From the viewpoint of the affinity of paper and resin, in order to achieve desired low temperature fixability 5 mg KOH / g or more is preferable, and 10 mg KOH / g or more is more preferable. On the other hand, 45 mg KOH / g or less is preferable in order to improve high-temperature offset resistance.

  There is no restriction | limiting in particular as a hydroxyl value of the said crystalline polyester resin, Although it can select suitably according to the objective, In order to achieve desired low-temperature fixability and achieve a favorable charging characteristic, 0 mgKOH / G to 50 mg KOH / g is preferable, and 5 mg KOH / g to 50 mg KOH / g is more preferable.

The molecular structure of the crystalline polyester resin can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement and the like in addition to NMR measurement with a solution or solid. Conveniently the infrared absorption spectrum, and a method of detecting those with absorption based on 965 ± 10 cm ^-1 or 990 of olefins ± 10cm ^-1 δCH (out-of-plane bending vibration) as a crystalline polyester resin.

  There is no restriction | limiting in particular as content of the said crystalline polyester resin, Although it can select suitably according to the objective, 1 mass part-10 mass parts are preferable with respect to 100 mass parts of said toners, and 2 mass parts -4 mass parts are more preferred. If the content is less than 1 part by mass, sharp melt formation by the crystalline polyester resin may be insufficient and the low temperature fixability may be poor. If it exceeds 10 parts by mass, the heat resistant storage stability may be deteriorated. And fogging of the image may occur. When the content is within the above-mentioned preferable range, it is advantageous in that all the high image quality and the low temperature fixability are excellent.

<Other ingredients>
The toner of the present invention may further contain other components such as a releasing agent, a colorant, a charge control agent, an external additive, a flowability improver, a cleaning property improver, a magnetic material, and the like, in addition to the components described above. It can be added.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, It can select suitably from well-known things.
Examples of mold release agents for waxes and waxes include plant waxes such as carnauba wax, cotton wax, and wood wax rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin And natural waxes such as petroleum waxes such as microcrystalline and petrolatum;
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene and polypropylene; synthetic waxes such as esters, ketones and ethers;

Further, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, etc .; poly-n-stearyl methacrylate which is a low molecular weight crystalline polymer resin, poly-n- A homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate and ethyl methacrylate); a crystalline polymer having a long alkyl group in a side chain may be used.
Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax and polypropylene wax are preferable.

  The melting point of the release agent is not particularly limited and may be appropriately selected depending on the purpose, but preferably 60 ° C to 80 ° C. If the melting point is less than 60 ° C., the release agent may be easily melted at low temperatures, and the heat resistant storage stability may be poor. On the other hand, if the melting point exceeds 80 ° C., even if the resin is melted and is in the fixing temperature region, the releasing agent may not be sufficiently melted to cause fixing offset, resulting in image loss.

  There is no restriction | limiting in particular in content of the said mold release agent, Although it can select suitably according to the objective, 2-10 mass parts is preferable with respect to 100 mass parts of toners, and 3-8 mass parts is more preferable. If the content is less than 2 parts by mass, the high temperature offset resistance and low temperature fixability at the time of fixing may be inferior, and if it exceeds 10 parts by mass, the heat resistant storage stability may be deteriorated or the image may be fogged. There is. When the content is within the above-mentioned preferable range, it is advantageous in improving the image quality and fixing stability.

-Colorant-
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably.
Examples include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10 G, 5 G, G), cadmium yellow, yellow iron oxide, yellow earth, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), balkan fast yellow (5 G, R), tartrazine lake, quinoline yellow lake, anthrazan yellow BGL, iso indorinone yellow, bengara, red lead, lead moth, cadmium red, cadmium mercurial red, antimony moth, permanent red 4R, para red, phi red, parachloro ortho nitro aniline red, resole fast scarlet G Brilliant Fast Scarlet, Brilliant Carn Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belcan Fast Rubin B, Brilliant Scarlet G, Lisor Rubin GX, Permanentred F5 R, Brilliant Carmin 6B, Pigment Scarlet 3B , Bordeaux 5B, Toru Izin Maroon, Permanent Bordeaux F2 K, Helio Bordeaux B, Bordeaux 10 B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidi Orange, Perinon Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo , Ultramarine blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese violet, dioxane violet, anthraquinone violet, chromium green, zinc green, chromium oxide, pyridinium, emerald green, pigment green B, naphthol green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Oxidized Titanium, zinc flower, lithobon etc. may be mentioned.

  There is no restriction | limiting in particular in content of the said coloring agent, Although it can select suitably according to the objective, 1-15 mass parts is preferable with respect to 100 mass parts of toners, and 3-10 mass parts is more preferable.

The coloring agent can also be used as a master batch complexed with a resin. In addition to the above-mentioned polyester resin, for example, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene, or a substituted product thereof, as the resin used for producing the master batch or the resin to be kneaded with the master batch Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Combined, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α -Chloro methacrylate methyl methacrylate copolymer, sty -Acrylonitrile Copolymer, Styrene-Vinyl Methyl Ketone Copolymer, Styrene-Butadiene Copolymer, Styrene-Isoprene Copolymer, Styrene-Acrylonitrile-Indene Copolymer, Styrene-Maleic Acid Copolymer, Styrene-Maleic Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be mentioned.
One of these may be used alone, or two or more may be used in combination.

  The masterbatch can be obtained by mixing and kneading a resin for masterbatch and a colorant under high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, the so-called flushing method, which is a method of mixing and kneading an aqueous paste containing water of a colorant with a resin and an organic solvent, transferring the colorant to the resin side, and removing water and organic solvent components Since a wet cake can be used as it is, it is not necessary to dry and is preferable. For mixing and kneading, a high shear dispersing device such as a three-roll mill is preferably used.

-Charge control agent-
There is no restriction | limiting in particular in the said charge control agent, According to the objective, it can select suitably. Examples thereof include 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), and alkyls. Examples thereof include amides, phosphorus singles or compounds, tungsten singles or compounds, fluorochemicals, salicylic acid metal salts, and metal salts of salicylic acid derivatives.

  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, E-89 (above, made by Orient Chemical Industries Ltd.) of a phenol condensation product, TP-302, TP-415 (above, made by Hodogaya Chemical Industry), quaternary ammonium salt molybdenum complex, LRA-901, Boron complexes such as LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other high molecular compounds having functional groups such as sulfonic acid groups, carboxyl groups, quaternary ammonium salts, etc. Be

  The content of the charge control agent is not particularly limited and may be appropriately selected according to the purpose, but is preferably 0.1 to 10 parts by mass, and 0.2 to 5 parts by mass with respect to 100 parts by mass of the toner. More preferable. When the content is more than 10 parts by mass, the chargeability of the toner is too large to reduce the effect of the main charge control agent, the electrostatic attraction force with the developing roller is increased, and the flowability of the developer decreases and the image density Can cause a decrease in These charge control agents can be dissolved and dispersed after being melt-kneaded together with the master batch or resin, or may be added when dissolved or dispersed directly in an organic solvent, or after producing toner particles on the toner surface , May be immobilized.

-External additive-
There is no restriction | limiting in particular as said external additive, According to the objective, it can select suitably. Examples thereof include various inorganic fine particles and hydrophobic treated inorganic fine particles. In addition, fatty acid metal salts (for example, zinc stearate, aluminum stearate, etc.), fluoropolymers, and the like can also be used.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, Examples include wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengalla, antimony trioxide, magnesium oxide, zirconium oxide, palladium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. Among these, silica and titanium dioxide are particularly preferred.

  Suitable additives include hydrophobicized silica, titania, titanium oxide and alumina fine particles. As a silica particle, R972, R974, RX200, RY200, R202, R805, R812 (all are Nippon Aerosil Co., Ltd. make) etc. are mentioned, for example. Further, as fine particles of titania, for example, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Kogyo Co., Ltd.), TAF-140 (manufactured by Fuji Titan Kogyo Co., Ltd.), MT- 150 W, MT-500B, MT-600B, MT-150A (all are manufactured by Tayca Corporation) and the like.

  As the titanium oxide fine particles subjected to hydrophobization treatment, for example, T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Kogyo Co., Ltd.), TAF-500T, TAF-1500T ( All of them are manufactured by Fuji Titanium Industry Co., Ltd., MT-100S, MT-100T (all manufactured by Tayca Corporation), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

  The hydrophobized oxide fine particles, hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles are, for example, hydrophilic fine particles such as methyltrimethoxysilane and methyltriethoxysilane. Can be obtained by treatment with a silane coupling agent such as octyl trimethoxysilane. In addition, silicone oil-treated oxide fine particles and inorganic fine particles, which are used for treatment by applying heat as required, are also suitable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino Modified silicone oil, epoxy modified silicone oil, epoxy polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, methacryl modified silicone oil, α-methylstyrene modified silicone oil and the like can be mentioned.

  There is no restriction | limiting in particular in the average particle diameter of the primary particle of the said inorganic fine particle, Although it can select suitably according to the objective, 100 nm or less is preferable and 3-70 nm is more preferable. When it is smaller than 3 nm, the inorganic fine particles are buried in the toner, and it is difficult to effectively exhibit its function. On the other hand, if it is larger than 100 nm, the surface of the photoreceptor is unevenly damaged.

1-100 nm is preferable and, as for the average particle diameter of the primary particle of hydrophobization treatment inorganic fine particle, 5-70 nm is more preferable. Preferably, the primary particles contain at least one type of inorganic fine particles having an average particle size of 20 nm or less, and at least one type of inorganic fine particles having a size of 30 nm or more. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.
There is no restriction | limiting in particular in content of the said external additive, Although it can select suitably according to the objective, 0.1-5 mass parts is preferable with respect to 100 mass parts of toners, 0.3-3 mass. Part is more preferred.

-Fluidity improver-
The flowability improver is not particularly limited as long as it can perform surface treatment to increase hydrophobicity and prevent deterioration of flowability and chargeability even under high humidity, and may be appropriately selected according to the purpose. Can. Examples thereof include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like. It is particularly preferable to use the above-mentioned silica and titanium oxide as hydrophobic silica and hydrophobic titanium oxide after surface treatment with such a fluidity improver.

-Cleanability improver-
The cleaning property improver is added to the toner to remove the developer after transfer remaining on the photosensitive member and the primary transfer medium, and is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, and polymer microparticles produced by soap-free emulsion polymerization such as polymethyl methacrylate microparticles and polystyrene microparticles. The fine polymer particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 to 1 μm.

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

<Glass transition temperature (Tg1st)>
The glass transition temperature (Tg1st) of the toner of the present invention at the first temperature elevation in differential scanning calorimetry (DSC) is 45 ° C. to 65 ° C., preferably 50 ° C. to 60 ° C. When the Tg is less than 45 ° C., toner aggregation is likely to occur due to temperature change in transportation of the toner assuming a summer or tropical region and in a storage environment. As a result, solidification in the toner bottle and fixation of the toner in the developing device occur. In addition, defective supply due to toner clogging in the toner bottle and image abnormality due to toner sticking in the developing device are likely to occur. If it is higher than 65 ° C., good low temperature fixability can not be obtained.

  The glass transition temperature (Tg1st) at the first temperature elevation of DSC of the toner of the present invention is the composition ratio of the aliphatic diol and the dicarboxylic acid component of the polyester resin component A, the glass transition temperature of the polyester resin component B, the polyester resin component It is possible to adjust in the desired range by changing the composition ratio of the glass transition temperature of C, the polyester resin component A, the polyester resin component B, and the polyester resin component C.

<Volume average particle size>
There is no restriction | limiting in particular in the volume average particle diameter of the toner of this invention, Although it can select suitably according to the objective, It is preferable that it is 3-7 micrometers. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Moreover, it is preferable to contain 1 to 10 number% of components having a volume average particle diameter of 2 μm or less.

<Method of calculating and analyzing various characteristics of toner and toner components>
Next, calculation methods and analysis methods of various characteristics of toner and toner constituent components will be described. The glass transition temperature Tg, the acid value, the hydroxyl value, the molecular weight and the melting point of the polyester resin components A, B and C, the crystalline polyester resin component and the toner constituent components such as the releasing agent are each measured about itself. Although the toner may be separated from the actual toner by Soxhlet extraction, gel permeation chromatography (GPC) or the like, the separated components may be measured. In the present invention, means for separating the toner components in the toner can be arbitrarily selected, but the measurement of the glass transition temperature Tg of the target sample is measured by the method described later.

First, an example will be described. An example is shown about the method of measuring the glass transition temperature of each of the polyester resin component A, the polyester resin component B, and the polyester resin component C in a toner. 1 g of the toner is put into 100 mL of THF, and Soxhlet extraction is performed to obtain THF soluble matter and insoluble matter. This is dried in a vacuum drier for 24 hours to obtain a mixture of polyester resin component C and crystalline polyester resin component from THF soluble matter, and a mixture of polyester resin component A and polyester resin component B from THF insoluble matter. Using these as target samples, the glass transition temperature is measured by the method described later.
As for the polyester resin component A and the polyester resin component B, since the glass transition temperature is different between the two, a mixture of the polyester resin component A and the polyester resin component B is obtained by the above, and the glass transition temperature is measured for this mixture. The glass transition temperature of the polyester resin component A and the polyester resin component B can be determined.

Next, other examples will be described. 1 g of the toner is placed in 100 mL of THF, and a soluble solution is obtained while stirring at 25 ° C. for 30 minutes. The resultant is filtered with a 0.2 μm membrane filter to obtain THF soluble matter in the toner. Next, this is dissolved in THF to make a sample for GPC measurement, and injected into GPC used for measuring the molecular weight of polyester resin component C. Further, as a sample for measurement of the polyester resin component A and the polyester resin component B, THF insoluble matter in the toner is used as a sample for GPC measurement.
On the other hand, a fraction collector is placed at the elution port of the GPC, and the eluate is separated for each predetermined count, and the eluate is eluted every 5% in area ratio from the elution start of the elution curve (rise of the curve). Get Next, for each eluate, 30 mg of a sample is dissolved in 1 mL of heavy chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance. The solution is filled in a 5 mm diameter glass tube for NMR measurement, and integration is performed 128 times at 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.) to obtain a spectrum. The monomer composition of polyester resin components A, B and C, crystalline polyester resin and the like contained in the toner, and the composition ratio can be determined from the peak integral ratio of the obtained spectrum.

  Next, an example of separation of each component by GPC will be described. In GPC measurement using THF as a mobile phase, the eluate is fractionated with a fraction collector or the like, and fractions corresponding to the desired molecular weight portion of the integral of the elution curve are put together. Then, the eluate is concentrated and dried by an evaporator or the like, and then the solid content is dissolved in a heavy solvent such as heavy chloroform or heavy THF, and 1H-NMR measurement is performed. Calculate the component monomer ratio of As another method, the eluate may be concentrated and then hydrolyzed with sodium hydroxide or the like, and the decomposition product may be qualitatively analyzed by high performance liquid chromatography (HPLC) or the like to calculate the constituent monomer ratio. Good.

  When toner base particles are formed while the toner production method forms a polyester resin by an extension reaction and / or a cross-linking reaction between a non-linear reactive precursor and a curing agent, the actual toner is used. The separation may be performed by GPC or the like to determine the Tg of the polyester resin, etc. Separately, the polyester resin is synthesized by the extension reaction and / or the crosslinking reaction of the non-linear reactive precursor and the curing agent, and the synthesis thereof The Tg and the like may be measured from the obtained polyester resin.

<< Method of measuring melting point and glass transition temperature Tg >>
The melting point and the glass transition temperature Tg in the present invention are measured using a DSC system (differential scanning calorimeter) ("Q-200", manufactured by TA Instruments).
Specifically, the melting point and the glass transition temperature of the target sample are measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, in a nitrogen atmosphere, the temperature is raised from -80 ° C to 150 ° C at a temperature rising rate of 1.0 ° C / min (first temperature rise). Then, it is made to cool to -80 degreeC by temperature-fall rate 1.0 degree-C / min from 150 degreeC, and also it heats up to 150 degrees C with a temperature increase rate 1.0 degree-C / min (temperature increase 2nd time). A DSC curve is measured using a differential scanning calorimeter ("Q-200", manufactured by TA Instruments) at each of the first temperature increase and the second temperature increase.

  From the obtained DSC curve, using an analysis program in the Q-200 system, the DSC curve at the first temperature rise can be selected to determine the glass transition temperature Tg1st of the target sample at the first temperature rise. Similarly, a DSC curve at the second temperature rise can be selected, and the glass transition temperature Tg2nd of the target sample at the second temperature rise can be determined.

  In the present invention, the onset value shown in FIG. 1 is calculated as Tg. The DSC curve obtained was obtained using an analysis program in the Q-200 system, and the onset value shown in FIG. 1 was taken as the Tg of the present invention.

  In addition, with respect to the component insoluble in THF of the toner, measurement is performed by giving a modulation temperature amplitude as shown below in that the glass transition temperature (Tg1st) at the first temperature rise can be separated into two parts. .

(Measurement condition)
Using a modulation mode, heat from −80 ° C. to 150 ° C. at a heating rate of 1.0 ° C./min while giving a modulation temperature amplitude of ± 1.0 ° C./min (first temperature increase). The DSC curve thus obtained is obtained by taking "Reversing Heat Frow" on the vertical axis using the analysis program in the Q-200 system in the same manner as described above, and the onset value shown in FIG. .

  Also, from the DSC curve obtained, select the DSC curve at the first temperature rise using the analysis program in the Q-200 system, and find the endothermic peak top temperature at the first temperature rise of the target sample as the melting point Can. Similarly, a DSC curve at the second temperature rise can be selected, and the endothermic peak top temperature at the second temperature rise of the target sample can be obtained as the melting point.

  The melting point of the polyester resin components A, B, and C, the melting point of the other components such as the releasing agent, and the glass transition temperature Tg are the endothermic peak top temperature at the time of the second temperature rise, and the glass transition unless otherwise noted. The temperature Tg2nd is taken as the melting point and the glass transition temperature Tg of each target sample.

<Mass ratio of polyester resin component>
In the present invention, the mass ratio of the polyester resin component A to the total mass of the polyester resin component A, the polyester resin component B and the polyester resin component C is a, the mass ratio of the polyester resin component B is b, and the mass ratio of the polyester resin component C Where c is
4 (a + b) <c
It is preferable to satisfy In this case, it is possible to prevent the resin from being separated and to prevent the poor dispersion of the pigment and the decrease in the degree of coloring. In addition, a good image can be obtained, and the fixed area and the storage stability can be secured.

  In the present embodiment, as described above, the mass ratio of the polyester resin component is the combination of the polyester resin component A and B in the toner, the combination of the polyester resin component C and the crystalline polyester resin by Soxhlet extraction or GPC. It can be obtained from its weight.

<Method of manufacturing toner>
The method for producing the toner is not particularly limited and may be appropriately selected according to the purpose. However, the polyester resin components A, B, and C are contained, and the crystalline polyester resin and the releasing agent may be further selected as needed. It is preferable to granulate by dispersing an oil phase containing a coloring agent and the like in an aqueous medium.
Further, the polyester resin components A and B include a polyester resin which is a prepolymer having a urethane bond and / or a urea bond, and a polyester resin which does not have a urethane bond and / or a urea bond, preferably the crystalline polyester resin It is further preferable to granulate by dispersing the oil phase containing the above-mentioned curing agent, mold release agent, coloring agent and the like in an aqueous medium.

As a method for producing such a toner, known dissolution and suspension methods can be mentioned.
As an example, a method of forming toner base particles while forming a polyester resin by an extension reaction and / or a crosslinking reaction of the prepolymer and the curing agent will be shown.
In this method, preparation of an aqueous medium, preparation of an oil phase containing a toner material, emulsification or dispersion of a toner material, and removal of an organic solvent are performed.

-Preparation of aqueous medium (water phase)-
The aqueous medium can be prepared, for example, by dispersing resin particles in an aqueous medium. There is no restriction | limiting in particular in the addition amount in the aqueous medium of the said resin particle, Although it can select suitably according to the objective, 0.5-10 mass parts is preferable with respect to 100 mass parts of aqueous media.
There is no restriction | limiting in particular in the said aqueous medium, According to the objective, it can select suitably, For example, the solvent miscible with water, water, these mixtures, etc. are mentioned. One of these may be used alone, or two or more may be used in combination. Among these, water is preferred.

  The solvent miscible with water is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include alcohols, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone.

-Preparation of oil phase-
In the present embodiment, the preparation of the oil phase containing the toner material comprises polyester resins A and B, which are prepolymers having a urethane bond and / or a urea bond, and a polyester resin C which does not have a urethane bond and / or a urea bond. It can be carried out by dissolving or dispersing a toner material containing the crystalline polyester resin, the curing agent, the releasing agent, the colorant and the like, as necessary, in an organic solvent.

  There is no restriction | limiting in particular in the said organic solvent, Although it can select suitably according to the objective, The organic solvent whose boiling point is less than 150 degreeC is preferable at the point which removal is easy.

Examples of the organic solvent having a boiling point of less than 150 ° C. include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, Methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be mentioned.
One of these may be used alone, or two or more may be used in combination.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is more preferable.

-Emulsification or dispersion-
The emulsification or dispersion of the toner material can be carried out by dispersing an oil phase containing the toner material in the aqueous medium. Then, when the toner material is emulsified or dispersed, the curing agent and the prepolymer can be subjected to an extension reaction and / or a crosslinking reaction.

  There are no particular limitations on the reaction conditions (reaction time, reaction temperature) for producing the prepolymer, and the reaction conditions can be appropriately selected depending on the combination of the curing agent and the prepolymer. The reaction time is preferably 10 minutes to 40 hours, and more preferably 2 to 24 hours. 0 degreeC-150 degreeC is preferable, and, as for the said reaction temperature, 40 degreeC-98 degreeC is more preferable.

  There is no restriction | limiting in particular in the method to form the dispersion liquid containing the said prepolymer stably in the said aqueous medium, According to the objective, it can select suitably. An example thereof is a method of adding an oil phase prepared by dissolving or dispersing a toner material in a solvent in an aqueous medium phase, and dispersing it by shear force.

  There is no restriction | limiting in particular in the dispersing machine for the said dispersion | distribution, According to the objective, it can select suitably. For example, a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, an ultrasonic disperser, etc. may be mentioned. Among these, a high-speed shear disperser is preferable in that the particle diameter of the dispersion (oil droplets) can be controlled to 2 to 20 μm.

  When the high-speed shear disperser is used, conditions such as the number of revolutions, the dispersion time, and the dispersion temperature can be appropriately selected according to the purpose. 1,000 to 30,000 rpm is preferable, and 5,000 to 20,000 rpm is more preferable. The dispersion time is preferably 0.1 to 5 minutes in the case of a batch system. The dispersion temperature is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C, under pressure. Generally, the higher the dispersion temperature, the easier the dispersion.

  The use amount of the aqueous medium at the time of emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected according to the purpose, but 50 to 2,000 parts by mass with respect to 100 parts by mass of the toner material Is preferable, and 100 to 1,000 parts by mass is more preferable. If the use amount of the aqueous medium is less than 50 parts by mass, the dispersion state of the toner material may be deteriorated, and toner base particles having a predetermined particle diameter may not be obtained. If it exceeds 2,000 parts by mass, the production cost Can be high.

When the oil phase containing the toner material is emulsified or dispersed, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets and making it into a desired shape and sharpening the particle size distribution. .
There is no restriction | limiting in particular in the said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, polymeric protection colloid, etc. are mentioned. One of these may be used alone, or two or more may be used in combination. Among these, surfactants are preferable.

  There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant etc. are used. Can. Examples of the anionic surfactant include alkyl benzene sulfonate, α-olefin sulfonate, and phosphoric acid ester. Among these, those having a fluoroalkyl group are preferable.

-Removal of organic solvent-
There is no restriction | limiting in particular in the method to remove an organic solvent from dispersion liquids, such as the said emulsification slurry, According to the objective, it can select suitably. Examples thereof include a method of gradually raising the temperature of the whole reaction system to evaporate the organic solvent in the oil droplets, and a method of spraying the dispersion into a dry atmosphere to remove the organic solvent in the oil droplets. .
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried and the like, and further classified and the like. The classification may be carried out by removing fine particle parts in a liquid by means of a cyclone, decanter, centrifugation or the like, or classification operation may be carried out after drying.

The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, it is possible to suppress detachment of particles such as the external additive from the surface of the toner base particles by applying a mechanical impact force.
There is no restriction | limiting in particular in the method of applying the said mechanical impact force, According to the objective, it can select suitably. Examples include a method of applying an impact force to the mixture using blades rotating at high speed, and a method of injecting the mixture into a high speed air stream and accelerating it to cause particles or particles to collide with an appropriate collision plate. Be

  There is no restriction | limiting in particular in the apparatus used for the said method, According to the objective, it can select suitably. Examples of such devices are Ong Mill (manufactured by Hosokawa Micron Corporation), an apparatus in which I-type mill (manufactured by Nippon Pneumatic Md.) Is modified to reduce the crushing air pressure, Hybridization System (manufactured by Nara Machinery Co., Ltd.), Kryptron System (Kawasaki) Heavy industry company), an automatic mortar, etc. are mentioned.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and optionally contains other appropriately selected components such as a carrier. Therefore, a high quality image can be stably formed with excellent transferability, chargeability and the like. The developer may be a one-component developer or a two-component developer, but when it is used for a high-speed printer or the like compatible with the recent improvement of the information processing speed, the life is improved. Thus, two-component developers are preferred.

  When the developer is used as a one-component developer, even if the toner balance is performed, the variation of the toner particle diameter is small, the toner filming to the developing roller, the member such as a blade for thinning the toner There is little adhesion of toner to the toner, and good and stable developability and an image can be obtained even on long-term stirring in a developing device.

  When the developer is used as a two-component developer, even if the toner balance is made over a long period, the fluctuation of the toner particle diameter is small, and the developability and the image are good and stable even in long-term stirring in the developing device. Is obtained.

<Carrier>
The carrier is not particularly limited and may be appropriately selected according to the purpose. However, it is preferable to have a core and a resin layer covering the core.

-Core material-
There is no restriction | limiting in particular in the material of the said core material, According to the objective, it can select suitably, For example, 50-90 emu / g manganese-strontium type material, 50-90 emu / g manganese-magnesium type material etc. It can be mentioned. Further, in order to secure the image density, it is preferable to use a high magnetization material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g. In addition, it is preferable to use a low-magnetization material such as a copper-zinc system of 30 to 80 emu / g because it can alleviate the impact of the developer in a brushed state on the photoreceptor and is advantageous for achieving high image quality. .
One of these may be used alone, or two or more may be used in combination.

  There is no restriction | limiting in particular in the volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10-150 micrometers is preferable and 40-100 micrometers is more preferable. When the volume average particle size is less than 10 μm, the amount of fine powder in the carrier may be increased, the magnetization per particle may be reduced, and carrier scattering may occur. On the other hand, if it exceeds 150 μm, the specific surface area may be reduced, and toner scattering may occur, and in the case of full color having many solid portions, reproduction of the solid portion may be deteriorated particularly.

The toner of the present invention can be mixed with the carrier and used in a two-component developer.
There is no restriction | limiting in particular in content of the said carrier in the said two-component developer, Although it can select suitably according to the objective, 90-98 mass parts is preferable with respect to 100 mass parts of said two-component developers. And 93 to 97 parts by mass are more preferable.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component developing method, a nonmagnetic one-component developing method, and a two-component developing method.

(Developer storage container)
The developer container for containing the developer of the present invention is not particularly limited, and can be appropriately selected from known ones. For example, what has a container main body and a cap etc. are mentioned.
Further, the size, shape, structure, material, and the like of the container body are not particularly limited, but the shape is preferably cylindrical or the like. In particular, spiral irregularities are formed on the inner peripheral surface, and by rotating the developer, the developer as a content can be transferred to the discharge port side, and some or all of the spiral irregularities have a bellows function. Is preferred. Further, the material is preferably one having high dimensional accuracy. Examples thereof include resin materials such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin component ABS resin, polyacetal resin and the like.

  The developer storage container is easy to store, transport, etc., and is excellent in handleability. Therefore, the developer storage container can be detachably attached to a process cartridge, an image forming apparatus, etc. to be described later, and can be used for developer replenishment.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention comprises at least an electrostatic latent image carrier, electrostatic latent image forming means, and developing means, and further has other means as required.
The image forming method relating to the present invention at least includes an electrostatic latent image forming step and a developing step, and further includes other steps as required.

<Electrostatic latent image carrier>
The material, structure, and size of the latent electrostatic image bearing member 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 view of long life.
The linear velocity of the electrostatic latent image carrier is preferably 300 mm / s or more.

<Electrostatic latent image forming means and electrostatic latent image forming process>
The electrostatic latent image forming unit is not particularly limited as long as it is a unit for forming an electrostatic latent image on the electrostatic latent image bearing member, and can be appropriately selected according to the purpose. The means includes at least a charging member for charging the surface of the electrostatic latent image carrier and an exposure member for exposing the surface of the electrostatic latent image carrier imagewisely.

  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 charging the surface of the electrostatic latent image carrier, it can be carried out by imagewise exposure, and it can be carried out using the electrostatic latent image forming means.

<< Charging member and charging >>
There is no restriction | limiting in particular as said charging member, According to the objective, it can select suitably, For example, the contact charger known per se provided with the electroconductive or semiconductive roller, a brush, a film, a rubber blade etc. Non-contact chargers using 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 be any form such as a magnetic brush or a fur brush other than the roller, and can be selected according to the specification and the form of the image forming apparatus.

  The charging member is not limited to the contact charging member. However, since an image forming apparatus in which ozone generated from the charging member is reduced can be obtained, it is preferable to use the contact charging member.

<< Exposure member and exposure >>
The exposure member is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charging member in the image-like manner to be formed, and is appropriately selected according to the purpose. be able to. For example, 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 can be mentioned.

  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, general luminescent materials such as fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers (LDs), electroluminescences (ELs) and the like can be mentioned.

  Moreover, in order to irradiate only the light of a desired wavelength range, various filters, such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, a color temperature conversion filter, can also be used.

The exposure can be performed, for example, by imagewise exposing the surface of the electrostatic latent image carrier using the exposure member.
In the present invention, a back light method may be employed in which exposure is performed imagewisely from the back side of the electrostatic latent image carrier.

<Developing means and developing process>
The developing unit is not particularly limited as long as it is a developing unit including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image which is a visible image. Can be selected appropriately according to the purpose.
The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a toner image which is a visible image. According to the purpose, it can select suitably, for example, can be performed by the said developing means.
The developing means includes an agitator for frictionally stirring and charging the toner and a magnetic field generating means fixed in the inside, and a developer carrying member that can carry and rotate a developer containing the toner on the surface thereof. Preferred is a developing device having a body.

<Other means and other processes>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a charge removing means, a recycling means, and a control means.
Examples of the other steps include a transfer step, a fixing step, a cleaning step, a charge removal step, a recycling step, and a control step.

<< Transfer means and transfer process >>
The transfer unit is not particularly limited as long as it is a unit for transferring a visible image to a recording medium, and may be appropriately selected according to the purpose. However, the visible image is transferred onto an intermediate transfer body to be composited. It is preferable to have a mode having a primary transfer means for forming a transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and may be appropriately selected according to the purpose. However, an intermediate transfer member may be used on the intermediate transfer member. It is preferable that the visible image be secondarily transferred onto the recording medium after the primary transfer of the visual image.
The transfer step can be performed, for example, by charging the photosensitive member using a transfer charger, and the transfer unit can perform the visible image.

Here, when the image to be secondarily transferred onto the recording medium is a color image composed of toners of a plurality of colors, the toner of each color is sequentially superimposed on the intermediate transfer body by the transfer unit, and the intermediate transfer is performed. An image may be formed on the body, and the image on the intermediate transfer member may be secondarily transferred collectively onto the recording medium by the intermediate transfer unit.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose, and suitable examples include a transfer belt.

The transfer unit (the first transfer unit, the second transfer unit) preferably includes at least a transfer unit that peels and charges the visible image formed on the photosensitive member to 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 the unfixed image after development, and can be appropriately selected according to the purpose. PET base etc. can also be used.

<< Fixing means and fixing process >>
The fixing unit is not particularly limited as long as it is a unit for fixing the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, a known heating and pressing member is preferable. Examples of the heat and pressure member include a combination of a heat roller and a pressure roller, and a combination of a heat roller, a pressure 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 transfer may be performed each time the toner of each color is transferred to the recording medium, or may be simultaneously performed in a state where the toner of each color is laminated.

The fixing step can be performed by the fixing unit.
As for the heating in the said heating-pressing member, 80 to 200 degreeC is preferable.
In the present invention, depending on the purpose, for example, a known optical fixing device may be used together with or instead of the fixing means.
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 unit is not particularly limited as long as it is a unit capable of removing the toner remaining on the photosensitive member, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner, etc. may be mentioned.
The cleaning step is not particularly limited as long as it is a step capable of removing the toner remaining on the photosensitive member, and can be appropriately selected according to the purpose. For example, it can be performed by the cleaning unit.

<< Discharge means and charge removal process >>
The charge removing unit is not particularly limited as long as it is a unit that applies a charge removing bias to the photosensitive member for charge removal, and can be appropriately selected according to the purpose. Examples thereof include a charge removing lamp.
The charge removal step is not particularly limited as long as it is a step of removing charge by applying a charge removal bias to the photosensitive member, and can be appropriately selected according to the purpose. For example, it can be performed by the charge removal unit .

<< Recycling Means and Recycling Process >>
The recycling unit is not particularly limited as long as the toner removed in the cleaning step is recycled to the developing device, and may be appropriately selected according to the purpose. It 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. Can.

Next, one aspect of carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. Although a printer is shown as an example as an image forming apparatus according to the present embodiment, the image forming apparatus is particularly capable of forming an image using toner of a copying machine, a facsimile, a multifunction machine, etc. It is not limited.
The image forming apparatus includes a sheet feeding unit 210, a conveyance unit 220, an image forming unit 230, a transfer unit 240, and a fixing unit 250.
The sheet feeding unit 210 includes a sheet feeding cassette 211 on which sheets P to be fed are stacked, and a sheet feeding roller 212 that feeds sheets P stacked on the sheet feeding cassette 211 one by one.

  The transport unit 220 holds a roller 221 for transporting the paper P fed by the paper feed roller 212 in the direction of the transfer unit 240 and the leading end of the paper P transported by the roller 221 and stands by for a predetermined amount of paper. A pair of timing rollers 222 which are fed to the transfer section 240 at timing and a paper discharge roller 223 which discharges the paper P on which the color toner image is fixed to the paper discharge tray 224 are provided.

The image forming unit 230 includes an image forming unit Y for forming an image using a developer having a yellow toner and a cyan toner in order from the left to the right at a predetermined interval. An image forming unit C using the developer, an image forming unit M using a developer having a magenta toner, an image forming unit K using a developer having a black toner, and an exposing device 233 are provided.
In addition, when showing an arbitrary image forming unit among image forming units (Y, C, M, K), it is called an image forming unit.

  The developer also has a toner and a carrier. The mechanical configurations of the four image forming units (Y, C, M, and K) are substantially the same except that the developers used for them are different.

  The transfer unit 240 is a photosensitive member with an intermediate transfer belt 243 capable of rotating counterclockwise in the figure as the drive roller 241 and the driven roller 242 and the drive roller 241 are driven, and the intermediate transfer belt 243 interposed therebetween. A primary transfer roller (244Y, 244C, 244M, 244K) provided opposite to the body drum 231, and a secondary opposite roller provided oppositely across the intermediate transfer belt 243 at the transfer position of the toner image to the paper And a secondary transfer roller 246.

  The fixing device 250 is provided with a heater inside, and includes a pressure roller 252 which forms a nip by rotatably pressing the fixing belt 251 which heats the paper P against the fixing belt 251. . As a result, heat and pressure are applied to the color toner image on the paper P, and the color toner image is fixed. The paper P on which the color toner image is fixed is discharged onto the discharge tray 224 by the discharge roller 223, and a series of image forming processes are completed.

(Process cartridge)
The process cartridge according to the present invention is detachably molded in various image forming apparatuses, and includes an electrostatic latent image carrier for carrying an electrostatic latent image, and an electrostatic latent image carried on the electrostatic latent image carrier. Are developed with the developer of the present invention to form a toner image. The process cartridge of the present invention may further have other means as needed.

  The developing unit has at least a developer containing portion for containing the developer of the present invention, and a developer carrying member for carrying and carrying the developer contained in the developer containing portion. The developing unit may further include a regulating member or the like in order to regulate the thickness of the developer to be carried.

  FIG. 3 shows an example of a process cartridge according to the present invention. The process cartridge 110 includes a photosensitive drum 10, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90.

  Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the following examples. In the following, “parts” means parts by mass and “%” means mass% unless otherwise described.

(Production Example A-1)
<Synthesis of Prepolymer A-1 (Amorphous Polyester Resin A-1)>
3-Methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimellitic anhydride in a molar ratio of hydroxyl group to carboxyl group in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe Some OH / COOH is 1.5, composition of diol component is 100 mol% of 3-methyl-1,5-pentanediol, composition of dicarboxylic acid component is 40 mol% of isophthalic acid and 60 mol% of adipic acid, all It was charged together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) such that the amount of trimellitic anhydride in the monomer was 1 mol%.
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester A-1].
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of [intermediate polyester A-1] and isophorone diisocyanate (IPDI) (isocyanate group of IPDI / hydroxyl group of intermediate polyester) The mixture was charged at 2.0, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain [prepolymer A-1].

  In addition, in [prepolymer A-1], [polyester resin component A-1] corresponding to polyester resin component A of the present invention is formed in the process of producing toners in Examples and Comparative Examples described later (hereinafter referred to as production) The same as in Examples A and B).

(Production Example A-2)
<Synthesis of Prepolymer A-2 (Amorphous Polyester Resin A-2)>
3-Methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimellitic anhydride in a molar ratio of hydroxyl group to carboxyl group in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe Some OH / COOH is 1.5, composition of diol component is 100 mol% of 3-methyl-1,5-pentanediol, composition of dicarboxylic acid component is 33 mol% of isophthalic acid and 67 mol% of adipic acid, all It was charged together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) such that the amount of trimellitic anhydride in the monomer was 1 mol%.
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester A-2].
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of [intermediate polyester A-2] and isophorone diisocyanate (IPDI) (isocyanate group of IPDI / hydroxyl group of intermediate polyester) After charging at 2.0, the mixture was diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain [prepolymer A-2].

(Production Example A-3)
<Synthesis of Prepolymer A-3 (Amorphous Polyester Resin A-3)>
3-Methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimellitic anhydride in a molar ratio of hydroxyl group to carboxyl group in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe A certain OH / COOH is 1.5, the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol, and the composition of the dicarboxylic acid component is 67 mol% of isophthalic acid and 33 mol% of adipic acid, all It was charged together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) such that the amount of trimellitic anhydride in the monomer was 1 mol%.
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester A-3].
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of [intermediate polyester A-3] and isophorone diisocyanate (IPDI) (isocyanate group of IPDI / hydroxyl group of intermediate polyester) After charging at 2.0, the mixture was diluted with ethyl acetate to be a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain [prepolymer A-3].

(Production Example A-4)
<Synthesis of Prepolymer A-4 (Amorphous Polyester Resin A-4)>
3-Methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimellitic anhydride in a molar ratio of hydroxyl group to carboxyl group in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe Some OH / COOH is 1.5, composition of diol component is 100 mol% of 3-methyl-1,5-pentanediol, composition of dicarboxylic acid component is 30 mol% of isophthalic acid and 70 mol% of adipic acid, all It was charged together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) such that the amount of trimellitic anhydride in the monomer was 1 mol%.
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
After that, reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate Polyester A-4].
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of [intermediate polyester A-4] and isophorone diisocyanate (IPDI) (isocyanate group of IPDI / hydroxyl group of intermediate polyester) After charging at 2.0, the mixture was diluted with ethyl acetate to be a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain [prepolymer A-4].

(Production Example A-5)
<Synthesis of Prepolymer A-5 (Amorphous Polyester Resin A-5)>
3-Methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimellitic anhydride in a molar ratio of hydroxyl group to carboxyl group in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe Some OH / COOH is 1.5, the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol, and the composition of the dicarboxylic acid component is 70 mol% of isophthalic acid and 30 mol% of adipic acid, all It was charged together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) such that the amount of trimellitic anhydride in the monomer was 1 mol%.
Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared.
Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester A-5].
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the molar ratio of [intermediate polyester A-5] and isophorone diisocyanate (IPDI) (isocyanate group of IPDI / hydroxyl group of intermediate polyester) After charging at 2.0, the mixture was diluted with ethyl acetate to be a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain [prepolymer A-5].

(Production Example B-1)
<Synthesis of Prepolymer B-1 (Amorphous Polyester Resin B-1)>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, an ethylene oxide 2 mol adduct of bisphenol A, a propylene oxide 2 mol adduct of bisphenol A, terephthalic acid and adipic acid, of hydroxyl group and carboxyl group, The molar ratio OH / COOH is 1.1, and the composition of the diol component is 80 mol% of the ethylene oxide 2 mol adduct of bisphenol A and 20 mol% of the propylene oxide 2 mol adduct of bisphenol A, the composition of the dicarboxylic acid component Together with titanium tetraisopropoxide (1,000 ppm with respect to the resin component) such that there were 60 mol% of terephthalic acid and 40 mol% of adipic acid. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared. After that, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester B-1].
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the obtained [intermediate polyester B-1] and isophorone diisocyanate (IPDI) in molar ratio (isocyanate group of IPDI / intermediate polyester The reaction was carried out at 100 ° C. for 5 hours to obtain [Prepolymer B-1].

<Synthesis of Prepolymer B-2 (Amorphous Polyester Resin B-2)>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, an ethylene oxide 2 mol adduct of bisphenol A, a propylene oxide 2 mol adduct of bisphenol A, terephthalic acid and adipic acid, of hydroxyl group and carboxyl group, The molar ratio OH / COOH is 1.1, and the composition of the diol component is 80 mol% of the ethylene oxide 2 mol adduct of bisphenol A and 20 mol% of the propylene oxide 2 mol adduct of bisphenol A, the composition of the dicarboxylic acid component Together with titanium tetraisopropoxide (1,000 ppm with respect to the resin component) such that there were 30 mol% of terephthalic acid and 70 mol% of adipic acid. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared. Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester B-2].
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the obtained [intermediate polyester B-2] and isophorone diisocyanate (IPDI) in molar ratio (isocyanate group of IPDI / intermediate polyester The reaction was carried out at 100 ° C. for 5 hours to obtain [Prepolymer B-2].

<Synthesis of Prepolymer B-3 (Amorphous Polyester Resin B-3)>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, an ethylene oxide 2 mol adduct of bisphenol A, a propylene oxide 2 mol adduct of bisphenol A, terephthalic acid and adipic acid, of hydroxyl group and carboxyl group, The molar ratio OH / COOH is 1.1, and the composition of the diol component is 80 mol% of the ethylene oxide 2 mol adduct of bisphenol A and 20 mol% of the propylene oxide 2 mol adduct of bisphenol A, the composition of the dicarboxylic acid component Together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) such that 80 mol% of terephthalic acid and 20 mol% of adipic acid are obtained. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours, and the reaction was carried out until the effluent water disappeared. Thereafter, the reaction was further performed under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester B-3].
Next, in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, the obtained [intermediate polyester B-3] and isophorone diisocyanate (IPDI) in molar ratio (isocyanate group of IPDI / intermediate polyester The reaction product was charged with a hydroxyl group of 2.0, diluted with ethyl acetate to a 50% ethyl acetate solution, and reacted at 100 ° C. for 5 hours to obtain [prepolymer B-3].

(Production Example C-1)
<Synthesis of Amorphous Polyester Resin C-1>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, bisphenol A ethylene oxide side 2 mole adduct, bisphenol A propylene oxide 3 mole adduct, terephthalic acid, adipic acid, and trimethylol Propane in 85/15 molar ratio of bisphenol A ethylene oxide side 2 moles adduct and bisphenol A propylene oxide 3 moles adduct (bisphenol A ethylene oxide side 2 moles adduct / bisphenol A propylene oxide 3 moles adduct) And the molar ratio of terephthalic acid to adipic acid (terephthalic acid / adipic acid) is 75/25, the amount of trimethylolpropane in all monomers is 1 mol%, and the molar ratio of hydroxyl group to carboxyl group OH / COOH is 1 Charge to 2 and react with titanium tetraisopropoxide (500 ppm relative to the resin component) at 230 ° C for 8 hours under normal pressure, then for 4 hours under reduced pressure of 10 mmHg to 15 mmHg, and then trimmerize in a reaction vessel The acid was added in an amount of 1 mol% with respect to all resin components, and reacted at 180 ° C. under normal pressure for 3 hours to obtain [amorphous polyester resin C-1].

(Production Example C-2)
<Synthesis of Amorphous Polyester Resin C-2>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, bisphenol A ethylene oxide side 2 mole adduct, bisphenol A propylene oxide 3 mole adduct, terephthalic acid, adipic acid, and trimethylol Propane in 85/15 molar ratio of bisphenol A ethylene oxide side 2 moles adduct and bisphenol A propylene oxide 3 moles adduct (bisphenol A ethylene oxide side 2 moles adduct / bisphenol A propylene oxide 3 moles adduct) And the molar ratio of terephthalic acid and adipic acid is 65/35 (terephthalic acid / adipic acid), the amount of trimethylolpropane in all monomers is 1 mol%, and the molar ratio of hydroxyl group to carboxyl group OH / COOH is 1 Charge to 2 and react with titanium tetraisopropoxide (500 ppm relative to the resin component) at 230 ° C for 8 hours under normal pressure, then for 4 hours under reduced pressure of 10 mmHg to 15 mmHg, and then trimmerize in a reaction vessel The acid was added so as to be 1 mol% with respect to all the resin components, and reacted at 180 ° C. under normal pressure for 3 hours to obtain [amorphous polyester resin C-2].

(Production Example C-3)
<Synthesis of Amorphous Polyester Resin C-3>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, bisphenol A ethylene oxide side 2 mole adduct, bisphenol A propylene oxide 3 mole adduct, terephthalic acid, adipic acid, and trimethylol Propane in 85/15 molar ratio of bisphenol A ethylene oxide side 2 moles adduct and bisphenol A propylene oxide 3 moles adduct (bisphenol A ethylene oxide side 2 moles adduct / bisphenol A propylene oxide 3 moles adduct) And the molar ratio of terephthalic acid to adipic acid (terephthalic acid / adipic acid) is 85/15, the amount of trimethylolpropane in all monomers is 1 mol%, and the molar ratio of hydroxyl group to carboxyl group OH / COOH is 1 Charge to 2 and react with titanium tetraisopropoxide (500 ppm relative to the resin component) at 230 ° C for 8 hours under normal pressure, then for 4 hours under reduced pressure of 10 mmHg to 15 mmHg, and then trimmerize in a reaction vessel The acid was added in an amount of 1 mol% with respect to all resin components, and reacted at 180 ° C. under normal pressure for 3 hours to obtain [amorphous polyester resin C-3].

(Production Example C-4)
<Synthesis of Amorphous Polyester Resin C-4>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, bisphenol A ethylene oxide side 2 mole adduct, bisphenol A propylene oxide 3 mole adduct, terephthalic acid, adipic acid, and trimethylol Propane in 85/15 molar ratio of bisphenol A ethylene oxide side 2 moles adduct and bisphenol A propylene oxide 3 moles adduct (bisphenol A ethylene oxide side 2 moles adduct / bisphenol A propylene oxide 3 moles adduct) And the molar ratio of terephthalic acid to adipic acid (terephthalic acid / adipic acid) is 60/40, the amount of trimethylolpropane in all the monomers is 1 mol%, and the molar ratio of hydroxyl group to carboxyl group OH / COOH is 1 Charge to 2 and react with titanium tetraisopropoxide (500 ppm relative to the resin component) at 230 ° C for 8 hours under normal pressure, then for 4 hours under reduced pressure of 10 mmHg to 15 mmHg, and then trimmerize in a reaction vessel The acid was added so as to be 1 mol% with respect to all the resin components, and reacted at 180 ° C. under normal pressure for 3 hours to obtain [amorphous polyester resin C-4].

(Production Example C-5)
<Synthesis of Amorphous Polyester Resin C-5>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, bisphenol A ethylene oxide side 2 mole adduct, bisphenol A propylene oxide 3 mole adduct, terephthalic acid, adipic acid, and trimethylol Propane at 90/10 in a molar ratio of bisphenol A ethylene oxide side 2 mole adduct and bisphenol A propylene oxide 3 mole adduct (bisphenol A ethylene oxide side 2 mole adduct / bisphenol A propylene oxide 3 mole adduct) And the molar ratio of terephthalic acid to adipic acid (terephthalic acid / adipic acid) is 75/25, the amount of trimethylolpropane in all monomers is 1 mol%, and the molar ratio of hydroxyl group to carboxyl group OH / COOH is 1 Charge to 2 and react with titanium tetraisopropoxide (500 ppm relative to the resin component) at 230 ° C for 8 hours under normal pressure, then for 4 hours under reduced pressure of 10 mmHg to 15 mmHg, and then trimmerize in a reaction vessel The acid was added in an amount of 1 mol% with respect to all resin components, and reacted at 180 ° C. under normal pressure for 3 hours to obtain [amorphous polyester resin C-5].

(Production Example D-1)
<Synthesis of Crystalline Polyester Resin D-1>
Dodecanedioic acid and 1,6-hexanediol in a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple: OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group The reaction is carried out at 180 ° C. for 10 hours with titanium tetraisopropoxide (500 ppm relative to the resin component), then the temperature is raised to 200 ° C. and the reaction is carried out for 3 hours. The mixture was reacted at a pressure of 3 kPa for 2 hours to obtain [crystalline polyester resin D-1].

<Preparation of Crystalline Polyester Resin Dispersion>
50 parts of [Crystalline polyester resin D-1] and 450 parts of ethyl acetate are charged into a container set with a stirring rod and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours, The mixture is cooled to 30 ° C. for 1 hour, and using a bead mill (Ultravisco Mill, manufactured by Imex Co., Ltd.), the feed speed is 1 kg / hr, the disc peripheral speed is 6 m / sec, and 0.5% diameter zirconia beads are packed by 80% Dispersion was performed under the conditions of pass to obtain [Crystalline polyester resin dispersion liquid 1].

Example 1
<Preparation of Masterbatch (MB)>
Add 1,200 parts of water, 500 parts of carbon black (made by Printex 35 Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], and 500 parts of [amorphous polyester resin C-1], The mixture was mixed using a two-roll mill at 150 ° C. for 30 minutes, rolled and cooled, and crushed using a pulper to obtain [Master batch 1].

<Preparation of WAX Dispersion>
50 parts of paraffin wax as mold release agent 1 (Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8), and ethyl acetate in a container in which a stirring rod and a thermometer are set Charge 450 parts, raise to 80 ° C with stirring, keep at 80 ° C for 5 hours, cool to 30 ° C in 1 hour, and send using a bead mill (Ultravisco Mill, made by Imex Co.) Dispersion was carried out under the conditions of 1 volume / kg, disk peripheral velocity 6 m / second, diameter 0.5 mm zirconia beads packed at 80 volume%, and 3 passes to obtain [WAX dispersion 1].

<Synthesis of ketimine compounds>
170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged in a reaction vessel set with a stirring rod and a thermometer, and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

<Preparation of oil phase>
[WAX dispersion 1] 500 parts, [prepolymer A-1] 76 parts, [prepolymer B-1] 152 parts, [amorphous polyester resin C-1] 836 parts, [master batch 1] 100 parts, And, 2 parts of [ketimine compound 1] was placed in a container as a curing agent, and mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo) at 5,000 rpm for 60 minutes to obtain [Oil phase 1].

<Synthesis of organic fine particle emulsion (fine particle dispersion)>
683 parts of water, 11 parts of sodium salt of methacrylic acid ethylene oxide adduct sulfuric acid ester (Eleminol RS-30: Sanyo Chemical Industries, Ltd.), 138 parts of styrene, 138 parts of methacrylic acid in a reaction vessel in which a stirring rod and a thermometer are set. Parts and 1 part of ammonium persulfate were charged and stirred for 15 minutes at 400 revolutions / minute to obtain a white emulsion. The mixture was heated to a system temperature of 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% aqueous ammonium persulfate solution is added, followed by aging at 75 ° C. for 5 hours to obtain an aqueous dispersion of vinyl resin (copolymer of sodium salt of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate) [fine particles Dispersion 1] was obtained.
The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 (manufactured by HORIBA) was 0.14 μm. A part of the [fine particle dispersion 1] was dried to isolate the resin component.

<Preparation of water phase>
A mixture of 990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (ELEMINOL MON-7: Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate is mixed and stirred to obtain milky white color. Got the liquid. This was designated as [water phase 1].

<Emulsification and desolvation>
1,200 parts of [aqueous phase 1] was added to a container containing [oil phase 1], and mixed with a TK homomixer at a rotational speed of 13,000 rpm for 20 minutes to obtain [emulsified slurry 1]. Next, [Emulsified slurry 1] was put into a container in which a stirrer and a thermometer were set, and after desolvation at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [dispersed slurry 1]. .

<Washing and drying>
After filtering and filtering 100 parts of [Dispersion slurry 1], the following operation was performed.
(1): 100 parts of ion exchanged water was added to the filter cake, mixed with a TK homomixer (rotational speed of 12,000 rpm for 10 minutes) and filtered.
(2): 100 parts of 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (rotation speed 12,000 rpm for 30 minutes), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotational speed of 12,000 rpm for 10 minutes) and filtered.
(4): 300 parts of ion-exchanged water is added to the filter cake of (3), and it is filtered after being mixed (rotational speed 12,000 rpm for 10 minutes) with a TK homomixer. Operation of the above (1) to (4) Was carried out twice to obtain [filtered cake].
[Filtered cake] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with a mesh of 75 μm mesh to obtain [Toner base particle 1].

<External processing>
[Toner Base Particle 1] Based on 100 parts by mass, 0.6 parts by mass of hydrophobic silica having an average particle size of 100 nm, 1.0 parts by mass of titanium oxide having an average particle size of 20 nm, and hydrophobic silica having an average particle size of 15 nm 0.8 parts of the fine powder was mixed with a Henschel mixer to obtain [Toner 1].

<Preparation of carrier>
100 parts by mass of silicone resin (organo straight silicone), 5 parts by mass of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black are added to 100 parts by mass of toluene, and dispersed for 20 minutes with a homomixer The resin layer coating solution was prepared. The resin layer coating solution was applied to the surface of 1,000 parts by mass of spherical magnetite having an average particle diameter of 50 μm using a fluidized bed type coating apparatus to produce [carrier].

<Preparation of developer>
Using a ball mill, 5 parts by mass of [Toner 1] and 95 parts by mass of [Carrier] were mixed to prepare a developer.

(Example 2)
In the same manner as in Example 1 except that [Prepolymer A-1] is replaced by [Prepolymer A-2] and [Polyester resin C-1] is replaced by [Polyester resin C-2]. , [Toner base particle 2] was obtained. [Toner 2] was produced using this [toner base particle 2].

(Example 3)
Example 1 is the same as Example 1 except that [Prepolymer A-1] is replaced by [Prepolymer A-2] and [Polyester resin C-1] is replaced by [Polyester resin C-3]. , [Toner base particle 3] was obtained. [Toner 3] was produced using this [toner base particle 3].

(Example 4)
In the same manner as in Example 1 except that [Prepolymer A-1] is replaced by [Prepolymer A-3] and [Polyester resin C-1] is replaced by [Polyester resin C-2]. , [Toner base particle 4] was obtained. [Toner 4] was produced using this [toner base particle 4].

(Example 5)
Example 1 except that [prepolymer A-1] is replaced by [prepolymer A-3] 152 parts, and [polyester resin C-1] by [polyester resin C-3] 798 parts in Example 1. [Toner base particle 5] was obtained in the same manner as in the above. [Toner 5] was produced using this [toner base particle 5].

(Example 6)
Example 1 is the same as example 1 except that [prepolymer A-1] is replaced by 134 parts, [prepolymer B-1] by 266 parts, and [polyester resin C-1] by 751 parts. Thus, [Toner base particle 6] was obtained. [Toner 6] was produced using this [toner base particle 6].

(Example 7)
[Toner base particle 7] was obtained in the same manner as in Example 1 except that [Prepolymer B-1] was changed to [Prepolymer B-2]. [Toner 7] was produced using this [toner base particle 7].

(Example 8)
[Toner base particle 8] was obtained in the same manner as in Example 1 except that [Prepolymer B-1] was changed to [Prepolymer B-3]. [Toner 8] was produced using this [toner base particle 8].

(Example 9)
In Example 1, 500 parts of [WAX dispersion liquid 1], 76 parts of [prepolymer A-1], 152 parts of [prepolymer B-1], 836 parts of [amorphous polyester resin C-1], [crystalline property] 300 parts of polyester resin dispersion 1], 100 parts of [master batch 1], and 2 parts of [ketimine compound 1] as a curing agent are placed in a container, and TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) for 60 minutes at 5,000 rpm [Toner base particle 9] was obtained in the same manner as in Example 1 except that the mixed [Oil phase 9] was used. [Toner 9] was produced using this [toner base particle 9].

(Example 10)
In Example 1, 500 parts of [WAX dispersion liquid 1], 76 parts of [prepolymer A-1], 152 parts of [prepolymer B-1], 836 parts of [amorphous polyester resin C-1], [crystalline property] 171 parts of polyester resin dispersion liquid 1], 100 parts of [master batch 1], and 2 parts of [ketimine compound 1] as a curing agent are put in a container, and TK homomixer (manufactured by Tokushu Kika Kogyo) at 5,000 rpm for 60 minutes [Toner base particle 10] was obtained in the same manner as in Example 1 except that the mixed [Oil phase 10] was used. [Toner 10] was produced using this [toner base particle 10].

(Example 11)
In Example 1, 500 parts of [WAX dispersion liquid 1], 76 parts of [prepolymer A-1], 534 parts of [prepolymer B-1], 836 parts of [amorphous polyester resin C-1], [crystalline property] In a container, 514 parts of polyester resin dispersion liquid 1], 100 parts of [master batch 1], and 2 parts of [ketimine compound 1] as a curing agent are placed in a container, and they are mixed for 60 minutes at 5,000 rpm [Toner base particle 11] was obtained in the same manner as in Example 1 except that the mixed [Oil phase 11] was used. [Toner 11] was produced using this [toner base particle 11].

(Example 12)
In Example 1, 500 parts of [WAX dispersion 1], 152 parts of [prepolymer A-2], 251 parts of [prepolymer B-2], 836 parts of [amorphous polyester resin C-3], [master batch 1) 100 parts and 2 parts of [ketimine compound 1] as a curing agent in a container and mixed for 60 minutes at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) [Oil phase 12] except using [Toner base particle 12] was obtained in the same manner as Example 1. [Toner 12] was produced using this [toner base particle 12].

(Example 13)
In Example 1, 500 parts of [WAX dispersion liquid 1], 34 parts of [prepolymer A-3], 534 parts of [prepolymer B-3], 836 parts of [amorphous polyester resin C-3], [master batch 1) 100 parts and 2 parts of [ketimine compound 1] as a curing agent in a container and mixed for 60 minutes at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) except for using [Oil phase 13] [Toner base particle 13] was obtained in the same manner as Example 1. [Toner 13] was produced using this [toner base particle 13].

(Comparative example 1)
[Toner base particles 14] were obtained in the same manner as in Example 1 except that [Prepolymer A-1] was changed to [Prepolymer A-4]. [Toner 14] was produced using this [toner base particle 14].

(Comparative example 2)
[Toner base particle 15] was obtained in the same manner as in Example 1 except that [Prepolymer A-1] was changed to [Prepolymer A-5]. [Toner 15] was produced using this [toner base particle 15].

(Comparative example 3)
[Toner base particle 16] was obtained in the same manner as in Example 1 except that [Polyester resin C-1] was changed to [Polyester resin C-4]. [Toner 16] was produced using this [toner base particle 16].

(Comparative example 4)
[Toner base particles 17] were obtained in the same manner as in Example 1 except that [Polyester resin C-1] was changed to [Polyester resin C-5]. [Toner 17] was produced using this [toner base particle 17].

(Comparative example 5)
[Toner base particles 18] were obtained in the same manner as in Example 1 except that in Example 1, the prepolymer B-1 was changed to 0 part (not used). [Toner 18] was produced using this [toner base particle 18].

(Comparative example 6)
[Toner base particle 19] was obtained in the same manner as in Example 1 except that prepolymer A-1 was changed to 0 part (not used). [Toner 19] was produced using this [toner base particle 19].

(Measurement)
<Glass transition temperature of Toner Tg1st, Toner Tg2nd, Tga1st, Tgb1st, Tg2nd ′, and polyester resin components A, B, and C of THF insoluble matter>
1 g of the toner was put into 100 mL of THF and subjected to Soxhlet extraction to obtain THF soluble matter and insoluble matter. This is dried in a vacuum drier for 24 hours to obtain a polyester resin component C (a mixture with a crystalline polyester resin D in Examples 9 to 11) from THF soluble, and a polyester resin component A and a polyester resin from THF insoluble matter A mixture of component B was obtained. These were used as target samples. Also, when measuring the toner Tg1st and the toner Tg2nd, the toner was used as a target sample.

Next, about 5.0 mg of a target sample was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Then, it was heated to 150 ° C. at a temperature rising rate of 1.0 ° C./min from a temperature of −80 ° C. in a nitrogen atmosphere (first temperature rise). Then, it was made to cool to -80 degreeC by temperature-fall rate 1.0 degree-C / min from 150 degreeC, and also it heated up to 150 degreeC by the temperature increase rate 1.0 degree-C / min. A DSC curve was measured using a differential scanning calorimeter ("Q-200", manufactured by TA Instruments) at each of the first temperature increase and the second temperature increase.
From the obtained DSC curve, using the analysis program in the Q-200 system, the DSC curve at the first temperature rise was selected, and the glass transition temperature Tg1st of the target sample at the first temperature rise was determined. Similarly, the DSC curve at the second temperature rise was selected, and the glass transition temperature Tg2nd at the second temperature rise of the target sample was determined.

  From the obtained DSC curve, using an analysis program in the Q-200 system, the DSC curve at the first temperature rise can be selected to determine the glass transition temperature Tg1st of the target sample at the first temperature rise. Similarly, a DSC curve at the second temperature rise can be selected, and the glass transition temperature Tg2nd of the target sample at the second temperature rise can be determined.

  Also, from the DSC curve obtained, select the DSC curve at the first temperature rise using the analysis program in the Q-200 system, and find the endothermic peak top temperature at the first temperature rise of the target sample as the melting point Can. Similarly, a DSC curve at the second temperature rise can be selected, and the endothermic peak top temperature at the second temperature rise of the target sample can be obtained as the melting point.

  The melting point of the polyester resin components A, B, and C, the melting point of the other components such as the releasing agent, and the glass transition temperature Tg are the endothermic peak top temperature at the time of the second temperature rise, and the glass transition unless otherwise noted. The temperature Tg2nd is taken as the melting point and the glass transition temperature Tg of each target sample.

  In addition, for components that are insoluble in THF, the modulation temperature is from -80 ° C to 150 ° C at a temperature rise rate of 1.0 ° C / min, using a modulation mode while giving a modulation temperature amplitude of ± 1.0 ° C / min. Heated (the first heating). Then, using the analysis program in the Q-200 system in the same manner as described above, the “Reversing Heat Frow” is taken along the vertical axis to obtain a DSC curve, and the onset value shown in FIG. And Thus, Tga1st, Tgb1st and Tg2nd 'were determined.

<Mass ratio of polyester resin components A, B and C>
The mass ratio of the polyester resin component C and the crystalline polyester resin D was determined from the THF soluble obtained by the Soxhlet extraction, and the composition ratio of the polyester resin component C and the crystalline polyester resin D was determined. The mass ratio of the mixture of polyester resin components A and B was determined from the THF insoluble matter obtained by the Soxhlet extraction, and the composition ratio of polyester resin component A to polyester resin component B was determined.

  Tables 1 and 2 show the composition ratios of the toner, Tg1st and Tg2nd, and the glass transition temperatures of the polyester resin components A, B and C.

(Evaluation)
The following evaluation was performed about the obtained toner and developer. The developer was produced in the same manner as in Example 1. The results are shown in Table 3.

<Low-temperature fixability of plain paper, evaluation of hot offset resistance>
The developer is loaded into the image forming apparatus shown in FIG. 2, and in the single color mode, a rectangular solid image of 2 cm × 15 cm is attached to the PPC paper type 6000 <70 W> A4 T (manufactured by Ricoh Co.) Was formed to be 0.40 mg / cm ² . At this time, the surface temperature of the fixing roller is changed, and it is observed whether or not an offset occurs in which the development residual image of the solid image is fixed at a place other than the desired place. evaluated. In addition, a solid image was created on the transfer paper at a position 3.0 cm from the leading edge in the sheet passing direction. The speed of passing through the nip portion of the fixing device is 300 mm / s.

[Cold offset evaluation criteria]
A: Fixing lower limit temperature is 130 ° C. or less ○: Fixing lower limit temperature is more than 130 ° C. but not more than 135 ° C. Δ: Fixing lower limit temperature is more than 135 ° C. but not more than 140 ° C. ×: Fixing lower limit temperature is more than 140 ° C.

[Hot offset evaluation criteria]
:: Upper limit temperature for fixing is 175 ° C. or higher ○: Upper limit temperature for fixing is 170 to 175 ° C. Δ: Upper limit temperature for fixing is 165 to 170 ° C. ×: Upper limit temperature is less than 165 ° C

<Evaluation of low temperature fixability on thick paper>
The developer is loaded into the image forming apparatus shown in FIG. 2, and a rectangular solid image of 2 cm × 15 cm is attached to the OK special art post +279.0 GSM A4T (manufactured by Ricoh Co., Ltd.) in the single color mode. The toner was formed to have a density of 40 mg / cm ² and fixed by changing the temperature of the fixing belt. Next, after drawing the surface of the fixed image with a ruby needle with a tip radius of 260 to 320 μm and a tip angle of 60 ° using a drawing tester AD-401 (manufactured by Ueshima Seisakusho Co., Ltd.) under a load of 50 g The surface on which the fixed image was drawn was strongly rubbed five times with a fiber hanicot # 440 (manufactured by Haniron Co., Ltd.), and the temperature of the fixing belt at which image scraping was almost eliminated was defined as the lower limit fixing temperature. In addition, a solid image was created on the transfer paper at a position 3.0 cm from the leading edge in the sheet passing direction. The speed of passing through the nip portion of the fixing device is 300 mm / s.

Evaluation standard for low-temperature fixability of thick paper
A: Fixing lower limit temperature is 160 ° C. or less ○: Fixing lower limit temperature is more than 160 ° C. but not more than 165 ° C. Δ: Fixing lower limit temperature is more than 165 ° C. but not more than 170 ° C. ×: Fixing lower limit temperature is more than 170 ° C.

<Heat resistant storage stability>
After storing the toner at 50 ° C. for 8 hours, the toner was sieved with a 42-mesh sieve for 2 minutes to measure the remaining rate on the wire mesh. At this time, the remaining rate is smaller as the toner is better in heat resistant storage stability.
In addition, the evaluation criteria of heat resistant storage stability were as follows.

〔Evaluation criteria〕
:: Residual rate less than 5% ○: Residual rate not less than 5% and less than 15% Δ: Residual rate not less than 15% and less than 30% ×: Residual rate not less than 30%

<Image gloss>
A copy test was performed on Type 6200 paper (manufactured by Ricoh Co., Ltd.) using an apparatus obtained by modifying the fixing unit of a copying machine MF2200 (manufactured by Ricoh Co., Ltd.) using a Teflon (registered trademark) roller as a fixing roller. Specifically, the fixing temperature is set to the fixing lower limit temperature + 20 ° C. obtained in the evaluation of the low temperature fixing property, the linear velocity of paper feeding is 120 mm / sec to 150 mm / sec, and the surface pressure is 1.2 kgf / cm ² , The nip width was 3 mm. The image after the copying test was measured for 60 degree gloss using a gloss meter VG-7000 (manufactured by Nippon Denshoku Co., Ltd.).

〔Evaluation criteria〕
:: 30% or more and less than 35% ○: 25% or more and less than 30%, or 35% or more and less than 40% Δ: 20% or more and less than 25%, or 40% or more and less than 45% x: less than 20% Or 45% or more

<Image density (coloring degree)>
A carrier and a toner used in Imageo MP C4300 (manufactured by Ricoh Co., Ltd.) were mixed so that the concentration of the toner was 5% by mass, to obtain a developer.
A developer is introduced into a unit of imageo MP C4300 (manufactured by Ricoh Co., Ltd.), and a rectangular solid image of 2 cm × 15 cm is attached to a PPC paper type 6000 <70 W> A4 T eye (manufactured by Ricoh Co.). It formed so that it might be set to 40 mg / cm < ² >. At this time, the surface temperature of the fixing roller was set to 120 ° C. Next, using a X-Rite 938 (manufactured by X-Rite), the image density (ID) of a solid image was measured with status A mode, d50 light.

〔Evaluation criteria〕
:: 1.5 or more ○: 1.4 or more and less than 1.5 △: 1.2 or more and less than 1.4 ×: less than 1.2

<Image ruby evaluation>
A carrier and a toner used in Imageo MP C4300 (manufactured by Ricoh Co., Ltd.) were mixed so that the concentration of the toner was 5% by mass, to obtain a developer. The developer was placed in imageo MP C4300 (manufactured by Ricoh Co., Ltd.), 250 sheets of an A4-sized document with a 25% image area ratio were continuously printed in single color, and each image was evaluated by the image garnish evaluation rank. The image wobbling evaluated the uniformity of the halftone part.

〔Evaluation criteria〕
:: no problem at all :: no problem △: some problems but acceptable level ×: problems

DESCRIPTION OF REFERENCE NUMERALS 10 photosensitive drum 40 developing unit 58 corona charger 80 transfer roller 90 cleaning device 110 process cartridge 210 sheet feeding unit 211 sheet feeding cassette 212 sheet feeding roller 220 conveying unit 221 roller 222 timing roller 223 sheet discharging roller 224 sheet discharging tray 230 Image unit 233 Exposure unit 240 Transfer unit 241 Drive roller 242 Drive roller 242 Intermediate transfer belt 244 Primary transfer roller 245 Secondary opposing roller 246 Secondary transfer roller 250 Fixing unit 251 Fixing belt 252 Pressure roller

Japanese Patent Application Laid-Open No. 11-133665 JP 2002-287400 A JP 2002-351143 A Patent No. 2579150 gazette JP 2001-158819 A Unexamined-Japanese-Patent No. 2004-46095 Unexamined-Japanese-Patent No. 2007-271789 Patent No. 5884797 gazette JP, 2015-118151, A JP, 2016-164616, A

Claims (13)

A toner containing a polyester resin,
The glass transition temperature (Tg1st) at the first temperature elevation of differential scanning calorimetry (DSC) of the toner is 45 ° C. to 65 ° C.
As components insoluble in tetrahydrofuran (THF) of the toner, glass transition temperatures (Tg1st) at the first temperature elevation of DSC are observed at two points of Tga1st and Tgb1st, and Tga1st is in the range of −45 ° C. to 5 ° C. Tgb1st is in the range of 45 ° C. to 70 ° C.,
The toner characterized in that the glass transition temperature (Tg2nd) at the second temperature increase of DSC of the component soluble in THF of the toner is 40 ° C to 65 ° C.   2. The toner according to claim 1, wherein the glass transition temperature (Tg2nd ′) at the second temperature increase of DSC of the component insoluble in tetrahydrofuran (THF) of the toner is 0 ° C. to 50 ° C. 3. The glass transition temperature (Tg1st) at the first temperature elevation in differential scanning calorimetry (DSC) of the toner and the glass transition temperature (Tg2nd) at the second temperature elevation are as follows:
Tg1st-Tg2nd ≧ 10 [° C.]
The toner according to claim 1 or 2, characterized in that The component insoluble in tetrahydrofuran (THF) of the toner is a polyester resin component A whose glass transition temperature (Tg2nd) at the second temperature rise of DSC is -50 ° C. to 0 ° C., and the glass transition at the second temperature rise of DSC. A polyester resin component B having a temperature (Tg2nd) of 45 ° C. to 65 ° C.,
The toner-soluble component of the toner includes a polyester resin component C which has a glass transition temperature (Tg2nd) of 40 to 65 ° C. at the second temperature rising of DSC. The toner described in. The mass ratio of the polyester resin component A to the total mass of the polyester resin component A, the polyester resin component B and the polyester resin component C is a, the mass ratio of the polyester resin component B is b, and the polyester resin component C When mass ratio is c,
4 (a + b) <c
The toner according to claim 4, wherein   The toner according to claim 4, wherein the polyester resin component A contains a trivalent or tetravalent aliphatic polyhydric alcohol component having 3 to 10 carbon atoms. The polyester resin component A contains a diol component,
The toner according to any one of claims 4 to 6, wherein the diol component has an odd number of 3 to 9 carbon atoms in a portion to be a main chain and has an alkyl group in a side chain.   The toner according to any one of claims 4 to 7, wherein the polyester resin component A has at least one of a urethane bond and a urea bond.   The toner according to any one of claims 4 to 8, wherein the polyester resin component B has at least one of a urethane bond and a urea bond.   The toner according to any one of claims 4 to 9, wherein the polyester resin component C contains a trivalent or tetravalent aliphatic polyhydric alcohol component having 3 to 10 carbon atoms.   A developer comprising the toner according to any one of claims 1 to 10 and a carrier. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image formed on the electrostatic latent image carrier And developing means comprising a toner for forming a visible image,
An image forming apparatus, wherein the toner is the toner according to any one of claims 1 to 10. The image forming apparatus according to claim 12, wherein a linear velocity of the electrostatic latent image carrier is 300 mm / s or more.

Images