JP2015118151A - Toner, developer, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has low-temperature fixability and heat-resistant storage property and prevents the occurrence of white patches.SOLUTION: <1> A toner that contains a polyester resin and satisfies the following requirements (1) and (2): (1) THF insolubles have a glass transition temperature at the second temperature rise [Tg2st(THF insolubles)] in a range of -40°C to 30°C, which is measured by differential scanning calorimetry (DSC); and (2) the THF insolubles include 2 to 10 mass% of a low molecular weight component having a molecular weight of 600 or less. <2> The toner according to <1>, wherein the peak top of a molecular weight distribution of the low weight molecular component in the THF insolubles is in a molecular weight range of 300 to 500.

Description

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

In recent years, toners have been able to withstand high temperature and high humidity during storage and transportation after production, as well as reduction in particle size for high quality output images, high temperature offset resistance, low temperature fixability for energy saving. High heat-resistant storage stability is required. In particular, since power consumption during fixing accounts for much of the power consumption in the image forming process, it is very important to improve low-temperature fixability.
Conventionally, toner produced by the kneading and pulverization method has been used, but this toner is difficult to reduce in particle size, and its shape is irregular and the particle size distribution is broad, so the quality of the output image However, there were problems such as insufficient energy and high fixing energy. Further, when a wax (release agent) is added to improve fixability, the wax is present at the toner surface because it is cracked at the interface of the wax during pulverization. As a result, the mold release effect was produced, but toner adhesion (filming) to the carrier, the photoconductor and the blade was likely to occur, and the overall performance was not satisfactory.

In order to overcome the above problems, a method for producing a toner by a polymerization method has been proposed. The toner produced by the polymerization method can be easily reduced in particle size, has a sharper particle size distribution than the toner produced by the kneading and pulverization method, and can also incorporate a release agent.
As a method for producing a toner by a polymerization method, for the purpose of improving low-temperature fixability and improving high-temperature offset resistance, a production method using a urethane-modified polyester extension reaction product for a toner binder is disclosed (for example, Patent Document 1).
In addition, a manufacturing method is disclosed that is excellent in powder flowability and transferability in the case of a toner having a small particle diameter, and excellent in all of heat-resistant storage stability, low-temperature fixability, and high-temperature offset resistance (for example, patents). References 2 and 3).
In addition, a production method 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 (for example, see Patent Documents 4 and 5).
However, these technologies do not satisfy the high level of low temperature fixability required in recent years.

Therefore, for the purpose of obtaining a high level of low temperature fixability, a toner containing a crystalline polyester resin and a release agent, and a resin and a wax that are incompatible with each other and having a sea-island phase separation structure has been proposed. (For example, refer to Patent Document 6).
Further, a toner containing a crystalline polyester resin, a release agent, and a graft polymer has been proposed (see, for example, Patent Document 7).
These techniques can achieve low-temperature fixing because the crystalline polyester resin melts more rapidly than the amorphous polyester resin. However, it is possible to achieve both low-temperature fixability and heat-resistant storage stability. However, in the case of a high-speed machine, the stress applied to the toner in the developing device becomes larger, and the toner is generated due to the occurrence of toner aggregates and doctor clogging. There is a problem of toner white spots (transfer white spots) on the toner image surface. Further, in the case of a toner containing a crystalline polyester resin, there is a problem that toner aggregates are generated in a high temperature and high humidity environment.
Therefore, the present situation is that a toner having fixing property and heat-resistant storage stability and having no white spot problem is demanded.

An object of the present invention is to provide a toner that can solve the above-mentioned problems of the prior art, has low-temperature fixability and heat-resistant storage stability, and has no white spot problem.

The above problem is solved by the following invention 1).
1) A toner containing at least a polyester resin and satisfying the following requirements (1) and (2).
(1) The glass transition temperature [Tg2nd (THF insoluble matter)] at the second temperature increase in differential scanning calorimetry (DSC) of the THF insoluble matter is -40 ° C to 30 ° C.
(2) The THF soluble component contains 2 to 10% by mass of a low molecular weight component having a molecular weight of 600 or less.

  According to the present invention, it is possible to provide a toner that has low-temperature fixability and heat-resistant storage stability and is free from white spots.

1 is a diagram illustrating an example of an image forming apparatus of the present invention. FIG. 4 is a diagram showing another example of the image forming apparatus of the present invention. The figure which shows the image formation means of each color. The figure which shows an example of a process cartridge.

Hereinafter, the present invention 1) will be described in detail. However, since the following 2) to 8) are also included in the embodiment of the present invention, these will be described together.
2) The toner according to 1), wherein the peak top of the molecular weight distribution of the low molecular weight component in the THF-soluble component is in a molecular weight range of 300 to 500.
3) The toner according to 1) or 2), wherein the glass transition temperature (Tg1st) at the first temperature increase in differential scanning calorimetry (DSC) is 20 ° C. to 50 ° C.
4) The toner according to any one of 1) to 3), wherein the glass transition temperature (Tg2nd) at the second temperature increase in differential scanning calorimetry (DSC) is 0 ° C. to 30 ° C.
5) The toner according to any one of 1) to 4), wherein the polyester resin contains a crystalline polyester resin.
6) The toner according to any one of 1) to 5), wherein the polyester resin contains a non-linear amorphous polyester resin having a crosslinked structure.
7) A developer comprising the toner according to any one of 1) to 6) and a carrier.
8) An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier An image forming apparatus comprising: a developing unit including a toner that forms a visible image by developing the toner, wherein the toner is the toner according to any one of 1) to 6).

(toner)
The toner of the present invention needs to satisfy the requirements (1) and (2) regarding the THF (tetrahydrofuran) insoluble and THF soluble components.
The THF-insoluble and THF-soluble components of the toner can be obtained by the following procedure.
First, 1 part of toner is added to 40 parts of THF, and the mixture is refluxed for 6 hours. Then, the insoluble component is settled by a centrifugal separator to separate the insoluble component and the supernatant liquid.
Next, the insoluble component is dried at 40 ° C. for 20 hours to obtain a THF insoluble matter. Further, after removing the solvent from the supernatant, it is dried at 40 ° C. for 20 hours to obtain a THF-soluble component.

<THF insoluble matter>
The THF-insoluble matter contains a non-linear amorphous polyester resin A as a main component. The toner of the present invention has a Tg lower than that of conventional toners, but can contain heat-resistant storage stability by containing a THF-insoluble component. In particular, when the non-linear amorphous polyester resin A has a urethane bond or a urea bond having a high cohesive force, the effect of maintaining heat resistant storage stability becomes more remarkable.
The proportion of the THF-insoluble component in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 15 to 35% by mass, and more preferably 20 to 30% by mass. If it is less than 15% by mass, the low-temperature fixability may be deteriorated, and if it exceeds 35% by mass, the heat resistant storage stability may be deteriorated.

<< [Tg2nd (THF insoluble matter)] >>
[Tg2nd (THF insoluble matter)] needs to be −40 ° C. to 30 ° C. as in the requirement (1), but preferably 0 ° C. to 20 ° C. When [Tg2nd (THF insoluble content)] is less than −40 ° C., heat-resistant storage stability is deteriorated, and when it exceeds 30 ° C., low-temperature fixability is deteriorated.
[Tg2nd (THF insoluble matter)] corresponds to Tg2nd of a non-linear amorphous polyester resin A described later, which is advantageous for low-temperature fixability.
[Tg2nd (THF insoluble content)] can be adjusted, for example, by changing the resin composition (that is, selecting a bifunctional or higher functional polyol and / or a bifunctional or higher acid component).
Specifically, when it is desired to lower Tg, a polyol having an alkyl group in the side chain is used as a resin component, and when it is desired to increase Tg, the ester bond distance in the resin may be shortened. .

<< Storage elastic modulus of THF-insoluble matter >>
The storage elastic modulus [G ′ (100) (THF insoluble matter)] at 100 ° C. of the THF insoluble matter is preferably 1.0 × 10 ^{5 to} 1.0 × 10 ⁷ Pa, and 5.0 × 10 ^{5 to} 5. 0 × 10 ⁶ Pa is more preferable. When [G ′ (100) (THF insoluble matter)] is less than 1.0 × 10 ⁵ Pa, hot offset may occur, and when it exceeds 1.0 × 10 ⁷ Pa, the minimum fixing temperature becomes high. There is.

<THF soluble component>
As in the requirement (2), the THF soluble component needs to contain 2 to 10% by mass of a low molecular weight component having a molecular weight of 600 or less, preferably 5 to 8% by mass. If the low molecular weight component having a molecular weight of 600 or less is less than 2% by mass, the low-temperature fixability may be deteriorated, and if it exceeds 10% by mass, the heat resistant storage stability may be deteriorated.
The THF soluble component is usually composed of a crystalline polyester resin C and an amorphous polyester resin B, which is a high Tg component. Since the crystalline polyester resin C has high crystallinity, it is near the fixing start temperature. Causes a sharp drop in viscosity due to heat melting. Therefore, when these two types of resins are used in combination, the heat-resistant storage stability is good due to crystallinity until just before the melting start temperature, and at the melting start temperature, the viscosity is rapidly reduced due to melting of the crystalline polyester resin C, and accordingly, the amorphous polyester Since the toner is compatible with the resin B and is rapidly fixed to cause a decrease in viscosity, a toner having both good heat storage stability and low temperature fixability can be obtained. Also, good results can be obtained with respect to the release width (difference between the fixing lower limit temperature and the high temperature resistant offset occurrence temperature).

<< [Tg2nd (THF soluble component)] >>
The glass transition temperature [Tg2nd (THF soluble content)] at the second temperature increase in the differential scanning calorimetry (DSC) of the THF soluble content is preferably 5 ° C to 35 ° C, more preferably 25 ° C to 35 ° C.
The value of [Tg2nd (THF soluble content)] can be adjusted by, for example, the Tg of the amorphous polyester resin, the Tg of the crystalline polyester resin, and the blending amount of each.

<Nonlinear Amorphous Polyester Resin A>
The non-linear amorphous polyester resin A constituting the THF-insoluble matter is obtained, for example, by a reaction between a non-linear reactive precursor and a curing agent.
The non-linear amorphous polyester resin 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 and / or the urea bond behave like a pseudo-crosslinking point, the rubber property of the resin becomes stronger, and the heat resistant storage stability and high temperature offset resistance of the toner are further improved.
Here, non-linear means having a branched structure imparted by a trivalent or higher alcohol and / or a trivalent or higher carboxylic acid.

-Non-linear reactive precursor-
The non-linear reactive precursor is not particularly limited as long as it is a polyester resin having a group capable of reacting with a curing agent (hereinafter sometimes referred to as “prepolymer”). You can choose.
Examples of the group capable of reacting with the curing agent in the prepolymer include a group capable of reacting with an active hydrogen group. Examples thereof include an isocyanate group, an epoxy group, a carboxylic acid group, and an acid chloride group. Among these, an isocyanate group is preferable because a urethane bond and / or a urea bond can be introduced into the non-linear amorphous polyester resin A. Moreover, as said prepolymer, the polyester resin which has an isocyanate group is preferable.

--Polyester resin having isocyanate group--
There is no restriction | limiting in particular as the polyester resin which has the said isocyanate group, According to the objective, it can select suitably, For example, the reaction product etc. of the polyester resin and polyisocyanate which have an active hydrogen group are mentioned.
The polyester resin having an active hydrogen group can be obtained, for example, by polycondensing a diol, a dicarboxylic acid, a trivalent or higher alcohol and / or a trivalent or higher carboxylic acid. The trivalent or higher alcohol and the trivalent or higher carboxylic acid impart a branched structure to the polyester resin having an isocyanate group.

--- Diol ---
There is no restriction | limiting in particular as said diol, According to the objective, it can select suitably. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8 -Aliphatic diols such as octanediol, 1,10-decanediol, 1,12-dodecanediol; having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Diols: 1,4-cyclohexanedimethanol, alicyclic diols such as hydrogenated bisphenol A; alicyclic diols added with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide; Nord A, bisphenol F, bisphenol such as bisphenol S; the bisphenols include ethylene oxide, propylene oxide, and alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. Among these, an aliphatic diol having 4 to 12 carbon atoms is preferable.
These diols may be used alone or in combination of two or more.

--- Dicarboxylic acid ---
There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably. Examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Moreover, you may use these anhydrides, a lower (C1-C3) alkylesterification thing, a halide, etc.
Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.
The aromatic dicarboxylic acid is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and the like.
Of these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred.
These dicarboxylic acids may be used individually by 1 type, and may use 2 or more types together.

--Alcohol having a valence of 3 or more ---
There is no restriction | limiting in particular as said trihydric or more alcohol, According to the objective, it can select suitably, For example, alkylene oxide of trihydric or more aliphatic alcohol, trihydric or more polyphenols, trihydric or more polyphenols Examples include adducts.
Examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to trihydric or higher polyphenols.

--Carboxylic acid having a valence of 3 or more ---
There is no restriction | limiting in particular as said trivalent or more carboxylic acid, According to the objective, it can select suitably, For example, trivalent or more aromatic carboxylic acid etc. are mentioned. Moreover, you may use these anhydrides, a lower (C1-C3) alkylesterification thing, a halide, etc.
The trivalent or higher aromatic carboxylic acid is preferably a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms. Examples thereof include trimellitic acid and pyromellitic acid.

--- Polyisocyanate ---
There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably, For example, diisocyanate, trivalent or more isocyanate etc. are mentioned.
Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate.
Examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.

Examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl. 4,4'-diisocyanato-3-methyldiphenylmethane, 4,4'-diisocyanato-diphenyl ether, and the like.
Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate.
Examples of the isocyanurates include tris (isocyanatoalkyl) isocyanurate and tris (isocyanatocycloalkyl) isocyanurate.
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 is a curing agent that reacts with the non-linear reactive precursor and generates the non-linear amorphous polyester resin A, and is appropriately selected according to the purpose. Examples thereof include active hydrogen group-containing compounds.

-Active hydrogen group-containing compound-
There is no restriction | limiting in particular as an 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. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as said active hydrogen group containing compound, Although it can select suitably according to the objective, Amines are preferable at the point which can form a urea bond.
Examples of the amines include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. These may be used individually by 1 type and may use 2 or more types together.
Among these, diamine and a mixture of diamine and a small amount of trivalent or higher amine are preferable.

Examples of the diamine include aromatic diamine, alicyclic diamine, and aliphatic diamine.
Examples of the aromatic diamine include phenylene diamine, diethyl toluene diamine, and 4,4′-diaminodiphenyl methane.
Examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, and isophorone diamine.
Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.

Examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid include aminopropionic acid and aminocaproic acid.
Examples of the blocked amino group include ketimine compounds and oxazoline compounds obtained by blocking amino groups with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

The non-linear amorphous polyester resin A preferably satisfies any of the following (a) to (c) in order to lower the Tg and to easily impart the property of being deformed at a low temperature.
(A) A diol component is included as a constituent component, and the diol component contains 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms.
(B) 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms is contained in all alcohol components.
(C) A dicarboxylic acid component is included as a constituent component, and the dicarboxylic acid component contains 50% by mass or more of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

The non-linear amorphous polyester resin A has a Tg of -60 ° C to 0 ° C, more preferably -40 ° C to -20 ° C. When the Tg is less than −60 ° C., the flow of toner at a low temperature cannot be suppressed, heat resistance storage stability is deteriorated, and filming resistance is deteriorated. If the Tg exceeds 0 ° C., the toner is not sufficiently deformed by heating and pressing during fixing, and the low-temperature fixability becomes insufficient.
The weight average molecular weight of the non-linear amorphous polyester resin A is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20,000 to 100,000 in GPC (gel permeation chromatography) measurement. When the weight average molecular weight is less than 20,000, the toner tends to flow at a low temperature and may have poor heat-preserving stability, viscosity at the time of melting may be low, and high-temperature offset property may be reduced. On the other hand, if it exceeds 100,000, the Tg of the toner may increase and the lower limit of fixing may deteriorate.

The molecular structure of the non-linear amorphous polyester resin A can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. At a convenient infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on olefin? Ch (out-of-plane deformation vibration) as an amorphous polyester resin .
The content of the non-linear amorphous polyester resin A is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferably 5 to 25 parts by mass with respect to 100 parts by mass of the toner, and 10 to 20 Part by mass is more preferable. When the content is less than 5 parts by mass, the low-temperature fixability and the high-temperature offset resistance may be deteriorated. When the content exceeds 25 parts by mass, the heat-resistant storage stability is deteriorated and the glossiness of an image obtained after fixing may be reduced. . When the content is in the more preferable range, it is advantageous in that it is excellent in all of low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability.

<Amorphous polyester resin B>
The amorphous polyester resin B is not particularly limited as long as Tg is 40 ° C. to 80 ° C., and can be appropriately selected according to the purpose.
As the amorphous polyester resin B, an unmodified polyester resin is preferable. The unmodified polyester resin here is a polyester resin obtained by using a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or a derivative thereof. It is a polyester resin that is not modified with an isocyanate compound or the like.

Examples of the polyhydric alcohol include diols.
Examples of the diol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Bisphenol A alkylene (2 to 3 carbon atoms) oxide (average addition mole number 1 to 10) adduct; ethylene glycol, propylene glycol; hydrogenated bisphenol A, hydrogenated bisphenol A alkylene (2 to 3 carbon atoms) Examples include oxide (average added mole number 1 to 10) adducts.
These may be used individually by 1 type and may use 2 or more types together.

Examples of the polyvalent carboxylic acid include dicarboxylic acid.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, dodecenyl succinic acid, octyl succinic acid and the like, or an alkyl group having 1 to 20 carbon atoms or 2 to 20 carbon atoms. And succinic acid substituted with an alkenyl group.
These may be used individually by 1 type and may use 2 or more types together.

Further, the amorphous polyester resin B may contain a trivalent or higher carboxylic acid and / or a trivalent or higher alcohol at the end of the resin chain in order to adjust the acid value or the hydroxyl value.
Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, or acid anhydrides thereof.
Examples of the trivalent or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.

The molecular weight of the amorphous polyester resin B is not particularly limited and may be appropriately selected depending on the purpose. However, if the molecular weight is too low, the toner may be inferior in heat resistance and durability against stress such as stirring in the developing machine. May be inferior. Further, if there are too many low molecular weight components having a molecular weight of 600 or less, the toner may have poor heat resistance and durability against stresses such as stirring in the developing machine, and if there are too few low molecular weight components having a molecular weight of 600 or less, the It may be inferior in fixability. Therefore, the weight average molecular weight (Mw) in GPC measurement is preferably 3000 to 10,000, and more preferably 4000 to 7000. Moreover, 1000-4000 are preferable and, as for a number average molecular weight (Mn), 1500-3000 are more preferable. Further, Mw / Mn is preferably 1.0 to 4.0, and more preferably 1.0 to 3.5.
However, in the present invention, in order to satisfy the requirement (2), if necessary, the amorphous polyester resin B is extracted with methanol to remove a part of the low molecular weight component having a molecular weight of 600 or less and purify it.

There is no restriction | limiting in particular in the acid value of the said amorphous polyester resin B, 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 mgKOH / g or more, the toner is likely to be negatively charged, and further, the affinity between the paper and the toner is improved during fixing on the paper, and the low-temperature fixability can be improved. On the other hand, when the acid value exceeds 50 mgKOH / g, the charging stability, particularly the charging stability against environmental fluctuations may be lowered.
There is no restriction | limiting in particular in the hydroxyl value of the said amorphous polyester resin B, Although it can select suitably according to the objective, It is preferable that it is 5 mgKOH / g or more.

The amorphous polyester resin B has a Tg of preferably 40 ° C to 80 ° C, more preferably 50 ° C to 70 ° C. When the Tg is less than 40 ° C., the heat resistant storage stability of the toner and the durability against stress such as stirring in the developing machine are inferior, and the filming resistance is deteriorated. On the other hand, if Tg exceeds 80 ° C., the deformation due to heating and pressurization at the time of fixing the toner is not sufficient, and the low-temperature fixability becomes insufficient.
The molecular structure of the amorphous polyester resin B can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. At a convenient infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on olefin? Ch (out-of-plane deformation vibration) as an amorphous polyester resin .

  The content of the amorphous polyester resin B is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 to 90 parts by weight, more preferably 60 to 80 parts by weight with respect to 100 parts by weight of the toner. preferable. When the content is less than 50 parts by mass, the dispersibility of the pigment and the release agent in the toner is deteriorated and the image may be easily fogged or disturbed. On the other hand, when the amount exceeds 90 parts by mass, the content of the crystalline polyester resin C and the non-linear amorphous polyester resin A is decreased, so that the low-temperature fixability may be inferior. When the content is in the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<Crystalline polyester resin C>
The thermal characteristics of the crystalline polyester resin C and the effect of the combined use with the amorphous polyester resin B are as described in <THF soluble matter>.
The crystalline polyester resin C in the present invention refers to one obtained from a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or a derivative thereof. Accordingly, the crystalline polyester resin C does not include a modified polyester resin, for example, the prepolymer and a resin obtained by crosslinking and / or elongation reaction of the prepolymer.

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

Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,14-eicosandecanediol. Among these, the crystalline polyester resin C has high crystallinity and is excellent in sharp melt properties, so that ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1, 10-decanediol and 1,12-dodecanediol are preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used individually by 1 type and may use 2 or more types together.

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

The crystalline polyester resin C 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, it is preferable to have a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. As a result, the crystallinity becomes high and the sharp melt property is excellent, so that excellent low-temperature fixability can be exhibited.
There is no restriction | limiting in particular in the melting | fusing point of the said crystalline polyester resin C, Although it can select suitably according to the objective, 60 to 80 degreeC is preferable. If the melting point is less than 60 ° C., the crystalline polyester resin C is likely to melt at low temperatures and the heat-resistant storage stability of the toner may be reduced. Insufficient, low-temperature fixability may decrease.

  The molecular weight of the crystalline polyester resin C is not particularly limited and may be appropriately selected depending on the purpose. However, those with sharp molecular weight distribution and low molecular weight are excellent in low-temperature fixability, and when there are many components with low molecular weight, the heat-resistant storage stability is lowered. Therefore, the soluble content of orthodichlorobenzene in crystalline polyester resin C is GPC. In measurement, it is preferable that they are weight average molecular weight (Mw) 3000-30000, number average molecular weight (Mn) 1000-10000, and Mw / Mn = 1.0-10. More preferably, it is weight average molecular weight (Mw) 5000-15000, number average molecular weight (Mn) 2000-10000, Mw / Mn = 1.0-5.0.

The acid value of the crystalline polyester resin C is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of affinity between paper and resin, in order to achieve desired low-temperature fixability, 5 mgKOH / g or more is preferable, and 10 mgKOH / g or more is more preferable. On the other hand, 45 mgKOH / g or less is preferable in order to improve the high temperature offset resistance.
The hydroxyl value of the crystalline polyester resin C is not particularly limited and may be appropriately selected according to the purpose. However, in order to achieve a desired temperature fixability and to achieve good charging characteristics, 0 to 50 mgKOH / g is preferable, and 5-50 mgKOH / g is more preferable.
The molecular structure of the crystalline polyester resin C can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. For example, in the infrared absorption spectrum, a method of detecting, as crystalline polyester resin C, those having absorption at 965 ± 10 cm ⁻¹ and 990 ± 10 cm ⁻¹ based on δCH (out-of-plane variable angular vibration) of olefin can be mentioned.

  There is no restriction | limiting in particular in content of the said crystalline polyester resin C, Although it can select suitably according to the objective, 3-20 mass parts is preferable with respect to 100 mass parts of toner, and 5-15 mass parts is more preferable. . If the content is less than 3 parts by mass, the low-temperature fixability may be inferior due to insufficient sharp-melting with the crystalline polyester resin C. If the content exceeds 20 parts by mass, the heat-resistant storage stability may be reduced, or the image may be fogged. May occur easily. When the content is within the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<Other ingredients>
In addition to the components described above, the toner of the present invention may contain additives such as a release agent, a colorant, a charge control agent, an external additive, a fluidity improver, a cleaning property improver, and a magnetic material as necessary. It can be included.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, It can select suitably from well-known things, For example, the following are mentioned.
Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin and microcrystalline And natural waxes such as petroleum waxes such as 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;
Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon; low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n -Polyacrylate homopolymer or copolymer such as lauryl methacrylate (eg, n-stearyl acrylate-ethyl methacrylate copolymer); crystalline polymer having a long alkyl group in the side chain, etc. Good.
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 intended purpose, but is preferably 60 ° C to 80 ° C. When the melting point is less than 60 ° C., the release agent tends to melt at low temperatures, and the heat resistant storage stability may be inferior. When the melting point exceeds 80 ° C., even when the resin is melted and is in the fixing temperature region, the release agent may not be sufficiently melted to cause a fixing offset and cause an image defect.
There is no restriction | limiting in particular in content of a 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 toner, and 3-8 mass parts is more preferable. If the content is less than 2 parts by mass, the high temperature offset resistance and the low temperature fixability at the time of fixing may be inferior. is there. When the content is in the more preferable range, it is advantageous in terms of improving the image quality and improving the fixing stability.

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

  Examples of colorants include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthra Zan Yellow BGL, Isoindolinone Yellow, Bengala, Red Plum, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, 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, ben Gin orange, Perinone orange, Oil orange, Cobalt blue, Cerulean blue, Alkaline blue rake, Peacock blue rake, Victoria blue rake, Metal-free phthalocyanine blue, phthalocyanine blue, Fast sky blue, Indanthrene blue (RS, BC), Indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B , Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium oxide, zinc white, ritbon, etc. are mentioned.

  The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded together with the production of the master batch or the master batch include, in addition to the amorphous polyester resin B, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, or a polymer of a substituted product thereof; styrene -P-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloro Methyl methacrylate copolymer, styrene-acrylic Nitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Examples thereof include resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used individually by 1 type and may use 2 or more types together.

  The masterbatch can be obtained by mixing and kneading the masterbatch resin and the colorant under high shearing force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called an aqueous paste of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed. This is preferable because it can be dried. For mixing and kneading, a high shear dispersion 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 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), alkyls. Examples include amide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, and metal salt of salicylic acid derivative. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), LRA-901, LR-147 (manufactured by Nippon Carlit) which is a boron complex, copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. It is done.

  The content of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 10 parts by weight, and preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the toner. Is more preferable. When the content exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, the flowability of the developer is reduced, and the image The concentration may decrease. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or may be added when directly dissolving and dispersing in an organic solvent, or after toner particles are produced on the toner surface. It may be fixed.

-External additive-
As the external additive, in addition to oxide fine particles, inorganic fine particles or hydrophobic treated inorganic fine particles can be used in combination. The average particle size of the hydrophobized primary particles is preferably 1 to 100 nm, preferably 5 to 70 nm. The inorganic fine particles are more preferable.
Further, it is preferable that at least one kind of inorganic fine particles having an average particle diameter of 20 nm or less of the hydrophobized primary particles and at least one kind of inorganic fine particles having an average particle diameter of the primary particles of 30 nm or more. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

Suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Examples of the silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.). Further, as titania fine particles, for example, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Titanium Industry Co., Ltd.), MT- 150W, MT-500B, MT-600B, MT-150A (all of which are manufactured by Teica), and the like.
Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T, TAF-1500T ( Any of them includes Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (both manufactured by Teika), IT-S (Ishihara Sangyo Co., Ltd.) and the like.

Hydrophobized oxide fine particles, hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles include, for example, methyltrimethoxysilane and methyltriethoxysilane as hydrophilic fine particles. It can be obtained by treating with a silane coupling agent such as octyltrimethoxysilane. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles 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 acid. Examples include 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, and α-methylstyrene-modified silicone oil.

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, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
The content of the external additive is not particularly limited and may be appropriately selected depending on the intended purpose. preferable.
The average particle size of the primary particles of the inorganic fine particles is not particularly limited and can be appropriately selected according to the purpose, but is preferably 100 nm or less, more preferably 3 to 70 nm. If it is smaller than 3 nm, the inorganic fine particles are buried in the toner, and the function thereof is not easily exhibited. On the other hand, if it is larger than 70 nm, the surface of the photoreceptor is not uniformly damaged, which is not preferable.

-Fluidity improver-
The fluidity improver is not particularly limited as long as it can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity, and can be appropriately selected according to the purpose. it can. Examples thereof include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. It is particularly preferable that the external additive silica or titanium oxide is surface-treated with such a fluidity improver and used as hydrophobic silica or hydrophobic titanium oxide.

-Cleaning improver-
The cleaning property improving agent is not particularly limited as long as it is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium, and can be appropriately selected according to the purpose. it can. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles.
The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

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

  As described above, the toner of the present invention contains 2 to 10% by mass of a low molecular weight component having a THF soluble content of 600 or less. Further, the molecular weight distribution of the low molecular weight component in the THF soluble component. Is preferably in the range of 300 to 500 molecular weight. When the peak top is less than 300, the heat resistant storage stability is deteriorated, and when it exceeds 500, the low temperature fixability is deteriorated.

The toner of the present invention preferably has a glass transition temperature (Tg1st) of 20 ° C. to 50 ° C. at the first temperature increase in differential scanning calorimetry (DSC).
In the conventional toner, when the Tg is about 50 ° C. or less, toner aggregation is likely to occur due to a temperature change in the storage environment and the toner transportation in the summer or the tropical region. As a result, solidification in the toner bottle and fixation of the toner in the developing machine occur. Also, replenishment failure due to toner clogging in the toner bottle and image abnormality due to toner fixation in the developing machine are likely to occur.
The toner of the present invention has a Tg lower than that of the conventional toner, but the amorphous polyester resin A, which is a low Tg component in the toner, is non-linear, and therefore can retain heat-resistant storage stability. In particular, when the non-linear amorphous polyester resin A has a urethane bond or a urea bond having a high cohesive force, the effect of maintaining heat resistant storage stability becomes more remarkable.
If the Tg1st is less than 20 ° C., the heat resistant storage stability is reduced, blocking in the developing machine and filming on the photoreceptor occur, and if it exceeds 50 ° C., the low temperature fixability of the toner is lowered.

Further, the glass transition temperature (Tg2nd) of the second temperature increase in differential scanning calorimetry (DSC) of the toner of the present invention is preferably 0 ° C. to 30 ° C., more preferably 10 ° C. to 25 ° C. . When the Tg2nd is less than 0 ° C., the heat-resistant storage stability is lowered, blocking in the developing machine and filming on the photosensitive member may occur.
Further, the difference between Tg1st and Tg2nd (Tg1st−Tg2nd) is not particularly limited, but is preferably 10 ° C. or higher in view of excellent low-temperature fixability. That the difference is 10 ° C. or more is that the crystalline polyester resin C, which was in an incompatible state before heating (before the first temperature increase), the non-linear amorphous polyester resin A, and It means that the amorphous polyester resin B is in a compatible state after heating (after the first temperature increase). In addition, the compatible state after a heating does not need to be a complete compatible state. The upper limit of the difference is not particularly limited and can be appropriately selected according to the purpose, but is preferably 50 ° C. or lower.

The melting point of the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C to 80 ° C.
The volume average particle diameter of the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 to 7 μm. 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 1-10 number% of components with a volume average particle diameter of 2 micrometers or less.

<Calculation method and analysis method of various characteristics of toner and toner component>
Various physical properties of the non-linear amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the release agent may be measured on their own. Each component may be separated by GPC or the like, and for these, physical properties such as Tg, molecular weight, melting point, etc. may be measured or the mass ratio of the constituent components may be obtained by an analysis method described later.

Separation of each component by GPC can be performed, for example, by the following method.
In GPC measurement using THF as a mobile phase, the eluate is fractionated by a fraction collector or the like, and fractions corresponding to a desired molecular weight portion of the entire integral of the elution curve are collected. The concentrated eluate is concentrated and dried with an evaporator and the like, and then the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and 1H-NMR measurement is performed. The constituent monomer ratio is calculated.
As another method, after concentrating the eluate, it is hydrolyzed with sodium hydroxide or the like, and the decomposition product is subjected to qualitative quantitative analysis by high performance liquid chromatography (HPLC) to calculate the constituent monomer ratio.

  The toner manufacturing method forms toner base particles while generating a non-linear amorphous polyester resin A by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent. In this case, the non-linear amorphous polyester resin A may be separated from the actual toner by GPC or the like, and the Tg thereof may be obtained separately. A non-linear amorphous polyester resin A may be synthesized by an extension reaction and / or a cross-linking reaction with a curing agent, and Tg and the like may be measured from the synthesized non-linear amorphous polyester resin A.

<Toner component separation means and molecular weight and molecular weight distribution measurement>
A measuring device HLC-8020GPC (manufactured by Tosoh Corporation) is used, and three TSKgel SuperHZM-H are connected and used as a column. The measurement is performed by the following method.
The column was stabilized in a 40 ° C. heat chamber, and a toner prepared by flowing THF as a solvent at a flow rate of 0.35 mL / min to the 40 ° C. column to prepare a sample concentration of 0.05 to 0.6% by mass or 10 μL of THF sample solution of resin is injected and measured. In measuring the weight average molecular weight Mw and the molecular weight distribution, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the number of counts. The standard polystyrene sample for creating a calibration curve uses Showdex STANDARD series, Mp 6540000, 3570000, 651000, 251000, 110000, 45000, 19300, 6700, 2800, 580 and toluene. Uses an RI (refractive index) detector.
The proportion of low molecular weight components having a molecular weight of 600 or less is examined from the intersection of the molecular weight 600 and the curve in the integral molecular weight distribution curve.

On the other hand, a fraction collector is placed at the eluate outlet of GPC, and the eluate is collected every predetermined count, and the eluate is eluted every 5% in area ratio from the elution curve elution start (curve rise). Get.
Next, for each elution, 30 mg of sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution is filled in a glass tube for NMR measurement having a diameter of 5 mm, and a spectrum is obtained by performing integration 128 times at a temperature of 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.).
The monomer composition and composition ratio of the non-linear amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C contained in the toner are determined from the peak integration ratio of the obtained spectrum. be able to.

For example, peak assignment is performed as follows, and the component ratio of the constituent monomer is determined from each integral ratio.
The assignment of the peak can be performed, for example, as follows.
-Near 8.25 ppm: derived from benzene ring of trimellitic acid (for one hydrogen)
-8.07-8.10 ppm vicinity: Derived from the benzene ring of terephthalic acid (for 4 hydrogen)
・ 7.1 to 7.25 ppm vicinity: derived from benzene ring of bisphenol A (for 4 hydrogens)
・ Approximately 6.8 ppm: Derived from the benzene ring of bisphenol A (for 4 hydrogens) and from the double bond of fumaric acid (for 2 hydrogens)
・ 5.2 to 5.4 ppm vicinity: bisphenol A propylene oxide adduct derived from methine (one hydrogen)
3.7-4.7 ppm vicinity: derived from methylene of bisphenol A propylene oxide adduct (for 2 hydrogens) and derived from methylene of bisphenol A ethylene oxide adduct (for 4 hydrogens)
-Around 1.6 ppm: derived from methyl group of bisphenol A (for 6 hydrogens)

From these results, for example, the extract recovered in the fraction in which the non-linear amorphous polyester resin A accounts for 90% by mass or more can be treated as the non-linear amorphous polyester resin A. . Similarly, the extract recovered in the fraction in which the amorphous polyester resin B occupies 90% by mass or more is regarded as the amorphous polyester resin B, and the crystalline polyester resin C is recovered in the fraction in which 90% by mass or more. The extracted products can be handled as the crystalline polyester resin C, respectively.

<< Measurement Method of Storage Elastic Modulus (G ') >>
The storage elastic modulus (G ′) under various conditions can be measured using, for example, a dynamic viscoelasticity measuring device (ARES, manufactured by TA Instruments). The frequency at the time of measurement is 1 Hz.
Specifically, a measurement sample was molded into a pellet having a diameter of 8 mm and a thickness of 1 to 2 mm, fixed to a parallel plate having a diameter of 8 mm, stabilized at 40 ° C., a frequency of 1 Hz (6.28 rad / s), and a distortion amount. Measurement is performed by increasing the temperature to 200 ° C. at a rate of 0.1% (strain amount control mode) and a temperature increase rate of 2.0 ° C./min.

<< Measurement Method of Melting Point and Glass Transition Temperature (Tg) >>
The melting point and Tg in the present invention can be measured, for example, using a DSC system (differential scanning calorimeter, Q-200: manufactured by TA Instruments).
Specifically, it can be 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, heating is performed from −80 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere (first temperature increase). Thereafter, the temperature is lowered from 150 ° C. to −80 ° C. at a temperature drop rate of 10 ° C./min, and further heated to 150 ° C. at a temperature rise rate of 10 ° C./min (second temperature rise). At each of the first temperature increase and the second temperature increase, a DSC curve is measured using a differential scanning calorimeter (Q-200: manufactured by TA Instruments).
From the obtained DSC curve, the DSC curve at the first temperature rise can be selected using the analysis program in the Q-200 system, and the Tg at the first temperature rise of the target sample can be obtained. Similarly, the DSC curve at the second temperature increase can be selected, and the Tg of the target sample at the second temperature increase can be obtained.
Further, from the obtained DSC curve, using the analysis program in the Q-200 system, the DSC curve at the first temperature rise is selected, and the endothermic peak top temperature at the first temperature rise of the target sample is obtained as the melting point. Can do. Similarly, the DSC curve at the second temperature increase can be selected, and the endothermic peak top temperature at the second temperature increase of the target sample can be obtained as the melting point.

In the present invention, when toner is used as the target sample, the glass transition temperature at the first temperature rise is Tg1st, and the glass transition temperature at the second temperature rise is Tg2nd.
In the present invention, the non-linear amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the Tg and melting point of other components such as the release agent As for, unless otherwise specified, the endothermic peak top temperature and Tg at the second temperature rise are defined as the melting point and Tg of each target sample.

<< Measurement Method of Particle Size Distribution >>
The volume average particle diameter (D4), the number average particle diameter (Dn), and the ratio (D4 / Dn) of the toner are determined using, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter). Can be measured. In the present invention, Coulter Multisizer II is used. The measurement method is as follows.
First, 0.1 to 5 mL of a surfactant [preferably polyoxyethylene alkyl ether (nonionic surfactant)] as a dispersant is added to 100 to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1 mass% NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Next, 2 to 20 mg of a measurement sample is added. The electrolytic aqueous solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are measured with the measuring device using a 100 μm aperture as the aperture, and the volume distribution is measured. And calculate the number distribution. From the obtained distribution, the volume average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

<< Method for measuring molecular weight >>
The molecular weight of each component of the toner can be measured, for example, by the following method.
・ Permeation chromatography (GPC) measuring device
: GPC-8220GPC (manufactured by Tosoh Corporation)
・ Column: TSKgel SuperHZM-H 15cm triple (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
・ Solvent: THF
・ Flow rate: 0.35 mL / min
Sample: 0.4 mL of 0.15% by mass sample was injected. Sample pretreatment: Toner was dissolved in THF (stabilized Wako Pure Chemical Industries, Ltd.) at a concentration of 0.15% by mass. Filter through a 2 μm filter and use the filtrate as a sample. 100 μL of the THF sample solution is injected and measured.

When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 are used. An RI (refractive index) detector is used as the detector.

<Toner production method>
A method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. The non-linear amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C may be selected. In addition, if necessary, it is preferably granulated by dispersing an oil phase containing the release agent, the colorant and the like in an aqueous medium.
Further, the toner includes the non-linear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C. If necessary, the toner further includes the curing agent, the release agent, and the coloring agent. It is preferable to granulate by dispersing an oil phase containing an agent in an aqueous medium.
An example of such a method for producing the toner is a known dissolution suspension method.
As an example of a toner manufacturing method, toner base particles are formed while generating a non-linear amorphous polyester resin A by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent. The method to do is shown below. In this method, the aqueous medium is prepared, the oil phase containing the toner material is prepared, the toner material is emulsified or dispersed, and the organic solvent is removed.

-Preparation of aqueous medium (aqueous 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 said aqueous media.
There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water, the solvent miscible with water, these mixtures etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, water is preferable.
The solvent miscible with water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. There is no restriction | limiting in particular as said alcohol, According to the objective, it can select suitably, For example, methanol, isopropanol, ethylene glycol etc. are mentioned. There is no restriction | limiting in particular as said lower ketone, According to the objective, it can select suitably, For example, acetone, methyl ethyl ketone, etc. are mentioned.

-Preparation of oil phase-
The preparation of the oil phase containing the toner material includes at least the non-linear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C, and if necessary, the curing A toner material containing an agent, the release agent, the colorant, and the like can be dissolved or dispersed in an organic solvent.
There is no restriction | limiting in particular as 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 is easy to remove.
The organic solvent having a boiling point of less than 150 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 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. These may be used individually by 1 type and may use 2 or more types together.
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 performed by dispersing the oil phase containing the toner material in the aqueous medium. Then, when emulsifying or dispersing the toner material, the nonlinear amorphous polyester resin A is obtained by subjecting the curing agent and the nonlinear reactive precursor to an extension reaction and / or a crosslinking reaction. Generate.

The non-linear amorphous polyester resin A can be produced, for example, by the following methods (1) to (3).
(1) An oil phase containing the non-linear reactive precursor and the curing agent is emulsified or dispersed in an aqueous medium, and the curing agent and the non-linear reactive precursor in the aqueous medium Is produced by subjecting to elongation reaction and / or crosslinking reaction.
(2) The oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium to which the curing agent is added in advance, and the curing agent and the non-linear reactive precursor are added in the aqueous medium. A method of producing a body by an extension reaction and / or a crosslinking reaction.
(3) After emulsifying or dispersing the oil phase containing the non-linear reactive precursor in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent is added from the particle interface in the aqueous medium. And a non-linear reactive precursor by an extension reaction and / or a crosslinking reaction.
When the curing agent and the nonlinear reactive precursor are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, the nonlinear amorphous polyester is preferentially formed on the surface of the toner to be produced. Since the resin A is formed, a concentration gradient of the non-linear amorphous polyester resin A can be provided in the toner.

There are no particular limitations on the reaction conditions (reaction time, reaction temperature) for producing the non-linear amorphous polyester resin A, and the combination of the curing agent and the non-linear reactive precursor is not limited. Depending on the situation, it can be appropriately selected.
The reaction time is preferably 10 minutes to 40 hours, more preferably 2 to 24 hours.
The reaction temperature is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C.

The method for stably forming the dispersion containing the non-linear reactive precursor in the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a method in which an oil phase prepared by dissolving or dispersing a toner material in a solvent is added to an aqueous medium phase and dispersed by shearing force.
The disperser for the dispersion is not particularly limited and can be appropriately selected depending on the purpose. For example, a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, Examples include an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the number of rotations, the dispersion time, and the dispersion temperature can be appropriately selected according to the purpose. The rotational speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch method, the dispersion time is preferably 0.1 to 5 minutes. The dispersion temperature is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C under pressure. In general, dispersion is easier when the dispersion temperature is higher.

  The amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 to 2000 parts by mass with respect to 100 parts by mass of the toner material. -1000 mass parts is more preferable. When the amount of the aqueous medium used is less than 50 parts by mass, the dispersion state of the toner material is deteriorated, and toner base particles having a predetermined particle diameter may not be obtained. When the amount exceeds 2000 parts by mass, the production cost is high. May be.

When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets to obtain 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, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. 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, using anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant etc. Can do.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, and phosphate esters. Among these, those having a fluoroalkyl group are preferable.

A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the non-linear amorphous polyester resin A.
There is no restriction | limiting in particular as said catalyst, According to the objective, it can select suitably, For example, a dibutyltin laurate, a dioctyltin laurate, etc. are mentioned.

-Removal of organic solvent-
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature of the entire reaction system is gradually raised, and the organic in the oil droplets Examples include a method of evaporating the solvent, and a method of removing the organic solvent in the oil droplets by spraying the dispersion liquid in a dry atmosphere.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. The classification may be performed by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, or may be performed after drying.

-Washing-
The method for cleaning the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method of washing with water and washing with acid after alkali cleaning is preferable.
By performing the alkali cleaning, it is possible to remove emulsifiers, dispersants, ionic impurities, and the like present on the toner particle surfaces.
In particular, in the toner including at least the adhesive substrate, the resin fine particles are used as a dispersion (emulsification) stabilizer in order to sharpen the particle size distribution. If the resin fine particles are excessively present on the toner surface, the fixing is performed. It is preferable to remove it because it may impair the chargeability or adversely affect the chargeability.
In this respect, since the resin fine particles contain an acidic component, they can be easily removed by swelling or dissolving them by alkali washing.

In addition, the amines are used for the production of the adhesive substrate, but unreacted amines form an association with an acidic group (carboxyl group) in the polyester resin, and the elongation reaction after emulsification is smooth. In addition, the acidity of the polyester resin may be lowered, and the chargeability may be impaired or the adhesion to paper may be reduced.
In this regard, when the alkali cleaning is performed, the hydrogen atom of the terminal carboxyl group in the polyester resin is replaced with a Na atom, and then the terminal carboxyl group in the polyester resin is restored when the acid cleaning is performed. Can proceed again.

The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent the particles such as the external additive from detaching from the surface of the toner base particles.
The method for applying the mechanical impact force is not particularly limited and may be appropriately selected depending on the purpose.For example, a method for applying an impact force to a mixture using a blade rotating at high speed, Examples include a method in which a mixture is charged and accelerated to cause particles or particles to collide with an appropriate collision plate.
The apparatus used in the above method is not particularly limited, and can be appropriately selected according to the purpose. For example, an ang mill (manufactured by Hosokawa Micron Co., Ltd.) and an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) are modified to lower the pulverization air pressure. Examples thereof include a device, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries Ltd.), and an automatic mortar.

(Developer)
The developer of the present invention contains at least the toner of the present invention and, if necessary, other components such as a carrier that are appropriately selected.
For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably.
The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. Agents are preferred.
When the developer is used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, the blade for thinning the toner, etc. The toner is less fused to the member, and good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer is used as a two-component developer, there is little fluctuation in the particle diameter of the toner even if the toner balance for a long period of time is performed, and good and stable developability and long-term agitation in the developing device. An image is obtained.

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

−Core material−
There is no restriction | limiting in particular as a 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. Can be mentioned. In order to ensure the image density, it is preferable to use a highly magnetized 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 30-80 emu / g of copper-zinc system because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for high image quality. .
These may be used individually by 1 type and may use 2 or more types together.
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. If the volume average particle diameter is less than 10 μm, fine particles are increased in the carrier, and the magnetization per particle may be reduced to cause carrier scattering. On the other hand, if the thickness exceeds 150 μm, the specific surface area may be reduced and toner scattering may occur, and in the case of a full color having many solid portions, the reproduction of the solid portions may be particularly poor.

When toner is used as a two-component developer, it is mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected according to the purpose, but is preferably 90 to 98 parts by mass with respect to 100 parts by mass of the two-component developer. 93-97 mass parts is 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 development method, a non-magnetic one-component development method, and a two-component development method.

[Developer container]
The developer of the present invention is accommodated in the developer accommodating container. The container is not particularly limited and can be appropriately selected from known ones, and examples thereof include a container having a container body and a cap. Further, the size, shape, structure, material, etc. of the container body are not particularly limited, but the shape is preferably a cylindrical shape, etc., and spiral concavo-convex is formed on the inner peripheral surface, and the contents are obtained by rotating. It is particularly preferable that the developer can move to the discharge port side, and part or all of the spiral irregularities have a bellows function. The material preferably has good dimensional accuracy, and examples thereof include resin materials such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.
Since the developer container is easy to store and transport and has excellent handleability, the developer container can be detachably attached to a process cartridge, an image forming apparatus, etc., which will be described later, and used for replenishing the developer.

[Image Forming Method, Image Forming Apparatus]
The image forming method using the toner of the present invention preferably has at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, more preferably a cleaning step, and if necessary. , A static elimination process, a recycling process, a control process, and the like may be included.
The image forming apparatus of the present invention preferably includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further includes a cleaning unit. Preferably, it may have a static elimination means, a recycling means, a control means, etc. as needed.
The image forming method can be carried out using the image forming apparatus of the present invention. The electrostatic latent image forming step uses an electrostatic latent image forming unit, and the developing step uses a developing unit. The step can be performed using a transfer unit, the fixing step can be performed using a fixing unit, and the other steps can be performed using other units.

(Electrostatic latent image forming process)
The electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image carrier such as a photoconductive insulator or a photoconductor. The material, shape, structure, size and the like of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape. Examples of the photoreceptor include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, an amorphous silicon photoconductor is preferable because of its long life.
The electrostatic latent image is formed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then exposing it like an image, and can be formed using electrostatic latent image forming means. The electrostatic latent image forming means includes, for example, a charger that applies a voltage to the surface of the electrostatic latent image carrier and uniformly charges it, and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Have at least.
The charger is not particularly limited. For example, a known contact charger including a conductive or semiconductive roll, brush, film, rubber blade, etc., non-contact charging using corona discharge such as corotron and scorotron. A vessel or the like can be used.
The exposure device is not particularly limited as long as it can be exposed like an image to be formed on the surface of the electrostatic latent image carrier charged by the charger. For example, a copying optical system, a rod lens array system, a laser optical Various exposure devices such as an optical system and a liquid crystal shutter optical system can be used. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of an electrostatic latent image carrier.

(Development process)
The developing step is a step of developing the electrostatic latent image with the developer of the present invention to form a toner image, and the visible image can be formed using a developing unit. The developing means is not particularly limited as long as it can be developed with the developer of the present invention. For example, a developing device that contains the developer of the present invention and can apply toner to the electrostatic latent image in a contact or non-contact manner. A developing device or the like provided with the developer container of the present invention is preferable.
The developing device may be either a dry developing method or a wet developing method, and may be either a single color developing device or a multicolor developing device. For example, the developer of the present invention may be obtained by friction stirring. Examples include a stirrer to be charged and a rotatable magnet roller. In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. The magnet roller is disposed in the vicinity of the electrostatic latent image carrier, and a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted by the electrostatic latent image carrier. Move to the surface. As a result, the electrostatic latent image is developed with toner, and a toner image is formed on the surface of the electrostatic latent image carrier. The developer housed in the developing device is the developer of the present invention, but may be a one-component developer or a two-component developer.

(Transfer process)
The transfer step is a step of transferring the toner image to a recording medium by charging the electrostatic latent image carrier on which the toner image is formed using, for example, a transfer charger, and transferring the image using a transfer unit. be able to. At this time, the transfer step preferably includes a primary transfer step of transferring the toner image onto the intermediate transfer member and a secondary transfer step of transferring the toner image transferred onto the intermediate transfer member onto the recording medium. The transfer process includes a primary transfer process in which a toner image of two or more colors, preferably a full color toner, is used to transfer a toner image of each color onto an intermediate transfer member to form a composite toner image, and on the intermediate transfer member. It is further preferable to have a secondary transfer step of transferring the formed composite toner image onto a recording medium.
The transfer unit includes a primary transfer unit that transfers a toner image onto an intermediate transfer member to form a composite toner image, and a secondary transfer unit that transfers the composite toner image formed on the intermediate transfer member onto a recording medium. It is preferable. The intermediate transfer member is not particularly limited, and examples thereof include an endless transfer belt. The transfer means (primary transfer means and secondary transfer means) preferably has at least a transfer device that charges and separates the toner image formed on the electrostatic latent image carrier on the recording medium side. The transfer means can have one or more transfer devices.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited, and can be appropriately selected from known recording media (recording paper).

(Fixing process)
The fixing step is a step of fixing the toner image transferred to the recording medium, and can be fixed using a fixing unit. When two or more color toners are used, the toner may be fixed each time the toner of each color is transferred to the recording medium, or the toner of all colors may be transferred to the recording medium and fixed in a stacked state. Also good. The fixing unit is not particularly limited, and a known heating and pressing unit can be used. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt. The heating temperature at this time is 80-200 degreeC normally. If necessary, for example, a known optical fixing device may be used together with the fixing unit or instead of the fixing unit.

(Static elimination process)
The neutralization step is a step of neutralizing by applying a neutralization bias to the electrostatic latent image carrier, and can be performed using a neutralization unit. The neutralization means is not particularly limited as long as a neutralization bias can be applied to the electrostatic latent image carrier. For example, a neutralization lamp can be used.

(Cleaning process)
The cleaning step is a step of removing toner remaining on the electrostatic latent image carrier, and can be performed using a cleaning unit. The cleaning means is not particularly limited as long as it can remove the toner remaining on the electrostatic latent image carrier. For example, a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner, etc. Can be used.

(Recycling process)
The recycling process is a process of recycling the toner removed in the cleaning process to the developing unit, and can be performed using the recycling unit. The recycling unit is not particularly limited, and a known transport unit or the like can be used.

(Control process)
A control process is a process of controlling each process, and can be performed using a control means.
The control means is not particularly limited as long as the operation of each means can be controlled. For example, a sequencer, a computer, or the like can be used.

FIG. 1 shows an example of an image forming apparatus of the present invention. The image forming apparatus 100A includes a photosensitive drum 10 as an electrostatic latent image carrier, a charging roller 20 as a charging unit, an exposure device (not shown) as an exposure unit, and a developing device 45 (K) as a developing unit. , Y, M, C), an intermediate transfer member 50, a cleaning device 60 having a cleaning blade as a cleaning means, and a static elimination lamp 70 as a static elimination means.
The intermediate transfer member 50 is an endless belt, is stretched by three rollers 51 arranged on the inner side thereof, and can move in the arrow direction. A part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50.
Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. Further, a transfer roller 80 serving as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) the toner image to the recording paper 95 is disposed to face the intermediate transfer member 50.

Further, around the intermediate transfer member 50, a corona charger 52 for applying a charge to the toner image on the intermediate transfer member 50, a contact portion between the photosensitive drum 10 and the intermediate transfer member 50, and the intermediate transfer member 50 are provided. And the contact portion of the recording paper 95.
The developing device 45 for each color of black (K), yellow (Y), magenta (M), and cyan (C) includes a developer container 42 (K, Y, M, C), a developer supply roller 43, A developing roller 44 is provided.
In the image forming apparatus 100A, the photosensitive drum 10 is uniformly charged by the charging roller 20, and then the exposure light L is exposed on the photosensitive drum 10 imagewise by an exposure device (not shown) to form an electrostatic latent image. Form. Next, the electrostatic latent image formed on the photosensitive drum 10 is developed by supplying a developer from the developing unit 45 to form a toner image, and then the toner image is transferred by a transfer bias applied from the roller 51. Is transferred (primary transfer) onto the intermediate transfer member 50. Further, the toner image on the intermediate transfer member 50 is given a charge by the corona charger 52 and then transferred (secondary transfer) onto the recording paper 95. The toner remaining on the photosensitive drum 10 is removed by the cleaning device 60, and the photosensitive drum 10 is once discharged by the discharging lamp 70.

FIG. 2 shows another example of the image forming apparatus of the present invention. The image forming apparatus 100B is a tandem color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can rotate in the direction of the arrow.
A cleaning device 17 for removing the toner remaining on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. Further, four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other on the intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 along the conveyance direction. A tandem developing device 120 is disposed.
As shown in FIG. 3, the image forming means 18 for each color includes a photosensitive drum 10, a charging roller 60 for uniformly charging the photosensitive drum 10, and a black electrostatic latent image formed on the photosensitive drum 10. (K), yellow (Y), magenta (M), and cyan (C) are developed with each color developer to form a toner image, and each color toner image is transferred onto the intermediate transfer member 50. A transfer roller 62, a cleaning device 63, and a static elimination lamp 64.

In the image forming apparatus of FIG. 2, an exposure device (not shown) is disposed in the vicinity of the tandem developing device 120. The exposure apparatus exposes exposure light on the photosensitive drum 10 to form an electrostatic latent image.
Further, a secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. The secondary transfer device 22 includes a secondary transfer belt 24 that is an endless belt stretched between a pair of rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 can contact each other. It has become.
A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26.
Further, in the vicinity of the secondary transfer device 22 and the fixing device 25, a reversing device 28 for reversing the recording paper in order to form images on both sides of the recording paper is disposed.

  Next, full color image formation (color copy) in the image forming apparatus 100B will be described. First, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300. close up. Next, when a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is placed on the contact glass 32. When set, the scanner 300 is immediately driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is emitted from the first traveling body 33, and reflected light from the document surface is reflected by a mirror in the second traveling body 34 and received by the reading sensor 36 through the imaging lens 35. . Thus, a color original (color image) is read, and image information of each color of black, yellow, magenta, and cyan is obtained.

Furthermore, after an electrostatic latent image of each color is formed on the photosensitive drum 10 based on the obtained image information of each color by the exposure device, the electrostatic latent image of each color is supplied from the developing device 120 of each color. Each toner image is formed by developing with the developer. The formed toner images of the respective colors are sequentially transferred (primary transfer) on the intermediate transfer member 50 that is rotated and moved by the support rollers 14, 15, and 16, thereby forming a composite toner image on the intermediate transfer member 50. .
In the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143 and separated one by one by the separation roller 145. Then, the sheet is fed to the sheet feeding path 146, conveyed by the conveying roller 147, guided to the sheet feeding path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the recording paper on the manual feed tray 54 is fed out, separated one by one by the separation roller 58, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the recording paper.

Then, the registration roller 49 is rotated in synchronization with the composite toner image formed on the intermediate transfer member 50, and the recording paper is sent between the intermediate transfer member 50 and the secondary transfer device 22, so that the composite toner image is transferred onto the recording paper. Transfer to (secondary transfer).
The recording sheet on which the composite toner image has been transferred is conveyed by the secondary transfer device 22 and sent out to the fixing device 25. In the fixing device 25, the composite toner image is fixed on the recording paper by being heated and pressed by the fixing belt 26 and the pressure roller 27. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55, reversed by the reversing device 28, guided again to the transfer position, formed on the back surface, discharged by the discharge roller 56, and stacked on the discharge tray 57.
The toner remaining on the intermediate transfer member 50 after the composite toner image is transferred is removed by the cleaning device 17.

[Process cartridge]
FIG. 4 shows an example of the process cartridge. The process cartridge 110 includes the photosensitive drum 10, the corona charger 52, the developing device 40, the transfer roller 80, and the cleaning device 90.
This process cartridge is detachably molded in various image forming apparatuses, and an electrostatic latent image carrier that carries an electrostatic latent image and an electrostatic latent image carried on the electrostatic latent image carrier. It has at least developing means for developing with the developer of the invention to form a toner image. The process cartridge may further include other means as necessary.
The developing means includes at least a developer container that contains the developer of the present invention and a developer carrier that carries and conveys the developer contained in the developer container. The developing means may further include a regulating member or the like for regulating the thickness of the developer carried.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples. Unless otherwise specified, “parts” and “%” refer to “parts by mass” and “mass%”.
Each measured value was measured by the method described above. Moreover, Tg, melting | fusing point, molecular weight, etc. of non-linear amorphous polyester resin A, amorphous polyester resin B, crystalline polyester resin C, etc. are the measured values of each resin obtained by the manufacture example.

(Production Example 1)
<Synthesis of ketimine>
170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer 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.

(Production Example A1)
<Synthesis of Non-Linear Amorphous Polyester Resin A1>
-Synthesis of prepolymer A1-
3-methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimethylolpropane were mixed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube with a molar ratio of hydroxyl group to carboxyl group “OH / COOH. "Is 1.5. The diol component was 100 mol% 3-methyl-1,5-pentanediol, and the dicarboxylic acid component was 40 mol% isophthalic acid and 60 mol% adipic acid. Further, trimethylpropanol was added together with titanium tetraisopropoxide (1000 ppm based on the whole resin component) so as to be 1 mol% with respect to the total amount of monomers. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate body polyester A1 was obtained.
Next, the intermediate polyester A1 and isophorone diisocyanate (IPDI) are mixed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe at a molar ratio (isocyanate group of IPDI / hydroxyl group of intermediate polyester) of 2.0. Then, after diluting with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100 ° C. for 5 hours to obtain Prepolymer A1.

-Synthesis of non-linear amorphous polyester resin A1-
The obtained prepolymer A1 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] is equimolar with respect to the amount of isocyanate in the prepolymer A1. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a nonlinear amorphous polyester resin A1. Table 1 shows the composition (mol%) of the alcohol component, the acidic component, and the crosslinking component.

<Synthesis of Non-Linear Amorphous Polyester Resin A2 to A7>
-Synthesis of prepolymers A2 to A7-
Prepolymers A2 to A7 were obtained in the same manner as the synthesis of the prepolymer A1, except that the alcohol component and acid content were changed as shown in the columns A2 to A7 in Table 1.
In addition, the numerical value of the column of the alcohol component in Table 1 and an acidic part is each compounding ratio (mol%).

-Synthesis of non-linear amorphous polyester resins A2-A7-
Non-linear amorphous polyester resins A2 to A7 were obtained in the same manner as the synthesis of the amorphous polyester resin A1, except that the prepolymer A1 was changed to the prepolymers A2 to A7.
In addition, since prepolymer A5 contains many aromatic monomers and does not have a crosslinked structure, trimellitic acid does not correspond to a crosslinking component.

上記表中の「ＢｉｓＡＥＯ」は「ビスフェノールＡエチレンオキサイド２モル付加物」を意味する。

“BisAEO” in the above table means “bisphenol A ethylene oxide 2-mole adduct”.

(Production Example B1)
<Synthesis of Amorphous Polyester Resin B1>
A four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple, bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, terephthalic acid, adipic acid, hydroxyl group and carboxyl The molar ratio “OH / COOH” to the group was 1.3. The ratio of bisphenol A ethylene oxide 2 mol adduct and bisphenol A propylene oxide 3 mol adduct was 60/40 (mol%), and the ratio of terephthalic acid to adipic acid was 93/7 (mol%). Then, titanium tetraisopropoxide (500 ppm with respect to the resin component) was reacted at 230 ° C. for 8 hours under normal pressure, and further reacted for 4 hours under reduced pressure of 10 to 15 mmHg, and then trimellitic anhydride was added to the reaction vessel. Was added at 1 mol% with respect to the total resin components and reacted at 180 ° C. under normal pressure for 3 hours to obtain amorphous polyester resin B1. Table 2 shows the composition (mol%) of the alcohol component and the acidic component.

<Synthesis of amorphous polyester resins B2 to B4>
Amorphous polyester resins B2 to B4 were obtained in the same manner as the synthesis of the amorphous polyester resin B1, except that the composition of the alcohol component and the acidic component was changed as shown in Table 2.

上記表中の「ＢｉｓＡＥＯ」は「ビスフェノールＡエチレンオキサイド２モル付加物」を意味し、「ＢｉｓＡＰＯ」は「ビスフェノールＡプロピレンオキサイド３モル付加物」を意味する。

In the above table, “BisAEO” means “bisphenol A ethylene oxide 2 mol adduct”, and “BisAPO” means “bisphenol A propylene oxide 3 mol adduct”.

(Production Example C1)
<Synthesis of Crystalline Polyester Resin C1>
In a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, sebacic acid and 1,6-hexanediol were mixed with a molar ratio of “OH / COOH” of hydroxyl group to carboxyl group. The mixture was charged to 0.9, and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours, and further 8.3 kPa. For 2 hours to obtain a crystalline polyester resin C1.

Example 1
<Synthesis of Masterbatch 1>
Add 1200 parts of water, 500 parts of carbon black (Printex 35, manufactured by Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5] and 500 parts of amorphous polyester resin B1, and add a Henschel mixer (made by Mitsui Mining Co., Ltd.). ) Was kneaded at 150 ° C. for 30 minutes using two rolls, and then cooled and pulverized with a pulverizer to obtain [Masterbatch 1].

<Preparation of WAX dispersion 1>
In a container equipped with a stirrer and a thermometer, 300 parts of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C.), 150 parts of a wax dispersant and 1800 ethyl acetate are used as a release agent 1. The temperature was raised to 80 ° C. with stirring and maintained at 80 ° C. for 5 hours. Next, it is cooled to 30 ° C. over 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed is 1 kg / hour, disk peripheral speed is 6 m / second, and 0.5 mm zirconia beads are 80% by volume. Dispersion was performed under conditions of filling and 3 passes to obtain [WAX Dispersion 1].

<Preparation of crystalline polyester resin dispersion 1>
In a container equipped with a stirring rod and a thermometer, 308 parts of crystalline polyester resin C1 and 1900 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Next, it is cooled to 30 ° C. over 1 hour and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (Ultra Visco Mill, manufactured by IMEX Co., Ltd.) with a liquid feeding speed of 1 kg / hour, a disk peripheral speed of 6 m / second. Dispersion was performed under conditions of 3 passes to obtain [Crystalline Polyester Resin Dispersion 1].

<Preparation of oil phase 1>
[WAX Dispersion 1] 190 parts, [Prepolymer A1] 32 parts, [Crystalline Polyester Resin Dispersion 1] 290 parts, [Amorphous Polyester Resin B1] 65 parts, [Masterbatch 1] 100 parts and [ketimine] [Compound 1] 0.2 part was put in a container and mixed with TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at 7000 rpm for 60 minutes to obtain [Oil Phase 1].

<Synthesis of fine particle dispersion 1 (organic fine particle emulsion)>
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 138 parts of styrene, 138 parts of methacrylic acid , And 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. This was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (styrene salt copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate) [ A fine particle dispersion 1] was obtained.
The volume average particle size of [Fine Particle Dispersion 1] measured with LA-920 (manufactured by HORIBA) was 0.14 μm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component.

<Preparation of aqueous phase 1>
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Kasei Kogyo Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This was designated as [Aqueous Phase 1].

<Emulsification / desolvation>
[Oil phase 1] 1200 parts of [Aqueous phase 1] was added to a container containing 677 parts, and was mixed with a TK homomixer at a rotation speed of 8000 rpm for 20 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

<Washing and drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure, the following operations (1) to (4) were performed twice on the obtained filter cake to obtain [Filter Cake 1].
(1): Add 100 parts of ion-exchanged water to the filter cake, mix with a TK homomixer (10 minutes at 12,000 rpm), and then filter.
(2): Add 100 parts of a 10% aqueous sodium hydroxide solution to the filter cake of (1), mix with a TK homomixer (30 minutes at 12,000 rpm), and then filter under reduced pressure.
(3): 100 parts of 10% hydrochloric acid is added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (rotation speed 12000 rpm for 10 minutes), and then filter.

Next, [Filter cake 1] was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with an opening of 75 μm mesh to obtain [Toner base 1].

Example 2
The toner of Example 2 was obtained in the same manner as in Example 1 except that the step of adding a 10% aqueous sodium hydroxide solution was omitted.

Example 3
In the above-mentioned “synthesis of amorphous polyester resin B1”, amorphous polyester resin B1 was similarly prepared except that an operation of extracting and removing low molecular weight components having a molecular weight of 600 or less of amorphous polyester resin B1 with methanol was performed. I got ′. A toner of Example 3 was obtained in the same manner except that this amorphous polyester resin B1 ′ was used.

Example 4
A toner of Example 4 was obtained in the same manner except that Prepolymer A1 in Example 2 was changed to Prepolymer A2.

Example 5
A toner of Example 5 was obtained in the same manner except that Prepolymer A1 in Example 2 was changed to Prepolymer A3.

Example 6
A toner of Example 6 was obtained in the same manner except that the amorphous polyester resin B1 in Example 4 was changed to the amorphous polyester resin B2.

Example 7
The amorphous polyester resin B1 in Example 4 was changed to the amorphous polyester resin B3, and in the “synthesis of the amorphous polyester resin B3”, the low molecular weight component of the amorphous polyester resin B3 having a molecular weight of 600 or less was replaced with methanol. A toner of Example 7 was obtained in the same manner except that the operation of extraction and removal was performed.

Example 8
A toner of Example 8 was obtained in the same manner except that Prepolymer A1 in Example 2 was changed to Prepolymer A5.

Example 9
A toner of Example 9 was obtained in the same manner except that the prepolymer A1 in Example 2 was changed to the prepolymer A6 and the amorphous polyester resin B1 was changed to the amorphous polyester resin B4.

Example 10
A toner of Example 10 was obtained in the same manner except that Prepolymer A1 in Example 3 was changed to Prepolymer A7.

Example 11
A toner of Example 11 was obtained in the same manner except that the prepolymer A1 in Example 7 was changed to the prepolymer A3.

Example 12
A toner of Example 12 was obtained in the same manner except that Prepolymer A1 in Example 7 was changed to Prepolymer A4.

Example 13
In the above-mentioned “synthesis of amorphous polyester resin B2”, amorphous polyester resin B2 was similarly prepared except that an operation of extracting and removing low molecular weight components of amorphous polyester resin B2 having a molecular weight of 600 or less with methanol was performed. I got ′. Using this amorphous polyester resin B2 ′, a toner of Example 13 was obtained in the same manner as in Example 6 except that a step of adding a 10% aqueous sodium hydroxide solution was added in “washing and drying”. .

Comparative Example 1
A toner of Comparative Example 1 was obtained in the same manner except that the amorphous polyester resin B1 in Example 2 was changed to the amorphous polyester resin B3. In this toner, since the amorphous polyester resin B3 contains many low molecular weight components having a molecular weight of 600 or less, the low molecular weight components having a molecular weight of 600 or less in the THF-soluble component are increased.

Comparative Example 2
A toner of Comparative Example 2 was obtained in the same manner except that the amorphous polyester resin B1 in Example 1 was changed to the amorphous polyester resin B1 ′ obtained in Example 3.

Comparative Example 3
A toner of Comparative Example 3 was obtained in the same manner except that Prepolymer A1 in Example 2 was replaced with Prepolymer A4.

Comparative Example 4
A toner of Comparative Example 4 was obtained in the same manner except that Prepolymer A1 in Example 7 was changed to Prepolymer A6.

<Production of developer>
For each toner obtained, a developer was prepared as follows.
-Production of carrier-
To 100 parts of toluene, 100 parts of silicone resin: organostraight silicone (manufactured by Shin-Etsu Silicone Co., Ltd .: KR-282), 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black are added, A resin layer coating solution was prepared by dispersing with a homomixer for 20 minutes. Using a fluid bed type coating apparatus, the resin layer coating solution was applied to the surface of 1000 parts of spherical magnetite having an average particle size of 50 μm to prepare a carrier.

-Production of developer-
Using a ball mill, 5 parts of each toner and 95 parts of the carrier were mixed to prepare a developer.

<Evaluation>
Using each toner and each developer, the characteristics were evaluated as follows.

-Soxhlet extraction-
1 part of each toner was refluxed with 100 parts of THF for 6 hours, and a THF-insoluble part and a soluble part were collected. The solid content obtained by removing the THF-soluble component of THF and the solid component of the THF-insoluble component were each dried at 40 ° C. for 20 hours. The THF-insoluble component was subjected to rheometer measurement, and the THF-soluble component was subjected to DSC measurement. . The measurement results are summarized in Table 3.

<< Low-temperature fixability and high-temperature offset resistance >>
A copy test was performed on type 6200 paper (manufactured by Ricoh) using an apparatus in which a fixing unit of a copying machine MF2200 (manufactured by Ricoh) using a Teflon (registered trademark) roller as a fixing roller was modified.
Specifically, the cold offset temperature (fixing lower limit temperature) and the hot offset temperature (fixing upper limit temperature) were determined by changing the fixing temperature.
The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 mm to 150 mm / sec, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm.
The evaluation conditions for the upper limit fixing temperature were a paper feed linear velocity of 50 mm / sec, a surface pressure of 2.0 kgf / cm ² , and a nip width of 4.5 mm.
The evaluation criteria are as follows.

[Fixed lower limit temperature evaluation criteria]
◎: Less than 110 ° C ○: 110 ° C or more, less than 120 ° C △: 120 ° C or more, less than 130 ° C ×: 130 ° C or more

[Fixing upper limit temperature evaluation criteria]
A: 170 ° C. or higher ○: 160 ° C. or higher, lower than 170 ° C. Δ: 150 ° C. or higher, lower than 160 ° C. ×: lower than 150 ° C.

<< Heat resistant storage stability >>
Each toner was stored at 50 ° C. for 8 hours and then sieved with a 42 mesh sieve for 2 minutes. The residual rate on the wire mesh was measured and evaluated according to the following criteria. At this time, the toner having better heat-resistant storage stability has a smaller remaining rate.
〔Evaluation criteria〕
◎: Residual rate is less than 10% ○: Residual rate is 10% or more and less than 20% △: Residual rate is 20% or more and less than 30% ×: Residual rate is 30% or more

<< Transfer White >>>
Each developer was mounted on Imagio C2802 (Ricoh printer), and 10,000 A4 images with an image area ratio of 5% were continuously printed. Thereafter, three solid images (toner adhesion amount 0.4 mg / cm ² ) were output on A4 paper, and the number of blank images in the image was visually measured. Then, the following criteria were evaluated based on the total number of the three blank images.
In addition, when there was a suspicion of white spot by visual confirmation, it confirmed with the optical microscope. That is, in the case of “◯”, clear white spots cannot be confirmed visually, but there is a suspicion of white spots, and white spots can be confirmed when observed with an optical microscope.
〔Evaluation criteria〕
A: The blank images are not visually recognized in all three sheets.
○: It can be confirmed by observing the third blank image with an optical microscope.
It is not a level.
Δ: 1 to 10 blank images can be confirmed in combination with 3 images, and there is a problem in practical use ×: 11 or more blank images can be confirmed in combination with 3 images, and there is a large problem level in practical use

L Exposure light 10 Electrostatic latent image carrier (photosensitive drum)
10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developer 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developing roller 44Y Developing roller 44M Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer belt 51 Roller 52 Corona charging device 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Separating roller 60 Cleaning device 61 Developing device 62 Transfer roller 63 Photoconductor cleaning device 64 Static elimination lamp 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A Image forming apparatus 100B Image forming apparatus 110 Process cartridge 120 Tandem type developer 130 Original Base 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 14 8 Feeding path 150 Copying machine body 160 Charging roller 200 Feeding table 300 Scanner 400 Automatic document feeder (ADF)

Japanese Patent Laid-Open No. 11-133665 JP 2002-287400 A JP 2002-351143 A Japanese Patent No. 2579150 JP 2001-158819 A JP 2004-46095 A JP 2007-271789 A

Claims (8)

A toner comprising at least a polyester resin and satisfying the following requirements (1) and (2).
(1) The glass transition temperature [Tg2nd (THF insoluble matter)] at the second temperature increase in differential scanning calorimetry (DSC) of the THF insoluble matter is -40 ° C to 30 ° C.
(2) The THF soluble component contains 2 to 10% by mass of a low molecular weight component having a molecular weight of 600 or less.   2. The toner according to claim 1, wherein a peak top of a molecular weight distribution of a low molecular weight component in the THF-soluble component is in a molecular weight range of 300 to 500. 3.   3. The toner according to claim 1, wherein a glass transition temperature (Tg1st) at the first temperature increase in differential scanning calorimetry (DSC) is 20 ° C. to 50 ° C. 4.   The toner according to any one of claims 1 to 3, wherein a glass transition temperature (Tg2nd) at a second temperature increase in differential scanning calorimetry (DSC) is 0 ° C to 30 ° C.   The toner according to claim 1, wherein the polyester resin contains a crystalline polyester resin.   The toner according to claim 1, wherein the polyester resin contains a non-linear amorphous polyester resin having a crosslinked structure.   A developer comprising the toner according to claim 1 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 An image forming apparatus, comprising: a developing unit including a toner that forms a visible image, wherein the toner is the toner according to claim 1.

Images