JP2018151546A - Toner, developer, toner storage unit, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in low-temperature fixability, a heat-resistant storage property, and mechanical strength.SOLUTION: A toner contains amorphous resin A1 and crystalline resin B. When HLB values of the amorphous resin A1 and the crystalline resin B are HLB(A1) and HLB(B), respectively, the following formula (1) and the following formula (2) are satisfied. The amorphous resin A1 contains an alcohol component, and contains a monomer of a diol component having an aromatic ring in an amount of 10 mol% or more in the alcohol component. The formula (1) -1.4≤HLB(A1)-HLB(B)≤1.7; and the formula (2) HLB(A1)≥3.6.SELECTED DRAWING: Figure 1

Description

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

  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.

  Conventionally, toner produced by the kneading and pulverizing method, which is one of the toner manufacturing methods, is difficult to reduce the particle size, and the shape of the toner is irregular and the particle size distribution is broad, so the quality of the output image is low. There were problems such as insufficient and high fixing energy. In addition, when a wax (release agent) is added to improve the fixability, the toner produced by the kneading and pulverization method cracks at the interface of the wax during pulverization, so that a large amount of wax exists on the toner surface. Resulting in. For this reason, while the releasing effect is produced, the toner (filming) easily adheres to the carrier, the photoreceptor and the blade, and the overall performance does not satisfy the required level.

  Therefore, in order to overcome the above-mentioned problems caused by the kneading and pulverizing method, a toner manufacturing method by a polymerization method has been proposed. The toner produced by the polymerization method can be easily reduced in particle size, the particle size distribution is sharper than that of the toner produced by the pulverization method, and the release agent can be included. . 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 method of producing a toner from an extension reaction product of urethane-modified polyester as a toner binder is disclosed. (For example, refer to Patent Document 1).

  Also disclosed is a method for producing a toner that is excellent in powder flowability and transferability in the case of a small particle size toner, and also excellent in all of heat-resistant storage stability, low-temperature fixability, and high-temperature offset resistance (for example, Patent Documents 2 and 3). Further, a method for producing a toner having an aging 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, since the power consumption during fixing accounts for much of the power consumption in the image forming process, low-temperature fixability is very important. However, these proposed technologies satisfy the high-level low-temperature fixability required in recent years. It was not a thing.

  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 proposed techniques can be expected to achieve low-temperature fixing because the crystalline polyester resin melts more rapidly than the amorphous polyester resin. In recent years, studies have been made to improve the compatibility between the crystalline resin and the main binder in order to further fix the toner at a low temperature.

  However, in this case, since the crystalline resin present on the surface plasticizes the main binder, the adhesion and hardness of the toner surface deteriorate, and satisfactory mechanical strength has not been obtained. For this reason, for example, a strong stress is applied to the toner in the developing device of a high-speed machine, so that the charging ability of the toner deteriorates over time due to aggregation between toners, burying of external additives, carrier contamination, etc., and filming on the photoreceptor Occurs, and there is a problem that an abnormal image such as a transfer white defect occurs.

  In addition, there is a method of adding a compatibilizing agent to control the amount of the crystalline resin on the surface. However, since the compatibility between the main binder and the crystalline resin is further increased, there is a concern that the toner hardness is lowered. Accordingly, there is a need for a toner that has a high level of low-temperature fixability, heat-resistant storage stability, and mechanical strength that has been increasing in recent years, and that can provide good image quality.

  An object of the present invention is to provide a toner excellent in low-temperature fixability, heat-resistant storage stability, and mechanical strength.

In order to solve the above-described problems, the present invention provides a toner including an amorphous resin A1 and a crystalline resin B, wherein the HLB values of the amorphous resin A1 and the crystalline resin B are set to HLB (A1). , HLB (B), the following formula (1) and the following formula (2) are satisfied, and the amorphous resin A1 contains an alcohol component, and a monomer of a diol component having an aromatic ring is included in the alcohol component. It is characterized by containing 10 mol% or more.
−1.4 ≦ HLB (A1) −HLB (B) ≦ 1.7 Formula (1)
HLB (A1) ≧ 3.6 Formula (2)

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

1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. It is a schematic block diagram which shows another example of the image forming apparatus of this invention. It is a schematic block diagram which shows another example of the image forming apparatus of this invention. FIG. 4 is a partially enlarged view of FIG. 3. It is a schematic block diagram which shows an example of a process cartridge.

  Hereinafter, a toner, a developer, a toner storage unit, an image forming apparatus, and an image forming method according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

(toner)
The present invention is a toner including an amorphous resin A1 and a crystalline resin B, and the HLB values of the amorphous resin A1 and the crystalline resin B are HLB (A1) and HLB (B), respectively. In addition to satisfying the following formula (1) and the following formula (2), the amorphous resin A1 includes an alcohol component, and the alcohol component includes 10 mol% or more of a monomer of a diol component having an aromatic ring. To do.
−1.4 ≦ HLB (A1) −HLB (B) ≦ 1.7 Formula (1)
HLB (A1) ≧ 3.6 Formula (2)
As a result, it is possible to provide a toner having excellent low-temperature fixability, heat-resistant storage stability, and mechanical strength.

<HLB values of amorphous resin A1 and crystalline resin B>
As described above, when the HLB values of the amorphous resin A1 and the crystalline resin B are HLB (A1) and HLB (B), the following formula (1) is satisfied.
−1.4 ≦ HLB (A1) −HLB (B) ≦ 1.7 Formula (1)

  When HLB (A1) -HLB (B) is −1.4 or more, it is possible to suppress the presence of excessive crystalline resin on the toner surface, and to improve the mechanical strength of the toner surface. For this reason, the generation of toner aggregates in the developing device can be suppressed, and the generation of abnormal images can be suppressed.

  When HLB (A1) -HLB (B) is 1.7 or less, the crystalline resin can be appropriately present on the toner surface. For this reason, the amount of the crystalline resin on the toner surface during fixing heating can be appropriately reduced, and the melt viscosity of the toner surface can be appropriately reduced. Therefore, the adhesion to a recording medium such as paper is improved, Low temperature fixability can be improved.

Further, the HLB value of the amorphous resin A1 satisfies the following formula (2).
HLB (A1) ≧ 3.6 Formula (2)
When the HLB (A1) is 3.6 or more, the surface exposure of toner components such as a crystalline resin, a release agent, and a colorant on the toner surface can be suppressed. For this reason, it is possible to effectively prevent abnormal images due to a decrease in the mechanical strength and adhesion of the toner surface and a decrease in the charge amount of the toner over time.

The HLB value in the present invention was calculated from the following calculation formulas by obtaining inorganic values and organic values according to “Interface and Surfactant” (published by Hiroshi Suzuki, published by Sangyo Toshosha, Chapter 3).
HLB = 10 × IOB
IOB = Inorganic value / Organic value IOB: Inorganic Organic Balance

  In the present invention, the terminal functional group is not included in the calculation when the HLB value is obtained. Similarly, the terminal functional group is not included in the calculation for the HLB values in the examples described later.

Moreover, it is preferable that HLB (A1) and HLB (B) satisfy | fill following formula (3).
0.2 ≦ HLB (A1) −HLB (B) ≦ 1.2 Formula (3)
In this case, low-temperature fixability and mechanical strength can be improved at a high level.

<SP value of amorphous resin A1 and crystalline resin B>
When the solubility parameter SP values ([cal / cm ³ ] ^1/2 ) of the amorphous resin A1 and the crystalline resin B are SP (A1) and SP (B), respectively, the following formula (4) is satisfied. It is preferable.
1.3 ≦ SP (A1) −SP (B) ≦ 1.7 Formula (4)

  When SP (A1) -SP (B) is 1.3 or more, it is possible to suppress the partial compatibility of the amorphous resin A1 and the crystalline resin B on the toner surface and improve the mechanical strength of the toner. it can. For this reason, the generation of toner aggregates in the developing device can be suppressed, and the generation of abnormal images can be suppressed. When SP (A1) -SP (B) is 1.7 or less, the melt viscosity of the toner can be appropriately reduced during fixing and heating, and adhesion to a recording medium such as paper can be improved. For this reason, low temperature fixability can be improved.

The solubility parameter SP value is expressed as the square root of the evaporation energy per unit volume, and according to the Fedors method,
SP value = (E / V) ^1/2
(In the formula, E is the evaporation energy [cal / mol], and V is the molar volume [cm ³ / mol].)
Can be used to calculate.

At this time, if the evaporation energy and molar volume of the atomic group are Δei and Δvi, respectively, E and V are
E = Σ △ ei
V = ΣΔvi
(Refer to "Basic Theory of Adhesion" (Mr. Imoto, published by Kobunshi Shuppankai, Chapter 5)).

  In the present invention, it is assumed that the terminal functional group is not included in the calculation when obtaining the SP value. Similarly, the terminal functional group is not included in the calculation for the SP value in Examples described later.

<Relationship of toner circumference>
When the peripheral length of the cross section of the toner is A and the peripheral length of the peripheral length A where the crystalline resin B is exposed is B, it is preferable that the following formula (5) is satisfied.
0.1 <B / A <0.4 Formula (5)

  When B / A is greater than 0.1, the melt viscosity can be appropriately lowered by the crystalline resin on the toner surface during fixing heating, and adhesion to a recording medium such as paper can be improved. Fixability can be improved. When B / A is less than 0.4, partial miscibility of the amorphous resin A1 and the crystalline resin B on the toner surface is suppressed, the mechanical strength of the toner surface is improved, and the toner aggregation in the developing device is improved. Aggregate generation can be suppressed. For this reason, generation | occurrence | production of an abnormal image can be suppressed.

<< Observation Method with Transmission Electron Microscope (TEM) >>
A and B can be determined by observing the fractured surface of the toner with a transmission electron microscope (TEM). The cross section of the toner is dyed with ruthenium, and the cross section of the ruthenium dyed toner is observed with a TEM. The obtained image is analyzed, A and B are obtained, and B / A is calculated.

  The ruthenium dyeing of the toner can be carried out by a usual method. For example, specifically, it can be measured by the following method. The toner or toner particles are embedded in an epoxy resin and sectioned to a thickness of 100 nm by a microtome. The cross section of the toner is observed with a scanning electron microscope to confirm the structure in which the crystalline resin is in contact with the release agent. For dyeing, a 0.5% aqueous solution of ruthenium tetroxide is used. In the toner, the crystalline resin and the release agent are determined from the contrast and shape. A bar-like or linear white-contrast part can be judged as a mold release agent, and a bar-like or linear part most darkly stained can be judged as a crystalline resin.

  The image analysis software uses “Image J”. The peripheral length A of the cross section of the toner and the peripheral length B of the peripheral length A where the crystalline resin B is exposed are designated on the cross sectional image of the toner, and B / A is calculated from the sum of the respective values. It is preferable to calculate an average value of 50 toners.

<Components of toner>
The toner of the present exemplary embodiment includes an amorphous resin A1 and a crystalline resin B, and preferably includes an amorphous resin A2 different from the amorphous resin A1 as an amorphous resin. Contains other ingredients such as molds and colorants.

<< Amorphous Resin A1 >>
The amorphous resin A1 in the present embodiment has a skeleton derived from an alcohol component and a skeleton derived from a carboxylic acid component. Hereinafter, the amorphous resin A1 will be described as an amorphous polyester resin A1.

-Alcohol component-
Examples of the alcohol component include divalent alcohols and trivalent or higher alcohols.
In this embodiment, the amorphous resin A1 contains 10 mol% or more of a diol component monomer having an aromatic ring in the alcohol component. As a result, the mechanical strength of the toner can be improved, the generation of toner aggregates in the developing device can be suppressed, and the occurrence of abnormal images can be prevented.

  Examples of the divalent alcohol include aliphatic diols, diols having an oxyalkylene group, alicyclic diols, those obtained by adding alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) to alicyclic diols, and bisphenols. And alkylene oxide adducts of bisphenols.

  Examples of the aliphatic diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol and the like.

  Examples of the diol having an oxyalkylene group include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

  Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S.

  Examples of the alkylene oxide adduct of bisphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to bisphenols.

Examples of the trihydric or higher alcohol include the trihydric or higher aliphatic alcohol.
Examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and dipentaerythritol.
The trihydric or higher aliphatic alcohol is preferably a trivalent to tetravalent aliphatic alcohol.

-Carboxylic acid component-
Examples of the carboxylic acid component include divalent carboxylic acids and trivalent or higher carboxylic acids. Moreover, these anhydrides may be used, a lower (C1-C3) alkyl esterified material may be used, and a halide may be used.

Examples of the divalent carboxylic acid include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.
There is no restriction | limiting in particular as said aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.

Examples of the trivalent or higher carboxylic acid include trimellitic acid and pyromellitic acid.
These carboxylic acid components may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said amorphous polyester resin A1, Although it can select suitably according to the objective, 50 mass parts-95 mass parts are preferable with respect to 100 mass parts of said toner, 70 Mass parts to 90 parts by mass are more preferable.

<< Amorphous Resin A2 >>
In addition to the amorphous resin A1, the toner preferably contains an amorphous resin A2 as a second amorphous resin component different in kind from the amorphous resin A1.

  The amorphous resin A2 is not particularly limited as long as it is a resin different from the amorphous resin A1, and can be appropriately selected according to the purpose. Hereinafter, the amorphous resin A2 will be described as an amorphous polyester resin A2.

  The amorphous polyester resin A2 includes, for example, a diol component or a diol component and a crosslinking component as a constituent component, and more preferably a dicarboxylic acid as a constituent component. The diol component preferably contains 50 mol% or more of an aliphatic diol having 3 to 10 carbon atoms.

  The cross-linking component preferably contains at least one of a trivalent or higher carboxylic acid and a trivalent or higher alcohol, more preferably contains a trivalent or higher alcohol, and more preferably contains a trivalent or higher aliphatic alcohol. It is particularly preferable to do this.

  The amorphous polyester resin A2 preferably has at least one of a urethane bond and a urea bond, and more preferably has a urethane bond and a urea bond, from the viewpoint of better adhesion to a recording medium such as paper. . Further, since the amorphous polyester resin A2 has either a urethane bond or a urea bond, the urethane bond or the urea bond behaves like a quasi-branching point, and the amorphous polyester resin A2 has a rubber-like behavior. The properties become stronger, and the heat resistant storage stability and high temperature offset resistance of the toner are more excellent.

The amorphous resin A2 is preferably insoluble in tetrahydrofuran (THF).
Therefore, as described above, it is preferable that the amorphous resin A2 is insoluble in tetrahydrofuran (THF) and has at least one of a urethane bond and a urea bond. In addition, an alcohol component is included, the alcohol component includes a diol component and a crosslinking component, an aliphatic diol having 3 to 10 carbon atoms is included as the diol component in an amount of 50 mol% or more, and the crosslinking component is a trivalent or higher valence. It preferably contains an aliphatic alcohol.

-Reactive precursor-
The amorphous polyester resin A2 is preferably obtained by a reaction between a reactive precursor and a curing agent. The reactive precursor is not particularly limited as long as it is a polyester resin having a group capable of reacting with the curing agent (hereinafter sometimes referred to as “prepolymer”), and is appropriately selected according to the purpose. be able to.

  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 of the group capable of reacting with the active hydrogen group include an isocyanate group, an epoxy group, a carboxylic acid, and an acid chloride group. Among these, an isocyanate group is preferable in that a urethane bond or a urea bond can be introduced into the amorphous polyester resin A2.

The prepolymer is preferably non-linear. The non-linear means having a branched structure imparted by at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid.
As the prepolymer, a polyester resin containing an isocyanate group is preferable.

--Polyester resin containing isocyanate group--
There is no restriction | limiting in particular as the polyester resin containing 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 component, a dicarboxylic acid component, at least one of a trivalent or higher valent alcohol and 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 containing the isocyanate group.

--- Diol component ---
Examples of the diol component include aliphatic diols, diols having an oxyalkylene group, alicyclic diols, alicyclic diols added with alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.), bisphenols, bisphenols. And alkylene oxide adducts.

  Examples of the aliphatic diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol and the like.

Examples of the diol having an oxyalkylene group include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S.
Examples of the alkylene oxide adduct of bisphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to bisphenols.

--- Dicarboxylic acid component ---
Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Moreover, these anhydrides may be used, a lower (C1-C3) alkyl esterified material may be used, and a halide may be used.
The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.
There is no restriction | limiting in particular as said aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.

--Alcohol having a valence of 3 or more
Examples of the trihydric or higher alcohol include the trihydric or higher aliphatic alcohol.
Examples of the trihydric or higher alcohol include trihydric to tetrahydric alcohols.
As the trihydric or higher aliphatic alcohol, trihydric to tetrahydric aliphatic alcohols are preferable in terms of improving low-temperature fixability, high-temperature and high-humidity storage stability, and stress resistance.
The trivalent to tetravalent aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

--Carboxylic acid having a valence of 3 or more ---
Examples of the trivalent or higher carboxylic acid include trivalent to tetravalent carboxylic acids. Examples of the trivalent to tetravalent carboxylic acid include trimellitic acid and pyromellitic acid.
When the amorphous polyester resin A2 contains the trivalent or higher carboxylic acid or the trivalent or higher alcohol as a constituent component, it exhibits rubber elasticity and is more excellent in blocking resistance. Furthermore, rubber elasticity can be exhibited while having high thermal deformability of the resin in the fixing temperature region, and the low-temperature fixing property and blocking resistance of the toner are more excellent.
Among the trivalent to tetravalent carboxylic acids or the trivalent to tetravalent alcohols, the trivalent to tetravalent aliphatic alcohols are preferable in that they are more excellent in low-temperature fixability.

--- 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.

  There is no restriction | limiting in particular as said aliphatic diisocyanate, According to the objective, it can select suitably. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decametin diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, etc. .

  The alicyclic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.

  There is no restriction | limiting in particular as said aromatic diisocyanate, According to the objective, it can select suitably. For example, tolylene diisocyanate, 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.

  There is no restriction | limiting in particular as said araliphatic diisocyanate, According to the objective, it can select suitably, For example, (alpha), (alpha), (alpha) ', (alpha)'-tetramethyl xylylene diisocyanate etc. are mentioned.

There is no restriction | limiting in particular as said isocyanurates, According to the objective, it can select suitably, For example, a tris (isocyanatoalkyl) isocyanurate, a tris (isocyanatocycloalkyl) isocyanurate, etc. are mentioned.
These polyisocyanates may be used alone or in combination of two or more.

-Curing agent-
The curing agent is not particularly limited as long as it reacts with the prepolymer, and can be appropriately selected according to the purpose. Examples thereof include an active hydrogen group-containing compound.

-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. 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.
The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamines, trivalent or higher valent amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, diamine and a mixture of a diamine and a small amount of a trivalent or higher amine are preferable.

There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aromatic diamine, alicyclic diamine, aliphatic diamine etc. are mentioned.
There is no restriction | limiting in particular as said aromatic diamine, According to the objective, it can select suitably, For example, phenylenediamine, diethyltoluenediamine, 4,4'- diaminodiphenylmethane etc. are mentioned.
The alicyclic diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane and isophorone diamine. It is done.
There is no restriction | limiting in particular as said aliphatic diamine, According to the objective, it can select suitably, For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine etc. are mentioned.

The trivalent or higher amine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
The amino alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.
The amino mercaptan is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminoethyl mercaptan and aminopropyl mercaptan.

The amino acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.
There is no restriction | limiting in particular as what blocked the said amino group, According to the objective, it can select suitably, For example, it is obtained by blocking an amino group with ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketimine compounds and oxazoline compounds.

The molecular structure of the amorphous polyester resin A2 can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. Conveniently the infrared absorption spectrum, and a method of detecting the one having no absorption based on 965 ± 10 cm ^-1 and 990 of olefins ± 10cm ^-1 δCH (out-of-plane bending vibration) as an amorphous resin.

  The content of the prepolymer that is the reactive precursor of the amorphous polyester resin A2 is not particularly limited and may be appropriately selected depending on the intended purpose. Parts to 25 parts by mass are preferable, and 7 to 12 parts by mass are more preferable. If the content is 5 parts by mass or more, the low temperature fixability and the high temperature offset resistance can be prevented from deteriorating. If the content is 25 parts by mass or less, the heat resistant storage stability is deteriorated and the image obtained after fixing is obtained. It is possible to prevent the problem that the glossiness of the toner is lowered. When the content is within the more preferable range, it is advantageous in that it is excellent in all of low-temperature fixability, high-temperature offset resistance, and blocking resistance.

<< Crystalline Resin B >>
The toner of the present invention contains a crystalline resin B, and the crystalline resin B is preferably a crystalline polyester resin. Hereinafter, the crystalline resin B will be described as the crystalline polyester resin B.

  Since the crystalline polyester resin B has high crystallinity, the crystalline polyester resin B exhibits a heat-melting characteristic that exhibits a sudden viscosity drop near the fixing start temperature. By using the crystalline polyester resin B having such characteristics together with the amorphous resin A1, the heat resistant storage stability due to crystallinity is good until just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin is melted. Causes a sharp drop in viscosity (sharp melt properties). Along with the sudden decrease in viscosity due to melting, it is compatible with the amorphous resin A1 and is fixed by rapidly decreasing the viscosity together. As a result, a toner having both good heat storage stability and low-temperature fixability can be obtained. Also, good results are shown for the release width (difference between the fixing lower limit temperature and the high temperature resistant offset occurrence temperature).

  As the crystalline polyester resin B, for example, a resin composed of a fatty acid and an aliphatic alcohol is used. The crystalline resin B is obtained by using a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester or a derivative thereof.

  In the present invention, the crystalline polyester resin is, as described above, a polyhydric alcohol, 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 refers to what is obtained by using. A modified polyester resin, for example, the prepolymer and a resin obtained by crosslinking and / or elongation reaction of the prepolymer do not belong to the crystalline polyester resin. The crystalline resin B is a resin different from the amorphous resin A1 and the amorphous resin A2.

-Polyhydric alcohol-
There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated fats having 2 to 12 carbon atoms are preferred. Group diols are more preferred. When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin 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. The number of carbon atoms is more preferably 12 or less.

Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,14-eicosandecanediol. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10 are preferred because the crystalline polyester resin has high crystallinity and excellent sharp melt properties. -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 B is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms.
That is, the crystalline polyester resin B has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. preferable. By doing so, since crystallinity is high and it is excellent in sharp melt property, it is preferable at the point which can exhibit the outstanding low-temperature fixability.

  There is no restriction | limiting in particular as melting | fusing point of the said crystalline polyester resin B, Although it can select suitably according to the objective, It is preferable that it is 60 to 80 degreeC. When the melting point is 60 ° C. or higher, the crystalline polyester resin can be easily melted at a low temperature and the heat-resistant storage stability of the toner can be prevented from being lowered. When the melting point is 80 ° C. or lower, the crystalline polyester is heated by fixing. It is possible to effectively prevent the problem that the resin is insufficiently melted and the low-temperature fixability may be lowered.

  The molecular weight of the crystalline polyester resin B is not particularly limited and may be appropriately selected depending on the intended purpose. A component having a sharp molecular weight distribution and a low molecular weight is excellent in low-temperature fixability and has a low molecular weight. If the amount is too large, the heat-resistant storage stability is lowered. From this point of view, the soluble content of orthodichlorobenzene in the crystalline polyester resin is determined by GPC measurement to have a weight average molecular weight (Mw) of 20,000 to 30,000 and a number average molecular weight (Mn) of 5,000 to 10,000. Mw / Mn is preferably 1.0 to 10. If the molecular weight is 20,000 or more, the problem of insufficient heat-resistant storage property and high-temperature high-humidity storage property due to residual oligomers can be effectively prevented, and if the molecular weight is 30,000 or less, low-temperature fixability is impaired. Can be effectively prevented.

  The acid value of the crystalline polyester resin B is not particularly limited and may be appropriately selected depending on the intended purpose. In order to achieve desired low-temperature fixability from the viewpoint of the affinity between paper and resin. Is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more. On the other hand, in order to improve the high temperature offset resistance, 45 mgKOH / g or less is preferable.

  The hydroxyl value of the crystalline polyester resin B is not particularly limited and may be appropriately selected depending on the intended purpose.To achieve desired temperature fixability and good charging characteristics, 0 mgKOH / g to 50 mgKOH / g is preferable, and 5 mgKOH / g to 50 mgKOH / g is more preferable.

The molecular structure of the crystalline 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. As a simple example, there is a method of detecting, as a crystalline polyester resin, an infrared absorption spectrum having an absorption based on δCH (out-of-plane variable vibration) of olefin at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ .

  There is no restriction | limiting in particular as content of the said crystalline polyester resin B, Although it can select suitably according to the objective, 3 mass parts-20 mass parts are preferable with respect to 100 mass parts of said toners, and 5 masses. Part-15 mass parts is more preferable. When the content is 3 parts by mass or more, the problem that the low-temperature fixability may be inferior due to insufficient sharp-melting with the crystalline polyester resin B can be effectively prevented. When the amount is 20 parts by mass or less, it is possible to effectively prevent the problem that the heat-resistant storage stability is lowered and the image is likely to be fogged. 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.

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

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.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 60 to 80 degreeC is preferable. When the melting point is 60 ° C. or higher, it is possible to effectively prevent the problem that the release agent is easily melted at a low temperature and the heat resistant storage stability is poor. If the melting point is 80 ° C. or less, even when the resin is melted and in the fixing temperature range, the release agent does not melt sufficiently, causing a fixing offset and causing an image defect. Can be prevented.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 2 mass parts-10 mass parts are preferable with respect to 100 mass parts of said toner, 3 mass parts- 8 parts by mass is more preferable. When the content is 2 parts by mass or more, it is possible to effectively prevent the problem that the high temperature offset resistance during fixing and the low temperature fixing property may be inferior. When the amount is 10 parts by mass or less, it is possible to effectively prevent the problem that the heat-resistant storage stability is lowered and the fogging of the image is likely to occur. When the content is within the more preferable range, it is advantageous in terms of improving image quality and improving fixing stability.

<< Other ingredients >>
Examples of other components include a colorant, a charge control agent, an external additive, a fluidity improver, a cleaning property improver, and a magnetic material.

-Colorant-
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof 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, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phisa red, para Lortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin 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, Tolujing 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, Lazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren 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, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Grits Enlake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and the like.

  The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded with the production of the masterbatch or the masterbatch include, for example, a polymer of styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, or a substituted product thereof, in addition to the amorphous polyester resin A1; 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-chloromethacrylate Methyl acid copolymer, styrene-acrylic acid Ronitrile 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 a masterbatch resin and a colorant under high shear force and kneading to obtain a masterbatch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet method of colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

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

-Charge control agent-
There is no restriction | limiting in particular as said charge control agent, According to the objective, it can select suitably. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus And a simple substance or a compound of tungsten, a simple substance or a compound of tungsten, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. 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 Co., Ltd.) which is a boron complex, copper phthalocyanine, perylene, quinacridone, azo pigment, other polymer compounds having a functional group such as sulfonic acid group, carboxyl group, quaternary ammonium salt, etc. Can be mentioned.

  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 parts by mass to 10 parts by mass with respect to 100 parts by mass of the toner. 2 mass parts-5 mass parts are more preferable. When the content is 10 parts by mass or less, 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, and the fluidity of the developer is lowered. In addition, it is possible to effectively prevent the problem that the image density may be lowered. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they may be added when dissolved and dispersed directly in an organic solvent, or fixed after preparation of toner particles on the toner surface. You may let them.

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

  There is no restriction | limiting in particular as said external additive, According to the objective, it can select suitably. Examples thereof include silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), and fluoropolymers.

  Suitable external 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 (both manufactured by Titanium Industry Co., Ltd.), TAF-500T, TAF-1500T ( All of them are manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika), IT-S (made by 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, hydrophilic fine particles such as methyltrimethoxysilane and methyltriethoxysilane. It can be obtained by treatment 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.

  There is no restriction | limiting in particular as an average particle diameter of the primary particle of the said inorganic fine particle, Although it can select suitably according to the objective, 100 nm or less is preferable and 3 nm or more and 70 nm or less are more preferable. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor may be damaged unevenly, which is not preferable.

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

-Fluidity improver-
The fluidity improver is not particularly limited as long as it is surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity, and is appropriately selected according to the purpose. can do. For example, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, modified silicone oil and the like can be mentioned. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and 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 photosensitive member or the primary transfer medium, and is appropriately selected according to the purpose. Can do. 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 μm 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, magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

<Toner characteristics>
There is no restriction | limiting in particular as melting | fusing point of the said toner, According to the objective, it can select suitably. 60 degreeC or more and 80 degrees C or less are preferable.
The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm or more and 7 μm or less. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Further, it is preferable to contain 1% by number or more and 10% by number or less of a component having a volume average particle diameter of 2 μm or less.

The glass transition temperature (Tg1st (toner)) at the first temperature increase in the differential scanning calorimetry (DSC) of the toner is preferably 20 ° C. or higher and 50 ° C. or lower.
In the case of a conventional toner, when the Tg is about 50 ° C. or less, toner aggregation is likely to occur due to temperature changes in the summer environment and the tropical region during transportation of the toner and in a storage environment. 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 this embodiment has a lower Tg than the conventional toner. For example, if the amorphous resin (particularly the amorphous resin A2), which is a low Tg component in the toner, is non-linear, the toner Heat resistant storage stability can be maintained. In addition, when the amorphous resin (particularly the amorphous resin A2) is an amorphous polyester resin having a urethane bond or a urea bond having a high cohesive force, the effect of maintaining heat resistant storage stability is more remarkable. Become.

  When [Tg1st (toner)] is 20 ° C. or higher, problems such as deterioration in heat-resistant storage stability, blocking in the developing machine, and filming on the photoreceptor can be prevented. Further, it is possible to prevent the low-temperature fixability of the toner from being lowered.

The toner preferably contains a tetrahydrofuran (THF) insoluble matter.
The THF-insoluble matter preferably contains the amorphous resin A2. As described above, as the amorphous resin A2, an amorphous polyester resin containing a diol component containing 50 mol% or more of an aliphatic diol having 3 to 10 carbon atoms and a crosslinking component containing a trihydric or higher aliphatic alcohol. A2 is preferred.

<Calculation method and analysis method of various characteristics of toner and toner component>
The Tg, acid value, hydroxyl value, molecular weight, and melting point of the amorphous resin A1, the amorphous resin A2, the crystalline resin B, and the release agent may be measured on their own. Further, by separating the actual toner by gel permeation chromatography (GPC) or the like and applying the analysis method described later for each separated component, the Tg, molecular weight, melting point, and mass ratio of the constituent components can be calculated. Good.

Separation of each component by GPC can be performed, for example, by the following method.
In GPC measurement using THF (tetrahydrofuran) 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 surface of the elution curve are collected.
After concentrating and drying the collected eluate with an evaporator or the like, the solid content is dissolved in a heavy solvent such as deuterated chloroform or THF, and ¹ H-NMR measurement is performed. From the integration ratio of each element, the resin in the elution component is dissolved. The constituent monomer ratio is calculated.

Another method is to calculate the constituent monomer ratio by concentrating the eluate, hydrolyzing with sodium hydroxide, etc., and performing qualitative quantitative analysis of the decomposition products using high performance liquid chromatography (HPLC). In this case, check the compatibility with the value obtained by the ¹ H-NMR measurement method in advance, or check the conversion table between the differences when there is a difference between the two values. Is preferred.

  In the case where the toner manufacturing method forms toner base particles while generating the amorphous resin A2 by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent. Alternatively, separation from actual toner by GPC or the like may be performed to obtain Tg of the amorphous resin A2. Alternatively, the amorphous resin A2 is synthesized by an extension reaction and / or a crosslinking reaction between the nonlinear reactive precursor and the curing agent, and Tg and the like are measured from the synthesized amorphous resin A2. May be.

<< Toner component separation means >>
An example of the separation means for each component when analyzing the toner will be described in detail.
First, 1 g of toner is put into 100 mL of THF, and a solution in which the soluble components are dissolved is obtained while stirring for 30 minutes at 25 ° C. This is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF soluble component in the toner. Subsequently, this is melt | dissolved in THF, it is set as the sample for GPC measurement, and it inject | pours into GPC used for the molecular weight measurement of each above-mentioned resin.
On the other hand, a fraction collector is arranged at the eluate outlet of GPC, and the eluate is collected at 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 the composition ratio of the amorphous resin A for toner, the amorphous resin A2, and the crystalline polyester resin contained in the toner can be determined from the peak integration ratio of the obtained spectrum.

For example, peak assignment is performed as follows, and the component ratio of the constituent monomer is determined from each integral ratio.
The attribution of the peak is, for example,
Near 8.25 ppm: derived from benzene ring of trimellitic acid (for one hydrogen),
8.07 ppm to around 8.10 ppm: derived from benzene ring of terephthalic acid (for 4 hydrogens),
7.1 ppm to around 7.25 ppm: derived from benzene ring of bisphenol A (for 4 hydrogens),
Around 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 ppm to around 5.4 ppm: derived from methine of bisphenol A propylene oxide adduct (one hydrogen),
3.7 ppm to around 4.7 ppm: 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),
It can be.

From these results, for example, the extract recovered in the fraction in which the amorphous resin A1 occupies 90% or more can be treated as the amorphous resin A1.
Similarly, the extract recovered in the fraction in which the amorphous resin A2 accounts for 90% or more can be handled as the amorphous resin A2.
Further, the extract recovered in the fraction in which the crystalline resin B occupies 90% or more can be handled as the crystalline resin B.

<< Method for measuring hydroxyl value and acid value >>
The hydroxyl value can be measured using a method based on JIS K0070-1966.
Specifically, first, 0.5 g of a sample is precisely weighed into a 100 mL volumetric flask, and 5 mL of an acetylating reagent is added thereto. Next, after heating in a 100 ± 5 ° C. warm bath for 1 to 2 hours, the flask is removed from the warm bath and allowed to cool. Furthermore, water is added and shaken to decompose acetic anhydride. Next, in order to completely decompose acetic anhydride, the flask is again heated in a warm bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.

Furthermore, the hydroxyl value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000.
For calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.

At this time, the measurement conditions are as follows.
〔Measurement condition〕
Still
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential1 No
Potentialial No
Stop for revaluation No

The acid value can be measured using a method based on JIS K0070-1992. Specifically, first, 0.5 g of a sample (0.3 g in the case where ethyl acetate is soluble) is added to 120 mL of toluene and dissolved by stirring at 23 ° C. for about 10 hours. Next, 30 mL of ethanol is added to prepare a sample solution. When the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used.
Furthermore, an acid value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are the same as in the case of the hydroxyl value described above.

  The acid value can be measured as described above. Specifically, titration is performed with a 0.1N potassium hydroxide / alcohol solution standardized in advance, and the acid value [mg KOH / g] = The acid value is calculated by titration [mL] × N × 56.1 [mg / mL] / sample [g] (where N is a factor of 0.1 N potassium hydroxide / alcohol solution).

<< Measurement Method of Melting Point and Glass Transition Temperature (Tg) >>
The melting point and glass transition temperature (Tg) in the present invention can be measured using, for example, a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments).
Specifically, the melting point and glass transition temperature of the target sample 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 decreased from 150 ° C. to −80 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min (second temperature increase). In each of the first temperature increase and the second temperature increase, the 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 glass transition temperature 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 glass transition temperature at the second temperature increase of the target sample 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, a 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 glass transition temperature and melting point of the amorphous resin A1, the amorphous resin A2, the crystalline resin B, and other components such as the release agent are not particularly specified. In this case, the endothermic peak top temperature and Tg at the second temperature increase are defined as the melting point and Tg of each target sample.

<< Measurement Method of Particle Size Distribution >>
For the volume average particle diameter (Dv) and number average particle diameter (Dn) of the toner, the ratio (Dv / Dn) is, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter, Inc.), etc. Can be measured. In the present invention, Coulter Multisizer II is used. The measurement method is described below.

  First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) as a dispersant is added to 100 mL 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. Here, 2 mg to 20 mg of a measurement sample is further added. The electrolytic aqueous solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and the number of toner particles or toner are measured with the measurement apparatus using a 100 μm aperture as the aperture. Calculate volume distribution and number distribution. From the obtained distribution, the volume average particle diameter (Dv) 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.

<< Measurement of molecular weight >>
The molecular weight of each component of the toner can be measured, for example, by the following method.
Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-H 15 cm triple (manufactured by Tosoh Corporation)
Temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Flow rate: 0.35 mL / min
Sample: 0.4 mL injection of 0.15% by mass sample Pretreatment of sample: Toner was dissolved in tetrahydrofuran THF (made by Wako Pure Chemical Industries, Ltd.) at 0.15% by mass and filtered through a 0.2 μm filter. The filtrate is used as a sample. 100 μL of the THF sample solution is injected and measured. In 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.

<< Method for extracting THF-insoluble matter and THF-soluble matter >>
Extraction of the THF-insoluble and THF-soluble components of the toner can be performed by the following procedure. After 1 g of toner and 100 g of THF are mixed, the mixture is refluxed for 12 hours. Then, it is fractionated into insoluble matter (solid matter) and soluble matter (liquid component). After desolvation of the soluble portion of THF, it is dried at 40 ° C. for 20 hours under normal pressure, and further dried under reduced pressure at 23 ° C. for 20 hours to obtain a THF soluble portion. The solid content of the insoluble matter is dried at 40 ° C. for 20 hours at normal pressure, and further dried under reduced pressure at 23 ° C. for 20 hours to obtain a THF insoluble matter.

<Toner production method>
There is no restriction | limiting in particular as a manufacturing method of the said toner, According to the objective, it can select suitably. For example, it is preferably granulated by dispersing an oil phase appropriately containing a resin, a release agent, a colorant and the like in an aqueous medium.

<< Preparation of aqueous medium (aqueous phase) >>
The aqueous medium can be prepared, for example, by dispersing resin particles in an aqueous medium. The amount of the resin particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the aqueous medium. .

  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 alcohols, 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 amorphous resin A, the crystalline resin B, and the release agent, and if necessary, the reactive precursor of the amorphous resin A2. The toner material containing the body (prepolymer), the curing 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.
There is no restriction | limiting in particular as an organic solvent whose boiling point is less than 150 degreeC, According to the objective, it can select suitably. 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 Etc. 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. When the toner material is emulsified or dispersed, the amorphous resin A2 can be generated by subjecting the curing agent and the non-linear reactive precursor to an extension reaction and / or a crosslinking reaction. .

The amorphous resin A2 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 A method of producing the amorphous resin A2 by subjecting the resin to an extension reaction and / or a 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 the amorphous resin A2 by subjecting the body to 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. A method of producing the amorphous resin A2 by subjecting the non-linear reactive precursor to an extension reaction and / or a crosslinking reaction.

  When the curing agent and the non-linear reactive precursor are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, the amorphous resin A2 is preferentially formed on the surface of the toner to be produced, and the toner A concentration gradient of the amorphous resin A2 can be provided in the inside.

  The reaction conditions (reaction time, reaction temperature) for producing the amorphous resin A2 are not particularly limited, and are appropriately determined depending on the combination of the curing agent and the non-linear reactive precursor. You can choose.

There is no restriction | limiting in particular as said reaction time, Although it can select suitably according to the objective, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.
There is no restriction | limiting in particular as said reaction temperature, Although it can select suitably according to the objective, 0 to 150 degreeC is preferable and 40 to 98 degreeC is more preferable.

  The method for stably forming the dispersion containing the non-linear reactive precursor in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the aqueous medium phase Examples thereof include a method in which an oil phase prepared by dissolving or dispersing a toner material in a solvent is added and dispersed by shearing force.

The disperser for the dispersion is not particularly limited and can be appropriately selected according to the purpose. For example, a low-speed shear disperser, a high-speed shear disperser, a friction disperser, and a high-pressure jet disperser. And an ultrasonic disperser.
Among these, a high-speed shearing disperser is preferable in that the particle diameter of the dispersion (oil droplets) can be controlled to 2 μm 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.

  There is no restriction | limiting in particular as said rotation speed, Although it can select suitably according to the objective, 1,000 rpm-30,000 rpm are preferable, and 5,000 rpm-20,000 rpm are more preferable.

There is no restriction | limiting in particular as said dispersion | distribution time, Although it can select suitably according to the objective, In the case of a batch system, 0.1 minute-5 minutes are preferable.
There is no restriction | limiting in particular as said dispersion | distribution temperature, Although it can select suitably according to the objective, 0 degreeC-150 degreeC is preferable under pressure, and 40 degreeC-98 degreeC is more preferable. 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 50 mass parts to 100 mass parts of the toner material. 2,000 parts by mass is preferable, and 100 parts by mass to 1,000 parts by mass is more preferable.
When the amount of the aqueous medium used is 50 parts by mass or more, it is possible to effectively prevent the problem that the dispersion state of the toner material is deteriorated and toner base particles having a predetermined particle diameter cannot be obtained. The production cost can be suppressed when the content is less than or equal to mass parts.

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 as said dispersing agent, According to the objective, it can select suitably. For example, surfactants, sparingly water-soluble inorganic compound dispersants, polymeric protective colloids and the like can be 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, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used.
There is no restriction | limiting in particular as said anionic surfactant, According to the objective, it can select suitably, For example, alkylbenzene sulfonate, (alpha) -olefin sulfonate, phosphate ester etc. are mentioned.
Among these, those having a fluoroalkyl group are preferable.

A catalyst can be used for the elongation reaction and / or the cross-linking reaction when the amorphous polyester resin B is produced.
The catalyst is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dibutyltin laurate and dioctyltin laurate.

<< Removal of organic solvent >>
There is no restriction | limiting in particular as a method of removing an organic solvent from dispersion liquids, such as the said emulsion slurry, According to the objective, it can select suitably. Examples thereof include a method in which the temperature of the entire reaction system is gradually raised to evaporate the organic solvent in the oil droplets, and a method in which the organic solvent in the oil droplets is removed by spraying the dispersion 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.

  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.

  There is no restriction | limiting in particular as a method of applying the said mechanical impact force, According to the objective, it can select suitably. For example, a method of applying an impact force to the mixture using blades that rotate at high speed, a method of injecting the mixture into a high-speed air stream, and accelerating the particles to collide with each other or an appropriate collision plate are exemplified.

  The apparatus used in the above method is not particularly limited and can be appropriately selected depending on the purpose. For example, an ang mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure are modified. And 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 and, if necessary, other components such as a carrier as appropriate.
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 that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.

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

(Toner storage unit)
The toner storage unit in the present invention refers to a unit in which toner is stored in a unit having a function of storing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, and a process cartridge.
The toner container is a container that contains toner.
The developing device is a unit having a means for containing and developing toner.
The process cartridge is a cartridge in which at least the image carrier and the developing unit are integrated, accommodates toner, and is detachable from the image forming apparatus. The process cartridge may further include at least one selected from a charging unit, an exposure unit, and a cleaning unit.

  By mounting the toner containing unit of the present invention on an image forming apparatus to form an image, it is possible to perform image formation utilizing the characteristics of the toner excellent in low-temperature fixability, heat-resistant storage stability, and mechanical strength.

(Image forming apparatus and image forming method)
An image forming apparatus according to the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and an electrostatic latent image formed on the electrostatic latent image carrier. Developing means for developing an electrostatic latent image with toner to form a visible image. Furthermore, it has other means as needed.
An image forming method according to the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image formed on the electrostatic latent image carrier with toner. And a developing step for forming a visible image. Furthermore, it has another process as needed.

  The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

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

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

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

<< Exposure means and exposure process >>
The exposure unit is not particularly limited and may be appropriately selected depending on the intended purpose as long as the surface of the electrostatic latent image carrier charged by the charging unit can be exposed like an image to be formed. Examples thereof include various exposure means such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.

<Developing means and development process>
The developing unit is not particularly limited as long as it is a developing unit including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image. Can be selected as appropriate.
The development step is not particularly limited as long as it is a step of developing the latent electrostatic image formed on the latent electrostatic image bearing member with toner to form a visible image. For example, it can be carried out by the developing means.
The developing means may be of a dry development type or a wet development type. Further, it may be a single color developing means or a multicolor developing means.
The developing means includes a stirrer for charging the toner by frictional stirring and a magnetic field generating means fixed inside, and a developer carrying that can carry and rotate the developer containing the toner on the surface. A developing device having a body is preferred.

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

<< Transfer means and transfer process >>
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, the visible image is transferred onto an intermediate transfer member and combined. An embodiment having a primary transfer unit for forming a transfer image and a secondary transfer unit for transferring the composite transfer image onto a recording medium is preferable.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, an intermediate transfer member is used, and the transfer step can be performed on the intermediate transfer member. It is preferable that the visual image is firstly transferred and then the visible image is secondarily transferred onto the recording medium.

<< Fixing means and fixing process >>
The fixing unit is not particularly limited as long as it is a unit that fixes the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose. However, a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, the recording medium for each color toner May be performed each time the toner is transferred to the toner image, or may be performed simultaneously in a state where the toners of the respective colors are stacked.

  Next, one mode for carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. A color image forming apparatus 100A shown in FIG. 1 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter also referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and the An exposure apparatus 30 as an exposure means, a developing device 40 as the development means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means. .

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. 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. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50.

  Also, in the vicinity of the intermediate transfer member 50, there is a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a recording medium. The intermediate transfer member 50 is disposed opposite to the intermediate transfer member 50. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. Further, the developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.

  In the color image forming apparatus 100A shown in FIG. 1, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  FIG. 2 shows another example of the image forming apparatus of the present invention. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are arranged directly facing each other around the photosensitive drum 10 without providing the developing belt 41. Other than this, the configuration is the same as that of the image forming apparatus 100A shown in FIG.

  FIG. 3 shows another example of the image forming apparatus of the present invention. The image forming apparatus shown in FIG. 3 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 3. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15.

  The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. In the vicinity of the tandem developing device 120, an exposure device 21 as the exposure member is disposed.

  A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. In the vicinity of the secondary transfer device 22, a fixing device 25 as the fixing means is arranged. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.

  In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. 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.

  When the start switch is pressed, when a document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32. On the other hand, when a document is set on the contact glass 32, immediately. The scanner 300 is driven. Then, 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 is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Forming means). In each image forming unit, black, yellow, magenta, and cyan toner images are formed.

  As shown in FIG. 4, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing device 120 is an electrostatic latent device. An image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C) is provided.

  In addition, the electrostatic latent image carrier 10 is exposed like a color image-corresponding image based on each color image information, with the charging device 160 as the charging means for uniformly charging the electrostatic latent image carrier 10 ( In FIG. 4, L) includes an exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier.

Further, the image forming apparatus includes a developing device 61 that is the developing unit that develops the electrostatic latent image using each color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image using each color toner.
Further, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64 are provided.

  Each image forming unit 18 can form each monochrome image (black image, yellow image, magenta image, and cyan image) based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer).

  Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one by the separation roller 145, sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copier body 150, and abutted against the registration roller 49 to stop. It is done. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. .
The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.

Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. Then, the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device 22. By doing so, a color image is transferred and formed on the sheet (recording paper).
The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

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

  FIG. 5 shows an example of a process cartridge as an example of the toner storage unit of the present invention. The process cartridge 110 includes a photosensitive drum 10, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example. “Part” represents “part by mass” unless otherwise specified. “%” Represents “% by mass” unless otherwise specified.

  Each measured value in the following examples was measured by the method described above. In addition, glass transition temperature (Tg), melting | fusing point (Tm), and molecular weight, such as amorphous resin and crystalline resin, were measured from each resin obtained by the manufacture example.

(Production of amorphous resin A1)
<Synthesis of Amorphous Polyester Resin A1-1>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A propylene oxide 3 mol adduct (BisA-PO), propylene glycol (PG), terephthalic acid, and adipic acid are added. The molar ratio (propylene glycol / bisphenol A propylene oxide 3 mol adduct) is 60/40, and the molar ratio of terephthalic acid and adipic acid (terephthalic acid / Adipic acid) is 90/10, and the molar ratio of hydroxyl group to carboxyl group is charged so that OH / COOH is 1.10, and titanium tetraisopropoxide (500 ppm with respect to the resin component) is used at normal pressure. It reacts at 230 ° C for 8 hours, and further decreases by 10mmHg ~ 15mmHg After 4 hours of reaction, trimellitic anhydride was added to the reaction vessel at 1 mol% with respect to the total resin components, and reacted at 180 ° C. and normal pressure for 3 hours to obtain [Amorphous Polyester Resin A1-1]. It was. The physical properties are shown in the following table.

<Synthesis of Amorphous Polyester Resin A1-2 to 13>
[Amorphous polyester resin A1-2 to 13] were obtained in the same manner as the synthesis of [Amorphous polyester resin A1-1] except that the acid component and the alcohol component were changed. The composition and physical property values are shown in the following table.

(Synthesis of ketimine)
170 parts of isophorone diamine 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.

(Preparation of prepolymer A2)
<Synthesis of Nonlinear Amorphous Polyester Resin A2 (Prepolymer A2) Having Reactive Groups>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 97 mol% of 3-methyl-1,5-pentanediol as an alcohol component, 3 mol% of trimethylolpropane (TMP), and adipine as an acid component The acid was 50 mol% and terephthalic acid 50 mol%, and was added together with titanium tetraisopropoxide (300 ppm to resin component) so that the molar ratio of hydroxyl group to carboxyl group was OH / COOH = 1.1. . 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 mmHg-15mmHg for 5 hours, and [intermediate polyester A2] was obtained.

  Next, in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, [middle ratio of intermediate polyester A2] and isophorone diisocyanate (IPDI) (IPDI isocyanate group / intermediate polyester hydroxyl group) 2. 1 and diluted to a 48% ethyl acetate solution with ethyl acetate, followed by reaction at 100 ° C. for 5 hours to produce a non-linear amorphous polyester resin A2 having a reactive group ([prepolymer A2] ) The number average molecular weight (Mn) of this resin was 5,800, the weight average molecular weight (Mw) was 26,000, and Tg was −5 ° C.

(Production of crystalline resin B)
<Synthesis of Crystalline Polyester Resin B-1>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, sebacic acid and hexanediol were mixed, and the molar ratio of hydroxyl group to carboxyl group was 0.85. Then, after reacting with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, the temperature is raised to 200 ° C. and reacted for 3 hours, and further at a pressure of 8.3 kPa. Reaction was performed for 2 hours to obtain [Crystalline Polyester Resin B-1]. The composition and physical property values are shown in the following table.

<Synthesis of Crystalline Polyester Resin B-2>
[Crystalline polyester resin B-2] was obtained in the same manner as in [Crystalline polyester resin B-1] except that the alcohol component was changed to ethylene glycol. The composition and physical property values are shown in the following table.

  The composition and physical properties of the obtained amorphous polyester resin A1 and crystalline polyester resin B are shown in the following table.

Example 1
<Synthesis of master batch (MB)>
1,200 parts of water, carbon black (Printtex 35, manufactured by Dexa) [500 parts of DBP oil absorption = 42 mL / 100 mg, pH = 9.5] and 500 parts of [amorphous polyester resin A1-1] are added, and Henschel is added. The mixture was mixed with a mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), and the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then cooled by rolling and pulverized with a pulverizer to obtain [Masterbatch 1].

<Preparation of WAX dispersion>
50 parts of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8) as a mold release agent in a container equipped with a stirring bar and a thermometer, and ethyl acetate 450 The temperature was raised to 80 ° C. with stirring and held at 80 ° C. for 5 hours, then cooled to 30 ° C. in 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by IMEX Co., Ltd.), the liquid feeding speed was 1 kg. / Wr, disk peripheral speed 6 m / sec, 80% by volume of 0.5 mm diameter zirconia beads were filled, and dispersion was performed under the conditions of 3 passes to obtain [WAX Dispersion 1].

<Preparation of crystalline polyester resin dispersion>
After charging 50 parts of [Crystalline Polyester Resin B-1] and 450 parts of ethyl acetate into a container equipped with a stir bar and a thermometer, the temperature was raised to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. Cooled to 30 ° C. in 1 hour, filled with 80% by volume of 0.5 mm zirconia beads having a diameter of 0.5 mm and a feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, using a bead mill (Ultra Visco Mill, manufactured by Imex). Dispersion was performed under pass conditions to obtain [Crystalline Polyester Resin Dispersion 1].

<Preparation of oil phase>
[WAX dispersion 1] 500 parts, [Prepolymer A2] 200 parts, [Crystalline polyester resin dispersion 1] 500 parts, [Amorphous polyester resin A-1] 750 parts, [Masterbatch 1] 100 parts, Then, 2 parts of [ketimine compound 1] as a curing agent were put in a container and mixed for 60 minutes at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika) to obtain [oil phase 1].

<Synthesis of organic fine particle emulsion (fine particle dispersion)>
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. The system was heated to raise the system temperature 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 (a copolymer of sodium salt of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate) [fine particles Dispersion 1] was obtained.
When [Fine Particle Dispersion 1] was measured with LA-920 (manufactured by HORIBA), the volume average particle diameter of the fine particles was 0.14 μm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component.

<Preparation of aqueous phase>
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) 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>
1,700 parts of [Aqueous phase 1] was added to the container containing [Oil phase 1], and mixed with a TK homomixer at a rotational speed of 8,000 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].
[Amorphous polyester resin A2] is generated in the toner preparation process.

<Washing and drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion exchange water to the filter cake of (3), mix with TK homomixer (10 minutes at 12,000 rpm), and then filter.
The operations (1) to (4) were performed twice to obtain [Filter cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner 1].

The composition ratio and physical properties of the obtained [Toner 1] are shown in the following table. Note that the composition ratios and physical properties of the toners obtained in the following examples and comparative examples are shown in the following table.
In the table below, “component ratio (mass%)” is [amorphous polyester resin A1], [prepolymer A2] which is a reactive precursor of [amorphous polyester resin A2], and [crystalline polyester resin B]. ], The composition ratio (% by mass) with respect to the total amount of the release agent and the colorant.

(Examples 2 to 10 and Comparative Examples 1 to 7)
Examples 2 to 10 and Comparative Examples 1 to 7 were the same as Example 1 except that [Amorphous Resin A-1], [Crystalline Resin B] and the toner composition ratio were changed as shown in the following table. No toner was obtained.

(Evaluation)
A developer was prepared for the obtained toner by the following method, and the following evaluation was performed. The results are shown in the table below.

<< Developer >>
-Fabrication of carrier-
Add 100 parts of silicone resin organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black to 100 parts of toluene, disperse with a homomixer for 20 minutes, and apply resin layer A liquid was prepared. Using a fluid bed type coating device, the resin layer coating solution was applied to the surface of 1,000 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 the toner and 95 parts of the carrier were mixed to prepare developer 1 corresponding to toner 1 of the example. (In the same manner in other examples and comparative examples, developers 2 to 17 corresponding to the toners 2 to 10 in the examples 2 to 10 and the toners 11 to 17 in the comparative examples 1 to 7 are obtained. )

<< Low-temperature fixability (fixing minimum temperature) >>
A copying test was performed on type 6200 paper (manufactured by Ricoh) using an apparatus in which a fixing unit of a copying machine Imagio 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) was determined by changing the fixing temperature. The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 mm / second to 150 mm / second, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm.
Evaluation criteria for low-temperature fixability were acceptable when the lower limit fixing temperature was 110 ° C. or lower and rejected when the temperature was higher than 110 ° C.

<< High temperature and high humidity storage stability >>
After 5 g of toner was stored in an environment of 40 ° C. and 70% for 2 weeks, it was sieved with a sieve having a mesh size of 106 μm for 5 minutes, and the amount of toner on the wire mesh was measured and evaluated according to the following evaluation criteria.

〔Evaluation criteria〕
A: Toner amount on wire mesh is 0 mg
○: Toner amount on wire mesh greater than 0 mg and less than 2 mg △: Toner amount on wire mesh is 2 mg or more and less than 50 mg ×: Toner amount on wire mesh is 50 mg or more

<< Transfer White >>>
Developer No. 1 was mounted on Imagio MP C2802 (manufactured by Ricoh), and 10,000 A4 images with an image area ratio of 5% were continuously printed. After the test was completed, 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. The following ranking was performed based on the total number of three blank images.

[Rank]
A: The blank images are not visually recognized in all three sheets.
○: The third blank image can be confirmed by observing with an optical microscope, but this is not a practically problematic level.
(Triangle | delta): The level which a problem appears practically in which 1-10 white-spotted images can be visually confirmed together.
×: Over 10 images of white spots can be visually confirmed by combining 3 images, and there is a large problem level in practical use.

<< Deteriorated charge >>
0.25 g of toner and 4.75 g of carrier were placed in a stainless steel container having a bottom diameter of 25 mm and a height of 30 mm, and the rotation of 300 rpm was applied in the circumferential direction for 20 minutes, and the toner and the carrier were stirred and brought into contact with each other. Here, as the carrier, ferrite particles (manufactured by Ricoh) having an average particle diameter of 35 μm were used.
The charge amount (Q / S) per unit area of the agitated toner was measured by a blow-off method using a charge amount measuring device TB-200 (manufactured by Toshiba Corporation). Specifically, a measurement sample is loaded into a sample part equipped with a 400 mesh stainless steel screen of the above charge amount measuring apparatus, and a blow pressure of 50 kPa (0.5 kgf) in a normal temperature and humidity environment (20 ° C., 55% RH). / Cm ² ) nitrogen gas was blown for 10 seconds to measure the charge.

〔Evaluation criteria〕
A: Absolute value of charge amount is 200 μC / m ² or more and less than 250 μC / m ² ○: Absolute value of charge amount is 150 C / m ² or more and less than 200 μC / m ² Δ: Absolute value of charge amount is 100 μC / m ² or more and 150 μC Less than / m ² ×: Transfer with an absolute value of the charge amount of 50 μC / m ² or more

The composition and physical properties of the obtained amorphous polyester resin A1 and crystalline polyester resin B are shown in the following table. Moreover, said measurement and evaluation result are shown collectively.
In addition, it is as follows in the following table | surface.
PG: Propylene glycol EG: Ethylene glycol BisA-PO: Bisphenol A propylene oxide 3 mol adduct BisA-EO: Bisphenol A ethylene oxide 3 mol adduct

(About Fig. 1 and Fig. 2)
DESCRIPTION OF SYMBOLS 100A Image forming apparatus 100B Image forming apparatus 10 Photoconductor 20 Charging roller 30 Exposure apparatus 40 Developer 41 Developer belt 42C Developer accommodating part 42M Developer accommodating part 42Y Developer accommodating part 42K Developer accommodating part 43C Developer supply roller 43M Development Agent supply roller 43Y Developer supply roller 43K Developer supply roller 44C Development roller 44M Development roller 44Y Development roller 44K Development roller 45C Cyan development unit 45M Magenta development unit 45Y Yellow development unit 45K Black development unit 50 Intermediate transfer body 51 Roller 58 Corona charging 60 Cleaning device 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper L Exposure device (about FIG. 3)
10 (K, Y, M, C) Photosensitive drum 14 Support roller 15 Support roller 16 Support roller 17 Supporting device 17 Cleaning device 18 Image forming means 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 26 27 Pressure roller 28 Reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 49 Registration roller 50 Intermediate transfer body 52 Separating roller 53 Manual feed path 54 Manual tray 55 Switching claw 56 Discharge Roller 57 Discharge tray 62 Transfer roller 120 Tandem developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying device main body 200 Paper feed table 30 Scanner 400 automatic document feeder (ADF)
(About Figure 4)
DESCRIPTION OF SYMBOLS 10 Electrostatic latent image carrier 18 Image forming means 50 Intermediate transfer body 61 Developing device 62 Transfer charger 63 Cleaning device 64 Charger 160 Charger L Exposure (about FIG. 5)
DESCRIPTION OF SYMBOLS 110 Process cartridge 10 Photosensitive drum 40 Developing device 58 Corona charger 80 Transfer roller 90 Cleaning device 95 Recording paper L Exposure light

Japanese Patent Laid-Open No. 11-305481 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 (9)

A toner comprising an amorphous resin A1 and a crystalline resin B,
When the HLB values of the amorphous resin A1 and the crystalline resin B are HLB (A1) and HLB (B), respectively, the following formula (1) and the following formula (2) are satisfied.
The amorphous resin A1 includes an alcohol component, and the toner includes 10 mol% or more of a diol component monomer having an aromatic ring in the alcohol component.
−1.4 ≦ HLB (A1) −HLB (B) ≦ 1.7 Formula (1)
HLB (A1) ≧ 3.6 Formula (2) The toner according to claim 1, wherein the HLB (A1) and the HLB (B) satisfy the following formula (3).
0.2 ≦ HLB (A1) −HLB (B) ≦ 1.2 Formula (3) When the solubility parameter SP values ([cal / cm ³ ] ^1/2 ) of the amorphous resin A1 and the crystalline resin B are SP (A1) and SP (B), respectively, the following formula (4) is satisfied. The toner according to claim 1, wherein:
1.3 ≦ SP (A1) −SP (B) ≦ 1.7 Formula (4) The following formula (5) is satisfied, where A is a peripheral length of a cross section of the toner, and B is a peripheral length of a portion of the peripheral length A where the crystalline resin B is exposed. The toner according to any one of 1 to 3.
0.1 <B / A <0.4 Formula (5) Furthermore, an amorphous resin A2 is included,
The amorphous resin A2 is insoluble in tetrahydrofuran (THF), has at least one of a urethane bond and a urea bond, and includes an alcohol component.
The alcohol component includes a diol component and a crosslinking component, the diol component includes an aliphatic diol having 3 to 10 carbon atoms in the alcohol component in an amount of 50 mol% or more, and the crosslinking component includes a trihydric or higher aliphatic alcohol. The toner according to claim 1, wherein the toner is a toner.   A developer comprising the toner according to claim 1 and a carrier.   A toner containing unit containing the toner according to claim 1. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a visible image;
An image forming apparatus, wherein the toner is the toner according to claim 1. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
Developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a visible image, and
An image forming method, wherein the toner is the toner according to claim 1.