JP2017227881A - Toner, toner storage unit, image forming apparatus, and method for manufacturing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in heat-resistant storage property and mechanical strength without impairing low-temperature fixability.SOLUTION: A toner contains at least an amorphous resin, crystalline resin, and mold release agent, and the crystalline resin is dispersed in the amorphous resin. On a torn surface of the toner observed by a transmission electron microscope (TEM), when the length of the periphery of the crystalline resin is A and the length of a portion of the length A of the periphery of the crystalline resin where the crystalline resin is in contact with the amorphous resin is B, the ratio of the length B to the length A (B/A) satisfies B/A<0.8.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a toner, a toner storage unit using the toner, an image forming apparatus, and a method for producing the toner.

In recent years, toners have been able to withstand high temperature and high humidity during storage and transportation after production, as well as reduction in particle size for high quality output images, high temperature offset resistance, low temperature fixability for energy saving. High heat-resistant storage stability is required. In particular, since power consumption during fixing accounts for much of the power consumption in the image forming process, it is very important to improve low-temperature fixability.
Conventionally, toner prepared by a kneading and pulverizing method has been used. The toner produced by the kneading and pulverization method is difficult to reduce the particle size, the shape is irregular and the particle size distribution is broad, so the quality of the output image is not sufficient, and the fixing energy is high. There were problems such as. 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, there is a problem in that, while the releasing effect is produced, the toner (filming) easily adheres to the carrier, the photoreceptor and the blade, and the overall performance is not satisfactory.
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, these proposed techniques do not satisfy the high level of low-temperature fixability required in recent years.
Therefore, for the purpose of obtaining a high level of low temperature fixability, a toner containing a crystalline polyester resin and a release agent, and a resin and a wax that are incompatible with each other and having a sea-island phase separation structure has been proposed. (For example, refer to Patent Document 6).
Further, a toner containing a crystalline polyester resin, a release agent, and a graft polymer has been proposed (see, for example, Patent Document 7).

  An object of the present invention is to provide a toner excellent in heat-resistant storage stability and mechanical strength without impairing low-temperature fixability.

Means for solving the problems are as follows. That is,
The toner of the present invention is a toner that includes at least an amorphous resin, a crystalline resin, and a release agent, and the crystalline resin is dispersed in the amorphous resin.
When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the circumference of the crystalline resin is A, and the crystalline resin of the circumference A of the crystalline resin is an amorphous resin. When the length of the contacting portion is B, the ratio of the length of B to the length of A (B / A) satisfies B / A <0.8.

  According to the present invention, it is possible to provide a toner excellent in heat-resistant storage stability and mechanical strength without impairing the low-temperature fixability.

FIG. 1 is a schematic configuration diagram showing an example of an image forming apparatus of the present invention. FIG. 2 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 3 is a toner sectional view showing an example of a section of the toner of the present invention.

The techniques described in Patent Documents 6 and 7 can achieve low-temperature fixing because the crystalline polyester resin melts more rapidly than the amorphous polyester resin.
However, in these proposed techniques, the partial mechanical strength of the toner is reduced due to the contact between the crystalline polyester resin corresponding to the island and the amorphous polyester resin corresponding to the sea in the sea-island phase separation structure. Due to the strong stress applied to the toner in the developing device of the high-speed machine, the toner's aggregating ability, burying of external additives, carrier contamination, etc., the toner's charging ability deteriorates over time and filming on the photoconductor occurs. There was a problem of abnormal images. Therefore, it does not satisfy the high level of low-temperature fixability and image quality that have been increasing in recent years.
Accordingly, the present inventors have conducted research to provide a toner that satisfies higher heat storage stability and mechanical strength without impairing the low-temperature fixability. As a result, the toner of the present invention shown below is heat-resistant storage. It has been found that it is more excellent in properties and mechanical strength.

(toner)
The toner of the present invention includes at least an amorphous resin, a crystalline resin, and a release agent, and the crystalline resin is dispersed in the amorphous resin.
When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the circumference of the crystalline resin is A, and the crystalline resin of the circumference A of the crystalline resin is an amorphous resin. Assuming that the length of the contacting portion is B, the ratio of the length of B to the length of A (B / A) satisfies B / A <0.8.
When B / A is 0.8 or more, the crystalline resin and the amorphous resin are partially compatible with each other in contact with each other, and the mechanical strength is reduced. The toner is strongly stressed in the developing unit, and the toner is agglomerated, the external additive is buried, the carrier is contaminated, etc., the charging ability of the toner is deteriorated over time, and the filming on the photoconductor occurs, and an abnormal image is generated. .
In order to set the B / A within the range specified in the present invention, the crystalline resin and the release agent are recrystallized in the toner manufacturing process, and the crystalline resin and the release agent are combined to be partially integrated. It is preferable to form a combined (composite) state. When forming a state in which the crystalline resin is dispersed in the amorphous resin, the amorphous resin, the crystalline resin, and the release agent are not simply mixed, but the crystalline resin and the release agent Is formed first, and the crystalline resin compounded with the mold release agent is mixed with the amorphous resin, so that the crystalline resin compounded with the mold release agent is made amorphous. It is good to disperse in the quality resin. The method for producing the toner of the present invention will be described in detail below.

<Observation of Toner by Transmission Electron Microscope (TEM)>
When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the circumference of the crystalline resin is A, and the crystalline resin of the circumference A of the crystalline resin is an amorphous resin. Assuming that the length of the contacting portion is B, the ratio of the length of B to the length of A (B / A) needs to satisfy B / A <0.8 as described above.
The B / A is preferably 0.15 to 0.79.
Further, from the viewpoint of achieving both low-temperature fixability and mechanical strength, the B / A is more preferably 0.5 to 0.6.
Further, when the fractured surface of the toner is observed with a transmission electron microscope (TEM), the length of the periphery of the toner is C, and the length of the portion where the crystalline resin is exposed in the peripheral length C of the toner. When the thickness is D, the ratio of the length of D to the length of C (D / C) preferably satisfies 0.05 <D / C <0.4.
If D / C is greater than 0.05, the melt viscosity will not be sufficiently lowered by the crystalline resin on the toner surface during fixing heating, and adhesion to a recording medium such as paper will be insufficient, resulting in poor low temperature fixability. The problem that there is can be effectively prevented. When the D / C is less than 0.4, the crystalline resin and the amorphous resin are partially compatible with each other on the toner surface, and a toner aggregate is generated in the developing unit due to a decrease in the mechanical strength of the toner surface. The problem that an abnormal image may occur can be effectively prevented.

<< Observation Method with Transmission Electron Microscope (TEM) >>
The section of the toner is stained with ruthenium, and the section of the ruthenium-stained toner is observed with TEM. Analyzing the obtained image, obtaining the A, B, C, and D, the ratio (B / A) where the crystalline resin and the amorphous resin are in contact, and the surface of the crystalline resin is exposed The ratio (D / C) 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 (TEM) 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. As shown in FIG. 3, the crystalline resin and the release agent are determined from the contrast and shape in the toner. In FIG. 3, symbol a represents a release agent, symbol b represents a crystalline resin, and symbol c represents an amorphous resin. 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 dyed can be judged as a crystalline resin.
The image analysis software used “Image J” was subjected to the following image analysis.
The peripheral length A of the crystalline resin, the peripheral length B where the crystalline resin and the amorphous resin are in contact, the peripheral length C of the toner, and the crystalline resin of the peripheral length C of the toner are exposed. The length D of the portion is designated on the cross-sectional image of the toner, B / B and D / C are calculated from the sum of the respective values, and the average value of 50 toners is calculated.

<Components of toner>
The toner contains at least a binder resin containing an amorphous resin and a crystalline resin, and a release agent. Further, it contains other components such as a colorant, if necessary.
A preferable embodiment of the binder resin includes, for example, containing two or more kinds of amorphous resins as the amorphous resin. Further, the amorphous resin or the crystalline resin may be a polyester resin such as an amorphous polyester resin or a crystalline polyester resin. Further, as a preferred embodiment of the binder resin, the amorphous polyester resin A for toner, which is mainly contained in the toner, and the amorphous polyester resin A for toner are different from each other except that the crystalline polyester resin is contained. Amorphous polyester resin B and amorphous hybrid resin may be further included.

<< Amorphous Polyester Resin A for Toner >>
The amorphous polyester resin A for toner of the present invention has a skeleton derived from an alcohol component and a skeleton derived from a carboxylic acid component.
As a method for producing the amorphous polyester resin for toner, a method in which an alcohol component containing a trihydric or higher aliphatic alcohol and a carboxylic acid component are reacted is preferable. By doing so, a polyester resin having a branched structure can be formed.
<<< Alcohol component >>>
Examples of the alcohol component include divalent alcohols and trivalent or higher alcohols.
The alcohol component may contain a trihydric or higher aliphatic alcohol.
Examples of the divalent alcohol include aliphatic diols, diols having an oxyalkylene group, alicyclic diols, alicyclic diols added with alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.), 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 amorphous polyester resin A for toners, Although it can select suitably according to the objective, 50 mass parts-95 mass parts are preferable with respect to 100 mass parts of the said toner. 70 parts by mass to 90 parts by mass is more preferable.

<< Amorphous Polyester Resin B >>
As the amorphous resin in the binder resin, in addition to the amorphous polyester resin A for toner, a second amorphous resin component different in kind from the amorphous polyester resin A for toner is used as an amorphous resin. It is preferable to contain the quality polyester resin B.
The amorphous polyester resin B is not particularly limited as long as it is a resin different from the amorphous polyester resin A for toner, and can be appropriately selected according to the purpose.
The amorphous polyester resin B includes, for example, a diol component or a diol component and a crosslinking component as its constituent components, 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 B 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 B has either a urethane bond or a urea bond, the urethane bond or the urea bond behaves like a quasi-branching point. The properties become stronger, and the heat resistant storage stability and high temperature offset resistance of the toner are more excellent.

<<< Reactive precursor >>>
The amorphous polyester resin B 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 B.
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 groups-
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.

--- 3 or more alcohols-
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 B 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.
The aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decametin Examples thereof include diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.
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.
The aromatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanato Examples include diphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like.
The araliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α, α, α ′, α′-tetramethylxylylene diisocyanate.
There is no restriction | limiting in particular as said isocyanurates, According to the objective, it can select suitably, For example, a tris (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 B can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. At a convenient infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on olefin? Ch (out-of-plane deformation vibration) as an amorphous polyester resin .
The content of the prepolymer that is a reactive precursor of the amorphous polyester resin B 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.

<< Amorphous hybrid resin >>
As the amorphous resin, an amorphous hybrid resin may be contained. The amorphous hybrid resin is composed of a composite resin including a condensation polymerization resin unit and a styrene resin unit, and the condensation resin unit and the styrene resin unit are partially chemically bonded.
By containing the amorphous hybrid resin, the dispersibility of the crystalline resin (particularly the crystalline polyester resin) in the toner can be improved. This makes it possible to uniformly disperse the crystalline resin (particularly the crystalline polyester resin) inside the toner, and prevent filming of the crystalline resin (particularly the crystalline polyester resin) and the release agent. In addition, the stress resistance can be improved and the low-temperature fixability of the toner can be achieved.
The styrenic resin unit contained in the amorphous hybrid resin is preferably made of styrene-acrylic resin. By including a styrene-acrylic resin, the affinity with other amorphous resins is increased, the dispersion effect on the crystalline resin (especially crystalline polyester resin) is improved, and the crystalline resin (especially crystalline polyester) is improved. Resin) is easily finely dispersed inside the toner.
In addition to the mixture of raw material monomers of two polymerization resins each having an independent reaction path of the condensation resin unit and the styrene resin unit, the amorphous hybrid resin is further added as one of the raw material monomers. It is preferable to produce by mixing monomers (both reactive monomers) that can react with any of the raw material monomers of the two polymerization resins.
Both reactive monomers have at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule, an ethylenically unsaturated bond, It is preferable to use a monomer having such a property, and by using such a bireactive monomer, the dispersibility of the resin to be a dispersed phase can be improved. Specific examples of the both reactive monomers include acrylic acid, fumaric acid, methacrylic acid, citraconic acid, maleic acid and the like. Among these, acrylic acid, methacrylic acid and fumaric acid are preferable.
The amount of both reactive monomers used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the raw material monomer of the condensation polymerization resin unit. In the present invention, the bi-reactive monomer is treated as a monomer different from the raw material monomer of the condensation polymerization resin unit and the raw material monomer of the addition polymerization resin unit because of the specificity of the performance.
In the present invention, when the amorphous hybrid resin is obtained by performing the polymerization reaction of the two polymerization resins using the raw material monomer mixture and the both reactive monomers, the progress of the polymerization reaction and It is not necessary for completion to be simultaneous in time, and the reaction temperature and time may be appropriately selected according to each reaction mechanism to advance and complete the reaction.
For example, in the method for producing an amorphous hybrid resin, a raw material monomer of a condensation polymerization resin unit, a raw material monomer of an addition polymerization resin unit, a bireactive monomer, a catalyst such as a polymerization initiator, etc. are mixed. An addition polymerization resin component having a functional group capable of a condensation polymerization reaction by a radical polymerization reaction at 50 ° C. to 180 ° C. is obtained, and then the reaction temperature is increased to 190 to 270 ° C., followed by a condensation polymerization system mainly by a condensation polymerization reaction. It is preferable to form the resin component.
The softening point of the amorphous hybrid resin is desirably 80 ° C to 170 ° C, preferably 90 ° C to 160 ° C, more preferably 95 ° C to 155 ° C.
The mass ratio of the crystalline resin (particularly crystalline polyester resin) and the amorphous hybrid resin is not particularly limited, but the ratio of the crystalline resin (particularly crystalline polyester resin): the amorphous hybrid resin is It is preferable that it is 50 / 100-200 / 100.
As the raw material monomer of the condensation polymerization resin unit, a succinic acid derivative is preferably used as the carboxylic acid component.
As a raw material monomer of the styrene resin unit, styrene derivatives such as styrene, α-methylstyrene and vinyltoluene are used.
The content of the styrene derivative is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more in the raw material monomer of the styrene resin unit.
Raw material monomers for styrene resin units that can be used in addition to styrene derivatives include (meth) acrylic acid alkyl esters; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; and halovinyls such as vinyl chloride. Vinyl esters such as vinyl acetate and vinyl propionate; esters of ethylenic monocarboxylic acid such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N- Examples thereof include N-vinyl compounds such as vinyl pyrrolidone.
Of these, (meth) acrylic acid alkyl esters are preferred from the viewpoint of low-temperature fixability and charge stability of the toner. From the above viewpoint, the number of carbon atoms of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 to 22, and more preferably 8 to 18. In addition, carbon number of this alkyl ester says carbon number derived from the alcohol component which comprises ester. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, and the like.
The content of the (meth) acrylic acid alkyl ester is preferably 50% by mass or less, more preferably 30% by mass or less, in the raw material monomer of the styrene-based resin unit, from the viewpoint of low-temperature fixability, storage stability and charge stability of the toner. Preferably, 20 mass% or less is more preferable.

<< Crystalline resin >>
In the present invention, a crystalline polyester resin is preferably contained as the crystalline resin.
Since the crystalline polyester resin has high crystallinity, it exhibits a heat-melting characteristic that exhibits a sudden viscosity drop near the fixing start temperature. By using the crystalline polyester resin having such characteristics together with the amorphous polyester resin A for toner, the heat-resistant storage stability due to crystallinity is good until just before the melting start temperature, and the crystalline polyester is used at the melting start temperature. Causes a sharp drop in viscosity (sharp melt) due to melting of the resin. It is compatible with the amorphous polyester resin A for toner as the viscosity is rapidly lowered by melting, and is fixed by suddenly lowering the viscosity. 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).
The crystalline polyester resin is obtained 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, as described above, the crystalline polyester resin uses a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or a derivative thereof. Refers to what is obtained. 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 polyester resin is a resin different from the amorphous polyester resin A for toner and the amorphous polyester resin B.

<<< 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 1,20-eicosanediol. 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.

<<< Polyvalent carboxylic acid >>>
There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, 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 is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms.
That is, the crystalline polyester resin preferably has a 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. . By doing so, since crystallinity is high and it is excellent in sharp melt property, it is preferable at the point which can exhibit the outstanding low-temperature fixability.

There is no restriction | limiting in particular as melting | fusing point of the said crystalline polyester resin, Although it can select suitably according to the objective, It is preferable that 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 is not particularly limited and may be appropriately selected depending on the intended purpose. However, those having a sharp molecular weight distribution and a low molecular weight are excellent in low-temperature fixability, and many components have a low molecular weight. And heat resistant storage stability is reduced. 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, it is possible to effectively prevent the problem of insufficient heat-resistant storage stability and high-temperature and high-humidity storage stability due to residual oligomers. 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 is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of the affinity between paper and resin, in order to achieve desired low-temperature fixability, 5 mgKOH / g or more is preferable and 10 mgKOH / g or more is more preferable. On the other hand, in order to improve the high temperature offset resistance, 45 mgKOH / g or less is preferable.
The hydroxyl value of the crystalline polyester resin is not particularly limited and may be appropriately selected according to the purpose. However, in order to achieve a desired temperature fixability and good charging characteristics, 0 mgKOH / G to 50 mgKOH / g are preferable, and 5 mgKOH / g to 50 mgKOH / g are more preferable.
The molecular structure of the crystalline polyester resin 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, Although it can select suitably according to the objective, 3 mass parts-20 mass parts are preferable with respect to 100 mass parts of the said toner, and 5 mass parts. -15 mass parts is more preferable. When the content is 3 parts by mass or more, it is possible to effectively prevent the problem that the low-temperature fixability may be inferior due to insufficient sharp melting by the crystalline polyester resin, and when the content is 20 parts by mass or less. It is possible to effectively prevent the problems that the heat-resistant storage stability is lowered and the fogging of the image tends to occur. 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 of being inferior in high-temperature offset resistance during fixing and low-temperature fixability. It is possible to effectively prevent the problem that the image is likely to be lowered and the image is likely to be fogged. 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 together with the production of the master batch or the master batch include, in addition to the amorphous polyester resin A for toner, a polymer of styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene, or a substituted product thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, styrene Acrylonitrile 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 shearing 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 >>>
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, Alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. Is mentioned. 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 phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), LRA- 901, boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigment, other polymer compounds having functional groups such as sulfonic acid group, carboxyl group, quaternary ammonium salt Etc.
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.
Further, it is preferable that at least one kind of inorganic fine particles having an average particle diameter of 20 nm or less of the primary particles subjected to the hydrophobization treatment is contained, and at least one kind of inorganic fine particles having a diameter of 30 nm or more is 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 (eg, zinc stearate, aluminum stearate, etc.), metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, and the like.
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.). Moreover, as titania fine particles, for example, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), Examples include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation).
Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T, TAF- Examples include 1500T (all manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured 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 is undesirably damaged.
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.

<<< Flowability 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. 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.
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 particle size of 2 μm or less.

<Toner characteristics>
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 the present invention has a lower Tg than conventional toners. However, for example, when the amorphous resin (particularly the amorphous polyester resin B), which is a low Tg component in the toner, is non-linear, the toner of the present invention can maintain heat-resistant storage stability. it can. In particular, when the amorphous resin (particularly the amorphous polyester resin B) is an amorphous polyester resin having a highly cohesive urethane bond or urea bond, the effect of maintaining heat-resistant storage stability is further improved. Become prominent.
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 fixing property of the toner from being lowered.

The toner preferably contains a tetrahydrofuran (THF) insoluble matter.
The THF-insoluble component preferably contains the amorphous resin, particularly the amorphous polyester resin B. Moreover, it is preferable that the component insoluble in the THF contains a specific alcohol component constituting the amorphous resin. Specifically, the THF-insoluble component preferably includes 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. .

<< SP value difference between amorphous resin and crystalline resin >>
When the SP value (solubility parameter (cal ^1/2 / cm ^3/2 )) of the amorphous resin is SP1, and the SP value of the crystalline resin is SP2, the following formula may be satisfied.
0.5 <SP1-SP2 <1.1
If the SP value difference (SP1-SP2) between the SP value (SP1) of the amorphous resin and the SP value (SP2) of the crystalline resin is greater than 0.5, the phase mixing of the amorphous resin and the crystalline resin By increasing the degree, the crystallinity of the crystalline resin can be lowered, and the problem that the high-temperature and high-humidity storage stability and mechanical strength may be reduced can be effectively prevented.
Further, when the (SP1-SP2) is 1.1 or less, the crystalline resin in the toner is unevenly distributed in the vicinity of the toner surface due to the polar interaction, and the high-temperature and high-humidity storage stability and mechanical strength are improved. It is possible to effectively prevent the problem that it may decrease.

<<< Calculation method of SP value >>>
The dissolution parameter (cal ^1/2 / cm ^3/2 ) is expressed by the square root of the evaporation energy per unit volume, and the equation dissolution parameter = (E / V) ^1/2 (where E is the evaporation) according to the Fedors method. Energy [cal / mol], and V is a molar volume [cm ³ / mol]).
At this time, assuming that the evaporation energy and molar volume of the atomic group are Δei and Δvi, respectively, E and V are expressed by the formula E = ΣΔeiV = ΣΔvi (“Fundamental theory of adhesion” (written by Imoto Satoshi, Polymer Publication)). Issued by the Association, Chapter 5)).
In addition, the terminal functional group shall not be included in calculation in SP value described in the table | surface in the following Example.

<Calculation method and analysis method of various characteristics of toner and toner component>
The amorphous polyester resin A for toner, the amorphous polyester resin B, the amorphous hybrid resin, the crystalline polyester resin, and the release agent Tg, acid value, hydroxyl value, molecular weight, and melting point are: Each may be measured on its 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 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.
The toner manufacturing method forms toner base particles while generating the amorphous polyester resin B by an extension reaction and / or a crosslinking reaction between the nonlinear reactive precursor and the curing agent. In this case, separation from actual toner by GPC or the like may be performed to obtain Tg of the amorphous polyester resin B or the like. Alternatively, the amorphous polyester resin B is synthesized by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent, and Tg and the like are synthesized from the synthesized amorphous polyester resin B. You may measure.

<< 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 resin mentioned above.
On the other hand, a fraction collector is placed at the eluate discharge port of GPC, and the eluate is collected every predetermined count, and the eluate is eluted every 5% in area ratio from the elution curve elution start (curve rise). Get.
Next, for each elution, 30 mg of sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution is filled in a 5 mm diameter glass tube for NMR measurement, and a spectrum is obtained by performing integration 128 times at a temperature of 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.). .
The monomer composition and composition ratio of the amorphous polyester resin A for toner, the amorphous polyester resin B, the amorphous hybrid resin, and the crystalline polyester resin contained in the toner are the peaks of the spectrum obtained. It can be obtained from the integral ratio.
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, an extract collected in a fraction in which the amorphous polyester resin A for toner accounts for 90% or more can be handled as the amorphous polyester resin A for toner.
Similarly, the extract recovered in the fraction in which the amorphous polyester resin B accounts for 90% or more can be handled as the amorphous polyester resin B. The extract recovered in the fraction in which the crystalline polyester resin accounts for 90% or more can be treated as the crystalline polyester resin.

<< 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 CH ₃ ONa
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 of an ethyl acetate-soluble component) 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 this specification, when the 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 specification, the glass transition temperature and the melting point of the other components such as the amorphous polyester resin A, the amorphous polyester resin B, and the amorphous hybrid resin are the second time unless otherwise specified. The endothermic peak top temperature and Tg at the time of temperature rise 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 measurement device is used to measure the volume and number of toner particles or toner 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: HLC-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 mass% sample Sample pretreatment: The object to be measured was dissolved in tetrahydrofuran THF (made by Wako Pure Chemical Industries, Ltd.) at 0.15 mass% and filtered through a 0.2 μm filter. The filtrate is used as a sample.
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>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the oil phase containing the amorphous resin, the crystalline resin, and the release agent is contained in an aqueous medium. And a method for obtaining a toner after granulation is preferable.
As such a production method, a known dissolution suspension method can be used.
However, for the toner defined in the present invention, the crystalline resin and the release agent are cooled by cooling a mixture of a solution obtained by heating and dissolving the crystalline resin and the release agent in an organic solvent. It is preferable to have a step of recrystallizing and preparing a dispersion of composite particles in which the crystalline resin and the release agent are partially integrated.
That is, one of the characteristics of the toner production method of the present invention is to have a step of producing a dispersion of composite particles of a crystalline resin and a release agent.
The production of the dispersion of the crystalline resin / release agent composite particles will be described in detail below.
In addition, by the dissolution suspension method described below, the amorphous polyester resin A for toner, the crystalline polyester resin, and the release agent are included, and if necessary, the amorphous polyester resin B, The toner of the present invention can be obtained by dispersing and granulating an oil phase containing an amorphous hybrid resin and the colorant in an aqueous medium.
According to this method, as described later, while forming the amorphous polyester resin B by an extension reaction and / or a crosslinking reaction between the non-linear reactive precursor and the curing agent, Can be formed.
The steps of preparing the aqueous medium, preparing the oil phase containing the toner material, emulsifying or dispersing the toner material, and removing the organic solvent in this method are also described in detail below.

<< Method for producing dispersion of crystalline resin / release agent composite particles >>
In the toner production method of the present invention, the crystalline resin and the release agent are recrystallized by cooling a solution mixture obtained by heating and dissolving the crystalline resin and the release agent in an organic solvent during the toner production process. And preparing a dispersion of composite particles in which the crystalline resin and the release agent are combined. At this time, the crystallization temperature of the release agent is set to 20 ° C. or more higher than the crystallization temperature of the crystalline resin.
Although it is possible to recrystallize the solute by cooling a solution obtained by heating and dissolving a crystalline resin or a release agent in an organic solvent, a fine particle dispersion of the crystalline resin or the release agent can be produced. At this time, the crystalline resin and the release agent solution are mixed and cooled, and the crystallization temperature of the release agent is 20 ° C. higher than the crystallization temperature of the crystalline resin. The mold begins to recrystallize, and a part of the crystalline resin is recrystallized starting from the crystal of the release agent. Thereby, a dispersion liquid of composite particles in which a part of the crystalline resin is combined with the release agent can be produced. By introducing this into the toner, a release agent is disposed between the amorphous resin and the crystalline resin, reducing the contact area between the crystalline resin and the amorphous resin, and suppressing partial compatibility. Is possible.

<< Organic solvent used, concentration >>
In the method for producing the toner of the present invention, the organic solvent used in preparing the dispersion is not soluble in the crystalline resin and the release agent at a low temperature, but can be dissolved by heating to form a uniform solution. If it is, there will be no restriction | limiting in particular and it can select suitably according to the objective. For example, toluene, ethyl acetate, methyl ethyl ketone or the like can be used alone or in combination.

<< Concentration, heating / cooling operation >>
In general, the size of the crystal grains to be recrystallized in the course of cooling varies depending on the solid content concentration of the solution and the cooling rate. In the present invention, since it is important to combine the crystalline resin and the release agent, it is preferable to control the solution concentration and temperature operation within a certain range.
The solid content concentration of the solution is 1% to 40%, preferably 5% to 20%. When the concentration is low, the recrystallized particles become small but disadvantageous in terms of productivity and cost. On the other hand, when the concentration is high, the particle size of the particles increases, but depending on the crystalline resin and the release agent used, the increase in viscosity is significant, and the handling properties during production may be reduced. Moreover, as a ratio of the crystalline resin and the release agent in the solution, the crystalline resin is 50% by mass to 200% by mass, preferably 100% by mass to 120% by mass with respect to the release agent. If the ratio of the crystalline resin to the release agent is too high, the effect of reducing the contact area between the amorphous resin and the crystalline resin may be insufficient when the toner is formed.
As heating and cooling operations, first, a crystalline resin and a release agent are added to an organic solvent, and the mixture is stirred for about 10 to 30 minutes below the boiling point of the organic solvent to be used to produce a transparent uniform solution mixture. At this time, the crystalline resin and the release agent may be mixed in advance, or the dissolved solution may be mixed after preparing each dissolved solution.
Subsequently, the obtained mixed solution is cooled, and the crystalline resin and the release agent are recrystallized. The cooling rate is preferably 0.1 ° C / min to 40 ° C / min, and more preferably 0.5 ° C / min to 30 ° C / min. The lower limit of the cooling rate is more preferably 0.51 ° C./min or more, and particularly preferably 2 ° C./min to 30 ° C./min.
For recrystallization, the crystallization temperature of the release agent is preferably 20 ° C. or more higher than the crystallization temperature of the crystalline resin. Thereby, the particle | grains which the mold release agent and crystalline resin were compounded moderately can be produced.

<< Additional grinding process >>
In the present invention, the fine particle dispersion obtained by recrystallization can be further pulverized by subjecting it to an additional pulverization treatment as necessary. According to the present invention, since the crystalline resin and the release agent are sufficiently finely combined at the time of recrystallization, the crystalline resin and the release agent are combined even if an additional pulverization treatment is performed. It is possible to keep Atomization is preferable because the crystalline resin and the release agent can be uniformly arranged in the toner. The volume average particle diameter of the composite particles of the crystalline resin and the release agent is preferably 0.2 μm to 2 μm.
There is no restriction | limiting in particular as a grinding | pulverization apparatus, A commercially available grinding | pulverization apparatus can be mention | raise | lifted. For example, a ball mill, a bead mill, a sand mill apparatus, etc. are mentioned.

<< Control means of B / A >>
The B / A can be controlled by the cooling rate when recrystallizing the solution of the crystalline resin and the release agent. In the present invention, the larger the cooling rate, the smaller the particle size of the recrystallized particles obtained. This is presumably because the rate of decrease in saturation solubility due to cooling is fast, and crystal nuclei are likely to be generated to eliminate the supersaturated state. On the other hand, if the cooling rate is slowed down, the rate of decrease in saturation solubility is slow, so that the growth of crystal particles becomes more dominant than the generation of crystal nuclei, and the particle size becomes large. For this reason, it is considered that the composite state can be controlled by controlling the cooling rate. In the present invention, the release agent is first precipitated by cooling. For example, when the cooling rate when the release agent is crystallized is increased, crystal nucleation of the release agent is promoted, and the release agent particles are The smaller the sum of the surface area of the release agent particles, the larger. Then, by slowing down the cooling rate from the crystallization start temperature of the crystalline resin, the crystalline resin grows from the existing release agent particles rather than generating crystal nuclei alone. The degree of compounding of the crystalline resin can be increased. Further, for example, when the cooling rate when the release agent is crystallized is decreased, the release agent particles are large and the total surface area of the release agent particles is small. After that, if the cooling rate is increased from the crystallization start temperature of the crystalline resin, the release agent particles as the starting point are few and the rate of decrease in saturation solubility is fast, so the crystalline resin tends to generate crystal nuclei alone. . Therefore, as a result, it is considered that the release agent and the crystalline resin exist separately from each other, and the degree of the composite is reduced.
In the present invention, the preferred temperature control range is 10 ° C./min to 30 ° C./min in the recrystallization process of the release agent, and 0.5 ° C./min to 10 ° C./min in the recrystallization process of the crystalline resin. It is preferable to cool at a rate of

<< 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 alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. There is no restriction | limiting in particular as said alcohol, According to the objective, it can select suitably, For example, methanol, isopropanol, ethylene glycol etc. are mentioned. There is no restriction | limiting in particular as said lower ketone, According to the objective, it can select suitably, For example, acetone, methyl ethyl ketone, etc. are mentioned.

<< Preparation of oil phase >>
Preparation of the oil phase containing the toner material includes at least the amorphous polyester resin A for toner, the crystalline polyester resin, and the release agent, and if necessary, the amorphous polyester resin B. The toner material containing the reactive precursor (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.
The organic solvent having a boiling point of less than 150 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is more preferable.

<< Emulsification or dispersion >>
The emulsification or dispersion of the toner material can be performed by dispersing the oil phase containing the toner material in the aqueous medium. Then, when the toner material is emulsified or dispersed, the amorphous polyester resin B is generated by extending and / or crosslinking the curing agent and the non-linear reactive precursor.
The amorphous polyester resin B 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 polyester resin B by subjecting the resin to an elongation 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 polyester resin B 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 polyester resin B 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 cross-linking reaction from the particle interface, the amorphous polyester resin B is preferentially formed on the surface of the toner to be generated, A concentration gradient of the amorphous polyester resin B can be provided in the toner.
The reaction conditions (reaction time, reaction temperature) for producing the amorphous polyester resin B are not particularly limited, and depending on the combination of the curing agent and the non-linear reactive precursor, It can be selected appropriately.
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 >>
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature of the entire reaction system is gradually raised, Examples include a method of evaporating the organic solvent, and a method of removing the organic solvent in the oil droplets by spraying the dispersion into 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.
The method for applying the mechanical impact force is not particularly limited and can be appropriately selected depending on the purpose. For example, a method for applying the impact force to the mixture using blades rotating at high speed, For example, a method may be used in which the mixture is charged and accelerated to cause the particles or particles to collide with an appropriate collision plate.
The apparatus used in the above method is not particularly limited and can be appropriately selected depending on the purpose. 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 forming an image by attaching the toner containing unit of the present invention to an image forming apparatus, it is possible to perform image formation utilizing the characteristics of the toner excellent in heat storage stability and mechanical strength without impairing low-temperature fixability. it can.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, and a developing unit, and further includes other units as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic 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 member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier imagewise.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. After the surface of the electrostatic latent image carrier is charged, the imagewise exposure can be performed, and the electrostatic latent image forming unit can be used.

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

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

<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. 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 every time the toner is transferred to the toner image, or may be performed simultaneously at the same time in a state where the toners of the respective colors are stacked.

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 100 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. The image forming apparatus shown in FIG. 2 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. 2. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. In the vicinity of the tandem developing device 120, an exposure device 21 as the exposure member is disposed. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. In the vicinity of the secondary transfer device 22, a fixing device 25 as the fixing means is arranged. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .
Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven. Then, the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.
Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Forming means). In each image forming unit, black, yellow, magenta, and cyan toner images are formed. In other words, 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 image carrier 10 ( Electrostatic latent image carrier for black 10K, electrostatic latent image carrier for yellow 10Y, electrostatic latent image carrier for magenta 10M, electrostatic latent image carrier for cyan 10C), and electrostatic latent image carrier 10 is a charging device 160 that uniformly charges 10 and the electrostatic latent image carrier is exposed like an image corresponding to each color image based on each color image information. An exposure apparatus for forming an electrostatic latent image corresponding to each color image, and developing the electrostatic latent image with each color toner (black toner, yellow toner, magenta toner, and cyan toner). A developing device 61 which is the developing means for forming a toner image by, and a transfer charger 62 for transferring the toner image on the intermediate transfer member 50, a cleaning device 63, and a discharger 64. 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 feeding 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 sheet 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. Is done.

Examples of the present invention will be described below, but the present invention is not limited to the following examples. “%” Represents “% by mass”, and “part” represents “part by mass” unless otherwise specified.
Each measured value in the following examples was measured by the method described above. In addition, Tg, Tm, and molecular weight, such as an amorphous resin and crystalline polyester resin, were measured from each resin obtained by the manufacture example.

(Production of amorphous polyester resin A for toner (first amorphous polyester resin A))
<Synthesis of First Amorphous Polyester Resin A-1>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was added to a bisphenol A ethylene oxide 2 mol adduct (BisA-EO), a bisphenol A propylene oxide 3 mol adduct (BisA-PO), Trimethylolpropane (TMP), terephthalic acid, and adipic acid are mixed in a molar ratio (bisphenol A ethylene oxide 2 mol), bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, and trimethylolpropane. Adduct / bisphenol A propylene oxide 3 mol adduct / trimethylolpropane), 38.6 / 57.9 / 3.5, and terephthalic acid and adipic acid are 85 in terms of molar ratio (terephthalic acid / adipic acid). / 15, and a hydroxyl group and a carboxyl group OH / COOH which is a molar ratio of 1.12 was charged and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230 ° C. for 8 hours at normal pressure, and further at a reduced pressure of 10 mmHg to 15 mmHg. After the reaction for 4 hours, trimellitic anhydride was added to the reaction vessel at 1 mol% with respect to the total resin components, and the reaction was performed at 180 ° C. and normal pressure for 3 hours. [First Amorphous Polyester Resin A-1] Got. The physical property values are shown in Table 1 below.

<Synthesis of First Amorphous Polyester Resin A-2>
The same as the synthesis of [First Amorphous Polyester Resin A-1] except that the acid component, alcohol component, OH / COO ratio, branch component type, and branch component amount were changed as shown in Table 1 below. Thus, [first amorphous polyester resin A-2] was obtained. The physical property values are shown in Table 1 below.
In Table 1, the amount of the branched component is the mol% of the trihydric or higher aliphatic alcohol relative to the alcohol component. In Table 1, “BisA-EO” represents a bisphenol A ethylene oxide 2-mol adduct. “BisA-PO” represents a bisphenol A propylene oxide 3 molar adduct.

(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.

(Production of prepolymer B)
<Synthesis of Nonlinear Amorphous Polyester Resin B-1 (Prepolymer B-1) Having Reactive Group>
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-15 mmHg for 5 hours, and [intermediate polyester B-1] was obtained.
Next, in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, [middle ratio of intermediate polyester B-1] and isophorone diisocyanate (IPDI) (IPDI isocyanate group / hydroxyl group of intermediate polyester) 2.1, and diluted with ethyl acetate to a 48% ethyl acetate solution, and then reacted at 100 ° C. for 5 hours to produce a non-linear amorphous polyester resin B-1 [pre-polymer having a reactive group. Polymer B-1] was obtained. 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 polyester resin C)
<Synthesis of Crystalline Polyester Resin C-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 ethylene glycol were added, and the molar ratio of hydroxyl group to carboxyl group was OH / COOH of 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 C-1]. The physical property values are shown in Table 2 below.

<Synthesis of crystalline polyester resins C-2 to C-3>
[Crystalline polyester resins C-2 to C-3] In the same manner as the synthesis of [Crystalline polyester resin C-1], except that the acid component, alcohol component, and OH / COO ratio were changed as shown in Table 2. ] Was obtained. Table 2 shows the physical property values.

(Manufacture of amorphous hybrid resin)
<Synthesis of amorphous hybrid resin>
To a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 7.2 g of 2,3-butanediol, 6.08 g of 1,2-propanediol, 18.59 g of terephthalic acid, After adding 0.18 g of tin (II) 2-ethylhexanoate and introducing nitrogen gas into the container to maintain the temperature in an inert atmosphere, the temperature was raised at 180 ° C. for 1 hour, and then from 180 ° C. to 230 ° C. to 10 ° C. The temperature was raised at / hr, and then a condensation polymerization reaction was carried out at 230 ° C. for 10 hours, followed by further reaction at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 160 ° C., 0.6 g of acrylic acid, 7.79 g of styrene, 1.48 g of 2-ethylhexyl acrylate, and dibutyl peroxide were added dropwise over 1 hour with a dropping funnel. After the dropwise addition, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C., and the temperature was raised to 210 ° C. Then, 4.61 g of trimellitic anhydride was added, and the reaction was performed at 210 ° C. for 2 hours. The reaction was carried out at 210 ° C. and 10 kPa until a desired softening point was reached to obtain an amorphous hybrid resin.
The amorphous hybrid resin had a weight average molecular weight of 55,000, a number average molecular weight of 2,800, a Tg of 55 ° C., and an acid value of 9.4 mgKOH / g.

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

<Preparation of Dispersion Liquid 1 of Compound Particles of Crystalline Polyester / Releasing Agent>
190 parts of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., crystallization start temperature 63 ° C.) as a release agent 1 in a container in which a stir bar and a thermometer are set, Polyester C-1] (319 parts) and ethyl acetate (3,190 parts) were charged, the temperature was raised to 80 ° C. with stirring, and maintained for 30 minutes to prepare a solution. Thereafter, cooling is performed at a cooling rate of 30 ° C./min (hereinafter referred to as “cooling rate 1”) from the crystallization start temperature of the release agent, and a cooling rate of 0. 0 from the crystallization start temperature of [crystalline polyester C-1]. It was cooled to 18 ° C. at 5 ° C./min (hereinafter referred to as “cooling rate 2”). Then, using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, 80% by volume of 0.5 mm zirconia beads were filled and dispersed [dispersion of composite particles Liquid 1] was obtained. [Composite Particle Dispersion 1] was measured with LA-920 (manufactured by HORIBA), and the volume average particle size of the composite particles was 0.54 μm.

<Preparation of oil phase>
[Composite Particle Dispersion 1] 962 parts, [Amorphous Polyester Resin A-1] 647 parts, [Masterbatch 1] 100 parts are put in a container and 7,000 rpm with a TK homomixer (manufactured by Tokushu Kika). The mixture was mixed for 60 minutes 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% aqueous solution of ammonium persulfate was added, and the mixture was aged at 75 ° C. for 5 hours. Dispersion 1] was obtained.
When [Fine Particle Dispersion 1] was measured by 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].

<Washing and drying>
[Dispersion Slurry 1] After 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 [Toner 1] obtained are shown in Table 3-1. In addition, the composition ratios and physical properties of the toners obtained in the following Examples and Comparative Examples are shown in Tables 3-1 to 3-3.
In Tables 3-1 to 3-3, “Constitution ratio (mass%)” is a prepolymer B which is a reactive precursor of the first amorphous polyester resin A and the second amorphous polyester resin B. , The composition ratio (% by mass) with respect to the total amount of the crystalline polyester resin C, the amorphous hybrid resin, the release agent, and the colorant.

<Evaluation>
A developer was prepared for the obtained toner by the following method, and the following evaluation was performed. The results are shown in Table 3-1.

<< Developer >>
-Production 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 fluidized bed type coating apparatus, 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 way in the following Examples and Comparative Examples, Developer 2 to Developer 11 corresponding to Toners 2 to 8 in Examples 2 to 8 and Toners 9 to 11 in Comparative Examples 1 to 3, respectively, are obtained. )

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

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

<< 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: The amount of toner on the wire mesh is 0 mg.
○: The amount of toner on the wire mesh is more than 0 mg and less than 2 mg.
Δ: The amount of toner on the wire mesh is 2 mg or more and less than 50 mg.
X: The amount of toner on the wire mesh is 50 mg or more.

<< Transfer White >>>
Developer No. 1 was mounted on Imagio MP C2802 (manufactured by Ricoh Co., Ltd.), and A4 images with an image area ratio of 5% were continuously printed on 10,000 sheets. 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 charging >>
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, ferrite particles (manufactured by Ricoh Co., Ltd.) having an average particle diameter of 35 μm were used as the carrier.
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) 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

(Example 2)
[Toner 2] was obtained in the same manner as in Example 1 except that [Cooling rate 1] was 20 ° C./min and [Cooling rate 2] was 2 ° C./min. The composition ratio and physical properties of [Toner 2] obtained are shown in Table 3-1.
In the same manner as in Example 1, a developer 2 corresponding to the toner 2 was produced, and the same evaluation as in Example 1 was performed. The results are shown in Table 3-1.

(Example 3)
[Toner 3] was obtained in the same manner as in Example 1 except that [Cooling rate 1] was 1 ° C./min and [Cooling rate 2] was 10 ° C./min. The composition ratio and physical properties of the obtained [Toner 3] are shown in Table 3-1.
In the same manner as in Example 1, a developer 3 corresponding to the toner 3 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3-1.

Example 4
[Toner 4] was obtained in the same manner as in Example 1, except that [Crystalline Resin C-1] was changed to [Crystalline Resin C-3]. The composition ratio and physical properties of [Toner 4] obtained are shown in Table 3-1.
In the same manner as in Example 1, a developer 4 corresponding to the toner 4 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3-1.

(Example 5)
In Example 1, [Amorphous Hybrid Resin] was used, and the amount of each material was adjusted to become a toner having the composition ratio shown in Table 3-2, to obtain [Toner 5]. The composition ratio and physical properties of [Toner 5] obtained are shown in Table 3-2.
In the same manner as in Example 1, a developer 5 corresponding to the toner 5 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3-2.

(Example 6)
[Toner 6] was obtained in the same manner as in Example 1, except that [Crystalline Resin C-1] was changed to [Crystalline Resin C-2]. The composition ratio and physical properties of [Toner 6] obtained are shown in Table 3-2.
In the same manner as in Example 1, a developer 6 corresponding to the toner 6 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3-2.

(Example 7)
In Example 1, [Toner 7] having a cooling rate and charging formulation as shown in Table 3-2 is obtained.
In the <Preparation of oil phase> step, [Prepolymer B-1] is further added to [Dispersion 1 of composite particles], [Amorphous polyester resin A-1], and [Masterbatch 1], and these are mixed. An amount of ketimine corresponding to an NCO value of 102% with respect to the NCO value of the prepolymer was added to the resulting oil phase, and the prepolymer B was elongated by a urethanization reaction to obtain [Toner 7].
The composition ratio and physical properties of [Toner 7] obtained are shown in Table 3-2.
In the same manner as in Example 1, a developer 7 corresponding to the toner 7 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3-2.
Further, the obtained [Toner 7] had a THF-insoluble content of 6.7% by mass. Moreover, as a result of the analysis of the structural component by NMR measurement of THF-insoluble matter, it contains 96.9 mol% of 3-methyl-1,5-pentanediol and 3.1 mol% of trimethylolpropane as alcohol components. It was confirmed.

(Example 8)
In Example 7, the prescription for preparation was as shown in Table 3-2 to obtain [Toner 8]. The composition ratio and physical properties of [Toner 8] obtained are shown in Table 3-2.
In the same manner as in Example 1, a developer 8 corresponding to the toner 8 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3-2.
Further, the obtained [Toner 8] had a THF-insoluble content of 6.5% by mass. Moreover, as a result of analysis of the structural component by NMR measurement of THF-insoluble matter, the alcohol component contains 97.0 mol% 3-methyl-1,5-pentanediol and 3.0 mol% trimethylolpropane. It was confirmed.

(Comparative Example 1)
<Preparation of WAX dispersion>
In a container equipped with a stir bar and a thermometer, 300 parts of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C.), 150 parts of [WAX dispersant], and acetic acid 1,800 parts of ethyl was charged, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, cooled to 30 ° C. in 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), Dispersion was carried out under the conditions of a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, a zirconia bead of 0.5 mm in diameter and 80% by volume filled in 3 passes to obtain [WAX Dispersion 1].

<Preparation of crystalline polyester resin dispersion>
A container equipped with a stir bar and a thermometer was charged with 308 parts of crystalline polyester resin C-1 and 1,900 parts of ethyl acetate, heated 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, using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), with a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 3 passes. Dispersion was performed under the conditions of [Crystalline Polyester Resin Dispersion 1].

<Preparation of oil phase>
[WAX Dispersion 1] 373 parts, [Crystalline Polyester Resin Dispersion 1] 592 parts, [Amorphous Polyester Resin A-1] 647 parts, [Masterbatch 1] 100 parts are put in a container, and TK homomixer ( (Made by Special Machine) for 60 minutes at 7,000 rpm to obtain [Oil Phase 9].
After the oil phase adjustment step, [Toner 9] was obtained in the same manner as Example 1. Table 3-3 shows the composition ratio and physical properties of the obtained [Toner 9].
In the same manner as in Example 1, a developer 9 corresponding to the toner 9 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3-3.

(Comparative Example 2)
In [Comparative Example 1], [Amorphous Hybrid Resin] was used, and [Toner 10] was prepared in the same manner as in Comparative Example 1, except that the amount of each material was changed to a charge amount that would result in a toner having a composition ratio shown in Table 3-3. Obtained. The composition ratio and physical properties of [Toner 10] obtained are shown in Table 3-3.
In the same manner as in Example 1, a developer 10 corresponding to the toner 10 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3-3.

(Comparative Example 3)
In Comparative Example 2, [Crystalline Polyester Resin C-1] was changed to [Crystalline Polyester Resin C-2], and Prepolymer B and Ketimine were reacted in the same manner as in Example 7 to make amorphous polyester resin B [Toner 11] was obtained in the same manner as in Comparative Example 2 except that. The composition ratio and physical properties of the obtained [Toner 11] are shown in Table 3-3.
In the same manner as in Example 1, a developer 11 corresponding to the toner 11 was produced and evaluated in the same manner as in Example 1. The results are shown in Table 3-3.

  From the above results, the image forming apparatus using the toner of the present invention exhibits stable charging characteristics and image characteristics due to excellent heat-resistant storage stability and mechanical strength without impairing low-temperature fixability. I was able to confirm.

Aspects of the present invention are as follows, for example.
<1> A toner comprising at least an amorphous resin, a crystalline resin, and a release agent, wherein the crystalline resin is dispersed in the amorphous resin,
When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the circumference of the crystalline resin is A, and the crystalline resin of the circumference A of the crystalline resin is an amorphous resin. The toner is characterized in that the ratio of the length of B to the length of A (B / A) satisfies B / A <0.8, where B is the length of the contacting portion. .
<2> The toner according to <1>, wherein a crystallization temperature of the release agent is 20 ° C. or more higher than a crystallization temperature of the crystalline resin.
<3> When the cut surface of the toner is observed with a transmission electron microscope (TEM), the length of the periphery of the toner is C, and the portion of the periphery of the toner where the crystalline resin is exposed is C. When the length is D, the ratio of the length of D to the length of C (D / C) satisfies any of <1> to <2> that satisfies 0.05 <D / C <0.4 The toner according to claim 1.
<4> The toner according to any one of <1> to <3>, wherein the B / A is 0.5 <B / A <0.6.
<5> The toner according to any one of <1> to <4>, wherein an SP value of the amorphous resin is SP1 and an SP value of the crystalline resin is SP2.
0.5 <SP1-SP2 <1.1
<6> The toner contains an amorphous hybrid resin,
<1> wherein the amorphous hybrid resin is composed of a composite resin including a condensation polymerization resin unit and a styrene resin unit, and the condensation resin unit and the styrene resin unit are partially chemically bonded. To <5>.
<7> The component insoluble in THF of the toner contains 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.
The toner according to any one of <1> to <6>, wherein the glass transition temperature (Tg1st) of the first temperature increase in differential scanning calorimetry (DSC) of the toner is 20 ° C. or higher and 50 ° C. or lower.
<8> A toner storage unit that stores the toner according to any one of <1> to <7>.
<9> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier. Developing means comprising toner for developing the image to form a visible image;
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <7>.
<10> A method for producing a toner comprising at least an amorphous resin, a crystalline resin, and a release agent, wherein the crystalline resin is dispersed in the amorphous resin,
The crystallization temperature of the release agent is 20 ° C. or more higher than the crystallization temperature of the crystalline resin;
The solution obtained by heating and dissolving the crystalline resin and the release agent in an organic solvent is cooled to recrystallize the crystalline resin and the release agent, so that the crystalline resin and the release agent are A method for producing toner, comprising a step of preparing a dispersion of partially integrated composite particles.

  The toner according to any one of <1> to <7>, the toner storage unit according to <8>, the image forming apparatus according to <9>, the method for producing the toner according to <10>, According to the present invention, the above-described problems can be solved and the object of the present invention can be achieved.

Japanese Patent Laid-Open No. 11-13366 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 (10)

A toner comprising at least an amorphous resin, a crystalline resin, and a release agent, wherein the crystalline resin is dispersed in the amorphous resin;
When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the circumference of the crystalline resin is A, and the crystalline resin of the circumference A of the crystalline resin is an amorphous resin. A toner in which the ratio of the length of B to the length of A (B / A) satisfies B / A <0.8, where B is the length of the contacting portion.   The toner according to claim 1, wherein a crystallization temperature of the release agent is 20 ° C. or more higher than a crystallization temperature of the crystalline resin.   When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the perimeter of the toner is C, and the length of the portion of the perimeter of the toner where the crystalline resin is exposed is C. 3. The toner according to claim 1, wherein a ratio of the length of D to the length of C (D / C) satisfies 0.05 <D / C <0.4.   The toner according to claim 1, wherein the B / A is 0.5 <B / A <0.6. The toner according to claim 1, wherein an SP value of the amorphous resin is SP1 and an SP value of the crystalline resin is SP2, satisfying the following formula.
0.5 <SP1-SP2 <1.1 The toner contains an amorphous hybrid resin;
2. The amorphous hybrid resin is composed of a composite resin including a condensation polymerization resin unit and a styrene resin unit, and the condensation resin unit and the styrene resin unit are partially chemically bonded. The toner according to any one of 5. The component insoluble in THF of the toner contains 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,
The toner according to any one of claims 1 to 6, wherein a first glass transition temperature (Tg1st) of temperature rise in differential scanning calorimetry (DSC) of the toner is 20 ° C or higher and 50 ° C or lower.   A toner storage unit containing the toner according to claim 1. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image formed on the electrostatic latent image carrier And a developing means comprising toner for forming a visible image,
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1. A method for producing a toner comprising at least an amorphous resin, a crystalline resin, and a release agent, wherein the crystalline resin is dispersed in the amorphous resin,
The crystallization temperature of the release agent is 20 ° C. or more higher than the crystallization temperature of the crystalline resin;
The solution obtained by heating and dissolving the crystalline resin and the release agent in an organic solvent is cooled to recrystallize the crystalline resin and the release agent, so that the crystalline resin and the release agent are A method for producing a toner, comprising a step of preparing a dispersion of partially integrated composite particles.