JP6962010B2 - Toner, toner accommodating unit, image forming apparatus, and toner manufacturing method - Google Patents

Description

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

In recent years, toner has withstood small particle size for high quality output images, high temperature offset resistance, low temperature fixability for energy saving, and high temperature and high humidity during storage and transportation after manufacturing. Heat-resistant storage stability is required. In particular, since the power consumption at the time of fixing occupies most of the power consumption in the image forming process, it is very important to improve the low temperature fixing property.
Conventionally, toner produced by the kneading and pulverizing method has been used. Toner produced by the kneading and crushing method has difficulty in reducing the particle size, and has an irregular shape and a broad particle size distribution, so that the quality of the output image is not sufficient and the fixing energy is high. There was a problem such as. In addition, when wax (release agent) is added to improve fixability, the toner produced by the kneading and crushing method cracks at the interface of the wax during crushing, so that a large amount of wax is present on the toner surface. Resulting in. Therefore, while the mold release effect is obtained, toner adhesion (filming) to the carrier, the photoconductor and the blade is likely to occur, and there is a problem that the overall performance is not satisfactory.
Therefore, in order to overcome the above-mentioned problems by the kneading and pulverizing method, a method for producing toner 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 encapsulated. .. As a method for producing toner by a polymerization method, a method for producing toner from an elongation reaction product of urethane-modified polyester as a toner binder is disclosed for the purpose of improving low-temperature fixability and high-temperature offset resistance. (See, for example, Patent Document 1).
Further, there is disclosed a method for producing a toner which is excellent in powder fluidity and transferability when a small particle size toner is used, and is also excellent in heat storage property, 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 (see, for example, 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 resin containing a crystalline polyester resin and a mold release agent, in which the resin and the wax are incompatible with each other and having a sea-island-like phase separation structure has been proposed. (See, for example, Patent Document 6).
Further, toners containing a crystalline polyester resin, a mold release agent and a graft polymer have been proposed (see, for example, Patent Document 7).

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

The means for solving the above-mentioned problems are as follows. That is,
The toner of the present invention is a toner containing at least an amorphous resin, a crystalline resin, and a mold 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 peripheral length of the crystalline resin is A, and the crystalline resin is an amorphous resin among the peripheral lengths A of the crystalline resin. When the length of the contacted portion is B, the ratio (B / A) of the length of B to the length of A is characterized in that B / A <0.8 is satisfied.

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

FIG. 1 is a schematic configuration diagram showing an example of the 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 cross-sectional view of the toner showing an example of a cross section of the toner of the present invention.

The techniques described in Patent Documents 6 and 7 can be fixed at a low temperature 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 lowered 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-like phase-separated structure, for example. When a strong stress is applied to the toner in the developer of a high-speed machine, the chargeability of the toner decreases over time due to aggregation of toners, burial of external additives, carrier contamination, etc., and filming to the photoconductor occurs. There was a problem that it became an abnormal image. Therefore, it does not satisfy the high level of low temperature fixability and image quality that have been further increased in recent years.
Therefore, the present inventors have conducted research in order to provide a toner that satisfies higher heat-resistant storage stability and mechanical strength without impairing low-temperature fixability. As a result, the toner of the present invention shown below is heat-resistant storage. It was found that the properties and mechanical strength are improved.

(toner)
The toner of the present invention contains at least an amorphous resin, a crystalline resin, and a mold 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 peripheral length of the crystalline resin is A, and the crystalline resin is an amorphous resin among the peripheral lengths A of the crystalline 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.
When the B / A is 0.8 or more, the crystalline resin and the amorphous resin are partially compatible with each other at the contact point, and the mechanical strength is lowered, so that, for example, in a high-speed machine. Strong stress is applied to the toner in the developing device, and due to aggregation of the toner, burial of the external additive, carrier contamination, etc., the charging ability of the toner decreases over time, and filming to the photoconductor occurs, resulting in an abnormal image. ..
In order to keep 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 and partially integrated. It is preferable to form a compounded state. Then, when forming a state in which the crystalline resin is dispersed in the amorphous resin, the amorphous resin, the crystalline resin, and the mold release agent are not simply mixed, but the crystalline resin and the mold release agent are used. Is formed first, and the crystalline resin in the compounded state with the mold release agent is mixed with the amorphous resin to form the crystalline resin in the composite state with the mold release agent in an amorphous state. It is preferable to disperse it in the quality resin. The method for producing the toner of the present invention will be described in detail below.

<Observation of toner with a transmission electron microscope (TEM)>
When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the peripheral length of the crystalline resin is A, and the crystalline resin is an amorphous resin among the peripheral lengths A of the crystalline 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) must 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 peripheral length of the toner is C, and the length of the peripheral length C of the toner where the crystalline resin is exposed. When the value is D, it is preferable that the ratio (D / C) of the length of D to the length of C satisfies 0.05 <D / C <0.4.
If the D / C is larger than 0.05, the decrease in melt viscosity due to the crystalline resin on the toner surface becomes insufficient during fixing heating, the adhesion to a recording medium such as paper becomes insufficient, and the low temperature fixability deteriorates. It is possible to effectively prevent the problem of having. 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 the mechanical strength of the toner surface is lowered, so that toner agglomerates are generated in the developer. , The problem that an abnormal image may occur can be effectively prevented.

<< Observation method with transmission electron microscope (TEM) >>
The split cross section of the toner is ruthenium-stained, and the cross-section of the ruthenium-stained toner is observed by TEM. The obtained image is analyzed to obtain the above A, B, C, and D, and the ratio of the crystalline resin and the amorphous resin in contact (B / A) and the surface of the crystalline resin are exposed. Calculate the ratio (D / C).
Ruthenium staining of toner can be carried out by a usual method, and specifically, for example, it can be measured by the following method. Toner or toner particles are embedded in epoxy resin and sectioned to a thickness of 100 nm by a microtome. This toner cross section is observed with a scanning electron microscope (TEM) to confirm the structure in which the crystalline resin is in contact with the release agent. A 0.5% aqueous solution of ruthenium tetroxide is used for dyeing. As shown in FIG. 3, the crystalline resin and the mold release agent are determined from the contrast and shape in the toner. In FIG. 3, reference numeral a is a mold release agent, reference numeral b is a crystalline resin, and reference numeral c is an amorphous resin. It can be determined that the rod-shaped or linear white contrast portion is a mold release agent, and the rod-shaped or linearly dyed most intensely is a crystalline resin.
The image analysis software used "Image J" to perform the following image analysis.
Of the peripheral length A of the crystalline resin, the peripheral length B in which the crystalline resin and the amorphous resin are in contact, the peripheral length C of the toner, and the peripheral length C of the toner, the crystalline resin is exposed. The length D of the portion is specified on the cross-sectional image of the toner, B / B and D / C are calculated from the total value of each, and the average value of 50 toners is calculated.

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

<< 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 of reacting an alcohol component containing a trivalent or higher fatty alcohol with a carboxylic acid component 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 trihydric or higher alcohols.
The alcohol component may contain a trivalent or higher aliphatic alcohol.
Examples of the divalent alcohol include an aliphatic diol, a diol having an oxyalkylene group, an alicyclic diol, an alicyclic diol to which an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) is added, and bisphenols. , Alkylene oxide adducts of bisphenols and the like.
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, polytetramethylene glycol and the like.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol S and the like.
Examples of the alkylene oxide adduct of the bisphenols include bisphenols to which an alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide is added.
Examples of the trihydric or higher alcohol include the trivalent or higher aliphatic alcohol.
Examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and dipentaerythritol.
As the trihydric or higher aliphatic alcohol, a trivalent to tetravalent aliphatic alcohol is preferable.

<<< Carboxylic acid component >>>
Examples of the carboxylic acid component include a divalent carboxylic acid and a trivalent or higher carboxylic acid. Further, these anhydrides may be used, lower (1 to 3 carbon atoms) alkyl esterified products may be used, or halides 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.
The aromatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.
Examples of the trivalent or higher carboxylic acid include trimellitic acid and pyromellitic acid.
These carboxylic acid components may be used alone or in combination of two or more.

The content of the amorphous polyester resin A for toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 parts by mass to 95 parts by mass with respect to 100 parts by mass of the 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, as a second amorphous resin component different from the amorphous polyester resin A for toner, amorphous 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 depending on the intended purpose.
The amorphous polyester resin B contains, for example, a diol component or a diol component and a cross-linking component as its constituent components, and more preferably contains 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 a trivalent or higher alcohol, and contains a trivalent or higher aliphatic alcohol. It is particularly preferable to do so.
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 being more excellent in adhesiveness to a recording medium such as paper. .. Further, when the amorphous polyester resin B has either a urethane bond or a urea bond, the urethane bond or the urea bond behaves like a pseudo-branch point, and the amorphous polyester resin B is rubber-like. The properties become stronger, and the heat-resistant storage resistance and high-temperature offset resistance of the toner are more excellent.

<<< Reactive precursor >>>
The amorphous polyester resin B is preferably obtained by the reaction of the reactive precursor and the 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, may be referred to as “prepolymer”), and is appropriately selected depending on the intended purpose. be able to.
Examples of the group that can react with the curing agent in the prepolymer include a group that can react 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-linearity means having a branched structure imparted by at least one of a trihydric or higher alcohol and a trivalent or higher carboxylic acid.
As the prepolymer, a polyester resin containing an isocyanate group is preferable.

-Polyester resin containing isocyanate group-
The polyester resin containing an isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a reaction product of a polyester resin having an active hydrogen group and polyisocyanate. The polyester resin having an active hydrogen group can be obtained, for example, by polycondensing a diol component, a dicarboxylic acid component, and at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid. The trihydric or higher valent alcohol and the trivalent or higher carboxylic acid impart a branched structure to the polyester resin containing an isocyanate group.

--Glycol component ---
Examples of the diol component include an aliphatic diol, a diol having an oxyalkylene group, an alicyclic diol, an alicyclic diol to which an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) is added, bisphenols, and bisphenol. Examples include alkylene oxide adducts of the same kind.
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, polytetramethylene glycol and the like.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol S and the like.
Examples of the alkylene oxide adduct of the bisphenols include bisphenols to which an alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide is added.

--Dicarboxylic acid component ---
Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Further, these anhydrides may be used, lower (1 to 3 carbon atoms) alkyl esterified products may be used, or halides 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.
The aromatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.

--- Alcohol with valence or higher ---
Examples of the trihydric or higher alcohol include the trivalent or higher aliphatic alcohol.
Examples of the trihydric or higher valent alcohol include trihydric to tetravalent alcohols.
As the trihydric or higher aliphatic alcohol, a trivalent to tetravalent aliphatic alcohol is preferable in that it improves low temperature fixability, high temperature and high humidity storage resistance, and stress resistance.
The trihydric 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 with valence or higher ---
Examples of the trivalent or higher valent 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, while having high thermal deformability of the resin in the fixing temperature range, rubber elasticity can be exhibited, and the low temperature fixing property and blocking resistance of the toner are more excellent.
Further, among the trivalent to tetravalent carboxylic acid or the trivalent to tetravalent alcohol, the trivalent to tetravalent aliphatic alcohol is preferable in that the low temperature fixability is more excellent.

--Polyisocyanate ---
The polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diisocyanate and trivalent or higher valent isocyanate.
Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aromatic aliphatic diisocyanates, isocyanurates, and those obtained by blocking these with phenol derivatives, oximes, caprolactam 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'-diisocyanate. Examples thereof include diphenyl, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 4,4'-diisocyanato-3-methyldiphenylmethane, 4,4'-diisocyanato-diphenyl ether and the like.
The aromatic aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α, α, α'and α'-tetramethylxylylene diisocyanate.
The isocyanurates are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tris (isocyanatoalkyl) isocyanurate and tris (isocyanatocycloalkyl) isocyanurate.
These polyisocyanates may be used alone or in combination of two or more.

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

-Active hydrogen group-containing compound-
The active hydrogen group in the active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, and a mercapto group. And so on. These may be used alone or in combination of two or more.
The active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose, but amines are preferable in that a urea bond can be formed.
The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those in which these amino groups are blocked. Can be mentioned. These may be used alone or in combination of two or more.
Among these, a mixture of diamine or diamine and a small amount of trivalent or higher valence amine is preferable.
The diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatic diamines, alicyclic diamines and aliphatic diamines. The aromatic diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenylenediamine, diethyltoluenediamine, and 4,4'-diaminodiphenylmethane. 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. Be done. The aliphatic diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylenediamine, tetramethylenediamine and hexamethylenediamine.
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.
The amino group blocked is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it can be obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Examples thereof include ketimine compounds and oxazoline compounds.

The molecular structure of the amorphous polyester resin B can be confirmed by NMR measurement using a solution or a solid, X-ray diffraction, GC / MS, LC / MS, IR measurement, or the like. A simple method is to detect as an amorphous polyester resin in the infrared absorption spectrum that 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 do not have absorption based on δCH (out-of-plane angular vibration) of the olefin. ..
The content of the prepolymer, which is a reactive precursor of the amorphous polyester resin B, is not particularly limited and may be appropriately selected depending on the intended purpose, but is 5% by mass with respect to 100 parts by mass of the toner. Parts to 25 parts by mass are preferable, and 7 to 12 parts by mass are more preferable. When the content is 5 parts by mass or more, it is possible to prevent deterioration of low temperature fixability and high temperature offset resistance, and when it is 25 parts by mass or less, deterioration of heat storage property and an image obtained after fixing are obtained. It is possible to prevent the problem that the glossiness of the image is lowered. When the content is within the more preferable range, it is advantageous in that it is excellent in all of low temperature fixing property, 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 containing a polypolymer 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. As a result, the crystalline resin (particularly the crystalline polyester resin) can be uniformly finely dispersed inside the toner, and the filming of the crystalline resin (particularly the crystalline polyester resin) and the release agent is prevented. However, the stress resistance can be improved and the low temperature fixability of the toner can be achieved.
The styrene-based resin unit contained in the amorphous hybrid resin is preferably made of a styrene-acrylic resin. By containing the styrene-acrylic resin, the affinity with other amorphous resins is increased, the dispersion effect on the crystalline resin (particularly crystalline polyester resin) is improved, and the crystalline resin (particularly crystalline polyester) is improved. Resin) is likely to be finely dispersed inside the toner.
The amorphous hybrid resin is obtained as a mixture of raw material monomers of two polymerization-based resins having independent reaction pathways for each of the condensed resin unit and the styrene-based resin unit, and further as one of the raw material monomers. It is preferably produced by mixing a monomer that can react with any of the raw material monomers of the polymerization resin (both reactive monomers).
The bireactive monomer contains 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, and an ethylenically unsaturated bond in the molecule. It is preferable that the monomer has the above, and by using such a bireactive monomer, the dispersibility of the resin serving as the dispersed phase can be improved. Specific examples of the bireactive monomer include acrylic acid, fumaric acid, methacrylic acid, citraconic acid, maleic acid and the like, and among these, acrylic acid, methacrylic acid and fumaric acid are preferable.
The amount of the bireactive monomer used is preferably 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of the raw material monomer of the polycondensation resin unit. In the present invention, the bireactive monomer is treated as a monomer different from the raw material monomer of the polycondensation resin unit and the raw material monomer of the addition polymerization resin unit because of the specificity of its performance.
In the present invention, when the amorphous hybrid resin is obtained by carrying out the polymerization reaction of the two polymerization-based resins using the above-mentioned raw material monomer mixture and bireactive monomer, the progress of the polymerization reaction and the progress of the polymerization reaction The completion does not have to be simultaneous in time, and the reaction temperature and time may be appropriately selected according to each reaction mechanism, and the reaction may proceed and be completed.
For example, in the method for producing an amorphous hybrid resin, a raw material monomer of a polycondensation polymer unit, a raw material monomer of an addition polymerization resin unit, a bireactive monomer, a catalyst such as a polymerization initiator, etc. are mixed, and first, mainly An addition polymerization resin component having a functional group capable of a polycondensation reaction at 50 ° C. to 180 ° C. is obtained, and then the reaction temperature is raised to 190 to 270 ° C., and then the polycondensation system is mainly carried out by a polycondensation reaction. It is preferable to form the resin component.
The softening point of the amorphous hybrid resin is preferably 80 ° C. to 170 ° C., preferably 90 ° C. to 160 ° C., and more preferably 95 ° C. to 155 ° C.
The mass ratio of the crystalline resin (particularly crystalline polyester resin) to the amorphous hybrid resin is not particularly limited, but the ratio of the crystalline resin (particularly crystalline polyester resin) to the amorphous hybrid resin is It is preferably 50/100 to 200/100.
As the raw material monomer of the polycondensation resin unit, it is preferable that a succinic acid derivative is used as the carboxylic acid component.
As the 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, still more preferably 80% by mass or more in the raw material monomer of the styrene resin unit.
Examples of the raw material monomer of the styrene resin unit that can be used other than the styrene derivative include (meth) acrylic acid alkyl ester; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; and halovinyl such as vinyl chloride. Classes; vinyl esters such as vinyl acetate and vinyl propionate; esters of ethylenic monocarboxylic acids 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 vinylpyrrolidone.
Among these, (meth) acrylic acid alkyl ester is preferable 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. The carbon number of the alkyl ester refers to the number of carbon atoms derived from the alcohol component constituting the ester. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, 2-ethylhexyl. Examples thereof include (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, and (iso) stearyl (meth) acrylate.
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 resin unit from the viewpoint of low temperature fixability, storage stability and charge stability of the toner. It is preferable, and 20% by mass or less is more preferable.

<< Crystalline resin >>
In the present invention, the crystalline polyester resin may be contained as the crystalline resin.
Since the crystalline polyester resin has high crystallinity, it exhibits a thermal melting property showing a rapid decrease in viscosity 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 the crystallinity is good until immediately before the melting start temperature, and the crystalline polyester is at the melting start temperature. It causes a rapid decrease in viscosity (sharp melt property) due to melting of the resin. Along with the rapid decrease in viscosity due to melting, it is compatible with the amorphous polyester resin A for toner, and both are fixed by the rapid decrease in viscosity. From this, a toner having both good heat-resistant storage property and low-temperature fixability can be obtained. In addition, good results are also shown for the mold release width (difference between the lower limit temperature of fixing and the temperature at which the high temperature offset is generated).
The crystalline polyester resin is obtained by using a polyvalent 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 the crystalline polyester resin, as described above, a polyvalent 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 are used. Refers to what can be obtained. A modified polyester resin, for example, the prepolymer and a resin obtained by cross-linking and / or extending the prepolymer thereof does not belong to the crystalline polyester resin. Further, the crystalline polyester resin is a resin different from the amorphous polyester resin A for toner and the amorphous polyester resin B.

<<< Multivalent alcohol >>>
The polyhydric alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diols and alcohols having a trihydric value or higher.
Examples of the diol include saturated aliphatic diols. Examples of the saturated aliphatic diol include a linear saturated aliphatic diol and a branched saturated aliphatic diol. Among these, a linear saturated aliphatic diol is preferable, and a linear saturated fat having 2 or more and 12 or less carbon atoms is preferable. Group diols are more preferred. If the saturated aliphatic diol is a branched type, the crystallinity of the crystalline polyester resin may decrease, and the melting point may decrease. Further, if the saturated aliphatic diol has more than 12 carbon atoms, it becomes 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, and 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, and 1,10 are excellent in that the crystalline polyester resin has high crystallinity and sharp meltability. -Decandiol and 1,12-dodecanediol are preferable.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like.
These may be used alone or in combination of two or more.

<<< Polyvalent Carboxylic Acid >>>
The polyvalent carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a divalent carboxylic acid and a trivalent or higher carboxylic acid.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, speric acid, azelaic acid, sebacic acid, 1,9-nonandicarboxylic acid, 1,10-decandicarboxylic acid, and 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; further, these anhydrides and lower (1 to 3 carbon atoms) alkyl esters thereof are also mentioned.
Examples of the trivalent or higher valent carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid and the like, and anhydrides thereof and these. Low-grade (1 to 3 carbon atoms) alkyl esters and the like can be mentioned.
Further, the polyvalent carboxylic acid may include a dicarboxylic acid having a sulfonic acid group in addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid. Further, 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 alone or in combination of two or more.
The crystalline polyester resin is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 or more and 12 or less carbon atoms and a linear saturated aliphatic diol having 2 or more and 12 or less carbon atoms.
That is, it is preferable that the crystalline polyester resin has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 or more and 12 or less carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 or more and 12 or less carbon atoms. .. By doing so, the crystallinity is high and the sharp melt property is excellent, which is preferable in that excellent low temperature fixability can be exhibited.

The melting point of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C. or higher and 80 ° C. or lower. When the melting point is 60 ° C. or higher, the crystalline polyester resin is likely to melt at a low temperature, and it is possible to prevent the toner from deteriorating the heat-resistant storage stability. When the melting point is 80 ° C. or lower, the crystalline polyester resin is heated by heating during fixing. It is possible to effectively prevent the problem that the resin is not sufficiently 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 have excellent low-temperature fixability and many components have a low molecular weight. And the heat-resistant storage stability is reduced. From this point of view, the soluble content of orthodichlorobenzene in the crystalline polyester resin has 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 in GPC measurement. , Mw / Mn 1.0-10. If the molecular weight is 20,000 or more, the problem that the heat-resistant storage property and the high-temperature and high-humidity storage property are insufficient due to the residual oligomer can be effectively prevented, and if the molecular weight is 30,000 or less, the low-temperature fixability is impaired. Can be effectively prevented.
The acid value of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, in order to achieve the desired low temperature fixability from the viewpoint of affinity between the paper and the resin. 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 depending on the intended purpose. However, in order to achieve the desired temperature fixability and good charging characteristics, 0 mgKOH is used. / G to 50 mgKOH / g is preferable, and 5 mgKOH / g to 50 mgKOH / g is more preferable.
The molecular structure of the crystalline polyester resin can be confirmed by NMR measurement using a solution or a solid, X-ray diffraction, GC / MS, LC / MS, IR measurement, or the like. Conveniently the infrared absorption spectrum, and a method of detecting those with absorption based on 965 ± 10 cm ^-1 or 990 of olefins ± 10cm ^-1 δCH (out-of-plane bending vibration) as a crystalline polyester resin.
The content of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 parts by mass to 20 parts by mass with respect to 100 parts by mass of the toner. ~ 15 parts by mass is more preferable. When the content is 3 parts by mass or more, the problem that the low temperature fixability may be inferior due to insufficient sharp melt formation by the crystalline polyester resin can be effectively prevented, and when the content is 20 parts by mass or less, it is said. It is possible to effectively prevent the problems that the heat-resistant storage property is lowered and the image is likely to be fogged. When the content is within the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<< Release agent >>
The release agent is not particularly limited and may be appropriately selected from known ones.
Examples of the wax and wax release agents include vegetable waxes such as carnauba wax, cotton wax, wood wax and rice wax; animal waxes such as honey wax and lanolin; mineral waxes such as ozokelite and cercin; Examples include natural waxes such as petroleum waxes such as paraffin, microcrystallin and petrolatum;
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fisher Tropsch wax, polyethylene and polypropylene; synthetic waxes such as esters, ketones and ethers; and the like can be mentioned.
Further, fatty acid amide compounds such as 12-hydroxystearic amide, stearic acid amide, phthalic anhydride, and chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n, which are low molecular weight crystalline polymer resins. -A homopolymer or copolymer of a polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate); a crystalline polymer having a long alkyl group in the side chain, etc. may be used. good.
Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fisher Tropsch wax, polyethylene wax, and polypropylene wax are preferable.
The melting point of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C. or higher and 80 ° C. or lower. When the melting point is 60 ° C. or higher, the release agent tends to melt at a low temperature, and the problem of inferior heat-resistant storage stability can be effectively prevented. If the melting point is 80 ° C. or lower, even if the resin is melted and is in the fixing temperature range, the problem that the mold release agent is not sufficiently melted and a fixing offset may occur, resulting in image loss, is effective. Can be prevented.
The content of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 parts by mass to 10 parts by mass and 3 parts by mass to 100 parts by mass with respect to 100 parts by mass of the toner. 8 parts by mass is more preferable. When the content is 2 parts by mass or more, the problem that the high temperature offset resistance at the time of fixing and the low temperature fixing property may be inferior can be effectively prevented, and when the content is 10 parts by mass or less, the heat storage property is improved. It is possible to effectively prevent the problem that the image is 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 the image quality and the fixing stability.

<< Other ingredients >>
Examples of other components include colorants, charge control agents, external additives, fluidity improvers, cleanability improvers, magnetic materials, and the like.

<<< Colorant >>
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, carbon black, niglosin dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, etc. Yellow Iron Oxide, Yellow Clay, 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), Tartrajin Lake, Kinolin Yellow Lake, Anthracan Yellow BGL, Isoindrinon Yellow, Bengala, Lead Tan, Lead Zhu, Cadmium Red, Cadmium Mercuri Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resole Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Khanmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resole Rubin GX, Permanent Red F5R, Brilliant Carmin 6B, Pigment Scarlet 3B, Bordeaux 5B, Truisin Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bonmaroon Light, Bonmaroon Medium, Eosin Lake, Rhodamin Lake B, Rhodamin Lake Y, Alizarin Lake, Thio Indigo Red B, Thio Indigo Maroon, Oil Red, Kinakridon Red, Pyrazolon Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinon Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake , Peacock Blue Lake, Victoria Blue Lake, Metal-free Phtalocyanin Blue, Phtalussin Blue, Fast Sky Blue, Indan Slen Blue (RS, BC), Indigo, Ultramarine, Navy Blue, Anthracinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple , Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zink Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naftor Green B, Green Gold, Acid Green Lake, Malachitoguri Examples include Nrake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Oxide, and Lithopone.
The colorant can also be used as a masterbatch compounded with a resin. Examples of the resin to be kneaded together with the production of the master batch include the amorphous polyester resin A for toner, and a polymer of styrene such as polystyrene, polyp-chlorostyrene, polyvinyltoluene, or a substitute thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer , Styrene-butyl acrylate copolymer, octyl styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chlormethylmethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethylketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-inden copolymer, styrene-malein Styrene-based copolymers such as acid copolymers and styrene-maleic acid ester copolymers; polymethylmethacrylate, polybutylmethacrylate, polyvinyl chloride, polyvinylacetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, Examples thereof include polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used alone or in combination of two or more.
In the masterbatch, the resin for the masterbatch and the colorant can be mixed by applying a high shearing force and kneaded to obtain a masterbatch. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, the so-called flushing method, in which an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and water and an organic solvent component are removed is also a wet colorant. Since the cake can be used as it is, it does not need to be dried and is preferably used. A high shear dispersion device such as a three-roll mill is preferably used for mixing and kneading.
The content of the colorant is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 part by mass to 15 parts by mass and 3 parts by mass to 10 parts by mass with respect to 100 parts by mass of the toner. Parts by mass are more preferred.

<<< Charge control agent >>
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a niglosin dye, a triphenylmethane dye, a chromium-containing metal complex dye, a molybdic chelate pigment, a rhodamine dye, etc. Alkoxy-based amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds, tungsten alone or compounds, fluorine-based activators, salicylate metal salts, salicylic acid derivative metal salts, etc. Can be mentioned. Specifically, bontron 03 of niglosin-based dye, bontron P-51 of quaternary ammonium salt, bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid-based metal complex, E- of salicylic acid-based metal complex. 84, E-89 of phenolic condensate (above, manufactured by Orient Chemical Industry Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Industry Co., Ltd.), LRA- 901, LR-147 (manufactured by Nippon Carlit), a boron complex, copper phthalocyanine, perylene, quinacridone, azo pigments, and other high molecular weight compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. And so on.
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 part by mass to 10 parts by mass with respect to 100 parts by mass of the toner. More preferably, 2 parts by mass to 5 parts by mass. When the content is 10 parts by mass or less, the chargeability of the toner is too large, the effect of the main charge control agent is diminished, the electrostatic attraction with the developing roller is increased, and the fluidity of the developer is lowered. Further, it is possible to effectively prevent the problem that the image density may be lowered. These charge control agents can be melt-kneaded together with the masterbatch and the resin and then dissolved and dispersed. Of course, they may be added when directly dissolved and dispersed in an organic solvent, or they are immobilized after forming toner particles on the toner surface. You may let me.

<<< External additive >>
In addition to the oxide fine particles, inorganic fine particles and hydrophobized inorganic fine particles can be used in combination as the external additive, but the average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, and is preferably 5 nm to 70 nm. Inorganic fine particles are more preferable.
Further, it is preferable that the hydrophobized primary particles contain at least one kind of inorganic fine particles having an average particle size of 20 nm or less and at least one kind of inorganic fine particles having an average particle size of 30 nm or more.
In addition, the specific surface area by BET method ^is preferably 20m ² / g~500m 2 / g.
The external additive is not particularly limited and may be appropriately selected depending on the intended purpose. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (for example, zinc stearate, aluminum stearate, etc.), metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers and the like can be mentioned.
Suitable external additives include hydrophobicized 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.). Examples of titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), and the like. MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by TAYCA CORPORATION) and the like can be mentioned.
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, and TAF-. Examples thereof include 1500T (all manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (all manufactured by Tayca Corporation), and IT-S (manufactured by Ishihara Sangyo Co., Ltd.).
Hydrophobicized 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 treating with a silane coupling agent such as octyl remethoxysilane. Further, silicone oil-treated oxide fine particles and inorganic fine particles in which silicone oil is treated with heat to form inorganic fine particles, if necessary, are also suitable.
The average particle size of the primary particles of the inorganic fine particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100 nm or less, more preferably 3 nm or more and 70 nm or less. If it is smaller than this range, the inorganic fine particles are buried in the toner, and it is difficult for the function to be effectively exhibited. On the other hand, if it is larger than this range, the surface of the photoconductor is unevenly damaged, which is not preferable.
The content of the external additive is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the toner. More preferably, 3 parts by mass to 3 parts by mass.

<<< Liquidity improver >>>
The fluidity improver is not particularly limited as long as it can be surface-treated to increase hydrophobicity and prevent deterioration of fluidity 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 an alkyl fluoride group, an organic titanate-based coupling agent, an aluminum-based coupling agent, a silicone oil, a 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 property 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 photoconductor or the primary transfer medium, and may be appropriately selected depending on the intended purpose. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, and polymer fine particles produced by soap-free emulsion polymerization such as polymethylmethacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle size of 0.01 μm to 1 μm.

<<< Magnetic material >>>
The magnetic material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include iron powder, magnetite and ferrite. Among these, white ones are preferable in terms of color tone.
The melting point of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 60 ° C. or higher and 80 ° C. or lower.
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. Further, 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% or more and 10% or less of the components having a volume particle size of 2 μm or less.

<Toner characteristics>
The glass transition temperature (Tg1st (toner)) at the first temperature rise of the differential scanning calorimetry (DSC) of the toner is preferably 20 ° C. or higher and 50 ° C. or lower.
With conventional toner, when Tg is about 50 ° C. or lower, toner agglutination is likely to occur during toner transportation assuming summer or tropical regions, and due to temperature changes in the storage environment. As a result, solidification in the toner bottle and sticking of the toner in the developing machine occur. In addition, poor replenishment due to toner clogging in the toner bottle and image abnormality due to toner sticking in the developing machine are likely to occur.
The toner of the present invention has a lower Tg than the conventional toner. 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. can. In particular, when the amorphous resin (particularly the amorphous polyester resin B) is an amorphous polyester resin having a urethane bond or a urea bond having a high cohesive force, the effect of maintaining heat-resistant storage stability is more effective. It becomes noticeable.
When the [Tg1st (toner)] is 20 ° C. or higher, problems such as deterioration of heat-resistant storage property, blocking in the developing machine, and filming on the photoconductor can be prevented, and when the temperature is 50 ° C. or lower, , It is possible to prevent deterioration of low temperature fixability of toner.

The toner preferably contains a tetrahydrofuran (THF) insoluble component.
The THF insoluble component preferably contains the amorphous resin, particularly the amorphous polyester resin B. Moreover, it is preferable that the constituent component of the THF insoluble component contains a specific alcohol component constituting the amorphous resin. Specifically, the constituent component of the THF insoluble matter preferably contains a diol component containing 50 mol% or more of an aliphatic diol having 3 to 10 carbon atoms and a cross-linking component containing a trivalent or higher valent aliphatic alcohol. ..

<< Difference in SP value between amorphous resin and crystalline resin >>
When the SP value of the amorphous resin (solubility parameter (cal ^1/2 / cm ^3/2 )) 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 larger than 0.5, the phase mixture of the amorphous resin and the crystalline resin is mixed. By increasing the degree, it is possible to effectively prevent the problem that the crystallinity of the crystalline resin is lowered and the high temperature and high humidity storage property and the mechanical strength may be lowered.
Further, when the (SP1-SP2) is 1.1 or less, the crystalline resin in the toner is unevenly distributed near the surface of the toner due to the interaction of polarities, resulting in high temperature and high humidity storage and mechanical strength. The problem that it may decrease can be effectively prevented.

<<< SP value calculation method >>>
The solubility parameter (cal ^1/2 / cm ^3/2 ) is expressed by the square root of the evaporation energy per unit volume, and the formula dissolution parameter = (E / V) ^1/2 (in the formula, E is evaporation) by the Fedors method. The energy is [cal / mol], and V can be calculated using the ^{molar volume [cm 3 / mol]).}
At this time, assuming that the evaporation energy and the molar volume of the atomic group are Δei and Δvi, respectively, E and V are expressed by the formula E = ΣΔeiV = ΣΔvi (“Basic theory of adhesion” (written by Minoru Imoto, published by Polymers). See (Chapter 5), published by the Society).
It is assumed that the SP values shown in the table in the following examples do not include the terminal functional groups in the calculation.

<Calculation method and analysis method of various characteristics of toner and toner components>
The Tg, acid value, hydroxyl value, molecular weight, and melting point of the amorphous polyester resin A for toner, the amorphous polyester resin B, the amorphous hybrid resin, the crystalline polyester resin, and the release agent are Each may be measured for itself. Further, even if Tg, molecular weight, melting point, and mass ratio of constituent components are calculated by separating the actual toner by gel permeation chromatography (GPC) or the like and adopting the analysis method described later for each separated component. good.
Separation of each component by GPC can be performed by, for example, the following method.
In the GPC measurement using THF (tetrahydrofuran) as the mobile phase, the eluate is fractionated by a fraction collector or the like, and the fraction corresponding to the desired molecular weight portion of the total integral of the elution curve is collected.
After concentrating and drying the collected eluate with an evaporator or the like, the solid content is dissolved in a deuterated solvent such as deuterated chloroform or THF, ^{1 1} H-NMR measurement is performed, and the integral ratio of each element is used to determine the resin in the elution component. Calculate the constituent monomer ratio.
As another method, after concentrating the eluate, hydrolysis is performed with sodium hydroxide or the like, and the decomposition product is qualitatively quantitatively analyzed by high performance liquid chromatography (HPLC) or the like to calculate the constituent monomer ratio. However, in this case, ^{check the compatibility with the value obtained by 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 preferable.
The method for producing the toner forms toner matrix particles while producing the amorphous polyester resin B by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent. In that case, Tg or the like of the amorphous polyester resin B may be obtained by separating the toner from the actual toner by GPC or the like. Alternatively, separately, 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 or the like is obtained from the synthesized amorphous polyester resin B. You may measure.

<< Means for separating toner components >>
An example of a means for separating each component when analyzing the toner is shown in detail.
First, 1 g of toner is put into 100 mL of THF, and a solution in which soluble components are dissolved is obtained while stirring for 30 minutes under the condition of 25 ° C.
This is filtered through a membrane filter having a mesh size of 0.2 μm to obtain a THF-soluble component in the toner.
Next, this is dissolved in THF to prepare a sample for GPC measurement, and the sample is injected into the GPC used for measuring the molecular weight of each of the above-mentioned resins.
On the other hand, a fraction collector is placed at the eluate discharge port of the GPC, the eluate is separated at predetermined counts, and the eluate is dispensed every 5% in terms of area ratio from the start of elution of the elution curve (rising of the curve). To get.
Then, for each eluate, 30 mg of the sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution is filled in a glass tube for NMR measurement having a diameter of 5 mm, and a spectrum is obtained by performing 128 times of integration 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 obtained spectrum. It can be obtained from the integration ratio.
For example, the peaks are assigned as follows, and the component ratios of the constituent monomers are obtained from the respective integration ratios.
Peak attribution is, for example,
Around 8.25 ppm: Derived from the benzene ring of trimellitic acid (for one hydrogen),
Around 8.07 ppm to 8.10 ppm: Derived from the benzene ring of terephthalic acid (for 4 hydrogens),
Around 7.1 ppm to 7.25 ppm: Derived from the benzene ring of bisphenol A (for 4 hydrogens),
Around 6.8 ppm: Derived from the benzene ring of bisphenol A (for 4 hydrogens) and derived from the double bond of fumaric acid (for 2 hydrogens),
Around 5.2 ppm to 5.4 ppm: Derived from methine as a bisphenol A propylene oxide adduct (for one hydrogen),
Around 3.7 ppm to 4.7 ppm: Methylene-derived bisphenol A propylene oxide adduct (for 2 hydrogens) and methylene-derived bisphenol A ethylene oxide adduct (for 4 hydrogens),
Around 1.6ppm: Derived from the methyl group of bisphenol A (for 6 hydrogens),
Can be.
From these results, for example, the extract recovered in the fraction in which the amorphous polyester resin A for toner occupies 90% or more can be treated 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 treated as the amorphous polyester resin B. The extract recovered in the fraction in which the crystalline polyester resin occupies 90% or more can be treated as the crystalline polyester resin.

<< Measurement method of hydroxyl value and acid value >>
The hydroxyl value can be measured using a method according to JIS K0070-1966.
Specifically, first, 0.5 g of a sample is precisely weighed in a 100 mL volumetric flask, and 5 mL of an acetylation reagent is added thereto. Next, after heating in a hot bath at 100 ± 5 ° C. for 1 to 2 hours, the flask is taken out from the hot bath and allowed to cool. Further, water is added and shaken to decompose acetic anhydride. Next, in order to completely decompose acetic anhydride, the flask is heated again in a warm bath for 10 minutes or more to allow to cool, and then the walls of the flask are thoroughly washed with an organic solvent.
Furthermore, the hydroxyl value was measured at 23 ° C. using the potential difference automatic titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and the electrode DG113-SC (manufactured by METTLER TOLEDO), and the analysis software LabX Light Voltage 1.00 Analyze using .000.
A mixed solvent of 120 mL of toluene and 30 mL of ethanol is used for calibration of the device.
At this time, the measurement conditions are as follows.
〔Measurement condition〕
Stir
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
Titration Addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium control
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest 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 connections No
Assessment
Procedure Standard
Potential1 No
Potential2 No
Stop for regeneration No
The acid value can be measured using a method according to JIS K0070-1992.
Specifically, first, 0.5 g of a sample (0.3 g in terms of ethyl acetate-soluble content) is added to 120 mL of toluene, and the sample is dissolved by stirring at 23 ° C. for about 10 hours. Next, 30 mL of ethanol is added to prepare a sample solution. If the sample does not dissolve, use a solvent such as dioxane or tetrahydrofuran. Furthermore, the acid value was measured at 23 ° C. using the potential difference automatic titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and the electrode DG113-SC (manufactured by METTLER TOLEDO), and the analysis software LabX Light Version 1.00 Analyze using .000. A mixed solvent of 120 mL of toluene and 30 mL of ethanol is used for calibration of the device.
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, the acid value is titrated with a predetermined 0.1N potassium hydroxide / alcohol solution, and the acid value [mgKOH / g] = The acid value is calculated by titration [mL] x N x 56.1 [mg / mL] / sample [g] (where N is a factor of 0.1N 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 calorimetry) (“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 the target sample is placed in an aluminum sample container, the sample container is placed on a holder unit, and the sample container is set in an electric furnace. Then, in a nitrogen atmosphere, the mixture is heated from −80 ° C. to 150 ° C. at a heating rate of 10 ° C./min (first temperature rise). Then, it is cooled from 150 ° C. to −80 ° C. at a temperature lowering rate of 10 ° C./min, and further heated to 150 ° C. at a temperature rising rate of 10 ° C./min (second temperature rise). At each of the first temperature rise and the second temperature rise, 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 time of the first temperature rise can be selected by 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 time of the second temperature rise can be selected, and the glass transition temperature at the time of the second temperature rise of the target sample can be obtained.
Further, from the obtained DSC curve, the DSC curve at the time of the first temperature rise is selected by using the analysis program in the Q-200 system, and the heat absorption peak top temperature at the first temperature rise of the target sample is obtained as the melting point. Can be done. Similarly, the DSC curve at the time of the second temperature rise can be selected, and the endothermic peak top temperature at the second temperature rise of the target sample can be obtained as the melting point.
In the present specification, when toner is used as the target sample, the glass transition temperature at the time of the first temperature rise is Tg1st, and the glass transition temperature at the time of the second temperature rise is Tg2nd.
Further, in the present specification, the glass transition temperature and melting point of other components such as the amorphous polyester resin A, the amorphous polyester resin B, and the amorphous hybrid resin are the second times unless otherwise specified. Let the heat absorption peak top temperature and Tg at the time of temperature rise be the melting point and Tg of each target sample.

<< Measurement method of particle size distribution >>
For the volume average particle size (Dv), the number average particle size (Dn), and the ratio (Dv / Dn) of the toner, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter), etc. are used. Can be measured. In the present invention, Coulter Multisizer II was used. The measurement method will be described below.
First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) is added as a dispersant 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 the measurement sample is further added. The electrolytic aqueous solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are measured by the measuring device using a 100 μm aperture as an aperture. , Calculate the volume distribution and the number distribution. From the obtained distribution, the volume average particle size (Dv) and the number average particle size (Dn) of the toner can be obtained.
The channels are 2.00 μm or more and less than 2.52 μm; 2.52 μm or more and less than 3.17 μm; 3.17 μm or more and less than 4.00 μm; 4.00 μm or more and less than 5.04 μm; 5.04 μm or more and less than 6.35 μm; 6 .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; 20.20 μm or more and 25. Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 13 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 by, for example, the following method.
Gel permeation chromatography (GPC) measuring device: HLC-8220 GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-H 15cm triple (manufactured by Tosoh)
Temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Flow velocity: 0.35 mL / min
Sample: Inject 0.4 mL of 0.15 mass% sample Sample pretreatment: Dissolve the object to be measured in tetrahydrofuran THF (manufactured by Wako Pure Chemical Industries, Ltd. containing stabilizer) at 0.15 mass% and filter with 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 the calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number.
As a standard polystyrene sample for preparing a calibration curve, Showa Denko's Showdex STANDARD Stdd. 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.

<< Extraction method for THF insoluble and THF soluble >>
Extraction of the THF-insoluble component and the THF-soluble component of the toner can be performed by the following procedure. After mixing 1 g of toner and 100 g of THF, reflux is performed for 12 hours. Then, it is separated into an insoluble component (solid content) and a soluble component (liquid component).
After removing the solvent from the soluble content of THF, the solution is dried at 40 ° C. for 20 hours at normal pressure, and further dried at 23 ° C. for 20 hours under reduced pressure to obtain a THF-soluble component.
The solid content of the insoluble matter is dried at 40 ° C. for 20 hours at normal pressure, and further dried at 23 ° C. for 20 hours under reduced pressure to obtain a THF insoluble matter.

<Toner manufacturing method>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an oil phase containing the amorphous resin, the crystalline resin and the release agent is contained in an aqueous medium. A method of obtaining toner after granulation by dispersing in the above is mentioned as a preferable production method.
As such a production method, a known dissolution / suspension method can be used.
However, in order to obtain the toner specified in the present invention, the mixture of the solution in which the crystalline resin and the release agent are heated and dissolved in an organic solvent is cooled to obtain the crystalline resin and the release agent. It is preferable to have a step of recrystallizing to prepare a dispersion liquid of composite particles in which the crystalline resin and the release agent are partially integrated.
That is, one of the features of the method for producing a toner of the present invention is to have a step of producing a dispersion liquid of composite particles of a crystalline resin and a release agent.
The production of a dispersion liquid of composite particles of a crystalline resin and a mold release agent will be described in detail below.
Further, by the dissolution / suspension method described below, the amorphous polyester resin A for toner, the crystalline polyester resin, and the mold release agent are contained, and if necessary, the amorphous polyester resin B, the said. The toner of the present invention can be obtained by dispersing an oil phase containing an amorphous hybrid resin, the colorant and the like in an aqueous medium and granulating the mixture.
According to this method, as will be described later, the toner matrix particles are produced while producing the amorphous polyester resin B by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent. Can be formed.
Each step of this method, such as preparation of an aqueous medium, preparation of an oil phase containing a toner material, emulsification or dispersion of a toner material, and removal of an organic solvent, will be described in detail below.

<< Manufacturing method of dispersion of composite particles of crystalline resin and mold release agent >>
In the method for producing a toner of the present invention, the crystalline resin and the release agent are recrystallized by cooling a mixture of a solution obtained by heating and dissolving the crystalline resin and the release agent in an organic solvent during the toner production process. It has a step of producing a dispersion liquid of composite particles in which a crystalline resin and a release agent are composited by crystallization. At this time, the crystallization temperature of the release agent is set to be 20 ° C. or more higher than the crystallization temperature of the crystalline resin.
It is possible to recrystallize the solute by cooling the solution obtained by heating and dissolving the crystalline resin or the release agent in an organic solvent to prepare a fine particle dispersion of the crystalline resin or the release agent. At this time, the crystalline resin and the solution of the mold release agent are mixed and cooled, and the crystallization temperature of the mold release agent is 20 ° C. or more higher than the crystallization temperature of the crystalline resin, so that the product is separated in the cooling process. The mold agent starts recrystallization, and a part of the crystalline resin is recrystallized starting from the crystal of the mold release agent. This makes it possible to prepare a dispersion liquid of composite particles in which a part of the crystalline resin is compounded with a release agent. By introducing this into the toner, a mold release agent is placed between the amorphous resin and the crystalline resin, the contact area between the crystalline resin and the amorphous resin is reduced, and partial phase compatibility is suppressed. Is possible.

<< Organic solvent used, concentration >>
In the method for producing a toner of the present invention, the organic solvent used when producing a dispersion liquid is one that does not dissolve in a crystalline resin and a mold release agent at a low temperature, but can dissolve them by heating to form a uniform solution. If so, there is no particular limitation, and it can be appropriately selected according to the purpose. For example, toluene, ethyl acetate, methyl ethyl ketone and the like can be used alone or in combination of two.

<< Concentration, heating / cooling operation >>
Generally, the size of the particle size of crystals that recrystallize during the cooling process varies depending on the solid content concentration of the solution and the rate of cooling. In the present invention, since it is important to combine the crystalline resin and the release agent, it is preferable to control the concentration and temperature control of the solution within a certain range.
The solid content concentration of the solution is preferably 1% to 40%, preferably 5% to 20%. When the concentration is low, the recrystallized particles become smaller, but it is disadvantageous in terms of productivity and cost. On the other hand, when the concentration is high, the particle size of the particles becomes large, but the viscosity increases remarkably depending on the crystalline resin and the mold release agent used, and the handleability at the time of manufacturing may decrease. The ratio of the crystalline resin to the release agent in the solution is 50% by mass to 200% by mass, preferably 100% by mass to 120% by mass of the crystalline resin 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 when the toner is formed may be insufficient.
As a heating and cooling operation, first, a crystalline resin and a mold release agent are added to an organic solvent, and the mixture is stirred at a boiling point or lower of the organic solvent to be used for about 10 to 30 minutes to prepare a transparent homogeneous solution mixture. At this time, the crystalline resin and the release agent may be mixed in advance, or the dissolution liquids may be mixed after preparing the respective dissolution liquids.
Subsequently, the obtained mixed solution is cooled to recrystallize the crystalline resin and the release agent. The cooling rate is preferably 0.1 ° C./min to 40 ° C./min, more preferably 0.5 ° C./min to 30 ° C./min. Further, 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.
Further, in recrystallization, the crystallization temperature of the release agent is preferably 20 ° C. or higher higher than the crystallization temperature of the crystalline resin. This makes it possible to produce particles in which the release agent and the crystalline resin are appropriately composited.

<< Additional crushing process >>
In the present invention, the dispersion liquid of the fine particles obtained by recrystallization can be further pulverized by subjecting it to an additional pulverization treatment, if necessary. According to the present invention, since the crystalline resin and the mold release agent are sufficiently finely composited at the time of recrystallization, the crystalline resin and the mold release agent are composited even if additional pulverization treatment is performed. It is possible to keep. Amplification 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.
The crushing device is not particularly limited, and a commercially available crushing device can be mentioned. For example, a ball mill, a bead mill, a sand mill device and the like can be mentioned.

<< B / A control means >>
The B / A can be controlled by the cooling rate at the time of recrystallizing the solution of the crystalline resin and the release agent. In the present invention, the faster the cooling rate, the smaller the particle size of the obtained recrystallized particles. It is considered that this is because the rate of decrease in saturation solubility due to cooling is fast, and crystal nuclei are likely to be generated in order 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 dominant and the particle size becomes larger than the formation of crystal nuclei. For this reason, it is considered that the combined state can be controlled by controlling the cooling rate. In the present invention, the release agent is precipitated first by cooling. For example, when the cooling rate when the release agent crystallizes is increased, the formation of crystal nuclei of the release agent is promoted, and the release agent particles are formed. It is small and the total surface area of the release agent particles is large. After that, by slowing the cooling rate from the crystallization start temperature of the crystalline resin, the crystalline resin grows from the existing mold release agent particles as a starting point rather than forming crystal nuclei by itself. The degree of compounding of the crystalline resin can be increased. Further, for example, when the cooling rate when the release agent crystallizes is slowed down, 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 number of mold release agent particles as a starting point is small, and the rate of decrease in saturation solubility is fast, so that the crystalline resin can easily generate crystal nuclei by itself. .. Therefore, as a result, the release agent and the crystalline resin exist separately from each other, and it is considered that the degree of compounding thereof becomes small.
In the present invention, the preferable range of temperature control 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 the ratio of.

<< Preparation of aqueous medium (aqueous phase) >>
The water-based medium can be prepared, for example, by dispersing the resin particles in the water-based 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. ..
The aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include water, a solvent miscible with water, and a mixture thereof. These may be used alone or in combination of two or more. Of 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, lower ketones and the like. The alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, isopropanol and ethylene glycol. The lower ketones are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acetone and methyl ethyl ketone.

<< Preparation of oil phase >>
The oil phase containing the toner material contains 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. This can be done by dissolving or dispersing the toner material containing the reactive precursor (prepolymer), the curing agent, the coloring agent and the like in an organic solvent.
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose, but an organic solvent having a boiling point of less than 150 ° C. is preferable in that it can be easily removed.
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, trichlorethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. These may be used alone or in combination of two or more.
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 produced by causing the curing agent and the non-linear reactive precursor to undergo an elongation reaction and / or a cross-linking reaction.
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 are mixed in the aqueous medium. A method for producing the amorphous polyester resin B by causing an elongation reaction and / or a cross-linking reaction.
(2) The oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium to which the curing agent has been added in advance, and the curing agent and the non-linear reactive precursor are mixed in the aqueous medium. A method for producing the amorphous polyester resin B by subjecting the body to an elongation reaction and / or a cross-linking reaction.
(3) After the oil phase containing the non-linear reactive precursor is emulsified or dispersed 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 for producing the amorphous polyester resin B by causing an elongation reaction and / or a cross-linking reaction between the non-linear reactive precursor and the non-linear reactive precursor.
When the curing agent and the non-linear reactive precursor are subjected to an elongation reaction and / or a cross-linking reaction from the particle interface, the amorphous polyester resin B is preferentially formed on the surface of the produced toner. It is also possible to provide a concentration gradient of the amorphous polyester resin B in the toner.
The reaction conditions (reaction time, reaction temperature) for producing the amorphous polyester resin B are not particularly limited, and may vary depending on the combination of the curing agent and the non-linear reactive precursor. It can be selected as appropriate.
The reaction time is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.
The reaction temperature is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C.
The method for stably forming the dispersion liquid 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 a shearing force.
The disperser for the above-mentioned dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a low-speed shear type disperser, a high-speed shear type disperser, a friction type disperser, and a high-pressure jet type disperser. , Ultrasonic disperser and the like.
Among these, the high-speed shearing type disperser is preferable in that the particle size of the dispersion (oil droplet) can be controlled to 2 μm to 20 μm.
When the high-speed shearing disperser is used, conditions such as rotation speed, dispersion time, and dispersion temperature can be appropriately selected according to the purpose.
The number of rotations is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1,000 rpm to 30,000 rpm, more preferably 5,000 rpm to 20,000 rpm.
The dispersion time is not particularly limited and may be appropriately selected depending on the intended purpose, but in the case of the batch method, 0.1 minutes to 5 minutes is preferable.
The dispersion temperature is not particularly limited and may be appropriately selected depending on the intended purpose, but under pressure, 0 ° C. to 150 ° C. is preferable, and 40 ° C. to 98 ° C. is more preferable. In general, the higher the dispersion temperature, the easier the dispersion.
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. However, from 50 parts by mass to 100 parts by mass of the toner material. It is preferably 2,000 parts by mass, more preferably 100 parts by mass to 1,000 parts by mass.
When the amount of the aqueous medium used is 50 parts by mass or more, the problem that the dispersed state of the toner material is deteriorated and the toner base particles having a predetermined particle size cannot be obtained can be effectively prevented, and 2,000. When it is less than a part by mass, the production cost can be suppressed.
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, forming a desired shape, and sharpening the particle size distribution. ..
The dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, and polymer-based protective colloids.
These may be used alone or in combination of two or more.
Of these, surfactants are preferred.
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose.
For example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and the like can be used.
The anionic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylbenzene sulfonate, α-olefin sulfonate and phosphoric acid ester.
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 liquid 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 to be contained in the oil droplets. Examples thereof include a method of evaporating the organic solvent and a method of spraying the dispersion liquid in a dry atmosphere to remove the organic solvent in the oil droplets.
When the organic solvent is removed, toner matrix particles are formed. The toner matrix particles can be washed, dried, etc., and further classified. The classification may be performed by removing fine particle portions in a liquid by cyclone, decanter, centrifugation or the like, or the classification operation may be performed after drying.
The obtained toner matrix 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 being detached from the surface of the toner matrix particles.
The method of applying the mechanical impact force is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method of applying an impact force to a mixture using blades rotating at high speed, in a high-speed air flow. Examples thereof include a method in which the mixture is put into the water and accelerated to cause the particles to collide with each other or with an appropriate collision plate.
The apparatus used in the above method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples include a device that lowers the pressure, 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 carriers which are appropriately selected.
Therefore, it is possible to stably form a high-quality image with excellent transferability and chargeability. The developer may be a one-component developer or a two-component developer, but when used in a high-speed printer or the like corresponding to an improvement in information processing speed in recent years, the service life is long. A two-component developer is preferable because it improves.

<Career>
The carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but a carrier having a core material and a resin layer covering the core material is preferable.

(Toner storage unit)
The toner accommodating unit in the present invention means a unit accommodating toner in a unit having a function of accommodating toner. Here, examples of the toner storage unit include a toner storage container, a developing device, a process cartridge, and the like.
The toner containing container means a container containing toner.
A developer has a means for accommodating and developing toner.
The process cartridge is a cartridge in which at least an image carrier and a developing means are integrated, accommodates toner, and is detachable from an image forming apparatus. The process cartridge may further include at least one selected from charging means, exposing means, and cleaning means.
By mounting the toner accommodating unit of the present invention on an image forming apparatus to form an image, it is possible to form an image utilizing the characteristics of the toner having excellent heat-resistant storage stability and mechanical strength without impairing low-temperature fixability. can.

(Image forming device and image forming method)
The image forming apparatus of the present invention has at least an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further has other means, if 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 if necessary.
The image forming method can be suitably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming means, and the developing step is the developing means. The other steps can be more 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 can be appropriately selected from known materials. The material thereof is, for example, an inorganic photoconductor such as amorphous silicon or selenium. , Polysilane, organic photoconductors such as phthalopolymethine and the like. Among these, amorphous silicon is preferable from the viewpoint of long life.

<Electrostatic latent image forming means and electrostatic latent image forming process>
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 depending on the intended purpose. Examples thereof include a means having at least a charging member for charging the surface of the electrostatic latent image carrier and an exposure member for exposing the surface of the electrostatic latent image carrier in an image manner.
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 depending on the intended purpose. This can be done by charging the surface of the electrostatic latent image carrier and then exposing it to an image, and it can be done by using the electrostatic latent image forming means.

<< Charging member and charging >>
The charging member is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a contact charging device known per se including a conductive or semi-conductive roller, brush, film, rubber blade or the like. , Corotron, non-contact charger using corona discharge such as scorotron, and the like.
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 as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed to an image to be formed, and is appropriately selected depending on the intended purpose. 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.

<Development means and development process>
The developing means is not particularly limited as long as it is a developing means including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image, depending on the purpose. Can be selected as appropriate.
The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a visible image, depending on the purpose. It can be appropriately selected, for example, by the developing means.
The developing means may be a dry developing method or a wet developing method. Further, it may be a single color developing means or a multicolor developing means.
The developing means includes a stirrer for frictionally stirring and charging the toner, and a magnetic field generating means fixed inside, and a developer containing the toner is supported on the surface to support a rotatable developer. A developing device having a body is preferable.

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

<< Transfer means and transfer process >>
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected depending on the intended purpose. However, the visible image is transferred onto an intermediate transfer body and composited. It is preferable to have a primary transfer means for forming a transfer image and a secondary transfer means for transferring the composite transfer image onto a recording medium.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected depending on the intended purpose. It is preferable that the visual image is first-transferred and then the visible image is secondarily transferred onto the recording medium.

<< Fixing means and fixing process >>
The fixing means is not particularly limited as long as it is a means for fixing the transferred image transferred to the recording medium, and can be appropriately selected depending on the intended purpose, but a known heating and pressing member is preferable. Examples of the heating / pressurizing member include a combination of a heating roller and a pressurizing roller, a combination of a heating roller, a pressurizing 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 depending on the intended purpose. For example, the recording medium is used for toner of each color. It may be carried out every time the toner is transferred to the toner, or it may be carried out at the same time in a state where the toners of each color are laminated.

Next, one aspect of carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. The color image forming apparatus 100A shown in FIG. 1 includes a photoconductor drum 10 as the electrostatic latent image carrier (hereinafter, may be referred to as “photoreceptor 10”), a charging roller 20 as the charging means, and the above. It includes an exposure device 30 as an exposure means, a developer 40 as the developing means, an intermediate transfer body 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static eliminator lamp 70 as the static eliminating means. ..
The intermediate transfer body 50 is an endless belt, and is designed to be movable in the arrow direction by three rollers 51 arranged inside the intermediate transfer body 50 and tensioning the intermediate transfer body 50. A part of the three rollers 51 also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer body 50. A cleaning device 90 having a cleaning blade is arranged in the vicinity of the intermediate transfer body 50. Further, in the vicinity of the intermediate transfer body 50, a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) a developed image (toner image) to a transfer paper 95 as a recording medium is provided. , Facing the intermediate transfer member 50. Around the intermediate transfer body 50, a corona charger 58 for applying an electric charge to the toner image on the intermediate transfer body 50 is provided between the photoconductor 10 and the intermediate transfer body 50 in the rotation direction of the intermediate transfer body 50. It is arranged between the contact portion and the contact portion between the intermediate transfer body 50 and the transfer paper 95.
The developing device 40 is composed of a developing belt 41 as the developer carrier, a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C arranged around the developing belt 41. .. The black developing unit 45K includes a developing agent accommodating portion 42K, a developing agent supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developing agent accommodating portion 42Y, a developing agent supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developing agent accommodating portion 42M, a developing agent supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developing agent accommodating portion 42C, a developing agent supply roller 43C, and a developing roller 44C. Further, the developing belt 41 is an endless belt, which is rotatably stretched on a plurality of belt rollers, and a part of the developing belt 41 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 uniformly charges the photoconductor drum 10. The exposure apparatus 30 exposes the photoconductor drum 10 in an image-like manner to form an electrostatic latent image. The electrostatic latent image formed on the photoconductor drum 10 is developed by supplying toner from the developer 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer body 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 static elimination 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 transporting apparatus (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-shaped intermediate transfer body 50 at the center. The intermediate transfer body 50 is stretched on the support rollers 14, 15 and 16 so as to be rotatable clockwise in FIG. An intermediate transfer body cleaning device 17 for removing residual toner on the intermediate transfer body 50 is arranged in the vicinity of the support roller 15. A tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged side by side on the intermediate transfer body 50 stretched by the support roller 14 and the support roller 15 along the transport direction. The developer 120 is arranged. An exposure device 21 which is an exposure member is arranged in the vicinity of the tandem developer 120. The secondary transfer device 22 is arranged on the side of the intermediate transfer body 50 opposite to the side on which the tandem developer 120 is arranged. In the secondary transfer device 22, the secondary transfer belt 24, which is an endless belt, is stretched on 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. It is possible. The fixing device 25, which is the fixing means, is arranged in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 which is an endless belt, and a pressure roller 27 which is pressed and arranged by the fixing belt 26.
In the tandem image forming apparatus, a sheet inversion device 28 for inverting the transfer paper in order to form an image on both sides of the transfer paper is arranged in the vicinity of the secondary transfer apparatus 22 and the fixing apparatus 25. ..
Next, the formation of a full-color image (color copy) using the tandem developer 120 will be described. That is, first, the original is set on the platen 130 of the automatic document transfer device (ADF) 400, or the original is set on the contact glass 32 of the scanner 300 by opening the automatic document transfer device 400 and the automatic document transfer device. Close 400.
When the start switch (not shown) is pressed, when the original is set in the automatic document conveying device 400, the original is conveyed and moved onto the contact glass 32, and then the original 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, the first traveling body 33 irradiates the light from the light source, the reflected light from the document surface is reflected by the mirror in the second traveling body 34, and the light is received by the reading sensor 36 through the imaging lens 35 and is colored. The manuscript (color image) is read and used as image information of black, yellow, magenta, and cyan.
Then, each image information of black, yellow, magenta, and cyan is obtained by each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image) in the tandem type developer 120. It is transmitted to each of the forming means). Then, in each image forming means, black, yellow, magenta, and cyan toner images are formed. That is, each of the image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developer 120 is an electrostatic latent image carrier 10 (a). Black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C) and the electrostatic latent image carrier. The charging device 160, which is the charging means for uniformly charging 10, and the electrostatic latent image carrier are exposed to each color image-corresponding image based on each color image information, and the electrostatic latent image carrier is exposed on the electrostatic latent image carrier. An exposure device that forms an electrostatic latent image corresponding to each color image, and the electrostatic latent image is developed with each color toner (black toner, yellow toner, magenta toner, and cyan toner) to develop each color toner. It is provided with a developing device 61 which is the developing means for forming a toner image according to the above, a transfer charging device 62 for transferring the toner image onto the intermediate transfer body 50, a cleaning device 63, and a static eliminator 64. Then, each image forming means 18 can form each monochromatic 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 thus formed are placed on the intermediate transfer member 50, which is rotationally moved by the support rollers 14, 15, and 16, respectively, on the black electrostatic latent image carrier 10K. Black image formed on, yellow image formed on the electrostatic latent image carrier 10Y for yellow, magenta image formed on the 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 body 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, and a sheet (recording paper) is fed out from one of the paper feed cassettes 144 provided in the paper bank 143 in multiple stages. The sheets are separated one by one by the separation roller 145 and sent out to the paper feed path 146, are conveyed by the transfer roller 147, are guided to the paper feed path 148 in the copying machine main body 150, and are abutted against the resist roller 49 to be stopped. Be done. Alternatively, the paper feed roller 142 is rotated to feed out the sheet (recording paper) on the manual feed tray 54, the sheets are separated one by one by the separation roller 52, put into the manual paper feed path 53, and similarly abutted against the resist roller 49 to be stopped. .. Although the resist roller 49 is generally grounded and used, it may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the resist roller 49 is rotated in time with the composite color image (color transfer image) synthesized on the intermediate transfer body 50, and a sheet (recording paper) is placed between the intermediate transfer body 50 and the secondary transfer device 22. Is sent out, and the synthetic 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 body 50 after image transfer is cleaned by the intermediate transfer body cleaning device 17.
The sheet (recording paper) formed by transferring the color image is conveyed by the secondary transfer device 22 and sent to the fixing device 25, and in the fixing device 25, the composite color image (color) is generated by heat and pressure. The transferred image) is fixed on the sheet (recording paper). After that, the sheet (recording paper) is switched by the switching claw 55, discharged by the discharge roller 56, and stacked on the paper discharge tray 57. Alternatively, the sheet is switched by the switching claw 55, inverted by the sheet reversing device 28, guided to the transfer position again, and after recording an image on the back surface, is ejected by the ejection roller 56 and stacked on the paper ejection tray 57. Will be done.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples. “%” Represents “mass%” unless otherwise specified, and “parts” represents “parts by mass”.
Each measured value in the following examples was measured by the method described above. The Tg, Tm, and molecular weight of the amorphous resin, the crystalline polyester resin, and the like were measured from each resin obtained in the production example.

(Manufacture of Amorphous Polyester Resin A for Toner (First Amorphous Polyester Resin A))
<Synthesis of the first amorphous polyester resin A-1>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, a bisphenol A ethylene oxide 2 mol addition (BisA-EO), a bisphenol A propylene oxide 3 mol addition (BisA-PO), The molar ratio of trimethylolpropane (TMP), terephthalic acid, and adipic acid to 2 mol of bisphenol A ethylene oxide, 3 mol of bisphenol A propylene oxide, and trimethylolpropane to 2 mol of bisphenol A ethylene oxide. Additive / Bisphenol A propylene oxide 3 mol Additive / Trimethylol propane) is 38.6 / 57.9 / 3.5, and terephthalic acid and adipic acid are 85 in molar ratio (terephthalic acid / adipic acid). It is / 15, and OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is charged to be 1.12, and is charged with titanium tetraisopropoxide (500 ppm with respect to the resin component) at normal pressure at 230 ° C. for 8 hours. The reaction was further carried out under a reduced pressure of 10 mmHg to 15 mmHg for 4 hours, then trimellitic anhydride was added to a reaction vessel so as to be 1 mol% with respect to all the resin components, and the reaction was carried out at 180 ° C. and normal pressure for 3 hours. Amorphous polyester resin A-1] was obtained. The physical property values are shown in Table 1 below.

<Synthesis of the first amorphous polyester resin A-2>
Same as the synthesis of [1st amorphous polyester resin A-1] except that the acid component, alcohol component, OH / COO ratio, branched component species, and branched component amount were changed as shown in Table 1 below. [1st 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 molar% of the trivalent or higher aliphatic alcohol with respect to the alcohol component. In Table 1, "BisA-EO" represents a 2 mol adduct of bisphenol A ethylene oxide. "BisA-PO" represents a 3 mol adduct of bisphenol A propylene oxide.

(Synthesis of ketimin)
170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged in a reaction vessel in which a stirring rod and a thermometer were set, and the reaction was carried out at 50 ° C. for 5 hours to obtain [Ketimin compound 1].
The amine value of [Ketimin Compound 1] was 418.

(Manufacturing of prepolymer B)
<Synthesis of non-linear amorphous polyester resin B-1 (prepolymer B-1) having a reactive group>
97 mol% of 3-methyl-1,5-pentanediol as an alcohol component, 3 mol% of trimethylolpropane (TMP) as an acid component, and adipine as an acid component in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. The acid was 50 mol% and terephthalic acid was 50 mol%, and the mixture was added together with titanium tetraisopropoxide (300 ppm vs. resin component) so that the molar ratio of the hydroxyl group to the carboxyl group was OH / COOH = 1.1. .. Then, the temperature was raised to 200 ° C. in about 4 hours, then to 230 ° C. over 2 hours, and the reaction was carried out until the runoff water disappeared. Then, the reaction was further carried out under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate Polyester B-1].
Next, in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the molar ratio of [intermediate polyester B-1] and isophorone diisocyanate (IPDI) (isocyanate group of IPDI / hydroxyl group of intermediate polyester) It was added in 2.1, diluted with ethyl acetate to form a 48% ethyl acetate solution, and then reacted at 100 ° C. for 5 hours to form a non-linear amorphous polyester resin B-1 having a reactive group [pre]. 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.

(Manufacturing of crystalline polyester resin C)
<Synthesis of crystalline polyester resin C-1>
Sebacic acid and ethylene glycol were added to a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and OH / COOH, which is the molar ratio of hydroxyl groups to carboxyl groups, was 0.85. After reacting with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, the temperature was raised to 200 ° C. for 3 hours, and the pressure was further increased to 8.3 kPa. The reaction was carried out 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>
[Crystallinic polyester resins C-2 to C-3] were the same as the synthesis of [Crystallinic polyester resin C-1] except that the acid component, alcohol component, and OH / COO ratio were changed as shown in Table 2. ] Was obtained. The physical property values are shown in Table 2.

(Manufacturing of amorphous hybrid resin)
<Synthesis of amorphous hybrid resin>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple, 7.2 g of 2,3-butanediol, 6.08 g of 1,2-propanediol, 18.59 g of terephthalic acid, 0.18 g of tin (II) 2-ethylhexanoate was added, nitrogen gas was introduced into the container to maintain an inert atmosphere and the temperature was raised, and then the temperature was kept at 180 ° C. for 1 hour and then 10 ° C. from 180 ° C. to 230 ° C. The temperature was raised at / hr, then the polycondensation reaction was carried out at 230 ° C. for 10 hours, and the reaction was further carried out 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 using a dropping funnel over 1 hour. After the dropping, the addition polymerization reaction was aged for 1 hour while being held at 160 ° C., the temperature was raised to 210 ° C., 4.61 g of trimellitic anhydride was added, and the reaction was carried out 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 masterbatch (MB)>
1,200 parts of water, 500 parts of carbon black (Printex35, manufactured by Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], and 500 parts of [first amorphous polyester resin A-1]. In addition, the mixture was mixed with a Henschel mixer (manufactured by Nippon Coke Industries, Ltd.), the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a palpelizer to obtain [Masterbatch 1].

<Preparation of dispersion liquid 1 of composite particles of crystalline polyester and mold release agent>
190 parts of paraffin wax (manufactured by Nippon Seikan Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., crystallization start temperature 63 ° C.), [Crystalline] 319 parts of polyester C-1] and 3,190 parts of ethyl acetate were charged, the temperature was raised to 80 ° C. with stirring, and the mixture was held for 30 minutes to prepare a solution. After that, it is cooled 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 the cooling rate is 0. It was cooled to 18 ° C. at 5 ° C./min (hereinafter referred to as [cooling rate 2]). Then, using a bead mill (Ultra Viscomill, manufactured by Imex), 80% by volume of 0.5 mm zirconia beads were filled and dispersed at a liquid feeding speed of 1 kg / hr and a disk peripheral speed of 6 m / sec [dispersion of composite particles]. Liquid 1] was obtained. When [dispersion liquid 1 of composite particles 1] was measured with LA-920 (manufactured by HORIBA), the volume average particle diameter of the composite particles was 0.54 μm.

<Preparation of oil phase>
Put 962 parts of [Composite particle dispersion 1], 647 parts of [Amorphous polyester resin A-1], and 100 parts of [Masterbatch 1] in a container, and use a TK homomixer (manufactured by Special Machinery Co., Ltd.) at 7,000 rpm. Mixing for 60 minutes gave [Oil Phase 1].

<Synthesis of organic fine particle emulsion (fine particle dispersion)>
In a reaction vessel with a stirring rod and a thermometer set, 683 parts of water, 11 parts of sodium salt of ethylene methacrylate oxide sulfate (eleminol RS-30: manufactured by Sanyo Kasei Kogyo Co., Ltd.), 138 parts of styrene, 138 parts of methacrylic acid. , And 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The mixture was heated to a temperature inside the system of 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to form an aqueous dispersion of a vinyl resin (copolymer of a sodium salt of a styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate ester) [fine particles]. Dispersion 1] was obtained.
When [fine particle dispersion liquid 1] was measured with LA-920 (manufactured by HORIBA), the volume average particle size of the fine particles was 0.14 μm. A part of [fine particle dispersion liquid 1] was dried to isolate the resin component.

<Preparation of aqueous phase>
990 parts of water, 83 parts of [fine particle dispersion liquid 1], 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (eleminol MON-7: manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate are mixed and stirred to make a milky white color. Obtained the liquid. This was designated as [Aquatic phase 1].

<Emulsification / solvent removal>
1,700 parts of [Aqueous phase 1] was added to a container containing [Oil phase 1] and mixed with a TK homomixer at a rotation speed of 8,000 rpm for 20 minutes to obtain [Emulsified slurry 1].
[Emulsified slurry 1] was put into a container in which a stirrer and a thermometer were set, the solvent was removed at 30 ° C. for 8 hours, and then aged at 45 ° C. for 4 hours to obtain [dispersed slurry 1].

<Washing / drying>
[Dispersed Slurry 1] After 100 parts are filtered under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filtered cake, mixed with a TK homomixer (rotation speed 12,000 rpm for 10 minutes), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filtered cake of (1), mixed with a TK homomixer (rotation speed 12,000 rpm for 30 minutes), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filtered 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-exchanged water to the filtered cake of (3), mix with a TK homomixer (rotation speed 12,000 rpm for 10 minutes), and then filter.
The above 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 circulation dryer, and sieved with a mesh having a mesh size of 75 μm to obtain [Toner 1].

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

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

<< Developer >>
-Creation of carriers-
To 100 parts of toluene, 100 parts of silicone resin organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black are added, dispersed for 20 minutes with a homomixer, and coated with a resin layer. The solution was prepared. Using a fluidized bed coating device, the resin layer coating liquid was applied to the front surface of 1,000 parts of spherical magnetite having an average particle size of 50 μm to prepare a carrier.
-Preparation of developer-
Using a ball mill, 5 parts of the toner and 95 parts of the carrier were mixed to prepare a developer 1 corresponding to the toner 1 of the example. (Note that, in the following Examples and Comparative Examples, the developer 2 to 8 corresponding to the toners 2 to 8 in Examples 2 to 8 and the toners 9 to 11 in Comparative Examples 1 to 3, respectively, are obtained. rice field.)

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

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

<< High temperature and high humidity storage >>
After storing 5 g of toner in an environment of 40 ° C. and 70% for 2 weeks, the toner was sieved for 5 minutes with a mesh sieve having a mesh opening of 106 μm, the amount of toner on the wire mesh was measured, and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
⊚: 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 whiteout >>
Developer No. 1 was mounted on an Imagio MP C2802 (manufactured by Ricoh Co., Ltd.), and 10,000 A4 images having an image area ratio of 5% were printed continuously. 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 white spot images in the images was visually measured.
The following ranking was performed based on the total number of three white-out images.
[Rank]
⊚: Whiteout images cannot be visually recognized on all three images.
◯: The third white-out image can be confirmed by observing it with an optical microscope, but it is not at a level that poses a problem in practical use.
Δ: 1 to 10 whiteout images can be visually confirmed in total, which is a level that causes practical problems.
X: A total of 3 white-out images can be visually confirmed, which is a level that is seriously problematic in practical use.

<< Deteriorated charging >>
0.25 g of toner and 4.75 g of carriers were placed in a stainless steel container having a bottom diameter of 25 mm and a height of 30 mm, and a rotation of 300 rpm was given in the circumferential direction for 20 minutes to stir and bring the toner and carriers into contact with each other. Here, as the carrier, ferrite particles (manufactured by Ricoh Co., Ltd.) having an average particle size of 35 μm were used.
The charged amount (Q / S) per unit area of the stirred toner was measured by a blow-off method using a charge amount measuring device TB-200 (manufactured by Toshiba Corporation).
Specifically, the measurement sample is loaded into the sample portion equipped with the 400 mesh stainless steel screen of the charge amount measuring device, and the blow pressure is 50 kPa (0.5 kgf) in a normal temperature and humidity environment (20 ° C., 55% RH). The charge was measured by blowing nitrogen gas of / cm2) for 10 seconds.
〔Evaluation criteria〕
⊚: 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 ×: Absolute value of charge amount is 50 μC / m ² or more Transfer

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

(Example 3)
In Example 1, [Toner 3] was obtained in the same manner as in Example 1 except that [Cooling rate 1] was set to 1 ° C./min and [Cooling rate 2] was set to 10 ° C./min. The composition ratio and physical properties of the obtained [Toner 3] are shown in Table 3-1.
A developer 3 corresponding to the toner 3 was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. 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 [Crystallinity resin C-3] in Example 1. The composition ratio and physical properties of the obtained [toner 4] are shown in Table 3-1.
A developer 4 corresponding to the toner 4 was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 3-1.

(Example 5)
In Example 1, [amorphous hybrid resin] was used, and each material was charged in an amount to be a toner having a composition ratio shown in Table 3-2 to obtain [toner 5]. Table 3-2 shows the composition ratio and physical properties of the obtained [Toner 5].
A developer 5 corresponding to the toner 5 was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. 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 [Crystallinity resin C-2] in Example 1. Table 3-2 shows the composition ratio and physical properties of the obtained [toner 6].
A developer 6 corresponding to the toner 6 was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 3-2.

(Example 7)
In Example 1, a [toner 7] having a cooling rate and a prescription for preparation as shown in Table 3-2 is obtained.
In the <preparation of oil phase> step, [prepolymer B-1] is further added to [dispersion liquid 1 of composite particles], [amorphous polyester resin A-1], and [master batch 1], and these are mixed. An amount of ketimine corresponding to the NCO value of 102% with respect to the NCO value of the prepolymer was added to the oil phase, and the prepolymer B was extended by a urethanization reaction to obtain [Toner 7].
Table 3-2 shows the composition ratio and physical properties of the obtained [Toner 7].
A developer 7 corresponding to the toner 7 was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 3-2.
The THF insoluble content of the obtained [Toner 7] was 6.7% by mass. As a result of analysis of the constituent components by NMR measurement of the THF insoluble matter, 96.9 mol% of 3-methyl-1,5-pentanediol and 3.1 mol% of trimethylolpropane are contained as alcohol components. It was confirmed.

(Example 8)
In Example 7, [Toner 8] was obtained by formulating the preparation as shown in Table 3-2. Table 3-2 shows the composition ratio and physical properties of the obtained [Toner 8].
A developer 8 corresponding to the toner 8 was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 3-2.
The THF insoluble content of the obtained [Toner 8] was 6.5% by mass. As a result of analysis of the constituent components by NMR measurement of the THF insoluble matter, 97.0 mol% of 3-methyl-1,5-pentanediol and 3.0 mol% of trimethylolpropane are contained as alcohol components. It was confirmed.

(Comparative Example 1)
<Preparation of WAX dispersion liquid>
300 parts of paraffin wax (manufactured by Nippon Seiko Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C.), 150 parts of [WAX dispersant], and acetic acid in a container in which a stirring rod and a thermometer are set. 1,800 parts of ethyl was charged, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, then cooled to 30 ° C. in 1 hour, and a bead mill (Ultra Viscomill, manufactured by Imex) was used. Dispersion was carried out under the conditions of a liquid feeding rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, a diameter of 0.5 mm zirconia beads filled in 80% by volume, and 3 passes to obtain [WAX dispersion liquid 1].

<Preparation of crystalline polyester resin dispersion>
308 parts of crystalline polyester resin C-1 and 1,900 parts of ethyl acetate were charged in a container in which a stirring rod and a thermometer were set, the temperature was raised to 80 ° C. under stirring, and the temperature was maintained at 80 ° C. for 5 hours. Cool to 30 ° C. in 1 hour, and use a bead mill (Ultra Viscomill, manufactured by Imex) to fill 80% by volume of 0.5 mm zirconia beads at a liquid feeding rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 3 passes. [Crystalline polyester resin dispersion liquid 1] was obtained under the conditions of.

<Preparation of oil phase>
373 parts of [WAX dispersion liquid 1], 592 parts of [Crystalline polyester resin dispersion liquid 1], 647 parts of [Amorphous polyester resin A-1], and 100 parts of [Masterbatch 1] were put into a container, and a TK homomixer (TK homomixer) The mixture was mixed at 7,000 rpm for 60 minutes with a special machine) to obtain [oil phase 9].
After the oil phase adjusting step, [toner 9] was obtained in the same manner as in Example 1. The composition ratio and physical properties of the obtained [toner 9] are shown in Table 3-3.
A developer 9 corresponding to the toner 9 was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 3-3.

(Comparative Example 2)
In Comparative Example 1, [Toner 10] was used in the same manner as in Comparative Example 1 except that [Amorphous hybrid resin] was used and each material was charged with a composition ratio of toner in Table 3-3. Obtained. The composition ratio and physical properties of the obtained [toner 10] are shown in Table 3-3.
A developer 10 corresponding to the toner 10 was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. 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 the prepolymer B and ketimine were reacted in the same manner as in Example 7 to cause the 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.
A developer 11 corresponding to the toner 11 was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. 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 because it has excellent heat-resistant storage stability and mechanical strength without impairing low-temperature fixability. It was confirmed that

Aspects of the present invention are, for example, as follows.
<1> A toner containing at least an amorphous resin, a crystalline resin, and a mold release agent, in which 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 peripheral length of the crystalline resin is A, and the crystalline resin is an amorphous resin among the peripheral lengths A of the crystalline resin. When the length of the contacted portion is B, the ratio of the length of B to the length of A (B / A) is B / A <0.8. ..
<2> The toner according to <1>, wherein the crystallization temperature of the release agent is 20 ° C. or more higher than the crystallization temperature of the crystalline resin.
<3> When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the peripheral length of the toner is C, and the peripheral length C of the toner is the portion where the crystalline resin is exposed. When the length is D, any of the above <1> to <2> in which the ratio (D / C) of the length of D to the length of C satisfies 0.05 <D / C <0.4. It is the toner described in Crab.
<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>, which satisfies the following formula, where the SP value of the amorphous resin is SP1 and the SP value of the crystalline resin is SP2.
0.5 <SP1-SP2 <1.1
<6> The toner contains an amorphous hybrid resin, and the toner contains an amorphous hybrid resin.
The amorphous hybrid resin is made of a composite resin containing a polypolymerized resin unit and a styrene resin unit, and the condensation resin unit and the styrene resin unit are partially chemically bonded. <1> The toner according to any one of <5>.
<7> The constituent component of the THF insoluble component of the toner contains a diol component containing 50 mol% or more of an aliphatic diol having 3 to 10 carbon atoms and a cross-linking component containing a trivalent or higher valent aliphatic alcohol.
The toner according to any one of <1> to <6>, wherein the first glass transition temperature (Tg1st) of the differential scanning calorimetry (DSC) of the toner is 20 ° C. or higher and 50 ° C. or lower.
<8> The toner accommodating unit is characterized by accommodating the toner according to any one of <1> to <7>.
<9> An electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier. It has a developing means provided with toner that develops the image to form a visible image.
The image forming apparatus is characterized in that the toner is the toner according to any one of <1> to <7>.
<10> A method for producing a toner containing at least an amorphous resin, a crystalline resin, and a mold release agent, in which the crystalline resin is dispersed in the amorphous resin.
The crystallization temperature of the release agent is 20 ° C. or higher higher than the crystallization temperature of the crystalline resin.
The solution obtained by heating and dissolving the crystalline resin and the mold release agent in an organic solvent is cooled to recrystallize the crystalline resin and the mold release agent, and the crystalline resin and the mold release agent are formed. A method for producing a toner, which comprises a step of producing a partially integrated composite particle dispersion.

The toner according to any one of <1> to <7>, the toner accommodating unit according to <8>, the image forming apparatus according to <9>, and the toner manufacturing method according to <10>. According to the above, it is possible to solve the conventional problems and achieve the object of the present invention.

Japanese Unexamined Patent Publication No. 11-13366 JP-A-2002-287400 Japanese Unexamined Patent Publication No. 2002-351143 Japanese Patent No. 2579150 Japanese Unexamined Patent Publication No. 2001-158819 Japanese Unexamined Patent Publication No. 2004-46095 Japanese Unexamined Patent Publication No. 2007-271789

Claims (10)

A toner containing at least an amorphous polyester resin A, a crystalline resin, and a mold release agent, in which the crystalline resin is dispersed in the amorphous polyester resin A.
When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the peripheral length of the crystalline resin is A, and the crystalline resin is an amorphous polyester resin among the peripheral lengths A of the crystalline resin. When the length of the portion in contact with A is B, the ratio (B / A) of the length of B to the length of A satisfies B / A <0.8. .. The toner according to claim 1, wherein the crystallization temperature of the release agent is 20 ° C. or higher higher than the crystallization temperature of the crystalline resin. When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the peripheral length of the toner is C, and the length of the peripheral length C of the toner where the crystalline resin is exposed is determined. The toner according to any one of claims 1 to 2, wherein the ratio (D / C) of the length of D to the length of C satisfies 0.05 <D / C <0.4. The toner according to any one of claims 1 to 3, wherein the B / A is 0.5 <B / A <0.6. The toner according to any one of claims 1 to 4, wherein the SP value of the amorphous polyester resin A is SP1 and the SP value of the crystalline resin is SP2, which satisfies the following formula.
0.5 <SP1-SP2 <1.1 The toner further contains an amorphous hybrid resin,
From claim 1, the amorphous hybrid resin is made of a composite resin containing a polypolymerized 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 toner further contains a component of THF insoluble,
The THF-insoluble component of the toner contains a diol component containing 50 mol% or more of an aliphatic diol having 3 to 10 carbon atoms and a cross-linking component containing an aliphatic alcohol having a trivalent value or more.
The toner according to any one of claims 1 to 6, wherein the first glass transition temperature (Tg1st) of the differential scanning calorimetry (DSC) of the toner is 20 ° C. or higher and 50 ° C. or lower. A toner accommodating unit comprising accommodating the toner according to any one of claims 1 to 7. The electrostatic latent image carrier, the electrostatic latent image forming means for forming the electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier are developed. With a developing means provided with toner, which forms a visible image.
An image forming apparatus according to any one of claims 1 to 7, wherein the toner is the toner according to any one of claims 1 to 7. A method for producing a toner containing at least an amorphous polyester resin A, a crystalline resin, and a mold release agent, in which the crystalline resin is dispersed in the amorphous polyester resin A.
The content of the crystalline resin is 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the toner.
The content of the release agent is 2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner.
The crystallization temperature of the release agent is 20 ° C. or higher higher than the crystallization temperature of the crystalline resin.
When the fractured surface of the toner is observed with a transmission electron microscope (TEM), the peripheral length of the crystalline resin is A, and the crystalline resin is an amorphous polyester resin among the peripheral lengths A of the crystalline resin. When the length of the portion in contact with A is B, the ratio of the length of B to the length of A (B / A) satisfies B / A <0.8.
The solution obtained by heating and dissolving the crystalline resin and the mold release agent in an organic solvent is cooled to recrystallize the crystalline resin and the mold release agent, and the crystalline resin and the mold release agent are formed. A method for producing a toner, which comprises a step of producing a partially integrated dispersion of composite particles and mixing the dispersion of the composite particles with the amorphous polyester resin A.

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