JP2021148853A - Toner and two-component developer using the same, and image forming apparatus - Google Patents

Abstract

To provide a toner excellent in cleanability and conveyability of the toner.SOLUTION: A toner includes a toner base that contains at least a binder resin and a colorant and inorganic fine particles as an external additive, and the accelerated aggregation of the inorganic fine particles is 20% or more and 80% or less.SELECTED DRAWING: Figure 1

Description

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

Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus, etc., an electric latent image or a magnetic latent image is visualized by a toner for developing an electrostatic latent image (also referred to as “toner” in the present invention). For example, in the electrophotographic method, an electrostatic latent image is formed on a photoconductor, and then the electrostatic latent image is developed with toner to form a toner image. The toner image is usually transferred onto a recording medium such as paper and then fixed by a method such as heating.

In recent years, many toners have been proposed in the art for improving image quality. For example, Patent Document 1 describes a binder resin and a colorant for the purpose of improving image quality and image density uniformity. Disclosed is a toner having toner particles containing the above and organic-inorganic composite fine particles, specifying the degree of aggregation and rest angle of the organic-inorganic composite fine particles, and defining Total Energy in a powder fluidity measuring device in a specific range. ing.

However, the current situation is that the toners of the prior art still have problems in cleanability and toner transportability.

Therefore, an object of the present invention is to provide a toner having excellent cleanability and toner transportability.

The above problem is solved by the following configuration 1).
1) A toner containing at least a binder resin and a colorant, and inorganic fine particles as an external additive.
A toner characterized in that the accelerated cohesion of the inorganic fine particles is 20% or more and 80% or less.

According to the present invention, it is possible to provide a toner having excellent cleanability and toner transportability.

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

Hereinafter, embodiments of the present invention will be described in more detail.
The toner of the present invention contains at least a toner base containing a binder resin and a colorant and inorganic fine particles, and the accelerated cohesion of the inorganic fine particles is 20% or more and 80% or less.

The problem with conventional toner is that cleaning defects occur when the toner slips through the cleaning blade at the nip portion on the surface of the photoconductor. There is a concern that the risk of cleaning defects will further increase due to the ease with which the cleaning blade can slip through as the particle size decreases and the increase in non-electrostatic adhesive force due to the low fixing temperature.

Therefore, the present inventors have made extensive studies on the problem of cleaning defects caused by the toner slipping through the cleaning blade, and the problem is solved by using a toner externally supplemented with highly cohesive inorganic fine particles. I found out what I could do.

In the toner of the present invention, inorganic fine particles desorbed from the toner accumulate in the nip to form a dam-like structure, which blocks the toner to prevent the toner from slipping through the cleaning blade for cleaning. It is possible to improve the sex. By using the inorganic fine particles having high cohesiveness, the inorganic fine particles tend to collect in the nip, which is advantageous for cleaning property.

According to the present invention, the degree of accelerated cohesion of the inorganic fine particles needs to be 20% or more, and more preferably 30% or more, in order to sufficiently improve the cleaning property. In order to further improve the cleaning property, it is particularly preferable that the accelerated aggregation degree of the inorganic fine particles is 40% or more. When the degree of accelerated cohesion of the inorganic fine particles is less than 20%, it is difficult for the inorganic fine particles to accumulate in the nip and it is difficult to form a dam-like structure. .. If the degree of accelerated cohesion of the inorganic fine particles is high, the cohesiveness of the toner becomes high, and there is a concern that the transportability may be deteriorated. In order to ensure sufficient transportability, it is necessary that the degree of accelerated cohesion of the inorganic fine particles is 80% or less.

Hereinafter, the method for producing the toner of the present invention will be specifically described.
The present invention is not limited to the method for producing toner exemplified here.
In emulsification or dispersion, it is preferable to use a dispersant from the viewpoint of stabilizing oil droplets and sharpening the particle size distribution while obtaining a desired shape, if necessary. The dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a surfactant, a poorly water-soluble inorganic compound dispersant, a polymer-based protective colloid, or the like can be used. These may be used alone or in combination of two or more. Of these, surfactants are preferred. Further, after removing the organic solvent, inorganic fine particles are externally added in the step of externally mixing the additives.

[Raw material used for manufacturing the toner of the present invention]
The binder resin used in the method for producing the toner of the present invention is not particularly limited and preferably contains at least two or more kinds of resins, such as polyester resin, silicone resin, styrene / acrylic resin, styrene resin, and acrylic resin. Known binder resins such as epoxy resin, diene resin, phenol resin, terpen resin, coumarin resin, amidimide resin, butyral resin, urethane resin, and ethylene / vinyl acetate resin can be used.
Among these, as the resin used for producing the toner of the present invention, a polyester resin having sufficient flexibility even if the molecular weight is reduced is preferable because it can be sharp-melted at the time of fixing and the image surface can be smoothed. Other resins may be combined with the based resin.

<Polyester resin>
(Amorphous polyester resin A)
The amorphous polyester resin A preferably has a structure represented by any of the following structural formulas 1) to 3), and R2, which is a polyester or modified polyester portion, and R1 corresponding to a branched structure are urethane. Alternatively, it has a structure bonded by a urea group.
Structural formula 1) R1- (NHCONH-R2) n-
Structural formula 2) R1- (NHCOO-R2) n-
Structural formula 3) R1- (OCONH-R2) n-
(In the above formula, n = 3, R1 represents an isocyanurate skeleton, and R2 represents a group derived from either a polyester containing a polycarboxylic acid and a polyol, or a modified polyester in which the polyester is isocyanate-modified. .)

Since the amorphous polyester resin A has at least one of a urethane bond and a urea bond in the branched structure portion, the urethane bond or the urea bond behaves like a pseudo-crosslink point, and the amorphous polyester The rubber-like property of the resin A becomes stronger, and a toner having excellent heat-resistant storage resistance and high-temperature offset resistance can be produced.
The amorphous polyester resin A contains a diol component as a constituent component, and more preferably contains a dicarboxylic acid component as a constituent component.

The amorphous polyester resin A is not particularly limited as long as R2 corresponding to the polyester or modified polyester portion and R1 corresponding to the branched structure portion are bonded by a urethane or urea group, and is appropriately used depending on the intended purpose. You can choose.
The method for binding R1 and R2 is not limited to the following, but there are, for example, the following methods.

a) A method in which a diol component and a dicarboxylic acid component are ester-reacted to prepare a polyester polyol (R2) having a hydroxyl group at the end, and the obtained polyester polyol is reacted with isocyanurates (R1).
b) The diol component and the dicarboxylic acid component are ester-reacted to prepare a polyester polyol (R2) having a hydroxyl group at the end, and the obtained polyester polyol is reacted with a divalent polyisocyanate to obtain an isocyanate-modified polyester (R2). A method for reacting isocyanurates (R1) with the obtained isocyanate-modified polyester in the presence of pure water.
It is also possible to further react the hydroxyl group remaining in the polyol obtained by any of the above a) to b) with a polyisocyanate having a divalent value or higher to form a polyester prepolymer, which is then reacted with a curing agent in the toner production process. ..
During the toner production process, urethane and urea bonds are formed by reaction with a curing agent, and by exhibiting behavior like a strong cross-linking point, the rubber-like property of the amorphous polyester resin A is strengthened, and heat-resistant storage stability is enhanced. Since it is more excellent in high temperature offset resistance, it is more preferable to use a modified polyester resin in which the R2 portion is modified with isocyanate.

In order to lower the Tg of the amorphous polyester resin A and easily impart the property of deforming at a low temperature, the amorphous polyester resin A contains a diol component as a constituent component, and the diol component has a carbon number of carbon atoms. It preferably contains an aliphatic diol of 3 or more and 12 or less, and more preferably contains an aliphatic diol having 4 or more and 12 or less carbon atoms.

The amorphous polyester resin A preferably contains 50 mol% or more of the aliphatic diol having 3 to 12 carbon atoms, more preferably 80 mol% or more, and further preferably 90 mol% or more.

Examples of the aliphatic diol having 3 to 12 carbon atoms include 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, and 3-methyl. Examples thereof include -1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol.

In particular, in the amorphous polyester resin A, the diol component is an aliphatic diol having 4 or more and 12 or less carbon atoms, and the carbon number of the portion serving as the main chain of the diol component is an odd number, and the diol component However, it is more preferable that the side chain has an alkyl group.
Examples of the aliphatic diol having an odd number of carbon atoms in the main chain portion and having an alkyl group in the side chain and having 4 to 12 carbon atoms include an aliphatic diol represented by the following general formula (1).
HO- (CR1R2) n-OH ... General formula (1)
However, in the general formula (1), R1 and R2 independently represent a hydrogen atom and an alkyl group having 1 to 3 carbon atoms. n represents an odd number of 3-9. In n repeating units, R1 may be the same or different. Further, in the n repeating units, R2 may be the same or different.

Further, in order to lower the Tg of the amorphous polyester resin A and easily impart the property of deforming at a low temperature, the amorphous polyester resin A is a fat having 3 or more and 12 or less carbon atoms in the total alcohol component. It is preferable to contain 50 mol% or more of the group diol.

In order to lower the Tg of the amorphous polyester resin A and facilitate imparting the property of deforming at a low temperature, the amorphous polyester resin A contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component contains a dicarboxylic acid component. It preferably contains an aliphatic dicarboxylic acid having 4 or more and 12 or less carbon atoms.

The polyester resin preferably contains 30 mol% or more of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms.
Examples of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.

-Glycol component-
The diol component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2-. Methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1, An aliphatic diol such as 12-dodecanediol; a diol having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; 1,4-cyclohexanedimethanol, hydrogenated bisphenol Alicyclic diols such as A; alicyclic diols supplemented with alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols with ethylene oxide and propylene Examples thereof include alkylene oxide adducts of bisphenols such as those to which alkylene oxides such as oxide and butylene oxide are added. Among these, an aliphatic diol having 4 to 12 carbon atoms is preferable.
These diols may be used alone or in combination of two or more.

-Dicarboxylic acid component-
The dicarboxylic acid component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic dicarboxylic acid and aromatic dicarboxylic acid. 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, but an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.
The aromatic dicarboxylic acid having 8 to 20 carbon atoms 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.
Among these, an aliphatic dicarboxylic acid having 4 to 12 carbon atoms is preferable.
These dicarboxylic acids may be used alone or in combination of two or more.

-Alcohol with a valence of 3 or more-
The trihydric or higher alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a trihydric or higher aliphatic alcohol, a trivalent or higher polyphenol, or an alkylene of a trivalent or higher polyphenol. Examples include oxide adducts.
Examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
Examples of the trivalent or higher valent polyphenols include trisphenol PA, phenol novolac, and cresol novolac.
Examples of the alkylene oxide adduct of the trivalent or higher valent polyphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide to the trivalent or higher valent polyphenols.

-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.
Examples of the trivalent or higher-valent isocyanate include lysine triisocyanate, a trivalent or higher-valent alcohol reacted with diisocyanate, and a polyisocyanate reacted with isocyanurate.
Above all, it is more preferable to use a polyisocyanate having an isocyanurate skeleton because it acts as a stronger cross-linking point and is further excellent in heat storage resistance and high temperature offset resistance.

The trivalent isocyanate component is preferably 0.2 mol% or more and 1.0 mol% or less with respect to the resin composition in the THF insoluble component of the toner. When a crosslinked structure is formed by a trivalent isocyanate component, the cohesive force of the molecular chain is increased by pseudo-crosslinking by urethane or urea bond at the crosslinking point, so that the heat-resistant storage stability can be improved even with a small crosslinking density, and the heat-resistant storage stability can be improved at a low temperature. Fixability can be achieved at a high level. When the trivalent isocyanate component is less than 0.2 mol%, the formation of the branched structure becomes insufficient, and the portion where the network structure becomes non-uniform becomes the starting point, so that the heat storage resistance and the filming resistance deteriorate. In some cases. When the trivalent isocyanate component is larger than 1.0 mol%, the low temperature fixability may be deteriorated by forming a dense crosslinked structure.

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, decamethylene. 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 a curing agent capable of reacting with a polyester prepolymer (a reaction product of the polyester portion of R2 and the polyisocyanate, that is, a reaction precursor that reacts with the curing agent) to produce the polyester resin. If there is, there is no particular limitation, and it can be appropriately selected depending on the intended purpose, and 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 glass transition temperature of the amorphous polyester resin A is preferably −60 ° C. or higher and 0 ° C. or lower, and more preferably −40 ° C. or higher and −20 ° C. or lower.
If the glass transition temperature is less than −60 ° C., the flow of toner at a low temperature cannot be suppressed, the heat-resistant storage stability may deteriorate, and the filming resistance may deteriorate.
If the glass transition temperature exceeds 0 ° C., the toner due to heating and pressurization during fixing may not be sufficiently deformed, and the low temperature fixing property may be insufficient.

In the amorphous polyester resin A, among the structural formulas 1) to 3), R1 has an isocyanurate skeleton represented by the following structural formula (I), which has heat storage resistance and high temperature offset resistance. It is preferable in terms of sex.

Further, in the amorphous polyester resin A, although the detailed reason is not clear, the three-dimensional network structure of the molecules is suitable for achieving both low temperature fixability, image gloss, heat storage resistance, and offset resistance. It is more preferable that n is 3 in the above structural formulas 1) to 3) because the state is reached.

The weight average molecular weight of the amorphous polyester resin A is not particularly limited and may be appropriately selected depending on the intended purpose. However, in GPC (gel permeation chromatography) measurement, 20,000 or more and 1,000,000 or more. The following is preferable.
The weight average molecular weight of the amorphous polyester resin A refers to the molecular weight of the reaction product obtained by reacting the reactive precursor with the curing agent.
If the weight average molecular weight is less than 20,000, the toner tends to flow at a low temperature, and the heat-resistant storage stability may be inferior.
In addition, the viscosity at the time of melting becomes low, and the high temperature offset property may decrease.

The content of the amorphous polyester resin A is not particularly limited and may be appropriately selected depending on the intended purpose. However, 1 part by mass to 10 parts by mass is preferable in 100 parts by mass of the toner, and 1 part by mass is preferable. ~ 5 parts by mass is more preferable.

<Other polyester resins>
The toner of the present invention may contain a polyester resin other than the above as a binder resin, if necessary.
Other polyester resins have a skeleton derived from an alcohol component and a skeleton derived from a carboxylic acid component.
The alcohol component contains a trivalent or higher aliphatic alcohol.
The other polyester resin satisfies the following formulas (1) to (3).

4,000 ≤ weight average molecular weight (Mw) ≤ 25,000 ... Equation (2)
0.5 ≤ (Amount of aliphatic alcohol of trivalent or higher) ≤ 6.5 ... Equation (3)

However, the amount of the trivalent or higher aliphatic alcohol in the formulas (1) and (3) (hereinafter, may be referred to as “branched component amount”) refers to the trivalent or higher valent fat with respect to the alcohol component. Mol% of group alcohol.

Here, when the trivalent or higher aliphatic alcohol is two or more kinds in the alcohol component, the "valence of the trivalent or higher aliphatic alcohol" is obtained from the molar fraction of the trivalent or higher aliphatic alcohol. It is the average valence that is given. For example, when the trihydric or higher aliphatic alcohol contains 50 mol% each of the trivalent aliphatic alcohol and the tetravalent aliphatic alcohol, the above-mentioned "valence of the trivalent or higher aliphatic alcohol". Is 3 × 0.5 + 4 × 0.5 = 3.5. Further, for example, when the trihydric or higher aliphatic alcohol contains 60 mol% of the trivalent aliphatic alcohol and 40 mol% of the hexavalent aliphatic alcohol, the above-mentioned "trivalent or higher aliphatic alcohol". The valence is 3 × 0.6 + 6 × 0.4 = 4.2.

When the other polyester resin satisfies the formulas (1) to (3), it is possible to improve the low temperature fixability, the stress resistance, and the blocking resistance of the toner image in the toner.

The following portion of the formula (1) represents the average distance between the branches of the polyester resin (hereinafter, may be referred to as “inter-branch distance”).

The other polyester resin preferably satisfies the above formula (1) and preferably the following formula (1-1).

However, the amount of the trivalent or higher aliphatic alcohol in the above formula (1-1) is mol% of the trivalent or higher aliphatic alcohol with respect to the alcohol component.

When the distance between the branches exceeds 4,000, the melt viscosity is hardly lowered, which is disadvantageous for low temperature fixability. If the distance between the branches is less than 500, the distance between the branches is shortened and the molecular size is reduced, so that the stress resistance of the toner is lowered. In addition, when cooled from a high temperature state, the start of entanglement of molecules is delayed, and the blocking resistance of the output toner image is lowered.

Since the polyester resin having a branched structure can reduce the melt viscosity in a high temperature range while maintaining the glass transition temperature, it is possible to improve low temperature fixability and heat storage stability. On the other hand, since it has a dense three-dimensional structural portion by increasing the amount of branched components inside, deformation is suppressed even when a large stress is applied, and it is considered that the toner has excellent stress resistance.

The weight average molecular weight of the other polyester resin preferably satisfies the above formula (2) and preferably the following (2-1).
8,000 ≤ weight average molecular weight (Mw) ≤ 20,000 ... Equation (2-1)
When the weight average molecular weight of the other polyester resin is less than 4,000, the high temperature and high humidity storage resistance of the toner and the stress resistance of the toner are deteriorated, and when it exceeds 30,000, the melt viscosity becomes high. Too much, the low temperature fixability of the toner cannot be exhibited.

The other polyester resin preferably satisfies the above formula (3) and preferably the following formula (3-1).
2.0 ≤ (Amount of aliphatic alcohol of trivalent or higher) ≤ 4.0 ... Equation (3-1)
However, the amount of the trivalent or higher aliphatic alcohol in the above formula (3-1) is mol% of the trivalent or higher aliphatic alcohol with respect to the alcohol component.
When the "trivalent or higher aliphatic alcohol amount" (branched component amount) is less than 0.5 mol%, the high temperature and high humidity storage resistance and filming property are inferior, and when it exceeds 6.5 mol%, the image gloss is obtained. , And low temperature fixability is inferior.

As the method for producing the other polyester resin, a method of reacting an alcohol component containing a trivalent or higher aliphatic alcohol with a carboxylic acid component is preferable. By doing so, a polyester resin having a branched structure can be formed.

The glass transition temperature (Tg) of the other polyester resin is preferably 40 ° C. or higher and 70 ° C. or lower, and more preferably 50 ° C. or higher and 60 ° C. or lower.
If the glass transition temperature is less than 40 ° C., the heat-resistant storage stability of the toner and the durability against stress such as stirring in the developing machine may be inferior, and the filming resistance may be deteriorated.
If the glass transition temperature exceeds 70 ° C., the toner may not be sufficiently deformed by heating and pressurizing during fixing, and the low temperature fixing property may be insufficient.

The other polyester resin is preferably soluble in tetrahydrofuran (THF) from the viewpoint of low temperature fixability and high gloss of the image.

<Alcohol component>
Examples of the alcohol component include divalent alcohols and trihydric or higher alcohols.
The alcohol component contains 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.

<Crystalline polyester 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, heat-resistant storage stability due to crystallization is good until just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin is rapidly melted. A toner that has both good heat-resistant storage stability and low-temperature fixability because it causes a sharp decrease in viscosity (sharp melt), is compatible with the amorphous polyester resin, and is fixed by a rapid decrease in viscosity. Is 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. The polyester resin is modified, for example, the prepolymer and the resin obtained by cross-linking and / or stretching the prepolymer do not belong to the crystalline polyester resin.

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

The measurement conditions for X-ray diffraction are described below.
〔Measurement condition〕
Tension kV: 45 kV
Current: 40mA
MPSS
Upper
Gonio
Scanmode: context
Start angle: 3 °
End angle: 35 °
Angle Step: 0.02 °
Lucident beam optics
Divergence slit: Divergence slit 1/2
Deflection beam optics
Anti scatter slit: As Fixed 1/2
Receiving slit: Prog rec slit

-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 1,14-eicosanedecanediol. 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.

-Multivalent 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. If the melting point is less than 60 ° C., the crystalline polyester resin tends to melt at a low temperature, and the heat-resistant storage stability of the toner may decrease. If the temperature exceeds 80 ° C., the crystalline polyester resin is heated by heating during fixing. Insufficient melting may reduce low temperature fixability.

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. From the viewpoint of reducing heat storage stability, the soluble content of orthodichlorobenzene in the crystalline polyester resin has a weight average molecular weight (Mw) of 3,000 to 30,000 and a number average molecular weight (Mn) in GPC measurement. It is preferably 1,000 to 10,000 and Mw / Mn 1.0 to 10. Further, it is preferable that the weight average molecular weight (Mw) is 5,000 to 15,000, the number average molecular weight (Mn) is 2,000 to 10,000, and Mw / Mn is 1.0 to 5.0.

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 low 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. If the content is less than 3 parts by mass, the sharp melt formation by the crystalline polyester resin is insufficient, so that the low temperature fixability may be inferior. If it exceeds 20 parts by mass, the heat-resistant storage stability is lowered. And the image may be fogged easily. When the content is within the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<Other ingredients>
The toner of the present invention contains a mold release agent, an external additive and a colorant as essential components, and can contain, for example, a charge control agent, a fluidity improver, a cleanability improver, a magnetic material and the like as other components.

-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 and wood wax and rice wax; animal waxes such as honey wax and lanolin; mineral waxes such as ozokelite and cercin; paraffin. , Petroleum waxes such as microcrystallin, petrolatum; and natural waxes.

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. If the melting point is less than 60 ° C., the release agent tends to melt at a low temperature, and the heat-resistant storage stability may be inferior. If the melting point exceeds 80 ° C., even if the resin is melted and is in the fixing temperature range, the mold release agent may not be sufficiently melted and a fixing offset may occur, resulting in image loss.

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. If the content is less than 2 parts by mass, the high-temperature offset resistance and low-temperature fixing property at the time of fixing may be inferior, and if it exceeds 10 parts by mass, the heat-resistant storage stability is lowered and the image is fogged. Etc. may easily occur. When the content is within the more preferable range, it is advantageous in terms of improving the image quality and the fixing stability.

-External agent-
Examples of the external additive include inorganic fine particles, hydrophobized inorganic fine particles, fatty acid metal salts, oxide particles, or a mixture thereof. The average particle size of the primary particles of the inorganic fine particles is preferably 1 nm to 300 nm, more preferably 5 nm to 200 nm.

Further, it is preferable that at least one kind of inorganic fine particles having an average particle size of 30 nm or less is contained and at least one kind of inorganic fine particles having an average particle size of 30 nm or more are contained. 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, etc. (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, ∨P RX40S, ∨P RY40S, RX200S, RY200S, 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 Aerodil 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.).

Hydrophobized oxide fine particles, hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles include, for example, hydrophilic fine particles such as methyltrimethoxysilane and methyltriethoxysilane. It can be obtained by 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.

Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorphenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, and amino. Examples thereof include modified silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.

Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, and mica. Examples thereof include siliceous stone, silica soil, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Of these, silica and titanium dioxide are particularly preferred.

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.

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 as described above, it is preferably 1 nm or more and 300 nm or less, and more preferably 5 nm or more and 200 nm or less. When the average particle size is 1 nm or more, the burial of the inorganic fine particles in the toner is suppressed, and the function is effectively exhibited. Further, since the average particle size is 300 nm or less, the surface of the photoconductor is not unevenly damaged.

If necessary, the inorganic fine particles may be crushed. At this time, it is possible to control the accelerated aggregation degree of the inorganic fine particles by adjusting the crushing strength. Examples of the inorganic fine particles to which the crushing treatment is applied include R972, R974, RX40, RY40, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.).

The crushing strength can be adjusted, for example, by adjusting the rotation speed and rotation time of the mixer.

-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, Malachite Guri Examples include Nrake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Oxide, and Litobon.

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.

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 or the master batch include polymers of styrene such as polystyrene, polyp-chlorostyrene, polyvinyltoluene and its substitutions in addition to the other polyester resins; styrene-p-. Chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-acrylic Butyl acid acid copolymer, octyl styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate Copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethylketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-inden copolymer, styrene-maleic acid copolymer , Sterite-based copolymers such as styrene-maleic acid ester copolymers; polymethylmethacrylate, polybutylmethacrylate, polyvinyl chloride, polyvinylacetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, Examples thereof include 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.

The masterbatch can be obtained by mixing the resin for the masterbatch and the colorant with a high shearing force and kneading them. 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.

-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 Hodoya 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. Can be mentioned.

The content of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 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. If the content exceeds 10 parts by mass, 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. , May cause a decrease in image density. These charge control agents can be melt-kneaded together with the masterbatch and 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 on the toner surface after forming toner particles. You may.

-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. Examples thereof include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate-based coupling agents, aluminum-based coupling agents, silicone oils, modified silicone oils, and the like. Be done. 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 agent-
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.

<Amount of external additive released>
The external additive desorbed from the toner is measured as follows.
(1) 3.75 g of a toner sample is dispersed in 50 mL of a 0.5 mass% polyoxyalkylene alkyl ether (Neugen ET-165, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) dispersion in a 110 mL vial.
(2) Using an ultrasonic homogenizer (trade name: homogenizer, type VCX750, CV33, manufactured by SONICS & MATERIALS), the output is set to 40 W at a frequency of 20 kHz, and ultrasonic waves are irradiated for 100 seconds. The amount of irradiation energy given at this time is calculated from the product of the output and the irradiation time (40 W × 100 seconds = 4 kJ). At this time, the treatment is carried out while cooling the toner dispersion liquid in a timely manner so that the temperature of the toner dispersion liquid does not exceed 40 ° C.
(3) The obtained dispersion is suction-filtered with a filter paper (trade name: qualitative filter paper (No. 2, 110 mm), manufactured by Advantech Toyo Co., Ltd.), washed twice with ion-exchanged water, filtered, and released from the outside. After removing the additive, the toner is dried.
(4) The amount of the toner added before and after the removal of the external agent is measured by a fluorescent X-ray analyzer (ZSX-100e manufactured by Rigaku Denki Co., Ltd.) based on the strength (or the difference in strength before and after the removal of the external agent) by the calibration curve. It can be quantified by calculating% to determine the amount of the external additive released.
Free amount = (mass of external additive before dispersion)-(mass of residual external additive after dispersion) ... Equation (4)

The release rate (mass%) of the external additive can be obtained by the following mathematical formula 5.
Free rate = [Free amount / Total amount of external additive added] x 100 ... Equation (5)

At this time, the total amount of the external additive added is defined as follows.
Using an ultrasonic homogenizer, the amount of external additive for the toner irradiated with ultrasonic waves of 1000 kJ and 1500 kJ was quantified by a fluorescent X-ray analyzer in the same manner as above, and the amount of additive was 1000 kJ and 1500 kJ. Make sure there is no decrease in. If there is no decrease, it can be determined that all the external additives have been removed.
Further, the surface of the treated toner may be observed with a field emission scanning electron microscope (FE-SEM) to confirm that all the external additives have been removed. If a change is observed, the irradiation energy amount is further increased by 500 kJ and the same treatment is performed.
The total amount of the external additive added is calculated from the difference between the amount of the external additive of the toner from which all the external additive has been removed and the untreated toner as described above.

After removing all the external additives as described above, when "the amount of the external additive of the toner from which all the external additives have been removed" is measured by fluorescent X-ray, the amount of the external additive is zero or the mother body. If the same substance as the external additive is contained in, it will be affected and will have a certain value. On the other hand, when the amount of the external additive of the untreated toner is measured by fluorescent X-ray, when the external additive and the material containing the same substance as the external additive are used in the toner base as described above, the amount is increased. Only the amount of the external additive will be added. Therefore, in order to calculate the "total amount of the external additive added", as described above, the total amount of the external additive is calculated from the difference between the amount of the external additive of the toner from which all the external additive has been removed and the untreated toner. The method of calculating the addition amount is taken.

The free amount of the toner external additive is preferably 20% by mass to 50% by mass when the irradiation energy amount is 4 kJ. When the liberated amount is 20% by mass or more, the cleaning property is further improved, and when it is 50% by mass or less, the filming or the like generated by the liberated external additive adhering to the transcript can be suppressed. By setting the irradiation energy to 4 kJ, it is possible to measure the amount of an external additive having a weak adhesive force that is easily released from the toner in the image forming apparatus.

Specific examples of the external additive are as described above.

<Volume average particle size>
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 reference particle size of 2 μm or less.

<< Calculation method and analysis method of various characteristics of toner and toner components >>
The SP value, Tg, acid value, hydroxyl value, molecular weight, and melting point of the amorphous polyester resin, the crystalline polyester resin, and the mold release agent may be measured for themselves, but the actual toner may be measured. The SP value, Tg, molecular weight, melting point, and mass ratio of the constituent components may be calculated by performing separation from gel permeation chromatography (GPC) or the like and adopting the analysis method described later for each of the separated components.

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 heavy THF, ^{1 1} H-NMR measurement is performed, and the resin in the eluate component is determined from the integrated ratio of each element. Calculate the constituent monomer ratio of.

As another method, the eluate is concentrated, hydrolyzed 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.

When the method for producing the toner forms polyester matrix particles by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent, it is actually a case. The polyester resin may be separated from the toner of the above by GPC or the like to obtain Tg or the like of the polyester resin, or separately, the polyester resin may be subjected to an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent. May be synthesized, and Tg or the like may be measured from the synthesized polyester resin.

<< 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 polyester resin and the crystalline polyester resin contained in the toner can be obtained from the peak integration ratio of the obtained spectrum.

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 3.7ppm to 4.7ppm: Derived from methylene of bisphenol A propylene oxide adduct (for 2 hydrogens) and derived from methylene of bisphenol A ethylene oxide adduct (for 4 hydrogens)
Around 1.6ppm: 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 having the structure represented by any of the above structural formulas 1) to 3) accounts for 90% or more is the above structural formula 1) to 3). It can be treated as a polyester resin having a structure represented by any of 3).
Similarly, the extract recovered in the fraction in which the other polyester resin accounts for 90% or more can be treated as the other polyester resin.
Further, the extract recovered in the fraction in which the crystalline polyester resin occupies 90% or more can be treated as the crystalline polyester resin.

<< Analysis of THF insoluble toner >>
Extraction of the THF insoluble component of the toner can be performed, for example, as follows.
After adding 1 part of toner to 40 parts of THF and refluxing for 6 hours, the insoluble component is precipitated by a centrifuge to separate the insoluble component and the supernatant. The insoluble component is dried at 40 ° C. for 20 hours to obtain a THF insoluble component. The THF insoluble component corresponds to a non-linear polyester resin. Therefore, the THF insoluble component has a plurality of structural portions derived from trivalent isocyanate.
The composition in the THF insoluble component can be analyzed by NMR measurement using a solution or a solid, X-ray diffraction, GC / MS, LC / MS, IR measurement, or the like.
Conveniently, it can be analyzed by the thermal decomposition simultaneous methylation GC-MS method using a methylation reaction reagent, for example, by the following method.
Device name: Shimadzu QP2010 Frontier Lab Py2020D
Data analysis software: GCMS solution manufactured by Shimadzu Corporation
Heating temperature: 280 ° C
Reaction pyrolysis temperature: 300 ° C
Column name: Ultra ALLOY-5 L = 30m ID = 0.25mm Film = 0.25μm
Constant temperature bath temperature: 50 ° C (holding 1 minute) 10 ° C / min to 330 ° C (holding 11 minutes)
Carrier gas: constant 53.6 kPa, He 1.0 mL / min
Injection mode: Split (1: 100)
Ionization method: EI method (70eV)
Measurement mode: Scan mode Library: NIST 20 MASS SPECTRAL

<< 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 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 as follows.

〔Measurement condition〕
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement MV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
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 matter) 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 particle size distribution >>
For the volume average particle size (D4), the number average particle size (Dn), and the ratio (D4 / 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 using 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 (D4) 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: GPC-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 toner in tetrahydrofuran THF (manufactured by Wako Pure Chemical Industries, Ltd. containing stabilizer) at 0.15 mass%, filter with a 0.2 μm filter, and filter. The filtrate is used as a sample.
100 μL of the THF sample solution is injected and measured.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of 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.

<< Measurement of accelerated cohesion >>
The accelerated cohesion was measured by the following method. As the measuring device, for example, a powder tester manufactured by Hosokawa Micron Co., Ltd. is used, and the accessory parts are set on the shaking table according to the following procedure.

(A) Vibro chute (b) Packing (c) Space ring (d) Fluy (3 types) Top>Middle> Bottom (e) Osaever

Next, fix it with a knob nut and operate the shaking table. The measurement conditions are as follows.

Fluy opening (upper) 75 μm
Fluy opening (middle) 45 μm
Fluy opening (lower) 20 μm
Swing width scale 2 mm
Sample (inorganic fine particles) collected 2g
Vibration time 160 seconds Vibration acceleration: 100 m / s ²

After the measurement, the accelerated cohesion is obtained from the calculation shown below.

Weight% of powder remaining in the upper flue x 1 ... (a)
Weight% of powder remaining in the middle flue x 0.6 ... (b)
Weight% of powder remaining in the lower flue x 0.2 ... (c)
The sum of the above three calculated values is taken as the accelerated cohesion degree (%).
That is, the accelerated cohesion degree (%) = (a) + (b) + (c).

Further, the toner of the present invention contains inorganic fine particles as an external additive, and the content of the entire inorganic fine particles in the toner of the present invention is, for example, 0.5 to 20.0 in 100 parts by mass of the toner of the present invention. It is preferably parts by mass, more preferably 0.5 to 10.0 parts by mass.

<Toner manufacturing method>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. However, the toner contains the amorphous polyester resin and, if necessary, the other polyester resin, and the crystals. It is preferable that the oil phase further contains the property polyester resin and contains the mold release agent, the colorant and the like is dispersed in an aqueous medium for granulation.

As an example of such a method for producing the toner, a known dissolution / suspension method can be mentioned. As an example of the method for producing the toner, a polyester resin having a structure represented by any of the above structural formulas 1) to 3) is produced by an extension reaction and / or a cross-linking reaction between the polyester prepolymer and the curing agent. However, the method of forming the toner matrix particles is shown below. In such a method, the aqueous medium is prepared, the oil phase containing the toner material is prepared, the toner material is emulsified or dispersed, and the organic solvent is removed.

-Preparation of aqueous medium (aqueous phase)-
The 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 precursor of the amorphous polyester and the crystalline polyester resin, and if necessary, the curing agent, the mold release agent, the coloring agent, and the like. It can be carried out by dissolving or dispersing the toner material containing the above 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 is produced by causing the curing agent and the polyester prepolymer to undergo an elongation reaction and / or a cross-linking reaction.

The amorphous polyester resin can be produced, for example, by the following methods (1) to (3).
(1) A method in which an oil phase containing the polyester prepolymer and the curing agent is emulsified or dispersed in an aqueous medium, and the curing agent and the polyester prepolymer are subjected to an extension reaction and / or a cross-linking reaction in the aqueous medium. ..
(2) The oil phase containing the polyester prepolymer is emulsified or dispersed in an aqueous medium to which the curing agent is added in advance, and the curing agent and the polyester prepolymer are extended and / or crosslinked in the aqueous medium. How to make it.
(3) After the oil phase containing the polyester prepolymer is emulsified or dispersed in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent and the polyester prepolymer are added from the particle interface in the aqueous medium. A method of causing an extension reaction and / or a cross-linking reaction with and.

The reaction conditions (reaction time, reaction temperature) for producing the amorphous polyester resin are not particularly limited and may be appropriately selected depending on the combination of the curing agent and the polyester prepolymer. ..

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 polyester prepolymer in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the toner material in the aqueous medium phase. An oil phase prepared by dissolving or dispersing the above in a solvent is added, and the oil phase is 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 amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose, but is 50 parts by mass to 2 parts by mass with respect to 100 parts by mass of the toner material. 000 parts by mass is preferable, and 100 parts by mass to 1,000 parts by mass is more preferable.

If the amount of the aqueous medium used is less than 50 parts by mass, the dispersed state of the toner material may deteriorate and toner base particles having a predetermined particle size may not be obtained, which exceeds 2,000 parts by mass. And the production cost may be high.

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 a surfactant, a poorly water-soluble inorganic compound dispersant, and a polymer-based protective colloid.
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, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like are used. be able to.

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.

-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 an organic solvent and a method of spraying a dispersion liquid in a dry atmosphere to remove the organic solvent in 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 with a lowered position, 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.

When the developer is used as a one-component developer, even if the toner is balanced, the particle size of the toner does not fluctuate much, and the filming of the toner on the developing roller and members such as blades for thinning the toner are formed. Toner is less fused to the developing device, and good and stable developability and an image can be obtained even with long-term stirring in a developing device.

When the developer is used as a two-component developer, even if the toner is balanced for a long period of time, the particle size of the toner does not fluctuate much, and even with long-term stirring in a developing device, good and stable developability and an image can be obtained. can get.

<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.

-Core material-
The material of the core material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 50 emu / g to 90 emu / g manganese-strontium-based material, 50 emu / g to 90 emu / g manganese- Examples include magnesium-based materials. Further, in order to secure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developing agent in the spiked state on the photoconductor can be alleviated and it is advantageous for improving the image quality, a low magnetization material such as copper-zinc of 30 emu / g to 80 emu / g should be used. Is preferable.

These may be used alone or in combination of two or more.

The volume average particle diameter of the core material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 μm to 150 μm, more preferably 40 μm to 100 μm. If the volume average particle diameter is less than 10 μm, fine powder may increase in the carrier, the magnetization per particle may decrease and carriers may scatter, and if it exceeds 150 μm, the specific surface area decreases and the toner may be scattered. Scattering may occur, and in full color with many solid parts, the reproduction of the solid part may be particularly poor.

When the toner is used as a two-component developer, it may be mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, but is 90 parts by mass to 98 parts by mass with respect to 100 parts by mass of the two-component developer. Parts are preferable, and 93 parts by mass to 97 parts by mass are more preferable.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component developing method, a non-magnetic one-component developing method, and a two-component developing method.

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, excellent low-temperature fixability, high-temperature offset resistance, high gloss, high color reproducibility, and heat-resistant storage stability can be obtained without filming. It is possible to form an image by taking advantage of the characteristics of the toner that it has.
In the following, a developer container containing a developer containing toner will be described in particular.

(Developer storage container)
The developer-containing container according to the present invention contains the developer of the present invention, but the container is not particularly limited and can be appropriately selected from known ones, but has a container body and a cap. And so on.

The size, shape, structure, material, etc. of the container body are not particularly limited, but the shape is preferably cylindrical, and spiral irregularities are formed on the inner peripheral surface, and the container body is rotated to form spiral irregularities. It is particularly preferable that the developer, which is the content, can be transferred to the discharge port side, and a part or all of the spiral irregularities has a bellows function. Further, the material is not particularly limited, but is preferably one having good dimensional accuracy. For example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, etc. Examples thereof include resin materials such as polyacetal resin.

Since the developer container is easy to store, transport, etc., and has excellent handleability, it can be detachably attached to a process cartridge, an image forming apparatus, etc., which will be described later, and used for replenishing the developer.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention is characterized by using the toner of the present invention, and has, for example, an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further, if necessary, Has other means.
The image forming method according to the present invention includes a charging step, an exposure step, a developing step, a primary transfer step, a secondary transfer step, a fixing step, and a cleaning step, and further includes other steps if necessary.
The image forming method can be suitably performed by the image forming apparatus, the charging step and the exposure step can be preferably performed by the electrostatic latent image forming means, and the developing step is performed by the developing means. It can be preferably performed, and the other steps can be preferably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and 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.

Examples of the amorphous silicon photoconductor include heating a support to 50 ° C. to 400 ° C., vacuum deposition method, sputtering method, ion plating method, and thermal CVD (chemical vapor deposition, Chemical Vapor Deposition) on the support. A photoconductor having a photoconductive layer made of a-Si can be used by a film forming method such as a method), an optical CVD method, or a plasma CVD method. Among these, the plasma CVD method, that is, the method of decomposing the raw material gas by direct current, high frequency, or microwave glow discharge to form an a-Si deposited film on the support is preferable.

The shape of the electrostatic latent image carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but a cylindrical shape is preferable. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, and 10 mm to 30 mm. Especially preferable.

<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.

The shape of the charging member may be any shape such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and the shape of the image forming apparatus.
The charging member is not limited to the contact-type charging member, but it is preferable to use the contact-type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

-Exposure members 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.
The light source used for the exposure member is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), or a semiconductor laser. (LD), electroluminescence (EL) and other light-emitting substances in general can be mentioned.
Further, in order to irradiate only light in a desired wavelength range, various filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can also be used.
The exposure can be performed, for example, by exposing the surface of the electrostatic latent image carrier as an image using the exposure member.
In the present invention, an optical back surface method may be adopted in which the back surface side of the electrostatic latent image carrier is exposed in an image-like manner.

<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.
In the developing means, for example, the toner and the carrier are mixed and agitated, and the toner is charged by the friction at that time and is held in a spiked state on the surface of a rotating magnet roller to form a magnetic brush. .. The magnet roller is arranged in the vicinity of the electrostatic latent image carrier. Therefore, a part of the toner forming the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier by an electric attraction force. As a result, the electrostatic latent image is developed by the toner, and a visible image by the toner is formed on the surface of the electrostatic latent image carrier.

<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.
The transfer step can be performed, for example, by charging the photoconductor with a transfer charger, and can be performed by the transfer means.
Here, when the image secondarily transferred onto the recording medium is a color image composed of toners of a plurality of colors, the intermediate transfer means by sequentially superimposing the toners of each color on the intermediate transfer body. An image can be formed on the body, and the image on the intermediate transfer body can be collectively secondarily transferred onto the recording medium by the intermediate transfer means.
The intermediate transfer material is not particularly limited and may be appropriately selected from known transfer materials depending on the intended purpose. For example, a transfer belt or the like is preferably used.

It is preferable that the transfer means (the primary transfer means, the secondary transfer means) has at least a transfer device for peeling and charging the visible image formed on the photoconductor toward the recording medium. Examples of the transfer device include a corona transfer device by corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose, and is used for OHP. A PET base or the like can also be used.

-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.
The fixing step can be performed by the fixing means.
The heating in the heating / pressurizing member is usually preferably 80 ° C. to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing means, depending on the purpose.

The surface pressure in the fixing step is not particularly limited and may be appropriately selected depending on the intended ^purpose, it is preferably ^{10N / cm 2 ~80N / cm 2} .

-Cleaning means and cleaning process-
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoconductor, and can be appropriately selected depending on the intended purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, or the like. Examples include magnetic roller cleaners, blade cleaners, brush cleaners, and web cleaners.
The cleaning step is not particularly limited as long as it is a step capable of removing the toner remaining on the photoconductor, and can be appropriately selected depending on the intended purpose. For example, the cleaning step can be performed.

-Static elimination means and static elimination process-
The static elimination means is not particularly limited as long as it is a means for applying a static elimination bias to the photoconductor to eliminate static electricity, and can be appropriately selected depending on the intended purpose. Examples thereof include a static elimination lamp.
The static elimination step is not particularly limited as long as it is a step of applying a static elimination bias to the photoconductor to eliminate static electricity, and can be appropriately selected depending on the intended purpose. For example, the static elimination step can be performed. ..

-Recycling means and recycling process-
The recycling means is not particularly limited as long as it is a means for recycling the toner removed by the cleaning step into the developing apparatus, and can be appropriately selected depending on the purpose. For example, a known transport means or the like can be used. Can be mentioned.
The recycling step is not particularly limited as long as it is a step of recycling the toner removed by the cleaning step to the developing apparatus, and can be appropriately selected depending on the purpose. For example, the recycling step is performed. Can be done.

-Control means and control process-
The control means is not particularly limited as long as it can control the movement of each of the means, and can be appropriately selected depending on the intended purpose. Examples thereof include devices such as sequencers and computers.
The control step is not particularly limited as long as it can control the movement of each step, and can be appropriately selected depending on the intended purpose. For example, the control step can be performed.

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 cyanide developing unit 45C includes a developer 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 100A 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. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are directly opposed to each other around the photoconductor drum 10 without providing the developing belt 41. Other than that, it has the same configuration as the image forming apparatus 100A shown in FIG.

FIG. 3 shows another example of the image forming apparatus of the present invention. The image forming apparatus shown in FIG. 3 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document transfer 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 conveying 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 document is set on the platen 130 of the automatic document transfer device (ADF) 400, or the document is set on the contact glass 40 of the scanner 300 by opening the document automatic transfer device 400 and the document automatic transfer device (ADF) 400. Close 400.

When the start switch (not shown) is pressed, when the original is set in the automatic document transfer 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.

The image information of black, yellow, magenta, and cyan is obtained from each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image) in the tandem developing device 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, as shown in FIG. 4, 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 static. Electro-latent image carrier 10 (electro-latent image carrier 10K for black, electrostatic latent image carrier 10Y for yellow, electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier 10C for cyan). The charging device 160, which is the charging means for uniformly charging the electrostatic latent image carrier 10, and the electrostatic latent image carrier are exposed so as to correspond to each color image based on each color image information (FIG. 4). Medium, L), an exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image on each color toner (black toner, yellow toner, magenta toner). The developing device 61, which is the developing means for forming a toner image with each color toner by developing with (and cyan toner), and the transfer charger 62 for transferring the toner image onto the intermediate transfer body 50. It includes 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.

(Process cartridge)
The process cartridge according to the present invention is detachably molded into various image forming devices, and has an electrostatic latent image carrier that carries an electrostatic latent image and an electrostatic latent image that is supported on the electrostatic latent image carrier. At least has a developing means for forming a toner image by developing the toner with the toner of the present invention. The process cartridge of the present invention may further have other means, if necessary.

The developing means includes at least a developer accommodating container for accommodating the developing agent of the present invention and a developing agent carrier for carrying and transporting the developing agent contained in the developing agent accommodating container. The developing means may further include a regulating member or the like in order to regulate the thickness of the developing agent to be carried.

FIG. 5 shows an example of a process cartridge according to the present invention. The process cartridge 110 includes a photoconductor drum 10, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90. Reference numeral 95 is transfer paper, and L is exposure light.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples. “Parts” represents “parts by mass” unless otherwise specified. “%” Represents “mass%” unless otherwise specified.

[Manufacturing of toner]
A specific production example of the toner used for the evaluation will be described. The toner used in the present invention is not limited to these examples.

(Example 1)
<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.

<Synthesis of amorphous polyester resin A>
-Synthesis of prepolymer A-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen cord introduction tube, 3-methyl-1,5-pentanediol, terephthalic acid and adipic acid are contained, and OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, is 1. Titanium tetraisopropoxide so that the composition of the diol component is 3-methyl-1,5-pentanediol 100 mol% and the composition of the dicarboxylic acid component is 50 mol% of terephthalic acid and 50 mol% of adipic acid. It was charged together with (1,000 ppm with respect to the resin component).
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 an intermediate polyester A'.
The Tg of the obtained intermediate polyester A'was −40 ° C., Mw15,000, and Mw / Mn2.0.
Next, in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the intermediate polyester A'and the hexamethylene diisocyanate (HDI) trimester were placed in a molar ratio (HDI isocyanate group / intermediate polyester hydroxyl group). ) 0.2, diluted with ethyl acetate to make a 50% ethyl acetate solution, and then reacted at 100 ° C. for 5 hours to obtain an intermediate polyester A solution.
The Tg of the obtained intermediate polyester A was −35 ° C., Mw 20,000, and Mw / Mn 2.2.
Next, in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the intermediate polyester A solution and isophorone diisocyanate (IPDI) were placed in a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) 1.5. After diluting with ethyl acetate to make a 50% ethyl acetate solution, the mixture was reacted at 100 ° C. for 5 hours to obtain a prepolymer A solution.

-Synthesis of amorphous polyester resin A-
The obtained prepolymer A is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] becomes equimolar to the amount of isocyanate in the prepolymer A. An amount of [ketimine compound 1] was added dropwise to the reaction vessel, and the prepolymer elongation product was taken out after stirring at 45 ° C. for 10 hours.
The obtained prepolymer stretched product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate became 100 ppm or less to obtain an amorphous polyester resin A.
The Tg of the amorphous polyester resin A was −25 ° C.

<Synthesis of crystalline polyester resin>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, dodecanedioic acid and 1,6-hexanediol were added to OH / COOH, which is the molar ratio of hydroxyl groups to carboxyl groups. Is prepared to be 0.9, reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours, and further 8. The reaction was carried out at a pressure of 3 kPa for 2 hours to obtain a crystalline polyester resin.

<Synthesis of other polyester resin B>
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 was / 15, and OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was charged to be 1.12, and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230 ° C. under normal pressure for 8 hours. Then, after further reacting at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours, trimellitic anhydride was added to the 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 to obtain the polyester resin B. Obtained.

<Preparation of masterbatch (MB)>
Add 1,200 parts of water and 500 parts of carbon black (manufactured by Printing 35 Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], mix with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and roll two rolls of the mixture. After kneading at 150 ° C. for 30 minutes, the mixture was rolled and cooled and pulverized with a palperizer to obtain [Master Batch 1].

<Preparation of WAX dispersion liquid>
50 parts of paraffin wax (manufactured by Nippon Seikan Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8), and acetic acid as a mold release agent 1 in a container in which a stirring rod and a thermometer are set. 450 parts of ethyl was charged, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, cooled to 30 ° C. at 1 o'clock, and fed using a bead mill (Ultra Viscomill, manufactured by Imex). A liquid rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, 80% by volume of zirconia beads having a diameter of 0.5 mm was filled, and dispersion was performed under the conditions of 3 passes to obtain [WAX dispersion liquid 1].

<Preparation of crystalline polyester resin dispersion>
50 parts of crystalline polyester resin and 450 parts of ethyl acetate were placed 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, and then 30 parts in 1 hour. Cool to ℃, and use a bead mill (Ultra Viscomill, manufactured by Imex) to fill 80% by volume of zirconia beads with a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and a diameter of 0.5 mm under the conditions of 3 passes. , Dispersion was carried out to obtain [Crystalline Polyester Resin Dispersion Liquid 1].

<Preparation of oil phase>
[WAX dispersion liquid 1] 500 parts, [amorphous polyester resin A] 820 parts, [crystalline polyester resin dispersion liquid 1] 750 parts, [polyester resin B] 7500 parts, [master batch 1] 100 parts, and curing Two parts of [Ketimine compound 1] as an agent were placed in a container and mixed with a TK homomixer (manufactured by Tokushu Kagaku) at 5,000 rpm for 60 minutes to obtain [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 adduct sulfate (Eleminol RS-30: manufactured by Sanyo Kasei Kogyo Co., Ltd.), 138 parts of styrene, methacrylic acid. When 138 parts and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The temperature was raised to 75 ° C. in the system by heating, and the reaction was carried out 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.
The volume average particle diameter of [fine particle dispersion liquid 1] measured by LA-920 (manufactured by HORIBA) 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 were mixed and stirred. A milky white liquid was obtained. This was designated as [Aquatic phase 1].

<Emulsification / solvent removal>
1,200 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 13,000 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): The operations of (1) to (4) above, in which 300 parts of ion-exchanged water is added to the filtered cake of (3), mixed with a TK homomixer (rotation speed of 12,000 rpm for 10 minutes), and then filtered. Was carried out twice to obtain a [filtered cake].
The [filtered cake] was dried at 45 ° C. for 48 hours in a circulation dryer, and sieved with a mesh having an opening of 75 μm to obtain [toner matrix particles 1].

<External processing>
2.5 parts by mass of hydrophobic silica having an average particle size of 80 nm, 0.3 part by mass of titanium oxide having an average particle size of 20 nm, and hydrophobic silica fine powder having an average particle size of 15 nm with respect to 100 parts by mass of the toner matrix particles 1. 1.2 parts of the body was mixed with a Henschel mixer to obtain toner 1.

As the hydrophobic silica, VP RX40S (manufactured by Nippon Aerosil Co., Ltd.) having a weakened crushing strength was used. Table 1 shows the crushing strength of the hydrophobic silica used in Example 1 when the crushing strength of VP RX40S before weakening the crushing strength was 100%. The mixed energies of the Henschel mixer are shown in Table 1.

The crushing strength is measured as follows.

<Creation of carrier>
To 100 parts by mass of toluene, 100 parts by mass of silicone resin (organo straight silicone), 5 parts by mass of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black are added and dispersed in a homomixer for 20 minutes. To prepare a resin layer coating liquid. A carrier was prepared by applying the resin layer coating liquid to the surface of 1,000 parts by mass of spherical magnetite having an average particle size of 50 μm using a fluidized bed coating device.

<Preparation of developer>
Using a ball mill, 5 parts by mass of the toner 1 and 95 parts by mass of the carrier were mixed to prepare a developer. Next, using each of the prepared developing agents, various characteristics were evaluated as follows. The evaluation results are shown in Table 1.

(Examples 2 to 24 and Comparative Examples 1 to 12)
Toners were prepared in the same manner as in Example 1 except that the mixing strength of the Henschel mixer was adjusted under the conditions shown in Table 1 using hydrophobic silica subjected to the crushing treatment at the crushing strength shown in Table 1.

The degree of accelerated cohesion of the inorganic fine particles and the amount of the external additive (referring to the inorganic fine particles in Examples and Comparative Examples) were measured as described above and are shown in Table 1 or Table 2. The evaluation results are shown in Table 2. The overall judgment in Table 2 is described as × evaluation when there is at least one × evaluation in the evaluation of cleanability and transportability.

[Evaluation item]
(Cleanability evaluation method)
Using an imageo MP C5002 (manufactured by Ricoh Corporation) as an image forming apparatus, a black monochromatic halftone image was output in a full color mode (high transfer current), and the cleanability of the intermediate transfer belt was evaluated. After the test was completed, a fibrous tape was attached to the surface of the belt to collect the toner remaining on the belt. The amount of collected toner was weighed and evaluated according to the following evaluation criteria. ◎, 〇, △ Evaluation is acceptable, × Evaluation is unsuccessful.
(Evaluation criteria for cleanability)
The judgment was made according to the following criteria.
⊚: less than 0.05 g ○: 0.05 g or more and less than 0.1 g Δ: 0.1 g or more and less than 0.5 g ×: 0.5 g or more

(Transportability evaluation method)
After performing the cleanability evaluation, the clogging of the toner at the replenishment port of the developing unit was confirmed and evaluated according to the following evaluation criteria. ○, △ Evaluation is acceptable, × Evaluation is unsuccessful.
◯: There is no toner clogging at the replenishment port.
Δ: Toner clogging can be confirmed in part, but toner can be transferred to the developing unit through the replenishment port.
X: The replenishment port is completely clogged with toner, and it is impossible to transfer the toner to the developing unit.

(Filming evaluation method)
Using an imageo MP C5002 (manufactured by Ricoh Co., Ltd.) as an image forming apparatus, a chart with a 20% image area was printed under the condition of an image density of 1.4 ± 0.2, and evaluated according to the following evaluation criteria. ◎, 〇, △ Evaluation is acceptable, × Evaluation is unsuccessful.
(Evaluation criteria for filming)
◎: There are few white spots and it is quite excellent ○: White spots are rarely seen △: White spots are conspicuous ×: There are very many white spots

From the results in Table 2, it is a toner containing a toner base containing a binder resin and a colorant and inorganic fine particles as an external additive, and the accelerated cohesion of the inorganic fine particles is 20% or more and 80% or less. Was confirmed to have excellent cleanability, transportability, and filming property.
On the other hand, Comparative Examples 1 to 3 and 7 to 9 were toners containing inorganic fine particles having an accelerated cohesion degree of less than 20%, so that the cleaning property was deteriorated.
Comparative Examples 4 to 6 and 10 to 12 are toners containing inorganic fine particles having an accelerated cohesion degree of more than 80%, so that the transportability was deteriorated.

10 Electrostatic latent image carrier (photoreceptor drum)
10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Cleaning device 18 Image Forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressurizing roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging Lens 36 Reading sensor 40 Developer 41 Developer belt 42K Developer storage 42Y Developer storage 42M Developer housing 42C Developer housing 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 43C 44K Develop Roller 44Y Develop Roller 44M Develop Roller 44C Develop Roller 45K Black Develop Unit 45Y Yellow Develop Unit 45M Magenta Develop Unit 45C Cyan Develop Unit 49 Resist Roller 50 Intermediate Transfer 51 Roller 52 Separation Roller 53 Manual Feed Channel 54 Manual Drawer 55 Switching Claw 56 Discharge roller 57 Discharge tray 58 Corona charging device 60 Cleaning device 61 Developing device 62 Transfer charging device 63 Cleaning device 64 Static elimination lamp 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A, 100B, 100C Image forming device 110 Process cartridge 120 Tandem processor 130 Paper stand 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Feed line 148 Paper feed path 150 Copying device main body 160 Charging device 200 Paper feed table 300 Scanner 400 Document automatic transfer Device (ADF)

JP-A-2018-36596

Claims (7)

A toner containing at least a binder resin and a colorant, and inorganic fine particles as an external additive.
A toner characterized in that the accelerated cohesion of the inorganic fine particles is 20% or more and 80% or less. The toner according to claim 1, wherein the accelerated cohesion of the inorganic fine particles is 30% or more and 80% or less. The toner according to claim 2, wherein the accelerated cohesion of the inorganic fine particles is 40% or more and 80% or less. When ultrasonic vibration is applied to the toner dispersion liquid in which the toner is dispersed in the dispersant with an irradiation energy amount of 4 kJ, the amount of release, which is the amount of the external additive desorbed from the toner, is contained in the toner. The toner according to any one of claims 1 to 3, wherein the toner is 20% by mass or more and 50% by mass or less with respect to the total amount of the external additive. The toner according to any one of claims 1 to 4, wherein the inorganic fine particles having an accelerated cohesion degree of 20% or more and 80% or less are hydrophobic silica and / or titanium oxide. A two-component developer comprising the toner according to any one of claims 1 to 5. An image forming apparatus according to any one of claims 1 to 5, wherein the toner is used.

Images