JP2022069168A - Toner, developer, toner storage unit, image forming apparatus and image forming method - Google Patents

Abstract

To provide toner having excellent low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability and chargeability.SOLUTION: Toner according to the present invention includes: toner base particles containing binder resin; organic resin fine particles having a core-shell structure, on a surface of the toner base particles, comprised of a core having a resin (a) containing a styrene-acrylic resin but not containing a carboxyl group, and a shell having a resin (b) containing a carboxyl group; and an anionic surfactant containing the carboxyl group.SELECTED DRAWING: None

Description

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

Image forming devices such as multifunction devices (MFPs) and printers using toner are widely used in various places such as offices. The toner has high temperature offset resistance and low temperature fixing in order to improve the quality of the output image, reduce power consumption during fixing to save energy, and increase resistance to high temperature and high humidity during storage and transportation. Properties and heat-resistant storage properties are required.

As a toner with improved high temperature offset resistance, low temperature fixability and heat storage resistance, for example, the weight average molecular weight (Mw) is 8,000 to 1,000,000 and the particle size is 20 to 400 nm. , Toners containing resin fine particles having a core-shell structure have been proposed (see, for example, Patent Document 1).

However, in the toner of Patent Document 1, improvement of charging performance has not been studied. When the chargeability of the toner decreases, ground stains and toner scattering may occur. Therefore, in order to further utilize the toner, there is a demand for a toner having excellent low temperature fixing property, high temperature offset resistance, heat storage property and chargeability.

One aspect of the present invention is to provide a toner having excellent low temperature fixing property, high temperature offset resistance, heat storage property and chargeability.

One aspect of the toner according to the present invention is a core containing toner matrix particles containing a binder resin and having a resin (a) containing a styrene acrylic resin and no carboxyl group on the surface of the toner matrix particles. It has an organic resin fine particle having a core-shell structure composed of a shell having a resin (b) containing a carboxyl group, and an anionic surfactant containing a carboxyl group.

One aspect of the present invention can provide a toner having excellent low temperature fixing property, high temperature offset resistance, heat storage property and chargeability.

It is a schematic block diagram which shows an example of the image forming apparatus which concerns on one Embodiment. It is a schematic block diagram which shows another example of the image forming apparatus which concerns on one Embodiment. It is a schematic block diagram which shows an example of the image forming apparatus which concerns on one Embodiment. It is a partially enlarged view of the image forming apparatus of FIG. It is a schematic block diagram which shows an example of the process cartridge which concerns on one Embodiment.

Hereinafter, embodiments of the present invention will be described in detail. The embodiment is not limited to the following description, and can be appropriately changed without departing from the gist of the present invention. Further, in the present specification, the tilde "-" indicating a numerical range means that the numerical values described before and after the tilde are included as the lower limit value and the upper limit value unless otherwise specified.

<Toner>
The toner according to one embodiment is a toner containing toner matrix particles containing a binder resin, and contains organic resin fine particles having a core-shell structure and an anionic surfactant containing a carboxyl group on the surface of the toner. I'm out. In addition to the binder resin, the toner according to the embodiment may contain other components such as a colorant and a mold release agent, if necessary.

[Bundling resin]
The binding resin can include a polyester resin. The toner according to the embodiment may contain a binder resin other than the polyester resin.

(Polyester resin)
The polyester resin preferably contains at least one of a crystalline polyester resin and an amorphous polyester resin.

((Crystalline polyester resin))
Since the crystalline polyester resin has crystallinity, it exhibits a thermal melting property showing a rapid decrease in viscosity near the fixing start temperature. By using a crystalline polyester resin having such characteristics together with a non-crystalline 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 rapid viscosity due to melting of the crystalline polyester resin is good. A toner having both good heat-resistant storage stability and low-temperature fixability can be obtained because the deterioration occurs, the resin is compatible with the non-crystalline polyester resin, and the viscosity is rapidly reduced together to fix the resin. In addition, good results are also shown for the mold release width (difference between the fixing lower limit temperature and the high temperature offset resistance generation temperature).

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 embodiment, the crystalline polyester resin refers to a resin obtained by using the above-mentioned components, and a resin obtained by modifying the polyester resin, for example, a prepolymer and a prepolymer described later, are crosslinked and / Or does not contain the resin obtained by the elongation reaction.

-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, the linear saturated aliphatic diol is preferable, and the linear saturated aliphatic diol having 2 to 12 carbon atoms is preferable. Is more preferable. 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 number of carbon atoms of the saturated aliphatic diol exceeds 12, 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, 1,18 -Octadecanediol, 1,14-eicosandecanediol and the like can be mentioned. 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. Decanediol and 1,12-dodecanediol are preferable.

Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used alone or in combination of two or more.

-Polyvalent carboxylic acid-
The polyvalent carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a divalent carboxylic acid and a trivalent or higher carboxylic acid.

Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, speric acid, azelaic acid, sebacic acid, 1,9-nonandicarboxylic acid, 1,10-decandicarboxylic acid and 1,12. -Saturated aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconin Aromatic dicarboxylic acids such as dibasic acids such as acids; and the like; further, these anhydrides and lower (1 to 3 carbon atoms) alkyl esters thereof are also mentioned.

Examples of trivalent or higher valent carboxylic acids include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid and the like, and anhydrides thereof and their anhydrides. Examples thereof include lower (1 to 3 carbon atoms) alkyl esters.

Further, the polyvalent carboxylic acid may contain a dicarboxylic acid having a sulfonic acid group in addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid. Further, the polyvalent carboxylic acid may contain a dicarboxylic acid having a double bond in addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid. 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 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. By doing so, 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 to 80 ° C. If the melting point is less than 60 ° C, the crystalline polyester resin is likely to melt at a low temperature, and the heat-resistant storage stability of the toner may decrease. If the melting point exceeds 80 ° C, the crystalline polyester resin is melted by heating during fixing. May be inadequate and the low temperature fixability may decrease.

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 lowering 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 in gel permeation chromatography (GPC) measurement. It is preferably 5,000 to 15,000, and more preferably 5,000 to 15,000. The number average molecular weight (Mn) is preferably 1,000 to 10,000, more preferably 2,000 to 10,000. Mw / Mn is preferably 1.0 to 10, and more preferably 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 the affinity between the paper and the resin, 5 mgKOH / g or more is preferable, and 10 mgKOH / g or more is more preferable. On the other hand, in order to improve the high temperature offset resistance, 45 mgKOH / g or less is preferable.

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

The molecular structure of the crystalline polyester resin can be confirmed by NMR measurement using a solution or a solid, X-ray diffraction, GC / MS, LC / MS, IR measurement, or the like. A simple method is to detect a crystalline polyester resin having absorption based on δCH (out-of-plane angular vibration) of an olefin at 965 ± 10 cm ^-1 or 990 ± 10 cm ^-1 in the infrared absorption spectrum.

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 and 5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the toner. Parts by mass are more preferred. 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 the content exceeds 20 parts by mass, the heat-resistant storage stability may be lowered and the image may be easily fogged. When the content is within the above-mentioned more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

((Amorphous polyester resin))
The amorphous polyester resin contains a diol component and a cross-linking component as constituent components.

The diol component contained in the amorphous polyester resin contains 50 mol% or more, preferably 80 mol% or more, and 90 mol of an aliphatic diol having 3 to 10 carbon atoms.
It is more preferable to contain% or more.

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

The non-crystalline polyester resin preferably has an odd number of carbon atoms in the portion serving as the main chain of the diol component, and the diol component preferably has an alkyl group in the side chain.

The aliphatic diol having 3 to 10 carbon atoms has an odd number of carbon atoms in the main chain portion, preferably has an alkyl group in the side chain, and is an aliphatic diol represented by the following general formula (1). Is preferable.
HO- (CR ¹ R ² ) _n -OH ... General formula (1)
However, in the general formula (1), R ¹ and R ² independently represent a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, respectively. n represents an odd number of 3-9. In n repeating units, R ¹ and R ² may be the same or different, respectively.

The cross-linking component contained in the non-crystalline polyester resin preferably contains a trihydric or higher fatty alcohol and preferably contains a trivalent to tetravalent fatty alcohol from the viewpoint of gloss and image density of the fixed image. The cross-linking component may be only a trihydric or higher aliphatic alcohol.

Examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and dipentaerythritol.

The ratio of the cross-linking component is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5% by mass to 5% by mass, more preferably 1% by mass to 3% by mass.

The ratio of the trihydric or higher aliphatic alcohol in the polyhydric alcohol component is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50% by mass to 100% by mass, and 90% by mass to 100% by mass. % Is more preferable.

The dicarboxylic acid component preferably contains an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and preferably contains 50 mol% or more of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

The dicarboxylic acid component preferably contains less than 60 mol% of an 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, dodecanedioic acid and the like.

The amorphous polyester resin may be used alone or in combination with other amorphous polyester resins.

((Other amorphous polyester resin))
Other non-crystalline polyester resins contain, for example, a diol component and a dicarboxylic acid component as constituent components. The other amorphous polyester resin may further contain a cross-linking component as a constituent component. Examples of the cross-linking component include trihydric or higher aliphatic alcohols.

-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, 1,12 -Alipid diols such as dodecanediol; diols having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol; 1,4-cyclohexanedimethanol, hydrogenated bisphenol A Alicyclic diols such as; alicyclic diols to which alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide are added; bisphenols such as bisphenol A, bisphenol F and bisphenol S; , An alkylene oxide adduct of bisphenols such as those to which an alkylene oxide such as butylene oxide is added can be mentioned. Among these, aliphatic diols having 4 to 12 carbon atoms are 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 acids and aromatic dicarboxylic acids. Further, these anhydrides may be used, a lower (1 to 3 carbon atoms) alkyl esterified product may be used, or a halide may be used.

The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid and fumaric acid.

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, naphthalenedicarboxylic acid and the like, and among these, the number of carbon atoms is 4 to 12. The aliphatic dicarboxylic acid of is preferred.

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

-Aliphatic alcohol with a valence of 3 or more-
The trihydric or higher aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol. .. Of these, trivalent to tetravalent aliphatic alcohols are preferable. These trihydric or higher aliphatic alcohols may be used alone or in combination of two or more.

The first glass transition point (also referred to as glass transition temperature) Tg _1st of the differential scanning calorimetry (DSC) of the polyester resin is preferably 20 ° C to 50 ° C.

In order to improve the low temperature fixability of the toner, a method of lowering the glass transition point (also referred to as glass transition temperature) Tg of the crystalline polyester resin or crystalline polyester so that the non-crystalline polyester resin is melted together with the crystalline polyester resin. A method of reducing the molecular weight of the resin can be considered. When the melt viscosity of the amorphous polyester resin is lowered by lowering the glass transition point Tg of the amorphous polyester resin or reducing the molecular weight of the crystalline polyester resin, the heat-resistant storage stability of the toner and the fixing The high temperature offset property of the time may be deteriorated.

In the present embodiment, the non-crystalline polyester resin preferably contains a diol component as a constituent component, and the diol component preferably contains 50 mol% or more of an aliphatic diol having 3 to 10 carbon atoms. As a result, the glass transition point Tg and the melt viscosity can be lowered, and low temperature fixability can be ensured. Further, the amorphous polyester resin preferably contains a trihydric or higher aliphatic alcohol as a cross-linking component. As a result, the non-crystalline polyester resin has a branched structure in the molecular skeleton, and the molecular chain has a three-dimensional network structure, so that it has a rubber-like property that it deforms at a low temperature but does not flow. Therefore, the heat-resistant storage stability and high-temperature offset resistance of the toner can be maintained.

The other amorphous polyester resin preferably has at least one of a urethane bond and a urea bond from the viewpoint of being more excellent in adhesiveness to a recording medium such as paper. When the other amorphous polyester resin has at least one of urethane bond and urea bond, the urethane bond or urea bond behaves like a pseudo-crosslink point, and the rubber-like property of the other amorphous polyester resin. Is stronger, and the heat-resistant storage resistance and high-temperature offset resistance of the toner are more excellent.

-Amorphous polyester resin having at least one of urethane bond and urea bond-
The amorphous polyester resin having at least one of a urethane bond and a urea bond is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an amorphous polyester resin having an active hydrogen group and a polyisocyanate. The reaction product with and the like can be mentioned. The reaction product can be used as a reaction precursor (hereinafter, may be referred to as "prepolymer") to react with a curing agent described later.

--Amorphous polyester resin with active hydrogen group ---
Examples of the amorphous polyester resin having an active hydrogen group include an amorphous polyester resin having a hydroxyl group.

－－Polyisocyanate－－
The polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diisocyanate and trivalent or higher valent isocyanate.

Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aromatic aliphatic diisocyanates, isocyanurates, and those obtained by blocking these with phenol derivatives, oximes, caprolactam and the like.

The aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decametin diisocyanate, etc. , Dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexanediisocyanate and the like.

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'-diisocyanatodiphenyl. , 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', α'-tetramethylxylylene diisocyanate and the like.

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.

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

--- Active hydrogen group-containing compound ---
The active hydrogen group in the active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group and the like can be selected. Can be mentioned. 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. Be done. 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 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, 4,4'-diaminodiphenylmethane and the like. 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, isophoronediamine and the like. 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 amine having a trivalent value or higher 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, ketimine obtained by blocking the amino group with a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. Examples thereof include compounds and oxazoline compounds.

The molecular structure of the 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. A simple method is to detect as a polyester resin in the infrared absorption spectrum that 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 do not have absorption based on δCH (out-of-plane angular vibration) of the olefin.

The content of the polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 parts by mass to 90 parts by mass and 70 parts by mass to 85 parts by mass with respect to 100 parts by mass of the toner. The unit is more preferable. If the content is less than 50 parts by mass, the low temperature fixing property and the high temperature offset resistance may be deteriorated, and if it exceeds 90 parts by mass, the heat storage property is deteriorated and the gloss of the image obtained after fixing is deteriorated. The degree and degree of coloring may decrease. When the content is within the more preferable range, it is advantageous in that it is excellent in all of low temperature fixing property, high temperature offset resistance, and heat resistance storage property.

(Other binding resin)
The toner according to one embodiment may contain other binder resin components other than the above polyester resin. Other binding resins include, for example, silicone resin, styrene / acrylic resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol resin, terpene resin, coumarin resin, amidimide resin, butyral resin, urethane resin, ethylene and A known binder resin such as vinyl acetate resin can be included.

[Organic resin fine particles]
The organic resin fine particles are arranged on the surface of the toner. The organic resin fine particles are arranged in a state of being scattered on the surface of the toner, not in a state of being laminated so as to cover the surface of the toner.

The organic resin fine particles have a core-shell structure composed of a core having a resin (a) containing a styrene acrylic resin and no carboxyl group, and a shell having a resin (b) containing a carboxyl group. The organic resin fine particles do not necessarily have to have a shell, and may be composed of only a core.

(Resin (a))
The resin (a) is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of the vinyl monomer include the following (1) to (10).

(1) Vinyl Hydrocarbons Examples of vinyl hydrocarbons include (1-1) aliphatic vinyl hydrocarbons, (1-2) alicyclic vinyl hydrocarbons, and (1-3) aromatic vinyl hydrocarbons.

(1-1) Aliphatic Vinyl Hydrocarbons Examples of the aliphatic vinyl hydrocarbons include alkenes and alkazienes. Specific examples of alkenes include ethylene, propylene and α-olefins. Specific examples of alkaziene include butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadien and the like.

(1-2) Alicyclic Vinyl Hydrocarbons Examples of the alicyclic vinyl hydrocarbons include mono- or di-cycloalkene and alkaziene, and specific examples thereof include (di) cyclopentadiene and terpenes. ..

(1-3) Aromatic Vinyl Hydrocarbons Examples of aromatic vinyl hydrocarbons include styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituents, and specific examples thereof are α-methyl. Examples thereof include styrene, 2,4-dimethylstyrene and vinylnaphthalene.

(2) Carboxyl group-containing vinyl monomer and its salt The carboxyl group-containing vinyl monomer and its salt include unsaturated monocarboxylic acid (salt) having 3 to 30 carbon atoms, unsaturated dicarboxylic acid (salt) and its anhydride (salt). ) And its monoalkyl (1 to 24 carbon atoms) ester or a salt thereof and the like.

Specifically, (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, Examples thereof include carboxyl group-containing vinyl monomers such as citraconic acid, citraconic acid monoalkyl ester, and cinnamon acid, and metal salts thereof.

In addition, in this embodiment, "(salt)" means an acid or a salt thereof. For example, an unsaturated monocarboxylic acid (salt) having 3 to 30 carbon atoms means an unsaturated monocarboxylic acid or a salt thereof.

"(Meta) acrylic" means methacrylic acid or acrylic acid. That is, "(meth) acryloyl" means methacryloyl or acryloyl, and "(meth) acrylate" means methacrylate or acrylate.

(3) Sulfonic group-containing vinyl monomer, vinyl sulfuric acid monoesteride and salts thereof The sulfonic acid group-containing vinyl monomer, vinyl sulfuric acid monoesteride and salts thereof include alkene sulfonic acid (salt) having 2 to 14 carbon atoms and carbon. Examples thereof include alkyl sulfonic acid (salt) of numbers 2 to 24, sulfo (hydroxy) alkyl- (meth) acrylate (salt) or (meth) acrylamide (salt), and alkylallyl sulfosuccinic acid (salt). Specific examples of the alken sulfonic acid having 2 to 14 carbon atoms include vinyl sulfonic acid (salt), and the alkyl sulfonic acid (salt) having 2 to 24 carbon atoms includes α-methylstyrene sulfonic acid (salt). Examples thereof include sulfo (hydroxy) alkyl- (meth) acrylate (salt) or (meth) acrylamide (salt) as sulfopropyl (meth) acrylate (salt), sulfate ester (salt) or sulfonic acid group-containing vinyl monomer. (Salt) and the like.

(4) Phosphoric acid group-containing vinyl monomer and its salt:
Examples of the phosphoric acid group-containing vinyl monomer and its salt include (meth) acryloyloxyalkyl (1 to 24 carbon atoms) phosphoric acid monoester (salt) and (meth) acryloyloxyalkyl (1 to 24 carbon atoms) phosphonic acid (salt). Can be mentioned.

Specific examples of (meth) acryloyloxyalkyl (1 to 24 carbon atoms) phosphoric acid monoester (salt) include 2-hydroxyethyl (meth) acryloyl phosphate (salt) and phenyl-2-acryloyloxyethyl phosphate (salt). And so on.

Specific examples of the (meth) acryloyloxyalkyl (1 to 24 carbon atoms) phosphonic acid (salt) include 2-acryloyloxyethyl phosphonic acid (salt).

Examples of the salts (2) to (4) include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.), ammonium salts, amine salts, and quaternary ammonium salts. Salt is mentioned.

(5) Hydroxy group-containing vinyl monomer As the hydroxyl group-containing vinyl monomer, hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, ( Meta) Allyl alcohol, clothyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-buten-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether and Examples thereof include sucrose allyl ether.

(6) Nitrogen-containing vinyl monomer Examples of the nitrogen-containing vinyl monomer include an amino group-containing vinyl monomer, an amide group-containing vinyl monomer, a nitrile group-containing vinyl monomer, a quaternary ammonium cation group-containing vinyl monomer, and a nitro group-containing vinyl monomer. ..

Examples of the amino group-containing vinyl monomer include aminoethyl (meth) acrylate and the like.

Examples of the amide group-containing vinyl monomer include (meth) acrylamide and N-methyl (meth) acrylamide.

Examples of the nitrile group-containing vinyl monomer include (meth) acrylonitrile, cyanostyrene, and cyanoacrylate.

Examples of the quaternary ammonium cation group-containing vinyl monomer include tertiary amine group-containing vinyls such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide and diallylamine. Examples thereof include a quaternized product of a monomer (a quaternized product using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, and dimethyl carbonate).

Examples of the nitro group-containing vinyl monomer include nitrostyrene.

(7) Epoxy group-containing vinyl monomer Examples of the epoxy group-containing vinyl monomer include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and p-vinylphenylphenyl oxide.

(8) Halogen element-containing vinyl monomer Examples of the halogen element-containing vinyl monomer include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorstyrene, bromstyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, and chloroprene. Can be mentioned.

(9) Vinyl ester The vinyl ester includes, for example, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, and the like. Phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) ) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, eikosyl (meth) acrylate, behenyl (meth) ) Acrylate, etc.)], Dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups with 2 to 8 carbon atoms), dialkyl maleates (two alkyl groups are , A linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkane [dialyloxyetane, trialiloxietan, tetraaryloxyetane, tetraaryloxy. Vinyl monomers having a polyalkylene glycol chain such as propane, tetraaryroxybutane, tetramethalyloxyetane, etc. [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylate [poly (meth) acrylate of polyhydric alcohol: ethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.] and the like.

(10) Vinyl (thio) ether Examples of the vinyl (thio) ether include vinyl methyl ether and the like.

(11) Vinyl Ketone Examples of the vinyl ketone include vinyl methyl ketone and the like.

(12) Other Vinyl Monomers Examples of other vinyl monomers include tetrafluoroethylene, fluoroacrylate, isocyanatoethyl (meth) acrylate and m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

As the resin (a), one of the vinyl monomers (1) to (12) may be used alone or in combination of two or more.

The resin (a) preferably contains a styrene- (meth) acrylic acid ester copolymer and a (meth) acrylic acid ester copolymer from the viewpoint of low-temperature fixability of the organic resin fine particles, and more preferably styrene- (meth). Meta) Contains an acrylic acid ester copolymer.

(Resin (b))
As the resin (b), a polymer obtained by homopolymerizing a vinyl monomer having a carboxyl group or copolymerizing it with another monomer can be used. As the vinyl monomer, the same polymer as the polymer used for the above resin (a) can be used.

The resin (b) is a resin having methacrylic acid and / or acrylic acid in a total amount of 10% by mass to 60% by mass, more preferably 30% by mass to 50% by mass, based on the total weight of the resin (b). be.

Similar to the resin (a), the resin (b) is preferably a styrene- (meth) acrylic acid ester copolymer and a (meth) acrylic acid ester copolymer from the viewpoint of low-temperature fixability of the organic resin fine particles. , More preferably a styrene- (meth) acrylic acid ester copolymer.

The acid values of the resin (a) and the resin (b) will be described.

The acid value of the resin (a) is preferably 0 mgKOH / g from the viewpoint of low temperature fixability and core shell structure formation.

The acid value of the resin (b) is preferably 75 mgKOH / g to 400 mgKOH / g, and more preferably 150 mgKOH / g to 300 mgKOH / g. When the acid value of the resin (b) is within this range, it is easy to form a structure in which the organic resin fine particles including the core resin (a) and the shell resin (b) are attached to the surface of the toner.

((Measurement of acid value))
The acid value was measured under the following conditions in accordance with the measuring method described in JIS K0070-1992. However, when the sample did not dissolve, dioxane, tetrahydrofuran or the like was used as the solvent. The acid value is specifically determined by the following procedure.
-Measurement condition-
-Measuring device: Potential difference automatic titrator (DL-53 Titrator, manufactured by METTLER TOLEDO)
-Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
-Analysis software: LabX Light Version 1.00.000
-Variation of equipment: A mixed solvent of 120 ml of toluene and 30 ml of ethanol was used.
・ Measurement temperature: 23 ° C

The measurement of oxidation can be calculated using the above-mentioned measuring device, and specifically, it is calculated as follows. That is, titration was performed with a pre-standardized alcohol solution of N / 10 potassium hydroxide, and the acid value was obtained by the following calculation from the consumption of the alcohol potassium hydroxide solution.
Acid value = KOH (number of ml) x N x 56.1 / sample weight (however, N is a factor of N / 10KOH)

The glass transition point Tg _1st in the first temperature rise of the resin (a) and the resin (b) will be described.

The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry (DSC) of the resin (a) and the resin (b) is preferably 30 ° C to 70 ° C. If the glass transition point Tg _1st at the first temperature rise is less than 30 ° C., the effect of heat-resistant storage cannot be obtained. When the glass transition point Tg _1st at the first temperature rise exceeds 70 ° C., the inhibition to low temperature fixing becomes large.

In this embodiment, the glass transition point Tg _1st is specifically determined by the following procedure. TA-60WS and DSC-60 manufactured by Shimadzu Corporation are used as measuring devices, and measurement is performed under the following measurement conditions.
((Measurement condition))
-Sample container: Aluminum sample pan (with lid)
・ Sample amount: 5 mg
-Reference: Aluminum sample pan (alumina 10 mg)
・ Atmosphere: Nitrogen (flow rate 50 ml / min)
((Temperature condition))
・ Starting temperature: 20 ° C
・ Temperature rise rate: 10 ° C / min
・ End temperature: 150 ℃
・ Holding time: None ・ Temperature down temperature: 10 ℃ / min
・ End temperature: 20 ℃
・ Retention time: None ・ Temperature rise rate: 10 ℃ / min
・ End temperature: 150 ℃

The measurement results were analyzed using data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. For the analysis method, specify a range of ± 5 ° C centering on the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the first temperature rise, and use the peak analysis function of the analysis software to specify the peak temperature. Ask for. Next, the maximum endothermic temperature of the DSC curve is obtained by using the peak analysis function of the analysis software in the range of the peak temperature of + 5 ° C. and −5 ° C. on the DSC curve. The temperature shown here corresponds to the glass transition point Tg _1st in the first temperature rise of the resin of the measurement sample.

The mass ratio of the resin (a) and the resin (b) contained in the organic resin fine particles is 5/95 to 95/5, preferably 25/75 to 75/25, and more preferably 40/60 to 40. It is 60/40. When the mass ratio is 95/5 or more, the heat-resistant storage stability of the organic resin fine particles is excellent. When the mass ratio is 5/95 or less, the organic resin fine particles easily form toner particles attached to the surface of the toner matrix particles.

Further, when the organic resin fine particles mixed in advance during emulsification are uniformly adhered to the surface of the toner matrix particles, and then the toner matrix particles are washed with an alkaline aqueous solution, the resin in the organic resin fine particles adhered to the surface of the toner matrix particles. By removing all or part of (b), the state of the organic resin fine particles on the surface of the toner matrix particles can be controlled.

As a method for producing the organic resin fine particles containing the resin (a) and the resin (b) as constituent components, a known production method can be mentioned. For example, the following production methods (I) to (V) and the like can be mentioned. Can be mentioned.
(I) A method of seed-polymerizing the constituent monomers of the resin (a) using the fine particles of the resin (b) in the aqueous dispersion as a seed.
(II) A method of seed-polymerizing the constituent monomers of the resin (b) using the fine particles of the resin (a) in the aqueous dispersion as a seed.
(III) A method of emulsifying a mixture of the resin (a) and the resin (b) into an aqueous medium to obtain an aqueous dispersion of resin fine particles.
(IV) A method in which a mixture of a resin (a) and a constituent monomer of a resin (b) is emulsified in an aqueous medium, and then the constituent monomers of the resin (b) are polymerized to obtain an aqueous dispersion of resin fine particles.
(V) A method in which a mixture of the constituent monomer of the resin (a) and the resin (b) is emulsified in an aqueous medium, and then the constituent monomer of the resin (a) is polymerized to obtain an aqueous dispersion of resin fine particles.

It should be noted that the fact that the organic resin fine particles contain the resin (a) and the resin (b) as constituents in the same particles means that the cut surface of the organic resin fine particles is known as a surface elemental analyzer (TOF-SIMS and EDX-SEM). Etc.) and by observing the elemental mapping image and the electron microscope observation image of the cut surface of the organic resin fine particles dyed with the dyeing agent corresponding to the functional group contained in the resin (a1) and the resin (a2). You can check.

Specific examples of (I) include the following methods. First, the constituent monomers of the resin (b) are dropped and polymerized to produce an aqueous dispersion of resin fine particles containing the resin (b). Then, the method of seed-polymerizing the constituent monomers of the resin (a) using the aqueous dispersion as a seed and the resin (b) previously produced by solution polymerization or the like are emulsified and dispersed in water. Then, the constituent monomer of the resin (a) is seed-polymerized using the emulsified dispersion as a seed.

Specific examples of (II) include the following methods. First, the constituent monomers of the resin (a) are dropped and polymerized to produce an aqueous dispersion of resin fine particles containing the resin (a). Then, the method of seed-polymerizing the constituent monomers of the resin (b) using the aqueous dispersion as a seed and the resin (a) previously produced by solution polymerization or the like are emulsified and dispersed in water. Then, the constituent monomer of the resin (b) is seed-polymerized using the emulsified dispersion as a seed.

Specific examples of (III) include a method of mixing a solution or a melt containing the resin (a) and the resin (b) previously produced by solution polymerization or the like, and then emulsifying and dispersing the mixed solution in an aqueous medium. Be done.

As a specific example of (IV), a mixture obtained by mixing a resin (a) previously produced by solution polymerization or the like with a constituent monomer of the resin (b) is emulsified and dispersed in an aqueous medium, and the mixture is emulsified and dispersed in an emulsified dispersion. Examples thereof include a method of producing the resin (b) by polymerizing the constituent monomers of the resin (b).

As a specific example of (V), a mixture obtained by mixing the constituent monomer of (a) with (b) previously produced by solution polymerization or the like is emulsified and dispersed in an aqueous medium, and a resin (a resin is used in the emulsified dispersion liquid. Examples thereof include a method of producing the resin (a) by polymerizing the constituent monomers of a).

Any of the production methods (I) to (V) is suitable.

The organic resin fine particles are preferably used as an aqueous dispersion, and the aqueous medium of the dispersion can be used without particular limitation as long as it is a liquid containing water as an essential constituent. In the present embodiment, since the organic resin fine particles and the surfactant are provided on the surface of the toner, it is preferable to use, for example, an aqueous solution containing the surfactant in water as the aqueous medium.

The particle size of the organic resin fine particles is preferably 10 nm to 100 nm. If the particle size is less than 10 nm, the coverage on the toner surface becomes high, and the low temperature fixing performance may deteriorate. If the particle size exceeds 100 nm, the voids on the toner surface become large, and the effect of heat-resistant storage performance is reduced.

The particle size of the organic resin fine particles can be measured by using a laser Doppler particle size distribution measuring device, a particle size distribution measuring device, and adding a sample to be measured to the measuring device using a dropper, a syringe, or the like. The measurement conditions are as follows.
(Measurement condition)
・ Equipment: nanotrac UPA-150EX (manufactured by Nikkiso Co., Ltd.)
・ Distribution display: Volume ・ Number of channels: 52
・ Measurement time: 30 sec
-Particle refractive index: 1.81
・ Temperature: 25 ℃
-Particle shape: Spherical-Viscosity (CP): High-temperature viscosity 0.797 Low-temperature viscosity 1.002
-Solvent refractive index: 1.333
・ Solvent: Water

The content of the organic resin fine particles A in the toner is preferably 0.2% by mass to 5% by mass. If the content is less than 0.2% by mass, the effect of heat-resistant storage cannot be sufficiently obtained. When the content exceeds 5%, the inhibition to low temperature fixing becomes large.

The content of the organic resin fine particles A in the toner can be measured by a pyrolysis gas chromatograph device. The measurement method is as follows.
(Measurement condition)
-Gas chromatograph device: 7890B (manufactured by Agilent Technologies)
-Pyrolysis device: EGA / PY-3030D (manufactured by Frontier Lab)
・ Pyrolysis condition temperature: 600 ℃
-Interface temperature: 400 ° C
・ Detector temperature: 320 ℃
-Oven temperature: 50 ° C (10 min)-<10 ° C / minn> -150 ° C (0 min)-<20 ° C / min> -320 ° C (3.5 min)
-Column: UA5-30M-1F (30 m x 0.25 mmi.d., 1.0 μm film)
-Detector: FID

[Anionic surfactant]
The anionic surfactant exists bound to the surface of the toner and contains a carboxyl group.

Examples of the anionic surfactant include ether carboxylic acids having a hydrocarbon group having 8 to 24 carbon atoms or salts thereof, sulfuric acid esters or ether sulfate esters having hydrocarbon groups having 8 to 24 carbon atoms, salts thereof, and carbon atoms thereof. Sulfates with 8 to 24 hydrocarbon groups, sulfosuccinates with one or two hydrocarbon groups with 8 to 24 carbon atoms, phosphate esters or ether phosphorus with hydrocarbon groups with 8 to 24 carbon atoms. Examples thereof include acid esters and salts thereof, fatty acid salts having a hydrocarbon group having 8 to 24 carbon atoms, and acylated amino acid salts having a hydrocarbon group having 8 to 24 carbon atoms.

Examples of the ether carboxylic acid having a hydrocarbon group having 8 to 24 carbon atoms or a salt thereof include sodium lauryl ether acetate and (poly) oxyethylene (additional moles 1 to 100) sodium lauryl ether acetate.

Examples of the sulfate ester or ether sulfate ester having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof include sodium lauryl sulfate, (poly) oxyethylene (additional moles 1 to 100) sodium lauryl sulfate, and (poly) oxyethylene. Examples thereof include (additional moles 1 to 100) sodium lauryl sulfate triethanolamine and (poly) oxyethylene (additional moles 1 to 100) coconut oil fatty acid monoethanolamide sodium sulfate.

Examples of the sulfonate having a hydrocarbon group having 8 to 24 carbon atoms include sodium dodecylbenzene sulfonate.

Examples of the phosphate ester or ether phosphate having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof include sodium lauryl phosphate and (poly) oxyethylene (additional moles 1 to 100) sodium lauryl ether phosphate and the like. Can be mentioned.

Examples of the fatty acid salt having a hydrocarbon group having 8 to 24 carbon atoms include sodium laurate, triethanolamine laurate and the like.

Examples of the acylated amino acid salt having a hydrocarbon group having 8 to 24 carbon atoms include coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosin sodium, coconut oil fatty acid sarcosin triethanolamine, and N-palm oil fatty acid acyl-L-glutamate tri. Examples thereof include ethanolamine, N-palm oil fatty acid acyl-L-sodium glutamate, and lauroylmethyl-β-alanine sodium.

Further, if necessary, sodium acetate, sodium citrate, sodium bicarbonate and the like may be contained as a buffer. These may be used alone or in combination of two or more.

Further, if necessary, the protective colloid may contain a water-soluble cellulose compound, an alkali metal salt of polymethacrylic acid, and the like. These may be used alone or in combination of two or more.

The acid value of the anionic surfactant is preferably 100 mgKOH / g to 200 mgKOH / g, more preferably 110 mgKOH / g to 180 mgKOH / g, and even more preferably 130 mgKOH / g to 160 mgKOH / g. .. When the acid value of the anionic surfactant is 100 mgKOH / g to 200 mgKOH / g, it is not easily affected by the humidity in the atmosphere and a negative chargeable effect can be obtained satisfactorily.

Specifically, as the anionic surfactant having a carboxyl group, it is preferable to use a succinic acid derivative such as a sulfosuccinic acid ester salt.

As the surfactant of the commercially available sulfosuccinic acid ester salt, the anionic surfactant having a carboxyl group includes Beaulite SSS (manufactured by Sanyo Chemical Industries, Ltd.), Carabon DA-72 (manufactured by Sanyo Chemical Industries, Ltd.), and Perex OT-P. (Made by Kao) etc. Further, a surfactant of a sulfosuccinic acid ester salt can be obtained by hydrolyzing an ester group with an acid.

When synthesizing a sulfosuccinic acid ester salt, it can be synthesized by a known method. For example, maleic acid is esterified with alkyl alcohols and sulfonated with a hydrogen sulfite metal salt to obtain a desired sulfosuccinic acid ester. Salt is obtained. In the case of this synthetic method, a sulfosuccinic acid ester salt having a desired alkyl chain can be obtained by freely changing the carbon number of the alkyl chain of the alkyl alcohols.

Confirmation of the presence of these surfactants in the toner can be performed by liquid chromatography and MS detector. For example, using a liquid chromatography system (AQUITY-UPLC / SQD system, manufactured by Japan Waters Corp.), the measurement can be performed by the following method.

About 0.2 g of the toner sample is carefully evaluated, and the mixture is poured into 20 mL of methanol and dispersed by stirring. Then, ultrasonic waves are applied for 30 minutes and the mixture is allowed to stand for 24 hours. The supernatant is filtered through a membrane filter having a pore size of 0.2 μm, and the obtained sample is diluted 100-fold with methanol before being subjected to the liquid chromatography. The MS detector confirms the presence of a peak derived from the carboxyl group.

The acid value of the surfactant having a carboxyl group is preferably 100 mgKOH / g to 200 mgKOH / g. In that range, it is less susceptible to the effects of atmospheric humidity and the negative charge effect is best obtained.

The acid value of the surfactant having a carboxyl group can be measured by the following method with an automatic potential difference titrator (DL-53 Titrator, manufactured by METTLER TOLEDO).

Titrate with a pre-standardized N / 10 caustic potassium to alcohol solution, and determine the acid value from the consumption of the alcohol potassium solution by the following calculation.
Acid value = KOH (number of ml) x N x 56.1 / sample weight (however, N is a factor of N / 10KOH)

[Other surfactants]
The toner according to one embodiment may contain other surfactants in addition to the anionic surfactant. Other surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and other emulsion dispersants.

Examples of the nonionic surfactant include an AO-addition type nonionic surfactant and a polyhydric alcohol type nonionic surfactant.

Examples of the AO-added nonionic surfactant include an EO adduct of an aliphatic alcohol having 10 to 20 carbon atoms, an EO adduct of phenol, an EO adduct of nonylphenol, an EO adduct of an alkylamine having 8 to 22 carbon atoms. Examples thereof include EO adducts of poly (oxypropylene) glycol.

As the polyhydric alcohol type nonionic surfactant, a fatty acid (8 to 24 carbon atoms) ester of a polyhydric (3 to 8 or more) alcohol (2 to 30 carbon atoms) (for example, glycerin monostearate, glycerin mono) Oleate, sorbitan monolaurate, sorbitan monooleate, etc.) and alkyl (carbon number 4 to 24) poly (polymerization degree 1 to 10) glycoside and the like can be mentioned.

Examples of the cationic surfactant include a quaternary ammonium salt type and an amine salt type. Specifically, examples of the quaternary ammonium salt type include stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, and lanolin fatty acid aminopropylethyldimethylammonium ethylsulfate.
Examples of the amine salt type include diethylaminoethylamide stearate, dilaurylamine hydrochloride, oleylamine lactate and the like.

Examples of the amphoteric tenside include a betaine-type amphoteric tenside agent and an amino acid-type amphoteric tenside agent.

Examples of the betaine-type amphoteric tenside include coconut oil fatty acid amide propyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and laurylhydroxysulfobetaine. Be.

Examples of the amino acid type amphoteric surfactant include β-sodium laurylaminopropionate and the like.

Examples of other emulsifying dispersants include reactive activators [specifically, Adecaria soap {registered trademark, manufactured by ADEKA Corporation} SE-10N, SR, as long as they have radical reactivity. -10, SR-20, SR-30, ER-20, ER-30, Aqualon {registered trademark, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.} HS-10, KH-05, KH-10, KH-1025, ester {Registered trademark, manufactured by Sanyo Kasei Kogyo Co., Ltd.} JS-20, Latemul {Registered trademark, manufactured by Kao Co., Ltd.} PD-104, PD-420, PD-430, Ionet {Registered trademark, Sanyo Kasei Kogyo Co., Ltd. MO-200], polyvinyl alcohol, starch and its derivatives, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, carboxyl group-containing (co) polymers such as sodium polyacrylic acid, and US Pat. No. 5,906,704. Examples thereof include the described emulsion dispersants having a urethane group or an ester group (for example, a polycaprolactone polyol in which a polyether diol is linked with a polyisocyanate).

In the present embodiment, the surfactant is an anionic surfactant and nonionic surfactant from the viewpoint of stabilizing the oil droplets and sharpening the particle size distribution while obtaining a desired shape during emulsification and dispersion. The combined use with at least one of the surfactant and other emulsifying dispersants is preferable, and the combined use of the anionic surfactant and other emulsifying dispersants is more preferable.

[Other resin components]
The organic resin fine particles may contain other resin components in addition to the resin (a) and the resin (b). Other resin components include initiators (and their residues), chain transfer agents, antioxidants, plasticizers, preservatives, reducing agents, organic solvents and the like.

Other resin components include vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, and urea other than the resin used for the resin (a) and the resin (b). Examples thereof include resins, aniline resins, ionomer resins and polycarbonate resins.

Examples of the initiator (and its residue) include known radical polymerization initiators and the like. Specifically, persulfate initiators such as potassium persulfate and ammonium persulfate, azo initiators such as azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, tertiary butyl. Examples thereof include organic peroxides such as peroxyisopropyl monocarbonate and tertiary butyl peroxybenzoate, hydrogen peroxide and the like.

Examples of the chain transfer agent include n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexylthioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid and α-methylstyrene dimer.

Examples of the antioxidant include phenol compounds, paraphenylenediamine, hydroquinone, organic sulfur compounds, organic phosphorus compounds and the like.

Examples of the phenol compound include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisol, 2,6-di-t-butyl-4-ethylphenol, and stearyl-β- (3,5-di-). t-Butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-t-) Butylphenol), 4,4'-thiobis- (3-methyl-6-t-butylphenol), 4,4'-butylidenebis- (3-methyl-6-t-butylphenol), 1,1,3-tris-( 2-Methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Tetrakiss- [Methyl-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] Methyl, bis [3,3'-bis (4'-hydroxy-3'-t-butyl) Phenyl) Butylic acid] Clicole ester, tocopherol and the like can be mentioned.

Examples of para-phenylenediamine include N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, and N-phenyl-N-sec-butyl-p-phenylenediamine. , N, N'-di-isopropyl-p-phenylenediamine and N, N'-dimethyl-N, N'-di-t-butyl-p-phenylenediamine and the like.

Hydroquinone includes 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone and 2-. (2-Octadecenyl) -5-methylhydroquinone and the like can be mentioned.

Examples of the organic sulfur compound include dilauryl-3,3'-thiodipropionate, disstearyl-3,3'-thiodipropionate and ditetradecyl-3,3'-thiodipropionate.

Examples of the organophosphorus compound include triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

Examples of the plasticizer include phthalic acid ester, aliphatic dibasic acid ester, trimellitic acid ester, phosphoric acid ester, fatty acid ester and the like.
Specifically, examples of the phthalate ester include dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, and diisodecyl phthalate.
Examples of the aliphatic dibasic acid ester include di-2-ethylhexyl adipic acid and -2-ethylhexyl sebacic acid.
Examples of the trimellitic acid ester include tri-2-ethylhexyl trimellitic acid and trioctyl trimellitic acid.
Examples of the phosphoric acid ester include triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate and the like.
Examples of the fatty acid ester include butyl oleate and the like.

Examples of the preservative include an organic nitrogen-sulfur compound preservative and an organic sulfur halide preservative.

Examples of the reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose and formaldehyde sulfoxylate metal salts, and reducing inorganic compounds such as sodium thiosulfite, sodium sulfite, sodium bicarbonate and sodium metabisulfite. Can be mentioned.

Examples of the organic solvent include a ketone solvent [for example, acetone and methyl ethyl ketone (hereinafter abbreviated as MEK)], an ester solvent (for example, ethyl acetate and γ-butyrolactone), an ether solvent (for example, THF), and an amide solvent (for example, N, N-dimethylformamide). , N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N-methylcaprolactam), alcohol solvents (eg isopropyl alcohol) and aromatic hydrocarbon solvents (eg toluene and xylene) and the like.

[Other ingredients]
The toner according to one embodiment may contain other components. Examples of other components include mold release agents, colorants, charge control agents, external additives, fluidity improvers, cleanability improvers, magnetic materials and the like.

(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 ozokerite and cercin; paraffin. , Microcrystallin, petrolatum and other petroleum waxes; and other 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, stearate 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 may be used. ..

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

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 8 parts by mass with respect to 100 parts by mass of the toner. Parts by mass are more preferred. 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 property may be deteriorated, image fog, etc. May be more likely to occur. If the content is within the above-mentioned more preferable range, it is advantageous in terms of improving the image quality and the fixing stability.

(Colorant)
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, carbon black, niglocin dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, 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), Balkan Fast Yellow (5G, R), Tartrajin Lake, Kinolin Yellow Lake, Anthracan Yellow BGL, Isoindrinon Yellow, Bengala, Lead Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sale 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 , Risole Rubin GX, Permanent Red F5R, Brilliant Carmine 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, Arizarin Lake, Thio Indigo Red B, Thio Indigo Maroon, Oil Red, Kinacridon 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, Metalless Futa Russian Nin Blue, Futa Russian Nin Blue, Fast Sky Blue, Indance Glen 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, Malakite Green Examples include rake, phthalocyanine green, anthraquinone green, titanium oxide, zinc oxide, and lithobon.

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. Is more preferable.

The colorant can also be used as a masterbatch compounded with a resin. As the resin to be kneaded together with the production of the master batch or the master batch, for example, in addition to the polyester resin, a polymer of styrene such as polystyrene, polyp-chlorostyrene, polyvinyltoluene or a substitute thereof; styrene-p-chlorostyrene together. Polymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer Polymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chlormethyl methacrylate polymer , Stylo-acrylonitrile copolymer, styrene-vinylmethylketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-inden copolymer, styrene-maleic acid copolymer, styrene- Styrene-based copolymers such as maleic acid ester copolymers; polymethylmethacrylate, polybutylmethacrylate, polyvinylchloride, polyvinylacetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, Examples thereof include polyacrylic acid resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes 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, niglosin dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes and alkoxys can be selected. System amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simplex or compounds, tungsten singles or compounds, fluoroactive agents, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. Can be mentioned.

Specifically, bontron 03 of niglocin-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, phenolic condensate E-89 (above, manufactured by Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodoya Chemical Industry Co., Ltd.), LRA -901, a boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer-based polymers having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. Examples include compounds.

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, and 0.2 part by mass with respect to 100 parts by mass of the toner. 5 parts by mass is more preferable. When 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, the fluidity of the developer is lowered, and the image is imaged. May lead to a decrease in concentration. These charge control agents can be melt-kneaded together with a masterbatch and a 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.

(External agent)
As the external additive, inorganic fine particles and hydrophobicized inorganic fine particles can be used in combination in addition to the oxide fine particles, but the average particle size of the hydrophobicized primary particles is preferably 1 nm to 100 nm, preferably 5 nm to 70 nm. Inorganic fine particles are more preferable.

Further, it is preferable that the hydrophobized primary particles contain at least one kind of inorganic fine particles having an average particle size of 20 nm or less and at least one kind of inorganic fine particles having an average particle size of 30 nm or more. The specific surface area by the BET method is preferably 20 m ² / g to 500 m ² / g.

The external additive is not particularly limited and may be appropriately selected depending on the intended purpose. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (for example, zinc stearate, aluminum stearate, etc.), metal oxides (for example, zinc stearate, aluminum stearate, etc.) For example, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers and the like can be mentioned.

Suitable additives include hydrophobized silica, titania, titanium oxide and alumina fine particles. Examples of the silica fine particles include R972, R974, RX200, RY200, R202, R805, R812 (all manufactured by Nippon Aerosil Co., Ltd.) and the like. The titania fine particles include, for example, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), MT- Examples thereof include 150W, MT-500B, MT-600B, and MT-150A (all manufactured by TAYCA).

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-1500T (manufactured by Titanium Industry Co., Ltd.). Examples thereof include Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (all manufactured by TAYCA Corporation), IT-S (manufactured by Ishihara Sangyo Co., Ltd.) and the like.

Hydrophobized oxide fine particles, hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobicized alumina fine particles include, for example, hydrophilic fine particles such as methyltrimethoxysilane and methyltriethoxysilane. , Octtilt can be obtained by treatment with a silane coupling agent such as remethoxysilane. Further, silicone oil-treated oxide fine particles and inorganic fine particles, which are treated with silicone oil by applying heat to 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-modified. Examples thereof include silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.

Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, and silica. Examples thereof include ash stone, silica soil, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. 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, preferably 0.3, with respect to 100 parts by mass of the toner. More preferably, it is 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 is preferably 100 nm or less, more preferably 3 nm or more and 70 nm or less. If it is smaller than this range, the inorganic fine particles are buried in the toner, and it is difficult for the function to be effectively exhibited. On the other hand, if it is larger than this range, the surface of the photoconductor is unevenly damaged, which is not preferable.

(Liquidity improver)
The fluidity improver is not particularly limited as long as it can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity, and 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. .. 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 cleanability 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 according to the purpose. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as 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.

<Characteristics of toner>
[Glass transition point Tg _1st ]
The toner according to the embodiment has a glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry (DSC) of 20 ° C to 50 ° C, more preferably 25 ° C to 50 ° C.

With conventional toner, when the glass transition point Tg is about 50 ° C. or lower, toner aggregation is likely to occur during toner transportation assuming summer or tropical regions, and due to temperature changes in the storage environment. As a result, solidification in the toner bottle and sticking of the toner in the developing machine occur. In addition, poor replenishment due to toner clogging in the toner bottle and image abnormality due to toner sticking in the developing machine are likely to occur.

The toner according to one embodiment has a lower glass transition point Tg than the conventional toner. However, since the polyester resin, which is a low Tg component in the toner, is non-linear, the toner according to one embodiment can maintain heat-resistant storage stability. In particular, when the polyester resin has a urethane bond or a urea bond having a high cohesive force, the effect of maintaining heat-resistant storage stability becomes more remarkable.

The toner according to one embodiment is not particularly limited as the glass transition point Tg _2nd (also referred to as glass transition temperature) in the second temperature rise of the differential scanning calorimetry (DSC), and may be appropriately selected according to the purpose. However, the temperature is preferably 0 ° C to 30 ° C, more preferably 10 ° C to 30 ° C.

The difference (Tg _1st -Tg _2nd ) between the first glass transition point Tg _1st of the temperature rise and the second glass transition point Tg _2nd of the temperature rise in the differential scanning calorimetry (DSC) of the toner according to one embodiment is particularly limited. However, it can be appropriately selected depending on the intended purpose, but it is preferably more than 0 ° C. (that is, Tg _1st > Tg _2nd ), and more preferably 10 ° C. or higher. The upper limit of the difference is not particularly limited and may be appropriately selected depending on the intended purpose, but the difference (Tg _1st − Tg _2nd ) is preferably 50 ° C. or lower.

When the toner according to one embodiment contains a crystalline polyester resin, the crystalline polyester resin that existed in an incompatible state before heating (before the first temperature rise) and the non-crystalline polyester resin are heated. After that (after the first temperature rise), it becomes compatible.

When the glass transition point Tg _1st at the first temperature rise is less than 20 ° C., deterioration of heat-resistant storage stability, blocking in the developing machine, and filming to the photoconductor are likely to occur. When the glass transition point Tg _1st at the first temperature rise exceeds 50 ° C., the low temperature fixability of the toner deteriorates.

If the glass transition point Tg _2nd at the second temperature rise is less than 0 ° C., the blocking resistance of the fixed image (printed matter) may decrease. If the glass transition point Tg _2nd at the second temperature rise exceeds 30 ° C., sufficient low temperature fixability and glossiness may not be obtained.

[Volume average particle size]
The volume average particle size of the toner according to one embodiment is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm to 7 μm. 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 average particle diameter of 2 μm or less.

<Calculation method of various characteristics of toner components>
The glass transition point Tg and the melting point of the polyester resin may be measured for themselves, respectively, but the constituent components contained in the toner are separated from the actual toner by GPC or the like, and the separated constituent components are subjected to the analysis method described later. The glass transition point Tg, the melting point, and the mass ratio of the constituent components may be calculated by using the glass transition point Tg.

Separation of each component by GPC can be performed by, for example, the following method.

First, 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 H-NMR measurement is performed, and the ratio of the constituent monomers is calculated from the integrated ratio of each element. Can be calculated.

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 ratio of constituent monomers. can do.

When the toner forms the toner matrix particles while producing the non-crystalline polyester resin by the elongation reaction and / or the crosslinking reaction between the non-linear reactive precursor and the curing agent, the actual toner is used. The non-crystalline polyester resin may be separated by GPC or the like to obtain the glass transition point Tg or the like of the non-crystalline polyester resin. In addition, a non-crystalline polyester resin is synthesized by an extension reaction and / or a cross-linking reaction between a non-linear reactive precursor and a curing agent, and the glass transition point Tg or the like is measured from the synthesized non-crystalline polyester resin. May be good.

[Means for separating toner components]
An example of a means for separating each component when analyzing 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. The solution is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF-soluble component in the toner. Next, the THF-soluble component 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 eluent discharge port of the GPC to separate the eluate 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 crystalline polyester resin, the non-crystalline polyester resin and the like contained in the toner can be obtained from the peak integration ratio of the obtained spectrum.

For example, as shown below, the component derived from the peak can be specified from the position of the peak, and the component ratio of the constituent monomer can be obtained from each integral ratio.
Peak around 8.25ppm: Derived from benzene ring of trimellitic acid (for 1 hydrogen)
Peak around 8.07ppm-8.10ppm: Derived from benzene ring of terephthalic acid (for 4 hydrogens)
Peak around 7.1ppm-7.25ppm: Derived from benzene ring of bisphenol A (for 4 hydrogens)
Peak around 6.8 ppm: Derived from benzene ring of bisphenol A (for 4 hydrogens) and derived from double bond of fumaric acid (for 2 hydrogens)
Peak around 5.2ppm to 5.4ppm: Derived from methine of bisphenol A propylene oxide adduct (for 1 hydrogen)
Peak around 4.0ppm to 5.0ppm: Derived from methylene, an aliphatic alcohol (for 2 hydrogens)
Peaks around 3.7 ppm to 4.7 ppm: Methylene-derived bisphenol A propylene oxide adduct (for 2 hydrogens) and bisphenol A ethylene oxide adduct derived from methylene (4 hydrogens)
Peak around 2.2ppm to 2.6ppm: Derived from methylene of aliphatic dicarboxylic acid (for 2 hydrogens)
Peak around 1.6ppm: Derived from methyl group of bisphenol A and aliphatic alcohol (for 6 hydrogens)

From these results, for example, the extract recovered in the fraction in which the crystalline polyester resin occupies 90% or more can be treated as the crystalline polyester resin. Similarly, the extract recovered in the fraction in which the amorphous polyester resin occupies 90% or more can be treated as the amorphous polyester resin.

[Measuring method of melting point and glass transition point Tg]
The melting point and the glass transition point Tg can be measured using, for example, a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments). Specifically, the melting point and the glass transition point of the target sample can be measured by the following procedure.

First, about 5.0 mg of the target sample is placed in an aluminum sample container, the sample container is placed on a holder unit, and the sample container is set in an electric furnace. Then, under a nitrogen atmosphere, the mixture is heated from −80 ° C. to 150 ° C. at a heating rate of 10 ° C./min (first temperature increase). Then, it is cooled from 150 ° C. to −80 ° C. at a temperature lowering rate of 10 ° C./min, and further heated to 150 ° C. at a temperature rising rate of 10 ° C./min (second temperature rise). At each of the first and second temperature rises, the DSC curve is measured using a differential scanning calorimeter (“Q-200”, manufactured by TA Instruments).

From the obtained DSC curve, the DSC curve at the time of the first temperature rise can be selected by using the analysis program in the Q-200 system, and the glass transition point at the first temperature rise of the target sample can be obtained. Similarly, the DSC curve at the time of the second temperature rise can be selected, and the glass transition point at the time of the second temperature rise of the target sample can be obtained.

Further, from the obtained DSC curve, the DSC curve at the time of the first temperature rise is selected by using the analysis program in the Q-200 system, and the heat absorption peak top temperature at the first temperature rise of the target sample is obtained as the melting point. Can be done. Similarly, the DSC curve at the time of the second temperature rise can be selected, and the endothermic peak top temperature at the second temperature rise of the target sample can be obtained as the melting point.

When toner is used as the target sample, the glass transition point at the time of the first temperature rise is Tg _1st , and the glass transition point at the time of the second temperature rise is Tg _2nd .

Unless otherwise specified, the melting point and glass transition point of the components of the toner such as polyester resin are the heat absorption peak top temperature and the glass transition point Tg at the time of the second temperature rise. And.

As described above, the toner according to the embodiment has a core having a resin (a) containing a styrene acrylic resin and no carboxyl group and a resin (b) containing a carboxyl group on the surface of the toner matrix particles. It has organic resin fine particles having a core-shell structure composed of a shell, and an anionic surfactant containing a carboxyl group.

Since the shell of the organic resin fine particles contains the resin (b) containing a carboxyl group, at least a part of the shell is dissolved when the toner is washed with an organic solvent at the time of manufacturing the toner, and the toner matrix particles are formed. A part of the organic resin fine particles adhering to the toner can be removed. Further, since the core is formed by containing the resin (a) containing the styrene acrylic resin and not the carboxyl group, even if the toner is washed with an organic solvent, it is difficult to dissolve in the organic solvent, and the toner matrix particles are formed. Can stay on the surface. Therefore, since the organic resin fine particles composed of the core can be scattered on the surface of the toner matrix particles, it is possible to suppress the inhibition of the low temperature fixing of the toner and ensure the low temperature fixing property. At the same time, heat resistance can be improved.

Further, the anionic surfactant can enhance the dispersibility of the toner matrix particles in the toner by adhering to the surface of the toner matrix particles. In addition, the carboxyl group contained in the anionic surfactant has the effect of imparting negative chargeability, and can suppress charge inhibition. Therefore, by including the anionic surfactant containing a carboxyl group, the toner can impart good dispersibility and excellent negative chargeability of the toner matrix particles.

Therefore, the toner according to one embodiment has excellent low-temperature fixability by having the above-mentioned organic resin fine particles having a core-shell structure and an anionic surfactant containing a carboxyl group on the surface of the toner matrix particles. It can have high temperature offset resistance, heat storage resistance and chargeability.

In the toner according to one embodiment, the glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resin (a) and the resin (b) can be set to 30 ° C to 70 ° C. As a result, the low-temperature fixability and heat-resistant storage stability of the toner can be maintained, so that blocking in the developing machine and occurrence of filming on the photoconductor can be reduced.

In the toner according to one embodiment, the particle size of the organic resin fine particles can be 10 nm to 100 nm. As a result, the coating ratio of the toner matrix particles on the surface can be optimized, the coverage on the toner surface can be prevented from becoming too high, and the size of the voids on the surface of the toner matrix particles can be large. It can be suppressed. Therefore, the toner according to the embodiment can maintain good low-temperature fixing performance and heat-resistant storage performance.

The toner according to the embodiment can have the content of the organic resin fine particles in an amount of 0.2% by mass to 5% by mass with respect to the toner. As a result, the effect of heat-resistant storage can be sufficiently obtained, and the increase in inhibition to low-temperature fixing can be suppressed. Therefore, the toner according to the embodiment can maintain good low-temperature fixing performance and heat-resistant storage performance.

In the toner according to one embodiment, the acid value of the anionic surfactant can be 100 mgKOH / g to 200 mgKOH / g. As a result, the toner matrix particles are less likely to be affected by the humidity in the atmosphere, and the negative chargeability effect can be improved, so that the toner chargeability can be maintained satisfactorily.

As the toner according to one embodiment, a succinic acid derivative can be used as an anionic surfactant. Since the carbon number of the alkyl chain contained in the succinic acid derivative can be freely changed and the succinic acid derivative having a desired alkyl chain can be obtained, the chargeability of the toner can be further enhanced.

<Toner manufacturing method>
The method for producing the toner according to one embodiment can be appropriately selected depending on the intended purpose, but contains a polyester resin, preferably further contains the above-mentioned crystalline polyester resin, and further contains a mold release agent or the like, if necessary. By dispersing the oil phase in an aqueous medium containing organic resin fine particles and an anionic surfactant containing a carboxyl group, the toner matrix particles are granulated, and the organic resin fine particles and the carboxyl group are formed on the surface thereof. It is preferable to include a granulation step of adhering the anionic surfactant to be contained.

Further, in the method for producing a toner according to one embodiment, in the above granulation step, the polyester resin is a non-crystalline polyester resin which is a prepolymer having at least one of a urethane bond and a urea bond, and a urethane bond and a urea bond. It is more preferable to use an oil phase containing a non-crystalline polyester resin having no bond, preferably a crystalline polyester resin, and further containing a curing agent or the like, if necessary.

As a method for producing toner, a dissolution / suspension method can be used. As a method for producing toner by using the dissolution / suspension method, for example, a method for producing toner matrix particles while stretching an amorphous polyester resin by an elongation reaction and / or a crosslinking reaction between a prepolymer and a curing agent is used. be able to.

The method for producing toner matrix particles using this dissolution / suspension method is a step of adjusting an aqueous medium (a step of preparing an aqueous medium) and a step of adjusting an oil phase containing a toner material (a step of preparing an oil phase). It also includes a step of emulsifying or dispersing the toner material (emulsification or dispersion step) and a step of removing the organic solvent (organic solvent removing step).

(Preparation process of water-based medium)
The aqueous medium (aqueous phase) can be prepared, for example, by dispersing resin particles, organic resin fine particles, and an anionic surfactant containing a carboxyl group in the aqueous medium. The amount of the resin particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the aqueous medium.

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 preferred.

The solvent miscible with water can be appropriately selected depending on the intended purpose, and examples thereof include alcohols, lower ketones, dimethylformamide, tetrahydrofuran, cellosolves 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 can be appropriately selected depending on the intended purpose, and examples thereof include acetone and methyl ethyl ketone.

(Oil phase preparation process)
The oil phase containing the toner material is a crystalline polyester resin, a non-crystalline polyester resin which is a prepolymer having at least one of a urethane bond and a urea bond, and a non-crystalline polyester resin having no urethane bond and a urea bond. It can be prepared by dissolving or dispersing a toner material containing at least the above and, if necessary, a curing agent, a mold release agent, a colorant and the like in an organic solvent.

The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose, but an organic solvent having a boiling point of less than 150 ° C. is preferable because 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, Examples thereof include 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 process)
By dispersing the oil phase containing the toner material in an aqueous medium, the toner material can be emulsified or dispersed. At this time, the organic resin fine particles can be arranged on the surface of the toner matrix particles, and an anionic surfactant containing a carboxyl group can be bonded and arranged on the surface of the toner matrix particles.

Further, when the toner material is emulsified or dispersed, the curing agent and the prepolymer are subjected to an extension reaction and / or a cross-linking reaction to produce an amorphous polyester resin.

The reaction conditions (reaction time, reaction temperature) for producing the prepolymer are not particularly limited and may be appropriately selected depending on the combination of the curing agent and the 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 prepolymer in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the toner material is used as a solvent in the aqueous medium phase. Examples thereof include a method in which an oil phase prepared by dissolving or dispersing is added and dispersed by a shearing force.

The disperser for dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, etc. An ultrasonic disperser and the like can be mentioned.

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 a high-speed shearing disperser is used, conditions such as rotation speed, dispersion time, and dispersion temperature can be appropriately selected according to the purpose.

The number of rotations is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1,000 rpm to 30,000 rpm, more preferably 5,000 rpm to 20,000 rpm.

The dispersion time is not particularly limited and may be appropriately selected depending on the intended purpose, but in the case of the batch method, 0.1 minutes to 5 minutes is preferable.

The dispersion temperature is not particularly limited and may be appropriately selected depending on the intended purpose, but under pressure, 0 ° C. to 150 ° C. is preferable, and 40 ° C. to 98 ° C. is more preferable. In general, the higher the dispersion temperature, the easier the dispersion.

The amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose. However, 50 parts by mass to 2, 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 be deteriorated and the toner base particles having a predetermined particle size may not be obtained. If the amount of the aqueous medium used exceeds 2,000 parts by mass, the production cost may increase.

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 may be used. Can be done.

The anionic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylbenzene sulfonates, α-olefin sulfonates and phosphoric acid esters. Among these, those having a fluoroalkyl group are preferable.

(Step of removing organic solvent)
Toner matrix particles are obtained by removing the organic solvent from the dispersion liquid such as an emulsified slurry. The method for removing the organic solvent from the dispersion 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 evaporate the organic solvent in the oil droplets. Examples thereof include a method of spraying a dispersion liquid in a dry atmosphere to remove an 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 the fine particle portions in the liquid by a cyclone, a decanter, centrifugation or the like, or the classification operation may be performed after drying.

(External process)
Further, an external additive, a charge control agent, or the like may be mixed with the obtained toner matrix particles. At this time, by applying a mechanical impact force, it is possible to suppress the desorption of particles such as the external additive from the surface of the toner matrix particles.

The method of applying the mechanical impact force can be appropriately selected according to the purpose. For example, a method of applying an impact force to the mixture using blades rotating at high speed, or a method of applying the impact force to the high-speed airflow to accelerate the mixture. Examples thereof include a method of causing the particles to collide with each other or the particles with an appropriate collision plate.

The device used for the method of applying the mechanical impact force can be appropriately selected according to the purpose. Examples include a device with a lowered weight, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic dairy bowl.

Next, the toner according to one embodiment is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

<Developer>
The developer according to the embodiment contains the toner according to the embodiment, and may contain other components appropriately selected such as a carrier, if necessary. As a result, 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 the improvement in information processing speed in recent years, the life is improved. Therefore, it is preferable to use a two-component developer.

When the toner according to one embodiment 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 the blade for thinning the toner are formed. There is little fusion of toner to such members, and good and stable developability and images can be obtained even with long-term stirring in a developing device.

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

The content of the carrier in the two-component developer can be appropriately selected depending on the intended purpose, but is preferably 90 parts by mass to 98 parts by mass, and 93 parts by mass to 97 parts by mass with respect to 100 parts by mass of the two-component developer. Parts by mass are more preferred.

The developer according to one embodiment 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.

[Career]
The carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferably one having a core material and a resin layer (coating layer) for coating the core material.

(Core material)
The material of the core material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a manganese-strontium-based material of 50 emu / g to 90 emu / g and a manganese-magnesium-based material of 50 emu / g to 90 emu / g. Materials and the like can be mentioned. Further, in order to secure the image density, it is preferable to use a highly magnetizing 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 size 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. When the volume average particle size is 10 μm or more, it is possible to effectively prevent the problem that fine powder increases in the carrier, the magnetization per particle decreases, and the carrier may scatter. On the other hand, if it is 150 μm or less, the specific surface area may decrease and toner may scatter, and it is possible to effectively prevent the problem that the reproduction of the solid part may be particularly deteriorated in the case of full color having many solid parts. can.

(Resin layer)
The resin layer may contain the resin and, if necessary, other components. As the resin used for the resin layer, a known material capable of imparting the required chargeability can be used. Specifically, it is preferable to use a silicone resin, an acrylic resin, or a combination thereof. Further, the composition for forming the resin layer preferably contains a silane coupling agent.

The average film thickness of the resin layer is preferably 0.05 to 0.50 μm.

<Developer storage container>
The developer container according to the embodiment contains the developer according to the embodiment. The developer containing container is not particularly limited and may be appropriately selected from known ones, and examples thereof include a container having a container body and a cap.

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 rotated. It is particularly preferable that the developer as 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 an image forming apparatus, a process cartridge, etc., which will be described later, and used for replenishing the developer.

<Toner storage unit>
The toner accommodating unit according to one embodiment can accommodate the toner according to one embodiment. The toner accommodating unit according to one embodiment 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 developer, and a process cartridge.

The toner container is a container that contains toner.

A developer has a means for accommodating and developing toner.

The process cartridge is a cartridge in which at least an electrostatic latent image carrier (also referred to as an image carrier) and a developing means are integrated, toner is stored, and the process cartridge is removable from the image forming apparatus. The process cartridge may further include at least one selected from charging means, exposure means, cleaning means and the like.

The toner according to the embodiment is accommodated in the toner accommodating unit according to the embodiment. By mounting the toner accommodating unit according to one embodiment on an image forming apparatus to form an image, image formation is performed using the toner according to one embodiment, so that low temperature fixing property, high temperature offset resistance, and heat resistant storage can be performed. It is possible to obtain a toner having excellent properties and chargeability.

<Image forming device>
The image forming apparatus according to one embodiment includes an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image carrier. It has a developing unit that develops the formed electrostatic latent image with toner to form a toner image, and may have other configurations if necessary.

The image forming apparatus according to one embodiment more preferably includes, in addition to the above-mentioned electrostatic latent image carrier, electrostatic latent image forming section and developing section, a transfer section for transferring the toner image to a recording medium. A fixing portion for fixing the transferred image transferred to the surface of the recording medium is provided.

In the developing unit, the toner according to one embodiment is used. Preferably, a toner image may be formed by using a developer containing the toner according to one embodiment and, if necessary, containing other components such as carriers.

(Electrostatic latent image carrier)
The material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as "electrophotographic photosensitive member" or "photoreceptor") are not particularly limited and may be appropriately selected from known ones. be able to. Examples of the material of the electrostatic latent image carrier include an inorganic photoconductor such as amorphous silicon and selenium, and an organic photoconductor (OPC) such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

As the amorphous silicon photoconductor, for example, the support is heated to 50 ° C. to 400 ° C., and the support is subjected to a vacuum vapor deposition method, a sputtering method, an ion plating method, and a thermal CVD (Chemical Vapor Deposition) method. , A photoconductor having a photoconductive layer made of a-Si can be used by a film forming method such as an optical CVD method or a plasma CVD method. Among these, the plasma CVD method, that is, a 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 particularly preferably 10 mm to 30 mm. preferable.

(Electrostatic latent image forming part)
The electrostatic latent image forming unit 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. The electrostatic latent image forming unit is, for example, a charging member (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure member that exposes the surface of the electrostatic latent image carrier in an image manner. (Exposure device) is provided.

The charger is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a contact charger provided with a conductive or semi-conductive roll, a brush, a film, a rubber blade, or the like, a corotron, or a scorotron. A non-contact charger or the like using a corona discharge such as the above can be mentioned.

The shape of the charger may be any form such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and form of the image forming apparatus.

The charger is preferably arranged in a contacted or non-contact state with the electrostatic latent image carrier, and charges the surface of the electrostatic latent image carrier by superimposing and applying direct current and AC voltage. Further, the charger is a charging roller that is non-contactly arranged close to the electrostatic latent image carrier via a gap tape, and the surface of the electrostatic latent image carrier is applied by superimposing direct current and AC voltage on the charging roller. It is preferable to charge the battery.

The charger is not limited to the contact type charger, but it is preferable to use the contact type charging member from the viewpoint of obtaining an image forming apparatus in which ozone generated from the charger is reduced.

The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger to the image to be formed, and can be appropriately selected depending on the intended purpose. Examples thereof include various exposure devices 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 in the exposure device is not particularly limited and may be appropriately selected depending on the intended purpose. For example, fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers ( Examples thereof include general light-emitting substances such as LD) and electroluminescence (EL).

Further, in order to irradiate only light in a desired wavelength range, various filters such as a sharp cut filter, a bandpass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can also be used.

An optical back surface method may be adopted in which the back surface side of the electrostatic latent image carrier is exposed to the image.

(Development unit)
The developing unit is not particularly limited as long as it can develop the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image, and can be appropriately selected depending on the intended purpose. As the developing unit, for example, one capable of accommodating toner and having a developer capable of contacting or non-contacting toner to an electrostatic latent image can be preferably used, and a developing unit provided with a container containing toner can be used. preferable.

The developer may be a monochromatic developer or a multicolor developer. As the developing device, for example, a developer carrier having a stirrer for frictionally stirring and charging toner and a magnetic field generating portion fixed inside, and carrying a developer containing toner on the surface and rotating is provided. A developing device having is preferable.

(Transfer part)
The transfer unit includes a primary transfer unit that transfers a visible image onto an intermediate transfer body to form a composite transfer image, and a secondary transfer unit that transfers the composite transfer image onto a recording medium. preferable. The intermediate transfer body is not particularly limited and can be appropriately selected from known transfer bodies according to the purpose. For example, a transfer belt or the like is preferably used.

The transfer unit (primary transfer means and secondary transfer unit) has at least a transfer device for peeling and charging the visible image formed on the electrostatic latent image carrier (photoreceptor) toward the recording medium. preferable. The number of transfer portions may be one or two or more.

Examples of the transfer device include a corona transfer device by corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, an adhesive transfer device, and the like.

The recording medium is typically plain paper, but there is no particular limitation as long as the unfixed image after development can be transferred, and it can be appropriately selected according to the purpose, and PET for OHP. A base or the like can also be used.

(Fixing part)
The fixing portion is not particularly limited and may be appropriately selected depending on the intended purpose, but a known heating and pressurizing portion is preferable. Examples of the heating and pressurizing unit 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 portion has a heating body provided with a heating element, a film in contact with the heating body, and a pressure member that is in pressure contact with the heating body via the film, and an unfixed image is formed between the film and the pressure member. It is preferable that the heat-pressurized portion can be heated and fixed by passing through the formed recording medium.

The heating in the heating and pressurizing section is usually preferably 80 ° C. to 200 ° C.

The surface pressure in the heating and pressurizing portion is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 N / cm ² to 80 N / cm ² .

In this embodiment, for example, a known optical fixing device may be used together with or in place of the fixing unit, depending on the purpose.

(others)
The image forming apparatus according to the primary form may also include, for example, a static elimination unit, a recycling unit, a control unit, and the like.

((Static elimination unit))
The static eliminator is not particularly limited as long as it can apply a static eliminator bias to the electrostatic latent image carrier, and can be appropriately selected from known static eliminators. For example, a static eliminator lamp or the like is preferable. Can be mentioned.

((Cleaning section))
The cleaning unit only needs to be able to remove the toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Examples of the cleaning unit include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner, and the like.

The image forming apparatus according to the primary form can improve the cleaning property by having a cleaning unit. That is, by controlling the adhesive force between the toners, the fluidity of the toner can be controlled and the cleaning property can be improved. Further, by controlling the characteristics of the deteriorated toner, excellent cleaning quality can be maintained even under harsh conditions such as long life and high temperature and humidity. Further, since the external additive can be sufficiently released from the toner on the photoconductor, high cleaning property can be achieved by forming a deposit layer (dam layer) of the external additive in the cleaning blade nip portion. can.

((Recycling Department))
The recycling unit is not particularly limited, and examples thereof include known transportation means.

((Control unit))
The control unit can control the movement of each of the above units. The control unit is not particularly limited as long as it can control the movement of each of the above units, and can be appropriately selected depending on the intended purpose. Examples thereof include control devices such as sequencers and computers.

Since the image forming apparatus according to one embodiment can form an image using the toner according to one embodiment, power consumption can be suppressed and high-quality images can be stably provided. ..

<Image formation method>
The image forming method according to one embodiment includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a toner image. The development step may be included, and if necessary, other steps may be included. The image forming method can be suitably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be more preferably performed by the other parts.

Further, the image forming method according to one embodiment is more preferably, in addition to the above-mentioned electrostatic latent image forming step and developing step, a transfer step of transferring the toner image to a recording medium and a surface of the recording medium. Includes a fixing step of fixing the transferred image transferred to the image.

In the developing process, the toner according to one embodiment is used. Preferably, a toner image may be formed by using a developer containing the toner according to one embodiment and, if necessary, containing other components such as carriers.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and is a charging step of charging the surface of the electrostatic latent image carrier and a charged electrostatic latent image carrier. It includes an exposure step of exposing the surface to form an electrostatic latent image. Charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using a charger. The exposure can be performed, for example, by exposing the surface of the electrostatic latent image carrier as an image using the exposure device. The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then exposing it to an image, or by the electrostatic latent image forming portion. ..

The developing step is a step of sequentially developing an electrostatic latent image with toners of a plurality of colors to form a visible image. The formation of the visible image can be performed, for example, by developing the electrostatic latent image with the toner, and can be performed by a developing device.

In the developer, for example, the toner and the carrier are mixed and agitated, the toner is charged by the friction at that time, and the toner is held in a spiked state on the surface of the rotating magnet roller to form a magnetic brush. Since the magnet roller is arranged near the electrostatic latent image carrier (photoreceptor), a part of the toner constituting the magnetic brush formed on the surface of the magnetic roller is electrostatically latent due to the electric attraction force. It moves to the surface of the image carrier (photoreceptor). 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 (photoreceptor).

The transfer step is a step of transferring a visible image to a recording medium. In the transfer step, it is preferable to use an intermediate transfer body, first transfer the visible image onto the intermediate transfer body, and then secondarily transfer the visible image onto a recording medium. The transfer step is a primary transfer step of transferring a visible image onto an intermediate transfer body to form a composite transfer image using two or more color toners, preferably full color toner, and a composite transfer image on a recording medium. A mode including a secondary transfer step of transferring is more preferable. The transfer can be performed, for example, by charging the visible image with the electrostatic latent image carrier (photoreceptor) using a transfer charger, and can be performed by the transfer unit.

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed for each color developer each time the visible image is transferred to the recording medium, or for each color developer. This may be performed at the same time in a laminated state.

The image forming method according to the primary form can further include other steps appropriately selected as necessary, such as a static elimination step, a cleaning step, a recycling step, and the like.

The static electricity elimination step is a step of applying a static electricity elimination bias to the electrostatic latent image carrier to perform static electricity elimination, and can be preferably performed by the static electricity elimination unit.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier, and can be more preferably performed by the cleaning unit.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, which can be more preferably performed by the recycling unit.

Since the image forming method according to the embodiment can form an image using the toner according to the embodiment, it is possible to suppress power consumption and stably provide a high-quality image. ..

[One aspect of the image forming apparatus]
Next, one aspect of the image forming apparatus according to the embodiment will be described with reference to FIG. FIG. 1 is a schematic configuration diagram showing an example of an image forming apparatus according to an embodiment. As shown in FIG. 1, the image forming apparatus 1A includes a photoconductor drum 10 which is an electrostatic latent image carrier, a charging roller 20 which is a charging unit, an exposure device 30 which is an exposure unit, and a developing unit which is a developing unit. The device 40, the intermediate transfer body (intermediate transfer belt) 50, the cleaning device 60 which is a cleaning unit, the transfer roller 70 which is a transfer unit, the static eliminator lamp 80 which is a static eliminator unit, and the intermediate transfer body cleaning device 90. Be prepared.

The intermediate transfer body 50 is an endless belt stretched by three rollers 51 arranged inside, and is designed to be movable in the arrow direction by the three rollers 51. 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. An intermediate transfer body cleaning device 90 is arranged in the vicinity of the intermediate transfer body 50. Further, a transfer roller 70 is arranged in the vicinity of the intermediate transfer body 50 so as to face the intermediate transfer body 50, and a transfer for transferring a developed image (toner image) to a transfer paper P as a recording medium (secondary transfer). Bias (secondary transfer bias) can be applied. Around the intermediate transfer body 50, a corona charger 52 for applying an electric charge to the toner image on the intermediate transfer body 50 is provided between the photoconductor drum 10 and the intermediate transfer body 50 in the rotation direction of the intermediate transfer body 50. It is arranged between the contact portion with the intermediate transfer body 50 and the contact portion between the intermediate transfer body 50 and the transfer paper P.

The developing apparatus 40 includes a developing belt 41 which is a developer carrier, a black (Bk) developing unit 42K, a yellow (Y) developing unit 42Y, a magenta (M) developing unit 42M, and cyan, which are arranged around the developing belt 41. (C) It is composed of a developing unit 42C.

The developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can be moved in the direction of an arrow in the drawing. Further, a part of the developing belt 41 is in contact with the photoconductor drum 10.

The black developing unit 42K includes a developer accommodating portion 421K, a developing agent supply roller 422K, and a developing roller (developer carrier) 423K. The yellow developing unit 42Y includes a developing agent accommodating portion 421Y, a developing agent supply roller 422Y, and a developing roller 423Y. The magenta developing unit 42M includes a developing agent accommodating portion 421M, a developing agent supply roller 422M, and a developing roller 423M. The cyan developing unit 42C includes a developing agent accommodating portion 421C, a developing agent supply roller 422C, and a developing roller 423C.

Next, a method of forming an image using the image forming apparatus 1 will be described. First, the surface of the photoconductor drum 10 is uniformly charged using the charging roller 20, and then the exposure light L is exposed to the photoconductor drum 10 using the exposure device 30 to form an electrostatic latent image. .. Next, the electrostatic latent image formed on the photoconductor drum 10 is developed with the toner supplied from the developing device 40 to form a toner image. Further, the toner image formed on the photoconductor drum 10 is transferred (primary transfer) onto the intermediate transfer body 50 by the transfer bias applied from the roller 51, and then transferred by the transfer bias applied from the transfer roller 70. , Transferred (secondary transfer) onto the transfer paper P fed by a paper feed unit (not shown). On the other hand, the photoconductor drum 10 on which the toner image is transferred to the intermediate transfer body 50 is statically eliminated by the static elimination lamp 80 after the toner remaining on the surface is removed by the cleaning device 60. The residual toner on the intermediate transfer body 50 after image transfer is removed by the intermediate transfer body cleaning device 90.

After the transfer step is completed, the transfer paper P is conveyed to the fixing unit, in which the transferred toner image is fixed to the transfer paper P.

FIG. 2 is a schematic configuration diagram showing another example of the image forming apparatus according to the embodiment. As shown in FIG. 2, in the image forming apparatus 1B shown in FIG. 1, in the image forming apparatus 1A, the black developing unit 42K, the yellow developing unit 42Y, and the magenta are arranged around the photoconductor drum 10 without providing the developing belt 41. It has the same configuration as the image forming apparatus 1A except that the developing unit 42M and the cyan developing unit 42C are directly opposed to each other.

FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus according to the embodiment. As shown in FIG. 3, the image forming apparatus 1C is a tandem type color image forming apparatus, and is a copying apparatus main body 110, a paper feed table 120, a scanner 130, an automatic document transfer apparatus (ADF) 140, and a secondary. It includes a transfer device 150, a fixing device 160 which is a fixing unit, and a sheet reversing device 170.

An endless belt-shaped intermediate transfer member 50 is provided at the center of the copying apparatus main body 110. The intermediate transfer body 50 is an endless belt stretched on three rollers 53A, 53B and 53C, and can be moved in the direction of an arrow in FIG. In the vicinity of the roller 53B, an intermediate transfer body cleaning device 90 for removing the toner remaining on the intermediate transfer body 50 on which the toner image is transferred to the recording paper is arranged. An image forming unit (yellow (Y) developing unit 42Y, cyan (C) developing unit 42C, magenta (M) developing unit) facing the intermediate transfer body 50 stretched by rollers 53A and 53B and along the transport direction. 42M and a black (Bk) developing unit 42K) are arranged.

Further, an exposure apparatus 30 is arranged in the vicinity of the image forming unit. Further, the secondary transfer device 150 is arranged on the side of the intermediate transfer body 50 opposite to the side on which the image forming unit is arranged. The secondary transfer device 150 includes a secondary transfer belt 151. The secondary transfer belt 151 is an endless belt stretched over a pair of rollers 152, and the recording paper and the intermediate transfer body 50 conveyed on the secondary transfer belt 151 are the rollers 53C and the rollers 152. Can be in contact with each other.

Further, a fixing device 160 is arranged in the vicinity of the secondary transfer belt 151. The fixing device 160 includes a fixing belt 161 which is an endless belt stretched on a pair of rollers, and a pressure roller 162 which is pressed and arranged by the fixing belt 161.

Further, in the vicinity of the secondary transfer belt 151 and the fixing device 160, a sheet reversing device 170 for reversing the recording paper is arranged when an image is formed on both sides of the recording paper.

Next, a method of forming a full-color image using the image forming apparatus 1C will be described. First, set the color document on the platen 141 of the automatic document transfer device (ADF) 140, or open the automatic document transfer device 140 and set the color document on the contact glass 131 of the scanner 130, and set the color document on the contact glass 131 of the scanner 130. Close.

When the start switch (not shown) is pressed, when a color document is set in the automatic document transfer device 140, the color document is conveyed and moved onto the contact glass 131, and then the scanner 130 is driven to turn on the light source. The first traveling body 132 and the second traveling body 133 to be provided travel. On the other hand, as soon as the document is set on the contact glass 131, the scanner 130 is driven and the first traveling body 132 and the second traveling body 133 provided with the light source travel. At this time, after the light reflected from the document surface of the light emitted from the first traveling body 132 is reflected by the mirror of the second traveling body 133, the color document is received by the reading sensor 136 through the imaging lens 135. (Color image) is read, and image information of black, yellow, magenta, and cyan is obtained.

The image information of each color is transmitted to the development unit of each color (yellow development unit 42Y, cyan development unit 42C, magenta development unit 42M and black development unit 42K), respectively, and a toner image of each color is formed.

FIG. 4 is a partially enlarged view of the image forming apparatus of FIG. As shown in FIG. 4, each developing unit (yellow developing unit 42Y, cyan developing unit 42C, magenta developing unit 42M, and black developing unit 42K) has a photoconductor drum 10 (black static photoconductor drum 10K, yellow photofinishing unit 42K), respectively. Based on the image information of each color, the photoconductor drum 10Y, the photoconductor drum 10M for magenta, and the photoconductor drum 10C for cyanide), and the charging roller 20 which is a charging unit that uniformly charges the electrostatic latent image carrier 10. Then, the exposure light L is exposed to the photoconductor drum 10 to form an electrostatic latent image of each color on the photoconductor drum 10, and the electrostatic latent image is developed with a developer of each color to develop the toner of each color. It includes a developing device 40 which is a developing unit for forming an image, a transfer charging device 62 for transferring a toner image onto the intermediate transfer body 50, a cleaning device 60, and a static elimination lamp 80.

The toner images of each color formed by the development units of each color (yellow development unit 42Y, cyan development unit 42C, magenta development unit 42M, and black development unit 42K) are stretched on rollers 53A, 53B, and 53C for intermediate transfer. It is sequentially transferred (primary transfer) onto the body 50. Then, the toner images of each color are superimposed on the intermediate transfer body 50 to form a composite toner image.

On the other hand, in the paper feed table 120, one of the paper feed rollers 121 is selectively rotated, and the recording paper is fed out from one of the paper feed cassettes 123 provided in the paper bank 122 in multiple stages. The recording paper is separated one by one by the separation roller 124 and sent to the paper feed path 125, is conveyed by the transfer roller 126, is guided to the paper feed path 111 in the copying apparatus main body 110, and abuts against the resist roller 112. Can be stopped. Alternatively, the manual feed roller 113 is rotated to feed out the recording paper on the manual feed tray 114, separated one by one by the manual feed roller 113, guided to the manual feed feed path 115, and abutted against the resist roller 112 to stop.

Although the resist roller 112 is generally grounded and used, it may be used in a state where a bias is applied in order to remove paper dust from the recording paper.

Next, the resist roller 112 is rotated in time with the composite toner image formed on the intermediate transfer body 50, and the recording paper is sent out between the intermediate transfer body 50 and the secondary transfer belt 151 to send the composite toner image. Is transferred (secondary transfer) on the recording paper. The toner remaining on the intermediate transfer body 50 on which the composite toner image is transferred is removed by the intermediate transfer body cleaning device 90.

The recording paper on which the composite toner image is transferred is conveyed by the secondary transfer belt 151, and then the composite toner image is fixed on the recording paper by the fixing device 160.

After that, the transport path of the recording paper is switched by the switching claw 116, and the recording paper is discharged onto the paper ejection tray 118 by the ejection roller 117. Alternatively, the chart paper is ejected after the transport path is switched by the switching claw 116, inverted by the sheet reversing device 170, guided to the secondary transfer belt 151 again, and an image is formed on the back surface in the same manner. It is discharged onto the output tray 118 by the roller 117.

<Process cartridge>
The process cartridge according to one embodiment is detachably molded into various image forming devices, and has an electrostatic latent image carrier that carries an electrostatic latent image and an electrostatic carrier that is carried on the electrostatic latent image carrier. It has a developing unit that develops a latent image with the developer according to the above embodiment to form a toner image, and may have other configurations if necessary.

Since the electrostatic latent image carrier is the same as the electrostatic latent image carrier of the above-mentioned image forming apparatus, the details will be omitted.

The developing unit has a developing agent accommodating container for accommodating the developing agent according to the embodiment, and a developing agent carrier for carrying and transporting the developing agent contained in the developing agent accommodating container. In addition, in order to regulate the thickness of the developer to be carried, the developing unit may further have a regulating member or the like.

FIG. 5 shows an example of a process cartridge according to an embodiment. As shown in FIG. 5, the image forming apparatus process cartridge 200 includes a photoconductor drum 10, a corona charger 22 which is a charging unit, a developing apparatus 40, a cleaning apparatus 60, and a transfer roller 70.

Hereinafter, embodiments will be described in more detail with reference to Examples and Comparative Examples, but the embodiments are not limited to these Examples and Comparative Examples.

<Adjustment of surfactant 1>
Hydrochloric acid was added to 200 parts by mass of dodecyl disodium sulfosuccinate (Bulite SSS manufactured by Sanyo Chemical Industries, Ltd.) until the pH reached 3.0, and then the mixture was stirred for 30 minutes. Then, the filtrate was collected by suction filtration, and the solid content was adjusted to 30% with ion-exchanged water to obtain a surfactant 1.

An anionic surfactant having a carboxyl group is obtained from the peak of the MS detector using the obtained surfactant 1 using a liquid chromatography system (AQUITY-UPLC / SQD system, manufactured by Japan Waters Corp.). It was confirmed. The acid value was 140 mgKOH / g as a result of measurement using an automatic potential difference titrator (DL-53 Titrator, manufactured by METTLER TOLEDO).

<Adjustment of surfactant 2>
Hydrochloric acid was added to 200 parts by mass of octyl sulfosuccinate (manufactured by Kao Corporation, Perrex OT-P) until the pH reached 5.0, and then the mixture was stirred for 30 minutes. Then, the filtrate was collected by suction filtration, and the solid content was adjusted to 30% with ion-exchanged water to obtain a surfactant 2.

Using a liquid chromatography system (AQUITY-UPLC / SQD system, manufactured by Japan Waters Corp.) for the obtained surfactant 2, an anionic surfactant having a carboxyl group can be obtained from the peak of the MS detector. It was confirmed. The acid value was 170 mgKOH / g as a result of measurement using an automatic potential difference titrator (DL-53 Titrator, manufactured by METTLER TOLEDO).

<Adjustment of surfactant 3>
After an equimolar reaction of maleic acid and pentanol, sodium sulfite was subjected to an equimolar reaction with maleic acid. Hydrochloric acid was added until the pH reached 5.0, and then the mixture was stirred for 30 minutes. Then, the filtrate was collected by suction filtration, and the solid content was adjusted to 30% with ion-exchanged water to obtain a surfactant 3.

Using a liquid chromatography system (AQUITY-UPLC / SQD system, manufactured by Japan Waters Corp.) for the obtained surfactant 3, an anionic surfactant having a carboxyl group can be obtained from the peak of the MS detector. It was confirmed. The acid value was 190 mgKOH / g as a result of measurement using an automatic potential difference titrator (DL-53 Titrator, manufactured by METTLER TOLEDO).

<Adjustment of surfactant 4>
After an equimolar reaction of maleic acid and pentadecanol, sodium sulfite was subjected to an equimolar reaction with maleic acid. Hydrochloric acid was added until the pH reached 5.0, and then the mixture was stirred for 30 minutes. Then, the filtrate was collected by suction filtration, and the solid content was adjusted to 30% with ion-exchanged water to obtain a surfactant 4.

Using a liquid chromatography system (AQUITY-UPLC / SQD system, manufactured by Japan Waters Corp.) for the obtained surfactant 4, an anionic surfactant having a carboxyl group is obtained from the peak of the MS detector. It was confirmed. The acid value was 110 mgKOH / g as a result of measurement with a potential difference automatic titrator (DL-53 Titrator, manufactured by METTLER TOLEDO).

Table 1 shows the acid values of each of the surfactants 1 to 4.

<Production example 1 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-01) containing organic resin fine particles (A-1S)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 3710 parts by mass of water, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester (Aquaron KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 200 A mass portion was charged and stirred at 200 rpm to make it uniform. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then 450 parts by mass of styrene, 250 parts by mass of butyl acrylate, and methacrylic acid. A mixed solution consisting of 300 parts by mass was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-01) containing organic resin fine particles (A-1S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-01) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-1S) in the fine particle dispersion (W-01) was 15.0 nm. Further, a part of the fine particle dispersion liquid (W-01) was dried to isolate organic resin fine particles (A-1S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-1S) was 53 ° C., and the acid value was 195 mgKOH / g. Table 2 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-1S).

<Production example 2 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-1) containing organic resin fine particles (A-1)]
Next, 667 parts by mass of the fine particle dispersion liquid (W-01) and 248 parts by mass of water were charged into a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. After adding 0.267 parts by mass of tertiary butyl hydroperoxide (NOF, Perbutyl H), the mixed solution was heated to raise the temperature in the system to 70 ° C. Then, 43.3 parts by mass of styrene, 23.3 parts by mass of butyl acrylate, and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to obtain a copolymer of styrene and butyl acrylate using the organic resin fine particles (A-1S) in the fine particle dispersion (W-01) as a seed. A fine particle dispersion (W-1) containing organic resin fine particles (A-1) containing the resin (a) (A-1C) and the resin (b) (A-1S) as constituents in the same particles was obtained. .. The fine particle dispersion (W-1) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-1) was 17.3 nm. The volume average particle size was measured using a laser Doppler particle size distribution measuring device (nanotrac UPA-150EX, manufactured by Nikkiso Co., Ltd.).

Further, the fine particle dispersion (W-1) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resins (a) and (A-1C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-1C) was 53 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-1) contains the organic resin fine particles (A-1) is that a part of the fine particle dispersion (W-1) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-1).

Table 2 shows the measurement results of the glass transition point Tg _1st and the acid value at the first temperature rise of the volume average particle size of the organic resin fine particles (A-1) and the differential scanning calorimetry of the resins (a) and (A-1C). ..

<Production example 3 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-02) containing resin fine particles (A-2S)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 3760 parts by mass of water and 150 parts by mass of polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium (Aqualon KH-1025) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. The parts were charged and stirred at 200 rpm to homogenize. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then 430 parts by mass of styrene, 270 parts by mass of butyl acrylate and 300 parts by mass of methacrylic acid. The mixed solution consisting of parts by mass was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-02) containing organic resin fine particles (A-2S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-02) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-2S) in the fine particle dispersion (W-02) was 30.0 nm. Further, a part of the fine particle dispersion liquid (W-02) was dried to isolate the organic resin fine particles (A-2S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-2S) was 53 ° C., and the acid value was 195 mgKOH / g. Table 2 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-2S).

<Production example 4 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-2) containing resin fine particles (A-2)]
Next, 667 parts by mass of the fine particle dispersion (W-02) and 248 parts by mass of water were charged in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, and tertiary butyl hydroperoxide (manufactured by Nichiyu, Perbutyl H) was charged. ) 0.267 parts by mass was added and then heated to raise the temperature inside the system to 70 ° C. Then, 43.3 parts by mass of styrene, 23.3 parts by mass of butyl acrylate and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to copolymerize styrene, butyl acrylate and an ascorbic acid aqueous solution using the organic resin fine particles (A-2S) in the fine particle dispersion (W-02) as a seed. Fine particle dispersion liquid (W-2) containing resin fine particles (A-2) containing the resin (a) (A-2C) and the resin (b) (A-2S) as constituents in the same particles. ) Was obtained. The fine particle dispersion (W-2) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-2) was 34.3 nm. The volume average particle size was measured in the same manner as the above-mentioned organic resin fine particles (A-1).

Further, the fine particle dispersion (W-2) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resins (a) and (A-2C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-2C) was 53 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-2) contains the organic resin fine particles (A-2) is that a part of the fine particle dispersion (W-2) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-2).

Table 2 shows the measurement results of the volume average particle diameter of the organic resin fine particles (A-2), the glass transition point Tg _1st of the resins (a) and (A-2C), and the acid value.

<Manufacturing of organic resin fine particles 5>
[Manufacturing of fine particle dispersion liquid (W-03) containing resin fine particles (A-3S)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 3810 parts by mass of water and 100 parts by mass of polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium (Aqualon KH-1025) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. The parts were charged and stirred at 200 rpm to homogenize. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added, and then from 400 parts by mass of styrene, 300 parts by mass of butyl acrylate, and 300 parts by mass of methacrylic acid. The mixture was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-03) containing organic resin fine particles (A-3S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-03) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-3S) in the fine particle dispersion (W-03) was 45.0 nm. In addition, a part of the fine particle dispersion liquid (W-03) was dried to isolate organic resin fine particles (A-3S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-3S) was 53 ° C., and the acid value was 195 mgKOH / g. Table 2 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-3S).

<Production example 6 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-3) containing resin fine particles (A-3)]
Next, 667 parts by mass of the fine particle dispersion (W-03) and 248 parts by mass of water were charged in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, and tertiary butyl hydroperoxide (manufactured by Nichiyu, Perbutyl H) was charged. ) 0.267 parts by mass was added and then heated to raise the temperature inside the system to 70 ° C. Then, 43.3 parts by mass of styrene, 23.3 parts by mass of butyl acrylate and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to obtain a copolymer of styrene and butyl acrylate using the organic resin fine particles (A-3S) in the fine particle dispersion (W-03) as a seed. A fine particle dispersion (W-3) containing resin fine particles (A-3) containing the resin (a) (A-3C) and the resin (b) (A-3S) as constituents in the same particles was obtained. The fine particle dispersion (W-3) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-3) was 51.5 nm. The volume average particle size was measured in the same manner as the above-mentioned organic resin fine particles (A-1).

Further, the fine particle dispersion (W-3) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resins (a) and (A-3C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-3C) was 53 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-3) contains the organic resin fine particles (A-3) is that a part of the fine particle dispersion (W-3) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-3).

Table 2 shows the measurement results of the volume average particle diameter of the organic resin fine particles (A-3), the glass transition point Tg _1st of the resins (a) and (A-3C), and the acid value.

<Production example 7 of organic resin fine particles>
[Manufacturing of aqueous dispersion (W-04) containing organic resin fine particles (A-4S)]
3710 parts by mass of water, 300 mass of polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium (Aqualon KH-1025) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. The parts were charged and stirred at 200 rpm to homogenize. After heating the mixed solution to a temperature of 75 ° C. in the system, 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added, and then 450 parts by mass of styrene, 250 parts by mass of butyl acrylate, and 300 parts by mass of methacrylic acid. The mixture was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-04) containing organic resin fine particles (A-4S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-04) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-4S) in the fine particle dispersion (W-04) was 8.0 nm. In addition, a part of the fine particle dispersion liquid (W-04) was dried to isolate organic resin fine particles (A-4S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-4S) was 53 ° C., and the acid value was 195 mgKOH / g. Table 2 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-4S).

<Production example of organic resin fine particles 8>
[Manufacturing of fine particle dispersion liquid (W-4) containing organic resin fine particles (A-4)]
A reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer was charged with 667 parts by mass of a fine particle dispersion (W-04) and 248 parts by mass of water, and tertiary butyl hydroperoxide (manufactured by Nichiyu, Perbutyl H) 0. After adding 267 parts by mass, the system was heated to raise the temperature in the system to 70 ° C. Then, 43.3 parts by mass of styrene, 23.3 parts by mass of butyl acrylate and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to use the fine particles in (W-01) as a seed, and the resin (a) (A-4C) and the resin which are copolymerized with styrene and butyl acrylate. (B) A fine particle dispersion (W-4) containing resin fine particles (A-4) containing (A-4S) as a constituent in the same particles was obtained. The fine particle dispersion (W-4) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the resin fine particles (A-4) was 10.0 nm. The volume average particle size was measured in the same manner as the above-mentioned organic resin fine particles (A-1).

Further, the fine particle dispersion (W-4) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resins (a) and (A-4C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-4C) was 53 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-4) contains the organic resin fine particles (A-4) is that a part of the fine particle dispersion (W-4) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-4).

Table 2 shows the measurement results of the volume average particle diameter of the organic resin fine particles (A-4), the glass transition point Tg _1st of the resins (a) and (A-4C), and the acid value.

<Production example 9 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-05) containing organic resin fine particles (A-5S)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 3710 parts by mass of water and 50 parts by mass of polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium (Aqualon KH-1025) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. The parts were charged and stirred at 200 rpm to homogenize. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then 450 parts by mass of styrene, 250 parts by mass of butyl acrylate, and methacrylic acid. A mixed solution consisting of 300 parts by mass was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-05) containing organic resin fine particles (A-5S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-05) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-5S) in the fine particle dispersion (W-05) was 88.0 nm. In addition, a part of the fine particle dispersion liquid (W-05) was dried to isolate organic resin fine particles (A-5S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-5S) was 53 ° C., and the acid value was 195 mgKOH / g. Table 2 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-5S).

<Production example 10 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-5) containing organic resin fine particles (A-5)]
A reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer was charged with 667 parts by mass of a fine particle dispersion (W-05) and 248 parts by mass of water, and tertiary butyl hydroperoxide (manufactured by Nichiyu, Perbutyl H) 0. After adding 267 parts by mass, the system was heated to raise the temperature in the system to 70 ° C. Then, 43.3 parts by mass of styrene, 23.3 parts by mass of butyl acrylate and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to use the fine particles in the fine particle dispersion (W-01) as a seed, and the resin (a) (A-) which is a polymer copolymerized with styrene and butyl acrylate. A fine particle dispersion (W-5) containing resin fine particles (A-5) containing 5C) and the resin (b) (A-4S) as constituents in the same particles was obtained. The fine particle dispersion (W-5) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the resin fine particles (A-5) was 100.0 nm. The volume average particle size was measured in the same manner as the above-mentioned organic resin fine particles (A-1).

Further, the fine particle dispersion (W-5) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resins (a) and (A-5C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-5C) was 53 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-5) contains the organic resin fine particles (A-5) is that a part of the fine particle dispersion (W-5) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-5).

Table 2 shows the measurement results of the volume average particle diameter of the organic resin fine particles (A-5), the glass transition point Tg _1st of the resins (a) and (A-5C), and the acid value.

<Production example 11 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-6) containing organic resin fine particles (A-6)]
A reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer was charged with 667 parts by mass of a fine particle dispersion (W-01) and 248 parts by mass of water, and tertiary butyl hydroperoxide (manufactured by Nichiyu, Perbutyl H) 0. After adding 267 parts by mass, the system was heated to raise the temperature in the system to 70 ° C. Then, 23.3 parts by mass of styrene, 43.3 parts by mass of butyl acrylate and 18.0 parts by mass of a 1% by mass ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to use the fine particles in the fine particle dispersion (W-01) as a seed, and the resin (a) (A-) which is a polymer copolymerized with styrene and butyl acrylate. A fine particle dispersion (W-6) containing resin fine particles (A-6) containing 6C) and the resin (b) (A-1S) as constituents in the same particles was obtained. The fine particle dispersion (W-6) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the resin fine particles (A-6) was 17.0 nm. The volume average particle size was measured in the same manner as the above-mentioned organic resin fine particles (A-1).

Further, the fine particle dispersion (W-6) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifuged precipitate is dried to dryness to obtain the resins (a) and (A-6C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-6C) was 30 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-6) contains the resin fine particles (A-6) is that a part of the fine particle dispersion (W-6) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-6).

Table 2 shows the measurement results of the volume average particle diameter of the organic resin fine particles (A-6), the glass transition point Tg _1st of the resins (a) and (A-6C), and the acid value.

<Production example 12 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-7) containing organic resin fine particles (A-7)]
A reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer was charged with 667 parts by mass of a fine particle dispersion (W-01) and 248 parts by mass of water, and tertiary butyl hydroperoxide (manufactured by Nichiyu, Perbutyl H) 0. After adding 267 parts by mass, the system was heated to raise the temperature in the system to 70 ° C. Then, 53.3 parts by mass of styrene, 13.3 parts by mass of butyl acrylate and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to use the fine particles in the fine particle dispersion (W-01) as a seed, and the resin (a) (A-) which is a polymer copolymerized with styrene and butyl acrylate. A fine particle dispersion (W-7) containing organic resin fine particles (A-7) containing 7C) and the resin (b) (A-1S) as constituents in the same particles was obtained. The fine particle dispersion (W-7) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the resin fine particles (A-7) was 17.0 nm. The volume average particle size was measured in the same manner as the above-mentioned organic resin fine particles (A-1).

Further, the fine particle dispersion (W-7) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resins (a) and (A-7C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resin resin (a) (A-7C) was 70 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-7) contains the organic resin fine particles (A-7) is that a part of the fine particle dispersion (W-7) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-5).

Table 2 shows the measurement results of the volume average particle diameter of the organic resin fine particles (A-7), the glass transition point Tg _1st of the resins (a) and (A-7C), and the acid value.

<Production example 13 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-8) containing organic resin fine particles (A-8)]
A reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer was charged with 667 parts by mass of a fine particle dispersion (W-01) and 57 parts by mass of water, and tertiary butyl hydroperoxide (manufactured by Nichiyu, Perbutyl H) 0. After adding 06 parts by mass, the temperature inside the system was raised to 70 ° C. by heating. Then, 9.6 parts by mass of styrene, 5.2 parts by mass of butyl acrylate, and 4 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to use the fine particles in the fine particle dispersion (W-01) as a seed, and the resin (a) (A-) which is a polymer copolymerized with styrene and butyl acrylate. A fine particle dispersion (W-8) containing organic resin fine particles (A-8) containing 8C) and the resin (b) (A-1S) as constituents in the same particles was obtained. The fine particle dispersion (W-8) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the resin fine particles (A-8) was 15.0 nm. The volume average particle size was measured in the same manner as the above-mentioned organic resin fine particles (A-1).

Further, the fine particle dispersion (W-8) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resins (a) and (A-8C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-8C) was 53 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-8) contains the organic resin fine particles (A-8) is that a part of the fine particle dispersion (W-8) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-8).

Table 2 shows the measurement results of the volume average particle diameter of the organic resin fine particles (A-8), the glass transition point Tg _1st of the resins (a) and (A-8C), and the acid value.

<Production example 14 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-9) containing organic resin fine particles (A-9)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 3710 parts by mass of water and 200 parts by mass of polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium (Aqualon KH-1025) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. The parts were charged and stirred at 200 rpm to homogenize. The mixed solution is heated to a temperature of 75 ° C. in the system, and then 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then a mixture consisting of 640 parts by mass of styrene and 360 parts by mass of butyl acrylate. The liquid was added dropwise over 4 hours. After dropping, the resin is a polymer obtained by copolymerizing a mixed solution of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium by aging at 75 ° C. for 4 hours. (A) A fine particle dispersion (W-9) containing organic resin fine particles (A-9) containing (a-9C) and the resin (b) (A-1S) as constituents in the same particles was obtained. .. The fine particle dispersion (W-9) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the fine particles in the fine particle dispersion (W-9) was 15.0 nm. The volume average particle size was measured in the same manner as the above-mentioned organic resin fine particles (A-1).

Moreover, a part of the fine particle dispersion liquid (W-9) was dried, and the resin (a) (A-9C) was isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-9C) was 53 ° C., and the acid value was 0 mgKOH / g.

<Production example 15 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-010) containing organic resin fine particles (A-10S)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 3710 parts by mass of water, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester (Aquaron KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 200 A mass portion was charged and stirred at 200 rpm to make it uniform. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then 122 parts by mass of styrene, 578 parts by mass of butyl acrylate, and methacrylic acid. A mixed solution consisting of 300 parts by mass was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-010) containing organic resin fine particles (A-10S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-010) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-10S) in the fine particle dispersion (W-010) was 15.0 nm. Further, a part of the fine particle dispersion liquid (W-010) was dried to isolate organic resin fine particles (A-10S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-10S) was 22 ° C., and the acid value was 195 mgKOH / g. Table 3 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-11S).

<Production example 16 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-10) containing organic resin fine particles (A-10)]
Next, 667 parts by mass of the fine particle dispersion liquid (W-010) and 248 parts by mass of water were charged in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. After adding 0.267 parts by mass of tertiary butyl hydroperoxide (NOF, Perbutyl H), the mixed solution was heated to raise the temperature in the system to 70 ° C. Then, 13.4 parts by mass of styrene, 53.2 parts by mass of butyl acrylate, and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to obtain a copolymer of styrene and butyl acrylate using the organic resin fine particles (A-10S) in the fine particle dispersion (W-010) as a seed. A fine particle dispersion (W-10) containing organic resin fine particles (A-10) containing the resin (a) (A-10C) and the resin (b) (A-10S) as constituents in the same particles was obtained. .. The fine particle dispersion (W-10) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-10) was 17.3 nm. The volume average particle size was measured using a laser Doppler particle size distribution measuring device (nanotrac UPA-150EX, manufactured by Nikkiso Co., Ltd.).

Further, the fine particle dispersion (W-10) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resins (a) and (A-10C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-10C) was 21 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-10) contains the organic resin fine particles (A-10) is that a part of the fine particle dispersion (W-10) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-10).

Table 3 shows the measurement results of the glass transition point Tg _1st and the acid value at the first temperature rise of the volume average particle size of the organic resin fine particles (A-10) and the differential scanning calorimetry of the resins (b) and (A-10C). ..

<Production example 17 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-011) containing organic resin fine particles (A-11S)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 3710 parts by mass of water, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester (Aquaron KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 200 A mass portion was charged and stirred at 200 rpm to make it uniform. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then 235 parts by mass of styrene, 465 parts by mass of butyl acrylate, and methacrylic acid. A mixed solution consisting of 300 parts by mass was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-011) containing organic resin fine particles (A-11S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-011) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-11S) in the fine particle dispersion (W-011) was 15.0 nm. Further, a part of the fine particle dispersion liquid (W-011) was dried to isolate organic resin fine particles (A-11S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-11S) was 30 ° C., and the acid value was 195 mgKOH / g. Table 3 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-11S).

<Production example 18 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-11) containing organic resin fine particles (A-11)]
Next, 667 parts by mass of the fine particle dispersion liquid (W-011) and 248 parts by mass of water were charged into a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. After adding 0.267 parts by mass of tertiary butyl hydroperoxide (NOF, Perbutyl H), the mixed solution was heated to raise the temperature in the system to 70 ° C. Then, 23.3 parts by mass of styrene, 43.3 parts by mass of butyl acrylate, and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to obtain a copolymer of styrene and butyl acrylate using the organic resin fine particles (A-11S) in the fine particle dispersion (W-011) as a seed. A fine particle dispersion (W-11) containing organic resin fine particles (A-11) containing the resin (a) (A-11C) and the resin (b) (A-11S) as constituents in the same particles was obtained. .. The fine particle dispersion (W-11) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-11) was 17.3 nm. The volume average particle size was measured using a laser Doppler particle size distribution measuring device (nanotrac UPA-150EX, manufactured by Nikkiso Co., Ltd.).

Further, the fine particle dispersion (W-11) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resin (b) (A-11C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-11C) was 31 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-11) contains the organic resin fine particles (A-11) is that a part of the fine particle dispersion (W-11) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-11).

Table 3 shows the measurement results of the glass transition point Tg _1st and the acid value at the first temperature rise of the volume average particle size of the organic resin fine particles (A-11) and the differential scanning calorimetry of the resins (a) and (A-11C). ..

<Production example 19 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-012) containing organic resin fine particles (A-12S)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 3710 parts by mass of water, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester (Aquaron KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 200 A mass portion was charged and stirred at 200 rpm to make it uniform. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then 506 parts by mass of styrene, 194 parts by mass of butyl acrylate, and methacrylic acid. A mixed solution consisting of 300 parts by mass was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-012) containing organic resin fine particles (A-12S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-012) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-12S) in the fine particle dispersion (W-012) was 15.0 nm. Further, a part of the fine particle dispersion liquid (W-012) was dried to isolate organic resin fine particles (A-12S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-12S) was 61 ° C., and the acid value was 195 mgKOH / g. Table 3 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-12S).

<Production example 20 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-12) containing organic resin fine particles (A-12)]
Next, 667 parts by mass of the fine particle dispersion liquid (W-012) and 248 parts by mass of water were charged in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. After adding 0.267 parts by mass of tertiary butyl hydroperoxide (NOF, Perbutyl H), the mixed solution was heated to raise the temperature in the system to 70 ° C. Then, 47.4 parts by mass of styrene, 19.2 parts by mass of butyl acrylate, and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to obtain a copolymer of styrene and butyl acrylate using the organic resin fine particles (A-12S) in the fine particle dispersion (W-012) as a seed. A fine particle dispersion (W-12) containing organic resin fine particles (A-12) containing the resin (a) (A-12C) and the resin (b) (A-12S) as constituents in the same particles was obtained. .. The fine particle dispersion (W-12) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-12) was 17.3 nm. The volume average particle size was measured using a laser Doppler particle size distribution measuring device (nanotrac UPA-150EX, manufactured by Nikkiso Co., Ltd.).

Further, the fine particle dispersion (W-12) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifuged precipitate is dried to dryness to obtain the resin (b) (A-12C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-12C) was 60 ° C., and the acid value was 0 mgKOH / g.

The fact that the fine particle dispersion (W-12) contains the organic resin fine particles (A-12) is that a part of the fine particle dispersion (W-12) is dried in the same manner as in the above <Organic Resin Fine Particle Production Example 1>. It was confirmed by isolating the organic resin fine particles (A-12).

Table 3 shows the measurement results of the glass transition point Tg _1st and the acid value at the first temperature rise of the volume average particle size of the organic resin fine particles (A-12) and the differential scanning calorimetry of the resins (b) (A-12C). ..

<Production example 21 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-013) containing organic resin fine particles (A-13S)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 3710 parts by mass of water, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester (Aquaron KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 200 A mass portion was charged and stirred at 200 rpm to make it uniform. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then 578 parts by mass of styrene, 122 parts by mass of butyl acrylate, and methacrylic acid. A mixed solution consisting of 300 parts by mass was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-013) containing organic resin fine particles (A-13S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-013) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-13S) in the fine particle dispersion (W-013) was 15 nm. In addition, a part of the fine particle dispersion liquid (W-013) was dried to isolate organic resin fine particles (A-13S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-13S) was 71 ° C., and the acid value was 195 mgKOH / g. Table 3 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-13S).

<Production example 22 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-13) containing organic resin fine particles (A-13)]
Next, 667 parts by mass of the fine particle dispersion liquid (W-013) and 248 parts by mass of water were charged into a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. After adding 0.267 parts by mass of tertiary butyl hydroperoxide (NOF, Perbutyl H), the mixed solution was heated to raise the temperature in the system to 70 ° C. Then, 53.3 parts by mass of styrene, 13.3 parts by mass of butyl acrylate, and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours, and the organic resin fine particles (A-13S) in the fine particle dispersion (W-013) are used as seeds, and a polymer copolymerized with styrene and a butyl acrylate monomer is polymerized. A fine particle dispersion (W-13) containing organic resin fine particles (A-13) containing the resin (a) (A-13C) and the resin (b) (A-13S) as constituents in the same particles. Obtained. The fine particle dispersion (W-13) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-13) was 17.3 nm. The volume average particle size was measured using a laser Doppler particle size distribution measuring device (nanotrac UPA-150EX, manufactured by Nikkiso Co., Ltd.).

Further, the fine particle dispersion (W-13) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resin (b) (A-13C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-13C) was 71 ° C., and the acid value was 0 mgKOH / g.

<Production example 23 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-014) containing organic resin fine particles (A-14S)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 3710 parts by mass of water, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester (Aquaron KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 200 A mass portion was charged and stirred at 200 rpm to make it uniform. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then 645 parts by mass of styrene, 55 parts by mass of butyl acrylate, and methacrylic acid. A mixed solution consisting of 300 parts by mass was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-014) containing organic resin fine particles (A-14S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-014) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-14S) in the fine particle dispersion (W-014) was 15.0 nm. Further, a part of the fine particle dispersion liquid (W-014) was dried to isolate organic resin fine particles (A-14S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-14S) was 81 ° C., and the acid value was 195 mgKOH / g. Table 3 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-14S).

<Production example 24 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-14) containing organic resin fine particles (A-14)]
Next, 667 parts by mass of the fine particle dispersion liquid (W-014) and 248 parts by mass of water were charged in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. After adding 0.267 parts by mass of tertiary butyl hydroperoxide (NOF, Perbutyl H), the mixed solution was heated to raise the temperature in the system to 70 ° C. Then, 59.2 parts by mass of styrene, 7.4 parts by mass of butyl acrylate, and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to obtain a copolymer of styrene and butyl acrylate using the organic resin fine particles (A-14S) in the fine particle dispersion (W-014) as a seed. A fine particle dispersion (W-14) containing organic resin fine particles (A-14) containing the resin (a) (A-14C) and the resin (b) (A-14S) as constituents in the same particles was obtained. .. The fine particle dispersion (W-14) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-14) was 17.3 nm. The volume average particle size was measured using a laser Doppler particle size distribution measuring device (nanotrac UPA-150EX, manufactured by Nikkiso Co., Ltd.).

Further, the fine particle dispersion (W-14) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resin (b) (A-14C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-14C) was 80 ° C., and the acid value was 0 mgKOH / g.

<Production example 25 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-015) containing organic resin fine particles (A-15S)]
3710 parts by mass of water, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester (Aqualon KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 175 in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. A mass portion was charged and stirred at 200 rpm to make it uniform. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then 450 parts by mass of styrene, 250 parts by mass of butyl acrylate, and methacrylic acid. A mixed solution consisting of 300 parts by mass was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-015) containing organic resin fine particles (A-15S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-015) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-15S) in the fine particle dispersion (W-015) was 23.0 nm. Further, a part of the fine particle dispersion liquid (W-015) was dried to isolate organic resin fine particles (A-15S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-15S) was 53 ° C., and the acid value was 195 mgKOH / g. Table 2 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-15S).

<Production example 26 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-15) containing organic resin fine particles (A-15)]
Next, 667 parts by mass of the fine particle dispersion liquid (W-015) and 248 parts by mass of water were charged into a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. After adding 0.267 parts by mass of tertiary butyl hydroperoxide (NOF, Perbutyl H), the mixed solution was heated to raise the temperature in the system to 70 ° C. Then, 43.3 parts by mass of styrene, 23.3 parts by mass of butyl acrylate, and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to obtain a copolymer of styrene and butyl acrylate using the organic resin fine particles (A-15S) in the fine particle dispersion (W-015) as a seed. A fine particle dispersion (W-15) containing organic resin fine particles (A-15) containing the resin (a) (A-15C) and the resin (b) (A-15S) as constituents in the same particles was obtained. .. The fine particle dispersion (W-15) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-15) was 26.0 nm. The volume average particle size was measured using a laser Doppler particle size distribution measuring device (nanotrac UPA-150EX, manufactured by Nikkiso Co., Ltd.).

Further, the fine particle dispersion (W-15) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resin (b) (A-15C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-15C) was 53 ° C., and the acid value was 0 mgKOH / g.

<Production example 27 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-016) containing organic resin fine particles (A-16S)]
3710 parts by mass of water, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester (Aqualon KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 75 in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. A mass portion was charged and stirred at 200 rpm to make it uniform. After heating the mixed solution to raise the temperature in the system to 75 ° C., 90 parts by mass of a 10 mass% ammonium persulfate aqueous solution is added to the mixed solution, and then 450 parts by mass of styrene, 250 parts by mass of butyl acrylate, and methacrylic acid. A mixed solution consisting of 300 parts by mass was added dropwise over 4 hours. After the dropping, the mixed solution was aged at 75 ° C. for 4 hours to copolymerize the mixed solution composed of styrene, butyl acrylate and methacrylic acid with polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium. A fine particle dispersion (W-016) containing organic resin fine particles (A-16S) made of the polymer resin (b) was obtained. The fine particle dispersion (W-016) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-16S) in the fine particle dispersion (W-016) was 67 nm. In addition, a part of the fine particle dispersion liquid (W-016) was dried to isolate organic resin fine particles (A-16S). The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the organic resin fine particles (A-16S) was 53 ° C., and the acid value was 195 mgKOH / g. Table 2 shows the measurement results of the volume average particle size, the glass transition point Tg _1st , and the acid value of the organic resin fine particles (A-16S).

<Production example 28 of organic resin fine particles>
[Manufacturing of fine particle dispersion liquid (W-16) containing organic resin fine particles (A-16)]
Next, 667 parts by mass of the fine particle dispersion liquid (W-016) and 248 parts by mass of water were charged into a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. After adding 0.267 parts by mass of tertiary butyl hydroperoxide (NOF, Perbutyl H), the mixed solution was heated to raise the temperature in the system to 70 ° C. Then, 43.3 parts by mass of styrene, 23.3 parts by mass of butyl acrylate, and 18.0 parts by mass of a 1 mass% ascorbic acid aqueous solution were added dropwise to the mixed solution over 2 hours. After the dropping, the mixed solution is aged at 70 ° C. for 4 hours to obtain a copolymer of styrene and butyl acrylate using the organic resin fine particles (A-16S) in the fine particle dispersion (W-016) as a seed. A fine particle dispersion (W-16) containing organic resin fine particles (A-16) containing the resin (a) (A-16C) and the resin (b) (A-16S) as constituents in the same particles was obtained. .. The fine particle dispersion (W-16) was adjusted so that the pure polymer content was 20%.

The volume average particle size of the organic resin fine particles (A-16) was 76.0 nm. The volume average particle size was measured using a laser Doppler particle size distribution measuring device (nanotrac UPA-150EX, manufactured by Nikkiso Co., Ltd.).

Further, the fine particle dispersion (W-16) is neutralized with a 10% by mass aqueous ammonia solution to adjust the pH to 9.0, and then the centrifugally separated precipitate is dried to dryness to obtain the resin (b) (A-16C). Isolated. The glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resins (a) and (A-16C) was 53 ° C., and the acid value was 0 mgKOH / g.

The properties of the fine particle dispersions (W-01) to (W-016) and (W-1) to (W-16) are shown in Tables 2 and 3.

<Production example of crystalline polyester>
[Synthesis of crystalline polyester resin]
Dodecanedioic acid and 1,6-hexanediol are placed in a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and OH / COOH is the molar ratio of hydroxyl group to carboxyl group. Was charged to be 0.9, and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours. Then, the mixed solution was heated to 200 ° C. and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain a crystalline polyester resin.

<Manufacturing example of amorphous polyester resin>
[Synthesis of amorphous polyester resin A1]
26.5 parts by mass of terephthalic acid, 2.2 mol of ethylene oxide adduct of bisphenol A 13.5 parts by mass, 2.2 mol of propylene oxide of bisphenol A in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. 59.9 parts by mass of the adduct and 0.2 parts by mass of dibutyltin oxide were added, and the mixture was reacted at 230 ° C. for 4 hours under normal pressure. Then, the mixture was reacted under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an amorphous polyester resin A1.

<Manufacturing example of amorphous polyester resin>
[Synthesis of amorphous polyester resin A2]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 25.8 parts by mass of terephthalic acid, 27.8 parts by mass of adipic acid, 44.9 parts by mass of 3-methyl-1,5-pentanediol, and trimethylolpropane. 1.5 parts by mass of trimethylolpropane and 0.2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 4 hours under normal pressure. Then, the mixture was reacted under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an amorphous polyester resin intermediate.

Next, 90 parts by mass of the amorphous polyester resin intermediate and 10 parts by mass of isophorone diisocyanate (IPDI) were put into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 100 parts by mass of ethyl acetate was added. Diluted. Then, the mixture was reacted at 80 ° C. for 5 hours to obtain an ethyl acetate solution of the amorphous polyester resin A2 as a prepolymer.

<Example 1>
[Manufacturing of toner]
(Preparation of masterbatch (MB))
1,200 parts by mass of water, 500 parts by mass of carbon black (manufactured by Printex35 Dexa, DBP oil absorption = 42 mL / 100 mg, pH = 9.5) and 500 parts by mass of amorphous polyester resin A1 were mixed with a Henshell mixer ( The mixture was mixed with Nippon Coke Industries, Ltd.), and the mixture was kneaded at 150 ° C. for 30 minutes using two rolls. Then, it was rolled and cooled and pulverized with a palperizer to obtain a masterbatch 1.

(Preparation of wax dispersion)
50 parts by mass of paraffin wax (manufactured by Nippon Seiko Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8) and ethyl acetate 450 as a mold release agent in a container in which a stirring rod and a thermometer are set. A mass portion was charged, the temperature was raised to 80 ° C. with stirring, and the temperature was maintained at 80 ° C. for 5 hours. After that, the mixture was cooled to 30 ° C. at 1 hour, and using a bead mill (Ultra Viscomill, manufactured by IMEX), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and a diameter of 0.5 mm zirconia beads were 80. A wax dispersion was obtained by dispersing under the conditions of volume% filling and 3 passes.

(Preparation of crystalline polyester resin dispersion)
50 parts by mass of crystalline polyester resin and 450 parts by mass of ethyl acetate were charged in a container in which a stirring rod and a thermometer were set, the temperature was raised to 80 ° C. under stirring, and the temperature was maintained at 80 ° C. for 5 hours. Then, the mixture was cooled to 30 ° C. in 1 hour, and using a bead mill (Ultra Viscomill, manufactured by Imex), 80 volumes of zirconia beads having a liquid feeding rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and a diameter of 0.5 mm were added. A crystalline polyester resin dispersion was obtained by dispersing under the conditions of% filling and 3 passes.

(Preparation of oil phase)
500 parts by mass of wax dispersion, 300 parts by mass of ethyl acetate solution of amorphous polyester resin A3, 500 parts by mass of crystalline polyester resin dispersion, 700 parts by mass of amorphous polyester resin A1, 100 parts by mass of master batch, and pre. Two parts by mass of isophorondiamine as a curing agent for the polymer was placed in a container and mixed with a TK homomixer (manufactured by Primix Co., Ltd.) at 5,000 rpm for 60 minutes to obtain an oil phase.

(Preparation of aqueous phase)
A milky white liquid is obtained by mixing and stirring 938 parts by mass of water, 50 parts by mass of an aqueous dispersion (W-1) containing organic resin fine particles (A-1), 120 parts by mass of a surfactant and 92 parts by mass of ethyl acetate. rice field. This was used as the aqueous phase.

(Emulsification / solvent removal)
1,200 parts by mass of an aqueous phase was added to a container containing 800 parts by mass of an oil phase, and the mixture was mixed with a TK homomixer at a rotation speed of 13,000 rpm for 20 minutes to obtain an emulsified slurry. The emulsified slurry was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 30 ° C. for 8 hours, and then aged at 45 ° C. for 10 hours to obtain a dispersed slurry.

(Washing / drying)
A 10% aqueous sodium hydroxide solution was added to 100 parts by mass of the dispersed slurry until the pH reached 11, and the mixture was stirred for 1 hour. Then, after the slurry was filtered under reduced pressure, the following operations (1) to (4) were performed.

(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): 300 parts of ion-exchanged water was added to the filtered cake of (3), mixed with a TK homomixer (rotation speed 12,000 rpm for 10 minutes), and then filtered.

The above operations (1) to (4) were performed twice to obtain a filtered cake.

The obtained 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. Approximately 0.2 g of the obtained toner matrix particles were carefully evaluated, and the mixture was added to 20 mL of methanol and dispersed by stirring. Then, ultrasonic waves are applied for 30 minutes, the mixture is allowed to stand for 24 hours, the supernatant is filtered through a membrane filter having a pore size of 0.2 μm, and the filtered supernatant is diluted 100-fold with methanol, and then a liquid chromatography system ( AQUITY-UPLC / SQD system, manufactured by Japan Waters Co., Ltd.). A peak derived from an anionic surfactant containing a carboxyl group was observed by the MS detector of the liquid chromatography system, and it was confirmed that the anionic surfactant containing a carboxyl group was present on the surface of the toner matrix particles. rice field. Further, the content of the organic resin fine particles (A-1) contained in the toner was measured by a pyrolysis gas chromatograph system (7890B, manufactured by Agilent Technologies, EGA / PY-3030D (manufactured by Frontier Lab)).

(External processing)
With respect to 100 parts by mass of the toner matrix particles, 0.6 parts by mass of hydrophobic silica having an average particle size of 100 nm, 1.0 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. Was mixed with 0.8 parts with a Henshell mixer to obtain toner. Table 4 shows the composition of the toner raw materials.

<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. Using a fluidized bed coating device, the resin layer coating liquid was applied to the surface of 1000 parts by mass of spherical magnetite having an average particle size of 50 μm to prepare a carrier.

<Preparation of developer>
Using a ball mill, 5 parts by mass of toner and 95 parts by mass of carriers were mixed to prepare a developer.

<Evaluation of toner characteristics>
Next, using each of the prepared developing agents, the characteristics of the toner were evaluated as follows. The evaluation results of each are shown in Tables 5 and 6.

[Offset resistance]
The carrier and the toner were mixed so that the concentration of the toner was 5% by mass to obtain a developer. After adding the developer to the unit of imageo MP C4300 (manufactured by Ricoh Co., Ltd.), the amount of toner adhered to the PPC paper type 6000 <70W> A4 T-th (manufactured by Ricoh Co., Ltd.) rectangular solid image of 2 cm x 15 cm. It was formed to be 0.40 mg / cm ² . At this time, the surface temperature of the fixing roller is changed, and the cold offset temperature (fixing lower limit temperature) and the hot offset temperature (fixing upper limit temperature) at which an offset occurs in which the development residual image of the solid image is fixed in a place other than the desired place. Was obtained, and the offset resistance was evaluated based on the following evaluation criteria.
(Cold offset evaluation criteria)
⊚: Fixing lower limit temperature is less than 110 ° C ○: Fixing lower limit temperature is 110 ° C or more and less than 120 ° C Δ: Fixing lower limit temperature is 120 ° C or more and less than 130 ° C ×: Fixing lower limit temperature is 130 ° C or more (hot offset) Evaluation criteria)
⊚: Fixing upper limit temperature is 170 ° C or higher ○: Fixing upper limit temperature is 160 ° C or higher and lower than 170 ° C Δ: Fixing upper limit temperature is 150 ° C or higher and lower than 160 ° C ×: Fixing upper limit temperature is lower than 150 ° C

[Heat-resistant storage]
A 50 mL glass container was filled with toner, left in a constant temperature bath at 50 ° C. for 24 hours, and then cooled to 24 ° C. Next, the needle insertion degree [mm] was measured by the needle insertion degree test (JISK2235-1991), and the heat-resistant storage stability was evaluated. It should be noted that the larger the degree of needle insertion, the better the heat-resistant storage stability. If the degree of needle insertion is less than 10 mm, there is a high possibility that problems will occur in use.
(Evaluation criteria)
⊚: Needle insertion degree is 20 mm or more ○: Needle insertion degree is 15 mm or more and less than 20 mm Δ: Needle insertion degree is 10 mm or more and less than 15 mm ×: Needle insertion degree is less than 10 mm

[Chargeability]
6 g of the two-component developer was weighed, charged into a metal cylinder that could be sealed, stirred at a stirring speed of 280 rpm, the amount of charge was determined by the blow-off method, and the chargeability was evaluated based on the following evaluation criteria. The stirring time was measured at 15 seconds (TA15), 60 seconds (TA60), and 600 seconds (TA600). As a carrier, TEFV200 / 300 (manufactured by Powdertech Co., Ltd.) was used.
(Evaluation criteria)
⊚: Charge amount is 36 or more ○: Charge amount is 33 or more and less than 36 Δ: Charge amount is 30 or more and less than 33 ×: Charge amount is less than 30

[Comprehensive evaluation]
The comprehensive evaluation was evaluated according to the following evaluation criteria. All evaluation items are ◎ or ○ with one ◎, ○ with two or more ○ but no problem in use ○, △ 1 or more but no problem in use △, × 1 One or more items were judged as x.
(Evaluation criteria)
◎: Very good ○: Excellent △: Slightly better than before ×: Not practical

<Examples 2 to 4>
In Example 1, except that the surfactant 1 used in (Preparation of the aqueous phase) of Example 1 was changed to any of the surfactants 2 to 4 as shown in Table 4, Example 1 I went in the same way. In Example 2, the surfactant 2 was used, in Example 3, the surfactant 3 was used, and in Example 4, the surfactant 4 was used. The composition of the toner raw materials is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

<Examples 5 to 11>
In Example 1, the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in (preparation of the aqueous phase) of Example 1 was replaced with the aqueous dispersion (A-2) of the organic resin fine particles (A-2). The procedure was the same as in Example 1 except that the solution was changed to any of W-2) to the aqueous dispersion (W-7) of the organic resin fine particles (A-7). In Example 5, an aqueous dispersion (W-2) of organic resin fine particles (A-2) was used. In Example 6, an aqueous dispersion (W-3) of organic resin fine particles (A-3) was used. In Example 7, an aqueous dispersion (W-4) of organic resin fine particles (A-4) was used. In Example 8, an aqueous dispersion (W-5) of organic resin fine particles (A-5) was used. In Example 9, an aqueous dispersion (W-6) of organic resin fine particles (A-6) was used. In Example 10, an aqueous dispersion (W-7) of organic resin fine particles (A-7) was used. In Example 11, an aqueous dispersion (W-8) of organic resin fine particles (A-8) was used. The composition of the toner raw materials of each example is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

<Example 12>
In Example 1, the content of the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in (Preparation of the aqueous phase) of Example 1 was changed from 50 parts by mass to 125 parts by mass. Except for the above, the procedure was the same as in Example 1. The composition of the toner raw materials of the examples is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

<Examples 13 to 19>
In Example 1, the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in (preparation of the aqueous phase) of Example 1 was replaced with the aqueous dispersion (A-10) of the organic resin fine particles (A-10). The procedure was the same as in Example 1 except that the mixture was changed to any of the aqueous dispersion (W-16) of W-10) to the organic resin fine particles (A-16). In Example 13, an aqueous dispersion (W-10) of organic resin fine particles (A-10) was used. In Example 14, an aqueous dispersion (W-11) of organic resin fine particles (A-11) was used. In Example 15, an aqueous dispersion (W-12) of organic resin fine particles (A-12) was used. In Example 16, an aqueous dispersion (W-13) of organic resin fine particles (A-13) was used. In Example 17, an aqueous dispersion (W-14) of organic resin fine particles (A-14) was used. In Example 18, an aqueous dispersion (W-15) of organic resin fine particles (A-15) was used. In Example 19, an aqueous dispersion (W-16) of organic resin fine particles (A-16) was used. The composition of the toner raw materials of each example is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

<Example 20>
In Example 1, the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in (preparation of the aqueous phase) of Example 1 is replaced with the aqueous dispersion (W) of the organic resin fine particles (A-8). The procedure was carried out in the same manner as in Example 1 except that the content was changed to -8) and the content was changed from 50 parts by mass to 37.5 parts by mass. The composition of the toner raw materials of the examples is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

<Example 21>
In Example 1, the content of the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in (Preparation of the aqueous phase) of Example 1 was changed from 50 parts by mass to 150 parts by mass. Except for the above, the procedure was the same as in Example 1. The composition of the toner raw materials of the examples is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

<Example 22>
In Example 1, the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in (preparation of the aqueous phase) of Example 1 is replaced with the aqueous dispersion (W) of the organic resin fine particles (A-8). The procedure was carried out in the same manner as in Example 1 except that the content was changed to -8) and the content was changed from 50 parts by mass to 62.5 parts by mass. The composition of the toner raw materials of the examples is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

<Example 23>
In Example 1, the content of the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in Example 1 (preparation of aqueous phase) was changed from 50 parts by mass to 37.5 parts by mass. Except for what was done, the same procedure as in Example 1 was performed. The composition of the toner raw materials of the examples is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

<Example 24>
In Example 1, the content of the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in (Preparation of the aqueous phase) of Example 1 was changed from 50 parts by mass to 75 parts by mass. Except for the above, the procedure was the same as in Example 1. The composition of the toner raw materials of the examples is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

<Example 25>
In Example 1, the content of the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in (Preparation of the aqueous phase) of Example 1 was changed from 50 parts by mass to 100 parts by mass. Except for the above, the procedure was the same as in Example 1. The composition of the toner raw materials of the examples is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

<Comparative Example 1>
In Example 1, the content of water used in Example 1 (preparation of aqueous phase) was changed from 938 parts by mass to 983 parts by mass, and the surfactant 1 was a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate. (Eleminor MON-7: manufactured by Sanyo Kasei Kogyo Co., Ltd.) The procedure was the same as in Example 1 except that the content was changed to 75 parts by mass. The composition of the toner raw materials is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

The acid value of the 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate used was measured with a potential difference automatic titrator (DL-53 Titrator, manufactured by Metler Toledo), and the acid value was 0 mgKOH / g. , It was confirmed that it did not contain a carboxyl group.

<Comparative Example 2>
In Example 1, the content of water used in (Preparation of aqueous phase) of Example 1 was changed from 938 parts by mass to 968 parts by mass, and the surfactant 1 was changed to a 40% aqueous solution of sodium alkanesulfonate (Latemuru PS). , Kao Co., Ltd.) The toner of Comparative Example 1 was obtained in the same manner as in Example 1 except that it was changed to 90 parts by mass. The composition of the toner raw materials is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

As a result of measuring the acid value of the used 40% aqueous solution of sodium alkanesulfonate with a potential difference automatic titrator (DL-53 Titrator, manufactured by Metler Toledo), the acid value was 0 mgKOH / g, and the carboxyl group was found. It was confirmed that it was not contained.

<Comparative Example 3>
In Example 1, the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in (preparation of the aqueous phase) of Example 1 was replaced with the aqueous dispersion (W-) of the organic resin fine particles A-1S. Except for the change to 01), the same procedure as in Example 1 was performed.

<Comparative Example 4>
In Example 1, the aqueous dispersion (W-1) of the organic resin fine particles (A-1) used in (preparation of the aqueous phase) of Example 1 was replaced with the aqueous dispersion (A-89) of the organic resin fine particles (A-89). The procedure was carried out in the same manner as in Example 1 except that the change was made to W-9), but the toner matrix particles could not be granulated.

<Comparative Example 5>
In Example 1, the content of water used in Example 1 (preparation of aqueous phase) was changed to 983 parts by mass, and the surfactant 1 was added to a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (eleminol MON-). 7. Sanyo Chemical Industries, Ltd.) Changed to 75 parts by mass. The aqueous dispersion (W-1) of the organic resin fine particles (A-1) was changed to the aqueous dispersion (W-01) of the organic resin fine particles A-1S. Other than that, the procedure was the same as in Example 1. The composition of the toner raw materials is shown in Table 4, and the evaluation results are shown in Tables 5 and 6.

When the acid value of the 48.5% aqueous solution of dodecyldiphenyl ether disulfonate used was measured with a potential difference automatic titrator (DL-53 Titrator, manufactured by Metler Toledo), the acid value was 0 mgKOH / g and carboxyl. It was confirmed that it did not contain a group.

From Tables 5 and 6, it was confirmed that the toners of Examples 1 to 25 satisfied the conditions for use in terms of low fixing property, high temperature offset resistance, heat storage property and chargeability. On the other hand, in the toners obtained in Comparative Examples 1 to 5, at least one of low fixing property, high temperature offset resistance, heat storage property and chargeability does not satisfy the conditions for use, or the toner matrix particles are used. It was confirmed that it could not be manufactured and had a problem in practical use.

Therefore, unlike the toners of Comparative Examples 1 to 5, the toners of Examples 1 to 25 contain a core having a resin (a) containing a styrene acrylic resin and no carboxyl group on the surface of the toner, and a carboxyl group. By having organic resin fine particles having a core-shell structure composed of a shell having resin (b) and an anionic surfactant containing a carboxyl group, low fixing property, high temperature offset resistance, heat storage property and chargeability It can be said that it is an excellent and high quality toner.

As described above, the embodiments have been described, but the above embodiments are presented as examples, and the present invention is not limited to the above embodiments. The above embodiment can be implemented in various other embodiments, and various combinations, omissions, replacements, changes, etc. can be made without departing from the gist of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are also included in the scope of the invention described in the claims and the equivalent scope thereof.

1A, 1B, 1C image forming apparatus 10 Electrostatic latent image carrier (photoreceptor drum)
20 Charging roller (charging part)
30 Exposure device (exposure section)
40 Developing equipment (development unit)
50 Intermediate transfer body (intermediate transfer belt)
60 Cleaning device (cleaning unit)
70 Transfer roller (transfer section)
80 Static elimination lamp (static elimination section)

Japanese Unexamined Patent Publication No. 2005-0554998

Claims (10)

Contains toner matrix particles containing a binder resin,
Organic resin fine particles having a core-shell structure composed of a core having a resin (a) containing a styrene acrylic resin and no carboxyl group and a shell having a resin (b) containing a carboxyl group on the surface of the toner matrix particles. And a toner having an anionic surfactant containing a carboxyl group. The toner according to claim 1, wherein the glass transition point Tg _1st at the first temperature rise of the differential scanning calorimetry of the resin (a) and the resin (b) is 30 ° C to 70 ° C. The toner according to claim 1 or 2, wherein the volumetric particle diameter of the organic resin fine particles is 10 nm to 100 nm. The toner according to any one of claims 1 to 3, wherein the content of the organic resin fine particles is 0.2% by mass to 5% by mass with respect to the toner. The toner according to claim 4, wherein the acid value of the anionic surfactant is 100 mgKOH / g to 200 mgKOH / g. The toner according to any one of claims 1 to 5, wherein the anionic surfactant contains a succinic acid derivative. A developer containing the toner according to any one of claims 1 to 6 and a carrier. A toner storage unit containing the toner according to any one of claims 1 to 6. Electrostatic latent image carrier and
An electrostatic latent image forming portion that forms an electrostatic latent image on the electrostatic latent image carrier,
A developing unit that develops the electrostatic latent image with toner to form a visible image,
A transfer unit that transfers the visible image to a recording medium,
A fixing portion for fixing the transferred image transferred to the recording medium is provided.
The image forming apparatus in which the toner is the toner according to any one of claims 1 to 6. An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier,
A developing step of developing the electrostatic latent image with toner to form a visible image,
A transfer step of transferring the visible image to a recording medium,
Including a fixing step of fixing a transferred image transferred to the recording medium.
The image forming method in which the toner is the toner according to any one of claims 1 to 6.

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