JP2022151547A - Resin particle, toner, method for manufacturing resin particle, method for manufacturing toner, developer, toner storage unit, and image forming apparatus - Google Patents

Abstract

To provide a resin particle that has a large contribution to carbon neutral and can satisfy low temperature fixability and cleaning properties.SOLUTION: A resin particle includes at least a crystalline polyester resin, an amorphous polyester resin, a mold release agent, and a coloring agent. An acid component of the crystalline polyester resin is a plant-derived dicarboxylic acid having 12 or less carbon atoms. The average major axis of domains of the crystalline polyester resin is 2.0 μm or less, and the average aspect ratio (major axis/minor axis) of the domains is 4.0 or more. The concentration of a radioactive carbon isotope 14C is 5.4 pMC or more.SELECTED DRAWING: None

Description

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

Carbon neutral is generally used as a definition for biomass materials composed of organic matter. When such biomass materials are burned, carbon dioxide is emitted, and the carbon contained in the carbon dioxide is derived from carbon dioxide absorbed from the atmosphere by photosynthesis during the growth process of the biomass materials. Therefore, it is considered that the use of biomass materials does not increase the amount of carbon dioxide in the atmosphere as a whole. Such properties are called carbon neutral.

Conventionally, toner constituent materials, particularly binder resins, have largely relied on fossil resources, and the carbon dioxide produced when toner and printed images are disposed of is released into the atmosphere, contributing to global warming. ing. In addition, the conversion from fossil resources, which are limited resources, to biomass resources, which are renewable resources, is a conversion to sustainable renewable resources in that organisms are generated from solar energy, water and carbon dioxide. No, it is a requested technology.

Examples of toner constituent materials obtained from such renewable resources include release agents such as carnauba wax and candelilla wax.
These are added to the toner in order to impart a release function during fixing, and the amount thereof is generally about several percent by weight.

On the other hand, the use of resins using renewable resources such as polylactic acid (PLA) and rosin compounds as binder resins for toners is being studied. For example, (1) a toner containing PLA obtained by direct dehydration condensation (see Patent Document 1), (2) a toner containing terminal-modified PLA (see Patent Document 2), and (3) a methacrylic acid-modified rosin as a monomer. A toner containing the polyester resin used in the above has been proposed (see Patent Document 3).

In order to function as a toner, basic properties such as low-temperature fixability and low adhesion are required.
Patent Document 4 states that the crystalline polyester having a large maximum major axis and having a sharp shape extending from the toner surface toward the inside can provide a toner excellent in low-temperature fixability.
Japanese Patent Laid-Open No. 2002-100003 states that a toner having a low adhesive force can be provided by making the toner flat.

However, the current situation is that it is difficult to use renewable resources, contribute to carbon neutrality, and satisfy low-temperature fixability and cleanability (low adhesion) required as toner properties at the same time.

An object of the present invention is to provide resin particles that greatly contribute to carbon neutrality and can satisfy low-temperature fixability and cleanability.

The present invention for solving the above problems relates to resin particles as described in (1) below.
(1) Resin particles containing at least a crystalline polyester resin, an amorphous polyester resin, a release agent, and a colorant,
The acid component of the crystalline polyester resin is a plant-derived dicarboxylic acid having 12 or less carbon atoms,
The average major axis of the domains of the crystalline polyester resin is 2.0 μm or less, and the average aspect ratio (long axis/minor axis) of the domains is 4.0 or more,
A resin particle characterized by having a radioactive carbon isotope ¹⁴ C concentration of 5.4 pMC or more.

According to the present invention, it is possible to provide resin particles that greatly contribute to carbon neutrality and can satisfy low-temperature fixability and cleanability.

FIG. 1 is a diagram for explaining the crystalline polyester resin inside the resin particles. FIG. 2 is a schematic configuration diagram showing an example of an image forming apparatus according to an embodiment of the invention. FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus according to the embodiment of the invention. FIG. 4 is a schematic configuration diagram showing another example of the image forming apparatus according to the embodiment of the invention. 5 is a partially enlarged view of FIG. 4. FIG. FIG. 6 is a schematic configuration diagram showing an example of a process cartridge.

Hereinafter, resin particles, toner, a method for producing resin particles, a method for producing toner, a developer, a toner containing unit, and an image forming apparatus according to the present invention will be described with reference to the drawings. In addition, the present invention is not limited to the embodiments shown below, and can be changed within the scope of those skilled in the art, such as other embodiments, additions, modifications, deletions, etc. is also included in the scope of the present invention as long as the functions and effects of the present invention are exhibited.

The resin particles of the present invention are suitable for use as toner. A toner is obtained by adding an external additive to toner base particles made of resin particles.
The toner using the resin particles of the present invention will be described below, and the resin particles will be described later in the section "Toner Base Particles".

(toner)
The toner should have a radioactive carbon isotope ¹⁴ C concentration (hereinafter sometimes referred to as “ ¹⁴ C concentration”) of 5.4 pMC or more, preferably 10.8 pMC or more.
pMC (percent modern carbon) is one of the units representing the ¹⁴ C concentration, and when the ¹⁴ C concentration of the standard sample in 1950 is 100%, the ¹⁴ C concentration of the unknown sample is expressed in % as a ratio to it. It represents
If the ¹⁴ C concentration is less than 5.4 pMC, the degree of biomass is low, and the object of the present invention may not be achieved.
The ¹⁴ C concentration is represented by the biomass degree of the following formula: Biomass degree (%) = ¹⁴ C concentration (pMC) x 0.935
The ¹⁴ C concentration of 5.4 pMC or more means that the biomass degree is 5% or more, which is a concentration desired also from the carbon-neutral viewpoint. ^{The 14} C concentration is more preferably 20% or higher, even more preferably 40% or higher.

The ¹⁴ C concentration defines how much carbon is plant-derived carbon in the carbon element component of the carbon-containing petrochemical product. The concentration of ¹⁴ C in carbon elements of petrochemical products can be measured, for example, according to ASTM standard ASTM-D6866 of the American Institute of Testing Materials.

_The ¹⁴ C exists ⁱⁿ the natural world ⁽ in the atmosphere) and is taken into the plant by photosynthesis while the plant is active. concentration is in equilibrium (107.5 pMC).
From the stage when the plant stops its life activity, the uptake of carbon by photosynthesis stops, and the ¹⁴ C concentration decreases according to the half-life of ¹⁴ C of 5730 years.
Since tens of thousands to hundreds of millions of years have passed since biological activity ceased, ¹⁴ C is hardly detected.

In the toner, the acid component of the crystalline polyester resin is a plant-derived dicarboxylic acid having 12 or less carbon atoms, the domain of the crystalline polyester resin has a major axis of 2.0 μm or less, and the aspect ratio of the domain (long axis/short diameter) is 4.0 or more.

According to the present invention, it is possible to provide a toner that greatly contributes to carbon neutrality and can achieve both low-temperature fixability and cleanability. Further, according to a preferred embodiment of the present invention, it is possible to improve the heat-resistant storage stability while making a large contribution to carbon neutrality and achieving both low-temperature fixability and cleanability.

The toner of the present invention comprises toner base particles composed of resin particles containing at least a crystalline polyester resin, an amorphous polyester resin, a release agent, and a colorant, and an external additive.
A configuration example of a toner according to an embodiment containing toner base particles and an external additive will be described below.

<Toner Base Particles (Resin Particles)>
The toner base particles contain a crystalline polyester resin, an amorphous polyester resin, a release agent, a colorant, and, if necessary, other components.

<<Crystalline polyester resin>>
The crystalline polyester resin (hereinafter, sometimes referred to as "crystalline polyester resin C") has high crystallinity, and therefore exhibits thermal melting properties in which the viscosity changes sharply near the fixing start temperature.

By using the crystalline polyester resin C having such properties together with the amorphous polyester resin, a toner having both good heat-resistant storage stability and low-temperature fixability can be obtained. For example, by using a crystalline polyester resin C and an amorphous polyester resin in combination, the crystallinity of the crystalline polyester resin C provides good heat resistance and storage stability until just before the melting start temperature, and the crystalline polyester resin C at the melting start temperature. (sharp melt property) occurs due to the melting of the resin, and along with this, it becomes compatible with the later-described amorphous polyester resin B, and both of them rapidly decrease in viscosity, so that good fixation can be achieved.
Good results are also obtained with respect to the release width (difference between minimum fixing temperature and high-temperature offset generating temperature).

The crystalline polyester resin C is obtained by using a polyhydric alcohol, a polycarboxylic acid such as a polycarboxylic acid, a polycarboxylic acid anhydride, a polycarboxylic acid ester, or a derivative thereof.

In the present invention, the crystalline polyester resin C is, as described above, a polyhydric alcohol, a polycarboxylic acid such as a polycarboxylic acid, a polycarboxylic anhydride, a polycarboxylic acid ester, or a derivative thereof. It refers to what can be obtained by using Modified polyester resins, for example, prepolymers described later and resins obtained by cross-linking and/or elongation reactions of the prepolymers do not belong to the crystalline polyester resin C.

-Polyhydric alcohol-
The polyhydric alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include diols and trihydric or higher alcohols.
Examples of the diols include saturated aliphatic diols. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Group diols are more preferred, and linear saturated aliphatic diols having 2 to 8 carbon atoms are even more preferred. If the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin C may be lowered and the melting point may be lowered. Moreover, when the number of carbon atoms of the saturated aliphatic diol exceeds 12, it becomes difficult to obtain the material for practical use. It is more preferable that the number of carbon atoms is 12 or less.

Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, 18-octadecanediol, 1,14-eicosandecanediol, and the like. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,8-octanediol, 1,8-octanediol, 1,8-octanediol, 10-decanediol and 1,12-dodecanediol are preferred.

Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used individually by 1 type, and may use 2 or more types together.

-Polyvalent carboxylic acid-
Examples of the dicarboxylic acid include saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, sebacic acid and dodecanedioic acid; unsaturated aliphatic dicarboxylic acids such as fumaric acid and maleic acid; aromatic dicarboxylic acids such as acids; and the like.
These may be used individually by 1 type, and may use 2 or more types together.

The dicarboxylic acid is preferably a plant-derived saturated aliphatic having 12 or less carbon atoms. Carbon neutrality can be enhanced by being derived from plants. On the other hand, if the number of carbon atoms exceeds 12, the compatibility with the non-crystalline polyester resin deteriorates, the aspect ratio of the crystalline polyester resin decreases, and the low-temperature fixability deteriorates for the reason described later. In addition, the saturated aliphatic group has the effect of increasing the recrystallization property of the crystalline polyester resin, thereby increasing the aspect ratio of the crystalline polyester resin and improving the low-temperature fixability.

The melting point of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 60° C. or higher and 80° C. or lower. When the melting point is 60° C. or higher, it is possible to prevent the crystalline polyester resin C from melting at a low temperature and lowering the heat-resistant storage stability of the toner. When the temperature is 80° C. or less, the melting of the crystalline polyester resin C due to heating during fixing can be improved, and deterioration of low-temperature fixability can be suppressed.

The molecular weight of the crystalline polyester resin C is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint that those having a sharp molecular weight distribution and a low molecular weight are excellent in low-temperature fixability, and that a large amount of low-molecular-weight components lowers the heat-resistant storage stability, the ortho-dichlorobenzene-soluble portion of the crystalline polyester resin C is In GPC measurement, it is preferable that the weight average molecular weight (Mw) is 3,000 to 30,000, the number average molecular weight (Mn) is 1,000 to 10,000, and the Mw/Mn is 1.0 to 10.
Furthermore, it is preferable that the weight average molecular weight (Mw) is 5,000 to 15,000, the number average molecular weight (Mn) is 2,000 to 10,000, and the Mw/Mn is 1.0 to 5.0.

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

The hydroxyl value of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose. In order to achieve desired low-temperature fixability and good charging properties, the hydroxyl value is preferably 0 mgKOH/g or more and 50 mgKOH/g or less, more preferably 5 mgKOH/g or more and 50 mgKOH/g or less.

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

The content of the crystalline polyester resin C is not particularly limited and can be appropriately selected according to the purpose. parts to 15 parts by mass is more preferable. When the content is 3 parts by mass or more, sharp melting by the crystalline polyester resin C can be improved, and low-temperature fixability can be improved. When the amount is 20 parts by mass or less, deterioration in heat-resistant storage stability can be suppressed, and occurrence of fogging in images can be suppressed. When the content is within the more preferable range, it is advantageous in that both high image quality and low-temperature fixability are excellent.

<<<amorphous polyester resin>>>
The amorphous polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose. preferable.

-Amorphous polyester resin A-
The amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the intended purpose. More preferably, the temperature is at least 20°C. Moreover, it is preferably obtained by a reaction between a non-linear reactive precursor and a curing agent.

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

--NONLINEAR REACTIVE PRECURSOR--
The non-linear reactive precursor is not particularly limited as long as it is a polyester resin (hereinafter sometimes referred to as a "prepolymer") having a group capable of reacting with the curing agent, depending on the purpose. can be selected as appropriate.
Examples of the groups in the prepolymer that can react with the curing agent include groups that can react with active hydrogen groups. Examples of the group capable of reacting with the active hydrogen group include isocyanate group, epoxy group, carboxylic acid group and acid chloride group. Among these, an isocyanate group is preferable in that a urethane bond or a urea bond can be introduced into the amorphous polyester resin.

Preferably, said prepolymer is non-linear. The term "non-linear" means having a branched structure provided by at least one of a trihydric or higher alcohol and a trihydric or higher carboxylic acid.
Moreover, as the prepolymer, a polyester resin containing an isocyanate group is preferable.

---Polyester resin containing isocyanate group---
The isocyanate group-containing polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include reaction products of a polyester resin having an active hydrogen group and a polyisocyanate. The polyester resin having an active hydrogen group can be obtained, for example, by polycondensing a diol, a dicarboxylic acid, and at least one of a trihydric or higher alcohol and a trihydric or higher carboxylic acid. The alcohol having a valence of 3 or more and the carboxylic acid having a valence of 3 or more give a branched structure to the polyester resin containing the isocyanate group.

---- Diol ----
The diol is not particularly limited and can be appropriately selected depending on the intended purpose. -aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol; diethylene glycol, triethylene glycol, dipropylene glycol , polyethylene glycol, polypropylene glycol, diol having an oxyalkylene group such as polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols, ethylene oxide, propylene oxide, Products obtained by adding alkylene oxides such as butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; alkylene oxides of bisphenols such as products obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to bisphenols Additions and the like can be mentioned. Among these, aliphatic diols having 4 to 12 carbon atoms are preferred. These diols may be used singly or in combination of two or more.

----Dicarboxylic acid----
The dicarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Anhydrides of these may be used, lower alkyl esters (having 1 to 3 carbon atoms), or halides thereof may be used.

The aliphatic dicarboxylic acid is not particularly limited and can 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 can be appropriately selected depending on the intended purpose, but an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable. The aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.
Among these, plant-derived saturated aliphatic succinic acid, sebacic acid, and dodecanedioic acid are preferably included.
Carbon neutrality can be enhanced by being derived from plants. A saturated aliphatic group has the effect of increasing the recrystallization property of the crystalline polyester resin, and can increase the aspect ratio of the crystalline polyester resin and improve the low-temperature fixability.
These dicarboxylic acids may be used individually by 1 type, and may use 2 or more types together.

---- Trihydric or higher alcohol ----
The trihydric or higher alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. and oxide adducts.

Examples of trihydric or higher aliphatic alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
Examples of the trivalent or higher polyphenols include trisphenol PA, phenol novolak, and cresol novolak.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.

The amorphous polyester resin A preferably contains a trihydric or higher aliphatic alcohol as a constituent component.
Since the amorphous polyester resin A contains a trihydric or higher aliphatic alcohol as a constituent component, it has a branched structure in the molecular skeleton, and the molecular chain has a three-dimensional network structure, so it deforms at low temperatures. However, it has a rubber-like property that it does not flow. Therefore, it is possible to maintain the heat-resistant storage stability and high-temperature offset resistance of the toner.

In the amorphous polyester resin A, a carboxylic acid having a valence of 3 or more, epoxy, or the like can be used as a cross-linking component. Due to the high ester bond density, a fixed image formed by heat-fixing the toner may not exhibit sufficient gloss. When a cross-linking agent such as epoxy is used, the cross-linking reaction must be carried out after the polyester is polymerized. It reacts with the oligomer at the time of formation and tends to form a portion with a high cross-linking density.

---- Carboxylic acid with a valence of 3 or more ----
The carboxylic acid having a valence of 3 or more is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aromatic carboxylic acids having a valence of 3 or more. Anhydrides of these may be used, lower alkyl esters (having 1 to 3 carbon atoms), or halides thereof may be used.

As the trivalent or higher aromatic carboxylic acid, a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms is preferable. Examples of the trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

---- Polyisocyanate ----
The polyisocyanate is not particularly limited and can be appropriately selected depending on the purpose. For example, diisocyanate, isocyanate having a valence of 3 or more, and the like can be mentioned.

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

The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate. .

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

The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the 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 araliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples include α,α,α',α'-tetramethylxylylene diisocyanate.

The isocyanurates are not particularly limited and can be appropriately selected depending on the purpose. Examples include tris(isocyanatoalkyl)isocyanurate, tris(isocyanatocycloalkyl)isocyanurate and the like.
These polyisocyanates may be used singly or in combination of two or more.

--Curing agent--
The curing agent is not particularly limited as long as it can react with the non-linear reactive precursor to form the amorphous polyester resin A, and can be appropriately selected according to the purpose. , and 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 can be appropriately selected depending on the intended purpose. etc. These may be used individually by 1 type, and may use 2 or more types together.
The active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the intended purpose, but amines are preferable because they can form a urea bond.

The amines are not particularly limited and can be appropriately selected depending on the intended purpose. mentioned. These may be used individually by 1 type, and may use 2 or more types together.
Among these, diamines and mixtures of diamines and a small amount of trivalent or higher amines are preferred.

The diamine is not particularly limited and can 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 can 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 can be appropriately selected depending on the intended purpose. be done. The aliphatic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ethylenediamine, tetramethylenediamine and hexamethylenediamine.

The trivalent or higher amine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
The aminoalcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.
The aminomercaptan is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aminoethylmercaptan and aminopropylmercaptan.

The amino acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.

The blocked amino group is not particularly limited and can be appropriately selected depending on the intended purpose. ketimine compounds, oxazoline compounds, and the like.

In order to lower the Tg of the amorphous polyester resin A and easily impart the property of being deformed at low temperature, the amorphous polyester resin A contains a diol component as a constituent component, and the diol component has a carbon number of It is preferable to contain 4 to 12 aliphatic diols in an amount of 50% by mass or more.

Further, the amorphous polyester resin A preferably contains 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms in all alcohol components. In this case, the Tg of the amorphous polyester resin A can be lowered, and the property of being deformed at low temperatures can be easily imparted.

The amorphous polyester resin A preferably contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component contains 50% by mass or more of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms. In this case, the Tg of the amorphous polyester resin A can be lowered, and the property of being deformed at low temperatures can be easily imparted.

The weight-average molecular weight of the amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the intended purpose. The following is preferable, 10,000 to 300,000 is more preferable, and 10,000 to 200,000 is particularly preferable. When the weight-average molecular weight is 10,000 or more, the toner can be prevented from flowing at low temperatures, and the heat-resistant storage stability can be improved. In addition, it is possible to suppress a decrease in viscosity when melted and a decrease in high-temperature offset properties.

The molecular structure of the amorphous polyester resin A can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc., in addition to NMR measurement using a solution or solid. A simple method is to detect an amorphous polyester resin that does not have absorption based on δCH (out-of-plane bending vibration) of an olefin at 965±10 cm ⁻¹ and 990±10 cm ⁻¹ in the infrared absorption spectrum. .

The content of the amorphous polyester resin A is not particularly limited and can be appropriately selected according to the purpose. Parts by mass to 20 parts by mass are more preferable. When the content is 5 parts by mass or more, deterioration of low-temperature fixability and high-temperature offset resistance can be suppressed. When the amount is 25 parts by mass or less, it is possible to suppress the deterioration of the heat-resistant storage stability and the reduction of the glossiness of the image obtained after fixing. When the content is within the more preferable range, it is advantageous in terms of excellent low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability.

-Amorphous polyester resin B-
As the amorphous polyester resin B, a linear polyester resin is preferable, and an unmodified polyester resin is preferable.
The unmodified polyester resin is a polyester resin obtained by using a polyhydric alcohol, a polycarboxylic acid such as a polycarboxylic acid, a polycarboxylic anhydride, a polycarboxylic acid ester, or a derivative thereof. , is a polyester resin that has not been modified with an isocyanate compound or the like.
The amorphous polyester resin B preferably does not have urethane bonds and urea bonds.

The amorphous polyester resin B preferably contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component preferably contains 50 mol % or more of terephthalic acid. By doing so, it is advantageous in terms of heat resistant storage stability.

Examples of the polyhydric alcohols include diols.
Examples of the diol include polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane. ethylene glycol, propylene glycol; hydrogenated bisphenol A, alkylene of hydrogenated bisphenol A (2 to 3 carbon atoms), etc. Oxide (average addition mole number 1 to 10) adducts and the like are included.
These may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyvalent carboxylic acid include dicarboxylic acids.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid; dodecenylsuccinic acid, octylsuccinic acid, and other alkyl groups having 1 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms. and succinic acid substituted with a group.
Among these, it is preferable to contain plant-derived saturated aliphatic succinic acid.
Carbon neutrality can be enhanced by being derived from plants. A saturated aliphatic group has the effect of increasing the recrystallization property of the crystalline polyester resin, and can increase the aspect ratio of the crystalline polyester resin and improve the low-temperature fixability.
These may be used individually by 1 type, and may use 2 or more types together.

For the purpose of adjusting the acid value and hydroxyl value, the amorphous polyester resin B may contain at least one of a trivalent or higher carboxylic acid and a trivalent or higher alcohol at the terminal of the resin chain. .
Examples of the tricarboxylic or higher carboxylic acid include trimellitic acid, pyromellitic acid, and acid anhydrides thereof.
Examples of the trihydric or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.

The molecular weight of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the purpose. In GPC (gel permeation chromatography) measurement, the weight average molecular weight (Mw) is preferably 3,000 to 10,000. The number average molecular weight (Mn) is preferably 1,000-4,000. Mw/Mn is preferably 1.0 to 4.0.

When the molecular weight is at least the above lower limit, it is possible to suppress deterioration of the heat-resistant storage stability of the toner and durability against stress such as agitation in the developing machine. When the molecular weight is equal to or less than the above upper limit, it is possible to prevent the viscoelasticity of the toner from increasing during melting and to prevent the low-temperature fixability from deteriorating.

The weight average molecular weight (Mw) is more preferably 4,000 to 7,000. The number average molecular weight (Mn) is more preferably 1,500 to 3,000. The Mw/Mn is more preferably 1.0 to 3.5.

The acid value of the amorphous polyester resin B is not particularly limited and can be appropriately selected according to the purpose. 1 mg KOH/g to 50 mg KOH/g is preferred, and 5 mg KOH/g to 30 mg KOH/g is more preferred. When the acid value is 1 mgKOH/g or more, the toner tends to be negatively charged, and furthermore, the affinity between the toner and the paper is improved when the toner is fixed on the paper, and the low-temperature fixability can be improved. . When the acid value is 50 mgKOH/g or less, it is possible to suppress deterioration of charging stability, particularly charging stability against environmental fluctuations.

The hydroxyl value of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 5 mgKOH/g or more.

The glass transition temperature (Tg) of the amorphous polyester resin B is preferably 40° C. or higher and 80° C. or lower, more preferably 50° C. or higher and 70° C. or lower. When the glass transition temperature is 40° C. or higher, the toner has sufficient heat-resistant storage stability and durability against stress such as agitation in a developing machine, and also has good filming resistance. When the glass transition temperature is 80° C. or lower, the toner is sufficiently deformed by heat and pressure during fixing, and good low-temperature fixability is obtained.

The molecular structure of the amorphous polyester resin B can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc., in addition to NMR measurement using a solution or solid. A simple method is to detect an amorphous polyester resin that does not have absorption based on δCH (out-of-plane bending vibration) of an olefin at 965±10 cm ⁻¹ and 990±10 cm ⁻¹ in the infrared absorption spectrum. .

The content of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the intended purpose. Parts by mass to 80 parts by mass are more preferable. When the content is 50 parts by mass or more, deterioration of dispersibility of the pigment and release agent in the toner can be suppressed, and fogging and distortion of images can be suppressed. When the content is 90 parts by mass or less, it is possible to prevent the contents of the crystalline polyester resin C and the amorphous polyester resin A from being reduced, and to suppress deterioration of the low-temperature fixability. When the content is within the above-mentioned more preferable range, it is advantageous in that both high image quality and low-temperature fixability are excellent.

In order to further improve the low-temperature fixability, it is preferable to use the amorphous polyester resin A and the crystalline polyester resin C together. In order to achieve both low-temperature fixability and high-temperature and high-humidity storage stability, the amorphous polyester resin A preferably has a very low glass transition temperature. Since it has a very low glass transition temperature, it has the property of being deformed at low temperature, deformed by heat and pressure during fixing, and has the property of being easily adhered to a recording medium such as paper at a lower temperature. In one aspect of the amorphous polyester resin A, since the reactive precursor is non-linear, it has a branched structure in the molecular skeleton and the molecular chain has a three-dimensional network structure. It deforms at low temperatures, but has rubber-like properties that do not flow. Therefore, it is possible to maintain the heat-resistant storage stability and high-temperature offset resistance of the toner.

When the amorphous polyester resin A has urethane bonds or urea bonds with high cohesive energy, the adhesiveness to recording media such as paper is more excellent. In addition, since the urethane bond or urea bond behaves like a pseudo-crosslinking point, the rubber-like properties become stronger, and as a result, the heat-resistant storage stability and high-temperature offset resistance of the toner become more excellent.

That is, in the toner of the present invention, when the amorphous polyester resin A, the crystalline polyester resin C, and, if necessary, another amorphous polyester resin B are used in combination, the toner exhibits excellent low-temperature fixability. becomes. Furthermore, by using the amorphous polyester resin A having a glass transition temperature in the low temperature range, it is possible to maintain the heat resistant storage stability and high temperature offset resistance even if the glass transition temperature of the toner is set lower than in the conventional toner. Excellent low-temperature fixability due to the low glass transition temperature of the toner.

<<coloring agent>>
The coloring agent is not particularly limited and can be appropriately selected depending on the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow ( GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazane Yellow BGL, Iso Indolinone Yellow, Red Iron Red, Red Lead, Red Lead, Cadmium Red, Cadmium Mercury Red, Antimony Vermillion, Permanent Red 4R, Para Red, Phise Red, Parachlororthonitroaniline Red, Risol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carn Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fastolvin B, Brilliant Scarlet G, Risol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon , Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, pyrazolone red, polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue lake, peacock blue lake, victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, ink Dansren Blue (RS, BC), Indigo, Ultramarine Blue, Prussian Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Violet, Manganese Violet, Dioxane Violet, Anthraquinone Violet, Chromium Green, Zinc Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Dioxide, Examples include zinc oxide and litbon.

The content of the coloring agent is not particularly limited and can be appropriately selected according to the intended purpose. Parts by mass are more preferred.

The colorant can also be used as a masterbatch combined with a resin. Examples of resins to be used in the production of the masterbatch or kneaded together with the masterbatch include, in addition to the above-mentioned amorphous polyester resins, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, or polymers of their substituted products; styrene-p; -chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene- Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylic acid Methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer Styrenic copolymers such as coalescence, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide , polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type, and may use 2 or more types together.

The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant by applying a high shearing force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, in which an aqueous paste containing colorant water is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and the water and organic solvent components are removed. Since the cake can be used as it is, there is no need to dry it, and it is preferably used. For mixing and kneading, a high-shear dispersing device such as a three-roll mill is preferably used.

<< Release agent >>
The release agent is not particularly limited and can be appropriately selected from known ones.
Release agents for waxes and waxes include, for example, plant waxes such as carnauba wax, cotton wax, wood wax and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cersin; petroleum waxes such as , microcrystalline, petrolatum; and other natural waxes.
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene and polypropylene; synthetic waxes such as esters, ketones and ethers;

Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride, and chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n, which are low-molecular-weight crystalline polymer resins; -Polyacrylate homopolymers or copolymers such as lauryl methacrylate (e.g., n-stearyl acrylate-ethyl methacrylate copolymers); crystalline polymers having long alkyl groups in side chains; good.

Among these, plant-based waxes and ester waxes using plant-derived materials are preferable. Carbon neutrality can be enhanced by being derived from plants.

The melting point of the release agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60° C. or higher and 80° C. or lower. When the melting point is 60° C. or higher, it is possible to prevent the releasing agent from melting at low temperatures, and to prevent deterioration of the heat-resistant storage stability. When the melting point is 80° C. or lower, when the resin melts and is in the fixing temperature range, the release agent is not sufficiently melted, thereby suppressing the occurrence of fixing offset, thereby suppressing the occurrence of image defects. be able to.

The content of the release agent is not particularly limited and can be appropriately selected according to the purpose. It is preferably 2 parts by mass or more and 10 parts by mass or less, more preferably 3 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the toner. When the content is 2 parts by mass or more, deterioration of high-temperature offset resistance and low-temperature fixability during fixing can be suppressed, and when the content is 10 parts by mass or less, deterioration of heat-resistant storage stability can be suppressed. Also, it is possible to suppress the occurrence of image fogging. When the content of the releasing agent is within the more preferable range, it is advantageous in terms of improving image quality and fixing stability.

<<Other Ingredients>>
Examples of the other components contained in the toner base particles include charge control agents, deforming agents, fluidity improvers, cleanability improvers, and magnetic materials.

<<<Charge Control Agent>>>
The charge control agent is not particularly limited and can be appropriately selected depending on the purpose. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like.

Specifically, nigrosine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid-based metal complex E-82, salicylic acid-based metal complex E- 84, E-89 of phenolic condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (manufactured by Hodogaya Chemical Industry Co., Ltd.), LRA- 901, LR-147 (manufactured by Nihon Carlit Co., Ltd.), which is a boron complex, copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymeric compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. is mentioned.

The content of the charge control agent is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the toner. When the content is 10 parts by mass or less, the toner can be prevented from being excessively charged, the effect of the main charge control agent can be maintained, and the electrostatic attraction force with the developing roller can be prevented from increasing. Therefore, it is possible to suppress the deterioration of the fluidity of the developer and the deterioration of the image density. These charge control agents can be dissolved and dispersed after being melted and kneaded together with the masterbatch and resin. Alternatively, they can be directly added to an organic solvent during dissolution and dispersion, or they can be fixed on the toner surface after the toner particles are prepared. may

<<<deformation agent>>>
In this embodiment, the toner may contain a deforming agent for the purpose of deforming the shape of the color toner. The deforming agent can be appropriately selected according to the purpose as long as it can achieve this purpose, but a layered inorganic mineral in which at least part of the ions between layers of the layered inorganic mineral is modified with organic ions is used. It is preferable to contain.

The layered inorganic mineral obtained by modifying at least part of the interlayer ions of the layered inorganic mineral that can be used as the deformation agent with organic ions is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferable to modify a material having a basic smectite crystal structure with an organic cation. Also, a metal anion can be introduced by substituting a part of the divalent metal of the layered inorganic mineral with a trivalent metal. However, since the introduction of a metal anion increases the hydrophilicity, a layered inorganic compound in which at least a portion of the metal anion is modified with an organic anion is desirable.

The organic cation modifier for the layered inorganic mineral in which at least part of the ions possessed by the layered inorganic mineral are modified with organic ions is not particularly limited as long as it can be modified with organic ions in this manner. Examples include alkylammonium salts, phosphonium salts and imidazolium salts. Among them, quaternary alkylammonium salts are desirable. The quaternary alkylammonium includes trimethylstearylammonium, dimethylstearylbenzylammonium, oleylbis(2-hydroxyethyl)methylammonium and the like.

The organic anion modifier for the layered inorganic mineral in which at least part of the ions possessed by the layered inorganic mineral are modified with organic ions is not particularly limited as long as it can be modified with organic ions as described above. Sulfates, sulfonates with branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, etc. Carboxylate or phosphate. A carboxylic acid having an ethylene oxide skeleton is desirable.

By modifying at least a part of the layered inorganic mineral with organic ions, the toner has appropriate hydrophobicity, the oil phase (described later) containing the toner composition has non-Newtonian viscosity, and the toner can be deformed. . At this time, the content of the layered inorganic mineral partially modified with organic ions in the toner material is preferably 0.05% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass. It is more preferable to have

Layered inorganic minerals partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among them, organically modified montmorillonite or bentonite is preferable because it does not affect toner properties, allows easy viscosity adjustment, and can be added in a small amount.

Commercially available layered inorganic minerals partially modified with organic cations include Bentone 3, Bentone 38, Bentone 38V (manufactured by Rheox), Thixogel VP (manufactured by United Catalyst), Clayton 34, Clayton 40, and Clayton XL. Quaternium 18 bentonite such as (manufactured by Southern Clay Co., Ltd.); Stearalkonium bentonite such as Bentone 27 (manufactured by Rheox), Thixogel LG (manufactured by United Catalyst), Kraton AF, and Kraton APA (manufactured by Southern Clay Co.) and quaternium 18/benzalkonium bentonite such as Kraton HT and Kraton PS (manufactured by Southern Clay). Kraton AF and Kraton APA are preferred.

As the layered inorganic mineral partially modified with an organic anion, DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) modified with an organic anion represented by the following general formula (III) is more preferable. Examples of organic anions represented by the following general formula (III) include Hitenol 330T (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
R ₁ (OR ₂ ) _n OSO ₃ M General formula (III)
[In the above formula, R ₁ represents an alkyl group having 13 carbon atoms, R ₂ represents an alkylene group having 2 to 6 carbon atoms, n represents an integer of 2 to 10, and M represents a monovalent metal element. ]

The content of the deforming agent is preferably 0.05% by mass or more and 10% by mass or less, and is preferably 0.05% by mass or more and 5% by mass or less in the toner, similarly to the content of the layered inorganic mineral. is more preferable.

<<<fluidity improver >>>
The fluidity improver is not particularly limited as long as it can be subjected to surface treatment to increase hydrophobicity and prevent deterioration of fluidity and charging characteristics even under high humidity, and can be appropriately selected according to the purpose. can do. Examples thereof include silane coupling agents, silylating agents, silane coupling agents having alkyl fluoride groups, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. It is particularly preferable that the silica and titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

<<<cleanability improver>>>
The cleaning property improver is not particularly limited as long as it is added to the toner in order to remove the developer remaining on the photoreceptor or the primary transfer medium after transfer, and can be appropriately selected according to the purpose. can be done. Examples thereof include zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, polymethyl methacrylate fine particles, polymer fine particles produced by soap-free emulsion polymerization such as polystyrene fine particles, and the like. The fine polymer 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 can 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.

<External Additives>
As the external additive, in addition to the oxide fine particles, inorganic fine particles and hydrophobically treated inorganic fine particles can be used in combination. Inorganic fine particles of 70 nm or less are more preferable.

In addition, it is preferable that at least one type of inorganic fine particles having an average particle size of 20 nm or less and at least one type of inorganic fine particles having an average particle size of 30 nm or more are included. Moreover, the specific surface area by the BET method is preferably 20 m ² /g or more and 500 m ² /g or less.

The external additive is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include silica fine particles, hydrophobic silica, fatty acid metal salts (eg, zinc stearate, aluminum stearate, etc.), metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, and the like.

Suitable additives include hydrophobized silica, titania, titanium oxide, alumina particulates.
Examples of silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.).
Examples of titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titan Kogyo Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Kogyo Co., Ltd.), Examples include MT-150W, MT-500B, MT-600B, and MT-150A (all manufactured by Tayca Corporation).

Hydrophobized titanium oxide fine particles include, for example, T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titan Kogyo Co., Ltd.), TAF-500T, TAF- 1500T (both manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (both manufactured by Tayca Corporation), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

Hydrophobic oxide microparticles, hydrophobilizing silica microparticles, hydrophobilizing titania microparticles, and hydrophobilizing alumina microparticles include hydrophilic microparticles such as methyltrimethoxysilane and methyltriethoxysilane. , octyltrimethoxysilane, or other silane coupling agent. Also suitable are silicon oil-treated oxide fine particles and inorganic fine particles, which are obtained by heating silicone oil if necessary to form inorganic fine particles.

Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino Modified silicone oil, epoxy-modified silicone oil, epoxy/polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil and the like.

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, Wollastonite, diatomaceous earth, 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. Among these, silica and titanium dioxide are particularly preferred.

The content of the external additive is not particularly limited and can be appropriately selected according to the purpose. 3 parts by mass to 3 parts by mass is more preferable.

The average particle size of the primary particles of the inorganic fine particles is not particularly limited and can be appropriately selected according to the purpose. 100 nm or less is preferable, and 3 nm or more and 70 nm or less is more preferable. When the thickness is 3 nm or more, it is possible to prevent the inorganic fine particles from being buried in the toner and not exhibiting their functions effectively. Further, when the thickness is 100 nm or less, it is possible to suppress uneven damage to the surface of the photoreceptor.

<Glass transition temperature>
<<Tg1st (toner)>>
The glass transition temperature [Tg1st (toner)] of the toner in the first temperature rise in differential scanning calorimetry (DSC) is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of low-temperature fixability, the temperature is preferably 20° C. or higher and 50° C. or lower, more preferably 35° C. or higher and 45° C. or lower.

In the case of conventional toners, if the Tg is about 50° C. or less, aggregation of the toner is likely to occur due to temperature changes during transportation of the toner assuming summertime or tropical regions and in the storage environment. As a result, solidification in the toner bottle and toner sticking in the developing machine occur. In addition, insufficient replenishment due to toner clogging in the toner bottle and image abnormality due to toner sticking in the developing machine tend to occur.

Even if the toner has a lower Tg than the conventional toner, the toner maintains heat-resistant storage stability when the amorphous polyester resin A, which is the low-Tg component in the toner, is non-linear. can be done. In particular, when the amorphous polyester resin A has a urethane bond or a urea bond with high cohesive strength, the effect of maintaining heat-resistant storage stability becomes more pronounced.

When the [Tg1st (toner)] is 20° C. or higher, it is possible to suppress deterioration of heat-resistant storage stability, blocking in the developing machine, and filming on the photoreceptor. When the temperature is 50° C. or less, it is possible to suppress deterioration of the low-temperature fixability of the toner.

<<[Tg2nd (toner)]>>
The glass transition temperature [Tg2nd (toner)] of the toner in the second temperature rise in differential scanning calorimetry (DSC) is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 0° C. or higher, and more preferably 0° C. or higher and 15° C. or lower. When the [Tg2nd (toner)] is 0° C. or higher, it is possible to suppress deterioration of the blocking resistance of the fixed image (printed matter). can be suppressed.
The value of [Tg2nd (toner)] can be adjusted by, for example, the Tg of the crystalline polyester resin and the blending amount.

<<[[Tg1st (toner)]-[Tg2nd (toner)]]>>
The difference [[Tg1st (toner)] between the glass transition temperature [Tg1st (toner)] at the first temperature increase and the glass transition temperature [Tg2nd (toner)] at the second temperature increase in differential scanning calorimetry (DSC) of the toner. -[Tg2nd (toner)] is not particularly limited and can be appropriately selected depending on the purpose, but is more preferably 10°C or higher. The upper limit of the difference is not particularly limited, and can be appropriately selected according to the purpose.

When the difference [[Tg1st (toner)]−[Tg2nd (toner)]] is 10° C. or more, it is advantageous in terms of excellent low-temperature fixability. The fact that the difference [[Tg1st (toner)] - [Tg2nd (toner)]] is 10°C or more means that the crystalline polyester that was present in an incompatible state before heating (before the first temperature rise) This means that the resin C, the amorphous polyester resin A, and the amorphous polyester resin B are in a compatible state after heating (after the first heating). In addition, the compatible state after heating does not need to be a complete compatible state.

<<Tg2nd (THF-insoluble matter)>>
The glass transition temperature [Tg2nd (THF-insolubles)] of the tetrahydrofuran (THF)-insolubles of the toner in the second temperature rise in differential scanning calorimetry (DSC) is not particularly limited and may be appropriately selected according to the purpose. can be done. For example, the temperature is preferably −40° C. or higher and 30° C. or lower, and more preferably 0° C. or higher and 20° C. or lower. When the [Tg2nd (THF-insoluble content)] is -40°C or higher, the advantage of being able to suppress the deterioration of the blocking resistance of the fixed image (printed matter) is obtained. An advantage is obtained that it is possible to suppress deterioration of low-temperature fixability and glossiness.

The value of [Tg2nd (THF-insoluble matter)] can be adjusted by changing the number of carbon atoms in the diol and dicarboxylic acid of the amorphous polyester resin A, for example.

<Storage modulus>
<<[G'(100) (THF-insoluble matter)] and [[G'(40) (THF-insoluble matter)]/[G'(100) (THF-insoluble matter)]]>>
The storage modulus of the tetrahydrofuran (THF)-insoluble portion of the toner at 100° C. [G′(100) (THF-insoluble portion)] is not particularly limited and can be appropriately selected according to the purpose. 0×10 ⁵ Pa to 1.0×10 ⁷ Pa is preferable, and 5.0×10 ⁵ Pa to 5.0×10 ⁶ Pa is more preferable. When the storage elastic modulus [G'(100) (THF-insoluble matter)] is within the more preferable range, it is advantageous in that the low-temperature fixability is more excellent.

The ratio [[ G'(40) (THF-insoluble matter)]/[G'(100) (THF-insoluble matter)]] is not particularly limited and can be appropriately selected depending on the purpose. The following are preferred. When the ratio [[G'(40) (THF-insoluble matter)]/[G'(100) (THF-insoluble matter)]] is 3.5×10 or less, deterioration in low-temperature fixability is suppressed. can do.

The toner has a [G'(100) (THF-insolubles)] of 1.0×10 ⁵ Pa to 1.0×10 ⁷ Pa and a ratio [[G'(40) (THF-insolubles )]/[G′(100) (THF-insoluble matter)]] is 3.5×10 or less, thereby promoting compatibility between the crystalline polyester resin and the amorphous polyester resin having a high Tg component. As a result, the outflow temperature is reduced by half, and the image gloss is improved.

The [G'(100) (THF-insoluble matter)] and the [G'(40) (THF-insoluble matter)] are, for example, depending on the resin composition (bifunctional or higher polyol, bifunctional or higher acid component). Numeric value can be adjusted.
Specifically, for example, it can be adjusted as follows. If G' is increased, the distance of the ester bond in the resin is shortened. Use a resin composition that has an aromatic ring. If G' is to be lowered, a linear polyester resin is used. A polyol having an alkyl group in a side chain is used as a component of the polyester resin.

<<THF insoluble matter>>
The THF-insoluble matter of the toner can be obtained as follows.
After 1 part of toner is added to 100 parts of tetrahydrofuran (THF) and refluxed for 6 hours, the insoluble components are sedimented by a centrifugal separator to separate the insoluble components from the supernatant.
The insoluble matter is dried at 40° C. for 20 hours to obtain a THF insoluble matter.

<<Method for measuring storage modulus G'>>
The storage elastic modulus (G') under various conditions can be measured using, for example, a dynamic viscoelasticity measuring device (ARES, manufactured by TA Instruments). The frequency for measurement is 1 Hz.
Specifically, the measurement sample is molded into a pellet with a diameter of 8 mm and a thickness of 1 mm to 2 mm, fixed to a parallel plate with a diameter of 8 mm, stabilized at 40 ° C., frequency 1 Hz (6.28 rad / s), strain amount The storage elastic modulus is measured by raising the temperature to 200° C. at a rate of 2.0° C./min at 0.1% (strain amount control mode).
In this specification, the storage elastic modulus at 40°C is sometimes expressed as G' (40°C), and the storage elastic modulus at 100°C is sometimes expressed as G' (100°C).

<Melting point>
The melting point of the toner is not particularly limited and can be appropriately selected depending on the intended purpose.

<Volume average particle size>
The volume average particle diameter of the toner is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 3 μm or more and 7 μm or less. Also, the ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Moreover, it is preferable to contain 1% by number or more and 10% by number or less of a component having a volume average particle diameter of 2 μm or less.

<Calculation method and analysis method for various characteristics of toner and toner constituents>
The Tg, acid value, hydroxyl value, molecular weight, and melting point of the amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the release agent are each measured on its own. However, the actual toner is separated by gel permeation chromatography (GPC) or the like, and the Tg, molecular weight, melting point, and mass ratio of the constituent components are calculated by adopting the analysis method described below for each separated component. may

Separation of each component by GPC can be performed, for example, by the following method.
In the GPC measurement using THF (tetrahydrofuran) as a mobile phase, the eluate is fractionated with a fraction collector or the like, and the fractions corresponding to the desired molecular weight portion from the total integration of the elution curve are collected.

After concentrating and drying the combined eluate with an evaporator or the like, the solid content is dissolved in a heavy solvent such as heavy chloroform or heavy THF, and ¹ H-NMR measurement is performed. A ratio of constituent monomers of the resin is calculated.

As another method, after concentrating the eluate, it is hydrolyzed with sodium hydroxide or the like, and the decomposition products are qualitatively and quantitatively analyzed by high performance liquid chromatography (HPLC) or the like to calculate the constituent monomer ratio.

In the case where the toner manufacturing method forms toner base particles while generating an amorphous polyester resin A through an elongation reaction and/or a cross-linking reaction between the non-linear reactive precursor and the curing agent. Alternatively, the Tg of the amorphous polyester resin A may be obtained by separating the actual toner by GPC or the like. In addition to this, an amorphous polyester resin A is separately synthesized by an elongation reaction and/or a cross-linking reaction between the non-linear reactive precursor and the curing agent, and from the synthesized amorphous polyester resin A Tg and the like may be measured.

<<Means for Separating Toner Components>>
An example of separation means for each component when analyzing the toner will be described in detail.
First, 1 g of toner is put into 100 mL of THF and stirred for 30 minutes at 25° C. to obtain a solution in which soluble components are dissolved. This is filtered through a membrane filter with an opening of 0.2 μm to obtain a THF-soluble component in the toner.
Next, this is dissolved in THF to prepare a sample for GPC measurement, and the sample is injected into the GPC used for molecular weight measurement of each resin described above.
On the other hand, a fraction collector is placed at the eluate outlet of GPC, and the eluate is collected at predetermined counts, and the eluate is collected every 5% in terms of area ratio from the elution start of the elution curve (curve rise). get
For each elution, 30 mg of sample is then 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 with a diameter of 5 mm, and a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.) is used to perform integration 128 times at a temperature of 23 ° C. to 25 ° C. to obtain a spectrum. .
The monomer compositions and composition ratios of the amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C contained in the toner can be obtained from the peak integral ratios of the spectrum obtained.

For example, the peaks are assigned as follows, and the component ratio of the constituent monomers is obtained from the respective integral ratios.
Peak assignments are, for example,
Around 8.25 ppm: Derived from the benzene ring of trimellitic acid (for one hydrogen)
Around 8.07 ppm to 8.10 ppm: Derived from the benzene ring of terephthalic acid (for 4 hydrogen atoms)
Around 7.1 ppm to 7.25 ppm: Derived from the benzene ring of bisphenol A (4 hydrogen atoms)
Around 6.8 ppm: derived from the benzene ring of bisphenol A (for 4 hydrogens) and from the double bond of fumaric acid (for 2 hydrogens)
Around 5.2 ppm to 5.4 ppm: derived from methine of bisphenol A propylene oxide adduct (for one hydrogen)
Around 3.7 ppm to 4.7 ppm: derived from methylene of bisphenol A propylene oxide adduct (2 hydrogens) and methylene derived from bisphenol A ethylene oxide adduct (4 hydrogens)
Around 1.6 ppm: It can be derived from the methyl group of bisphenol A (for 6 hydrogen atoms).

From these results, for example, the extract collected in the fraction containing 90% or more of the amorphous polyester resin A can be treated as the amorphous polyester resin A. Similarly, the extract collected in the fraction containing 90% or more of the amorphous polyester resin B can be treated as the amorphous polyester resin B. The crystalline polyester resin C can be treated as the crystalline polyester resin C as the extract collected in the fraction in which the crystalline polyester resin C accounts for 90% or more.

<<Method for measuring melting point and glass transition temperature (Tg)>>
The melting point and glass transition temperature (Tg) in the present invention can be measured using, for example, a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments).
Specifically, the melting point and glass transition temperature of the target sample can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, the sample container is placed on a holder unit, and set in an electric furnace. Next, in a nitrogen atmosphere, it is heated from −80° C. to 150° C. at a rate of temperature increase of 10° C./min (first temperature increase). After that, it is cooled from 150° C. to −80° C. at a temperature decrease rate of 10° C./min, and further heated to 150° C. at a temperature increase rate of 10° C./min (second temperature increase). In each of the first temperature rise and the second temperature rise, a DSC curve is measured using a differential scanning calorimeter (“Q-200”, manufactured by TA Instruments).

From the obtained DSC curve, the analysis program in the Q-200 system can be used to select the DSC curve at the time of the first heating, and the glass transition temperature of the target sample at the first heating can be obtained. Similarly, by selecting the DSC curve at the time of the second temperature rise, the glass transition temperature of the target sample at the second time of temperature rise can be obtained.

Also, from the obtained DSC curve, using the analysis program in the Q-200 system, select the DSC curve at the time of the first heating, and obtain the endothermic peak top temperature at the first heating of the target sample as the melting point. can be done. Similarly, by selecting the DSC curve at the time of the second temperature rise, the endothermic peak top temperature of the target sample at the second time of temperature rise can be determined as the melting point.

In this specification, when toner is used as a target sample, the glass transition temperature during the first heating is Tg1st, and the glass transition temperature during the second heating is Tg2nd.
Further, in the present specification, the glass transition temperature and melting point of the amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and other constituent components such as the release agent are , Unless otherwise specified, the endothermic peak top temperature Tg at the time of the second heating is taken as the melting point Tg of each target sample.

<<Method for measuring particle size distribution>>
The volume-average particle diameter (D4) and number-average particle diameter (Dn) of the toner and their ratio (D4/Dn) are determined using, for example, Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). can be measured by Coulter Multisizer II was used in the present invention. The measurement method is described below.

First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) is added as a dispersing agent to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1 mass % NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of the measurement sample is added. The electrolytic aqueous solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes in an ultrasonic disperser, and the volume and number of toner particles or toner are measured by the measuring device using a 100 μm aperture as an aperture. , to calculate the volume distribution and the number distribution. From the obtained distribution, the volume average particle diameter (D4) and number average particle diameter (Dn) of the toner can be obtained.

2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 25.40 μm to less than 32.00 μm; 32.00 μm to less than 40.30 μm using 13 channels, targeting particles with a particle size of 2.00 μm to less than 40.30 μm.

<<Average particle size, average circularity>>
In this embodiment, for example, a flow-type particle image analyzer FPIA-3000 (manufactured by Sysmex Corporation) is used to measure the average particle diameter and average circularity.

As a specific measurement method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzenesulfonate, is added as a dispersant to 100 to 150 ml of water in a container from which solid impurities have been removed in advance, and the measurement sample is Add about 0.1 to 0.5 g of The suspension in which the sample is dispersed is subjected to dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the concentration of the dispersion liquid is set to 3000 to 10,000 particles/μl. Measure the standard deviation (SD).

However, the particle diameter is the circle equivalent diameter, the average particle diameter is determined by the circle equivalent diameter (number basis), and the analysis conditions of the flow type particle image analyzer are as follows.
Particle size limit: 0.5 μm ≦ circle equivalent diameter (number basis) ≦ 200.0 μm
Particle shape limitation: 0.93 < circularity ≤ 1.00
Further, the definition of the average circularity in this embodiment is as follows.
(average circularity) = (perimeter of circle equal to projected area) / (perimeter of projected image)

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

In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Showdex STANDARD Std. No. S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 are used. An RI (refractive index) detector is used as the detector.

<<long axis and aspect ratio of crystalline polyester resin>>
The long diameter and aspect ratio of the crystalline polyester resin of the toner can be measured, for example, by the following method.
The toner was embedded in a visible light curable embedding resin (D-800, manufactured by Nisshin EM), cut to a thickness of 60 nm using an ultrasonic ultramicrotome (EM5, manufactured by Leica), and subjected to a vacuum dyeing apparatus (Filgen). (manufactured) for Ru staining. After that, observation is performed at an acceleration voltage of 120 kV with a transmission electron microscope (H7500, manufactured by Hitachi). As the toner to be observed, 50 particles having a weight average particle diameter within ±2.0 μm are selected and photographed. In the case of the configuration of the present invention, when RuO ₄ dyeing is performed, the shade of the polyester resin C in the toner is deep, and when wax is used, the wax is projected even darker. The average major diameter and average aspect ratio of the domains made of the polyester resin C can be determined from the observed image, but the average aspect ratio can be calculated using image processing software as necessary.

Image-Pro Plus 5.1J (manufactured by Media Cybernetics) can be used as image processing software. A cross-sectional image of a toner particle photographed by the method described above is used. First, a toner particle portion is selected to separate the toner particles and the background portion in order to extract the toner particles for analysis. Select Image-Pro Plus 5.1J "Measurement" - "Count/Size". From the "Count/Size" window, select "Measurement" - "Measurements". Select "Diameter (minimum)" and "Diameter (maximum)" from the measurement items. In the "brightness range selection", it is necessary to adjust the brightness range so that only the polyester resin A is selected. Depending on the RuO ₄ dyeing conditions, the brightness range must be changed each time, but the polyester resin A can be easily distinguished from the above-mentioned difference in shade. Select "Count" to display the measurement results. After that, the obtained "diameter (minimum)" is taken as the minor axis, and the "diameter (maximum)" is taken as the major axis, and the aspect ratio (major axis/minor axis) can be obtained. From the data of the aspect ratio of one toner particle thus obtained, the average value of 10 points is obtained in descending order of the diameter (maximum), and this is repeated for 10 toner particles to obtain the average aspect ratio.
The length of the crystalline polyester resin is preferably 2.0 μm or less, more preferably 1.0 μm or less. If the major axis is large, the crystalline polyester resin is likely to be exposed on the toner surface, the adhesion of the toner is increased, and the cleanability is deteriorated.
The aspect ratio is preferably 4.0 or more, more preferably 10.0 or more. When the aspect ratio becomes small, the contact area with the amorphous polyester resin becomes small, the compatibility between the amorphous polyester resin and the crystalline polyester resin deteriorates during fixing, and the low-temperature fixability deteriorates.

<Measurement of particle size of wax in wax dispersion>
The particle size of the wax dispersion in the present invention can be measured, for example, using a Nanotrack particle size distribution analyzer UPA-EX150 (Nikkiso Co., Ltd., dynamic light scattering method/laser Doppler method). As a specific measurement method, a dispersion liquid in which resin fine particles are dispersed is adjusted to a measurement concentration range and measured. At that time, background measurement is performed in advance using only the dispersion solvent of the dispersion. By this measurement method, it is possible to measure the volume average particle size of the resin fine particles used in the present invention, which is from several tens of nm to several μm.
The particle diameter of wax as used in the present invention means volume average particle diameter (volume average diameter).
In the present invention, the dispersed particle size of the wax in the wax dispersion is preferably 50 nm or more and 600 nm or less, more preferably 50 nm or more and 300 nm or less.

<Particle size measurement of crystalline polyester resin in crystalline polyester resin dispersion>
The particle size of the crystalline polyester resin dispersion in the present invention can be measured, for example, using a Nanotrack particle size distribution analyzer UPA-EX150 (Nikkiso Co., Ltd., dynamic light scattering method/laser Doppler method). As a specific measurement method, a dispersion liquid in which resin fine particles are dispersed is adjusted to a measurement concentration range and measured. At that time, background measurement is performed in advance using only the dispersion solvent of the dispersion. By this measurement method, it is possible to measure the volume average particle size of the resin fine particles used in the present invention, which is from several tens of nm to several μm.
The particle size of the crystalline polyester resin referred to in the present invention means the volume average particle size (volume average diameter).
In the present invention, the dispersed particle size of the crystalline polyester resin in the crystalline polyester resin dispersion is preferably 20 nm or more and 500 nm or less, more preferably 50 nm or more and 300 nm or less.

<Toner manufacturing method>
The method for producing the toner is not particularly limited and can be appropriately selected depending on the purpose, but preferably includes a mixing step of mixing the toner base particles and the external additive.

The toner base particles preferably contain the amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C, and if necessary, the release agent, the colorant, and the like. It is preferably granulated by dispersing the oil phase containing in an aqueous medium.

In addition, the toner base particles preferably contain the non-linear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C. Further, if necessary, the curing agent, the Granulation is preferably carried out by dispersing an oil phase containing a release agent, the colorant, etc. in an aqueous medium.

An example of a method for producing such toner base particles is a known emulsion aggregation method. As an example of the method for producing the toner base particles, a method for forming the toner base particles while elongating the amorphous polyester resin A by an elongation reaction and/or a cross-linking reaction between the prepolymer and the curing agent is shown below. . In such a method, preparation of an aqueous medium, preparation of an oil phase containing a toner material, phase inversion emulsification of the toner material, and removal of an organic solvent are performed to obtain a fine particle dispersion. Toner base particles are obtained by aggregating and fusing the fine particle dispersion. After that, the toner is obtained by mixing the obtained toner base particles and the external additive.

<<Preparation of aqueous medium (aqueous phase)>>
The aqueous medium is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include water, water-miscible solvents, and mixtures thereof. These may be used individually by 1 type, and may use 2 or more types together. Among these, water is preferred.

The water-miscible solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include alcohols, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones and the like.
The alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include methanol, isopropanol, ethylene glycol and the like.
The lower ketones are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include acetone and methyl ethyl ketone.

<<Preparation of oil phase>>
Preparation of the oil phase containing the toner material includes, for example, the non-linear reactive precursor, the amorphous polyester resin B, the crystalline polyester resin C, and optionally the It can be carried out by dissolving or dispersing a toner material containing a curing agent, the releasing agent, the coloring agent, etc. in an organic solvent. The oil phase may also contain a profile agent.

The organic solvent is not particularly limited and can 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 is easy to remove.
The organic solvent having a boiling point of less than 150° C. is not particularly limited and can be appropriately selected depending on the intended purpose. , 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. These may be used individually by 1 type, and may use 2 or more types together.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferred, and ethyl acetate is more preferred.

<<Phase inversion emulsification>>
Phase inversion emulsification of the toner material can be performed by dispersing an oil phase containing the toner material in the aqueous medium. Then, when emulsifying or dispersing the toner material, the amorphous polyester resin A is produced by subjecting the curing agent and the non-linear reactive precursor to elongation reaction and/or cross-linking reaction.

The amorphous polyester resin A can be produced, for example, by the following methods (1) to (3).
(1) An oil phase containing the non-linear reactive precursor and the curing agent is emulsified or dispersed in an aqueous medium, and the curing agent and the non-linear reactive precursor are mixed in the aqueous medium. A method of producing the amorphous polyester resin A by elongating and/or cross-linking.
(2) The oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium to which the curing agent is added in advance, and the curing agent and the non-linear reactive precursor are emulsified or dispersed in the aqueous medium. A method of producing the amorphous polyester resin A by elongation reaction and/or cross-linking reaction with a body.
(3) After emulsifying or dispersing the oil phase containing the non-linear reactive precursor in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent is dispersed from the particle interface in the aqueous medium. and the non-linear reactive precursor are subjected to an elongation reaction and/or cross-linking reaction to form the amorphous polyester resin A.

When the curing agent and the non-linear reactive precursor are subjected to an elongation reaction and/or a cross-linking reaction from the particle interface, the amorphous polyester resin A is preferentially formed on the surface of the generated toner, A concentration gradient of the amorphous polyester resin A may be provided in the toner.

The reaction conditions (reaction time, reaction temperature) for producing the amorphous polyester resin A are not particularly limited, and depending on the combination of the curing agent and the non-linear reactive precursor, It can be selected as appropriate.
The reaction time is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.
The reaction temperature is not particularly limited and can be appropriately selected depending on the intended purpose.

The method for phase inversion emulsification of the dispersion containing the non-linear reactive precursor in the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. is neutralized with a base or the like, an aqueous phase is added thereto, and a fine particle dispersion is obtained by phase inversion emulsification in which the water-in-oil dispersion is phase-inverted to an oil-in-water dispersion.

The base for neutralizing the oil phase is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include sodium hydroxide, potassium hydroxide, aqueous ammonia and the like.

The amount of the aqueous medium to be used for phase inversion emulsification of the oil phase containing the toner material is not particularly limited and can be appropriately selected according to the purpose. It is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the toner material.
When the amount of the aqueous medium used is 50 parts by mass or more, deterioration of the dispersed state of the toner material can be prevented, and failure to obtain toner base particles having a predetermined particle size can be suppressed. When the amount is 2,000 parts by mass or less, it is possible to prevent the production cost from increasing.

When the oil phase containing the toner material is subjected to phase inversion emulsification, 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 can be appropriately selected depending on the intended purpose. Examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, polymeric protective colloids, and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, surfactants are preferred.

The surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc. be able to.

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

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

<<Removal of organic solvent>>
The method for removing the organic solvent from the dispersion liquid such as the emulsified slurry is not particularly limited, and can be appropriately selected depending on the purpose. For example, a method of gradually raising the temperature of the entire reaction system to evaporate the organic solvent in the oil droplets, a method of spraying the dispersion into a dry atmosphere to remove the organic solvent in the oil droplets, and the like can be used.
<<aggregation, fusion>>

Existing methods such as addition of a flocculating agent and pH adjustment can be used as the aggregating method. When a flocculant is added, it may be added as it is, but it is preferable to prepare an aqueous solution of the flocculant because local high concentration can be avoided. Further, it is preferable to gradually add the aggregated salt while observing the particle size of the colored particles.
The temperature of the dispersion during aggregation is preferably around the Tg of the amorphous polyester B described above. If the liquid temperature is too low, aggregation does not progress so much, resulting in poor efficiency.
Agglomeration is stopped when the target particle size is reached. Methods for stopping aggregation include a method of adding a salt having an ionic valence lower than that of the aggregation salt or a chelating agent, a method of adjusting the pH, a method of lowering the temperature of the dispersion, and a method of adding a large amount of an aqueous medium. A method of diluting the concentration can be used.
A dispersion liquid of colored aggregated particles can be obtained by the above method.

In the aggregation step, a release agent may be added, or a crystalline polyester resin C may be added for low temperature fixability. In that case, a dispersion liquid in which a release agent is dispersed in an aqueous medium or a dispersion liquid of crystalline polyester resin C is prepared in the same manner, mixed with the coloring fine particle dispersion liquid, and then agglomerated to uniformly disperse the particles. Aggregated particles in which a release agent and a crystalline polyester resin are dispersed can be obtained.

Next, the obtained agglomerated particles are fused by heat treatment to reduce unevenness. The fusion may be carried out by heating while stirring the dispersion liquid of the colored aggregated particles. The temperature of the liquid is preferably Tg or more and Tg+20° C. or less of the amorphous polyester B, more preferably Tg or more and Tg+10° C. or less. If the temperature exceeds Tg+20° C., the compatibility between the amorphous polyester resin and the crystalline polyester resin progresses too much, and the major axis of the domain during recrystallization of the crystalline polyester resin becomes large, and is likely to be exposed on the toner surface. put away.

After that, the toner base particles can be washed, dried, etc., and further classified. The classification may be carried out by removing fine particles in a liquid using a cyclone, decanter, centrifugation, or the like, or may be carried out after drying.

<<Mixing process>>
The obtained toner base particles are mixed with the external additive. At this time, by applying a mechanical impact force, it is possible to suppress detachment of the particles of the external additive from the surface of the toner base particles.

The method of applying the mechanical impact force is not particularly limited, and 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, a method of injecting the mixture into a high-speed air current and accelerating it to collide the particles with each other or against an appropriate collision plate, and the like.

The apparatus used in the method is not particularly limited and can be appropriately selected according to the purpose. For example, Ong Mill (manufactured by Hosokawa Micron Corporation), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) modified to reduce pulverizing air pressure, Hybridization System (manufactured by Nara Machinery Works), Kryptron System (Kawasaki Heavy Industries, Ltd.) made), automatic mortar and the like.

(developer)
The developer of the present invention contains at least the toner described above, and optionally other components such as a carrier that are appropriately selected.
Therefore, it is possible to stably form a high-quality image with excellent transferability, chargeability, and the like. The developer may be a one-component developer or a two-component developer. Two-component developers are preferred because of their improved performance.

When the developer is used as a one-component developer, even if the toner balance is performed, the variation in the particle size of the toner is small, and the filming of the toner on the developing roller and members such as blades that thin the toner layer. The toner is less fused to the toner, and good and stable developability and images can be obtained even during long-term agitation in the developing device.

When the developer is used as a two-component developer, even if the toner balance is maintained over a long period of time, the toner particle size fluctuates little, and good and stable developability and images can be obtained even during long-term agitation in the developing device. can get.

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

<< core material >>
The material of the core material is not particularly limited and can be appropriately selected according to the purpose. Examples include magnesium-based materials. Further, in order to ensure image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu/g or more and magnetite of 75 emu/g to 120 emu/g. In addition, a low magnetization material such as a copper-zinc system having a concentration of 30 emu/g to 80 emu/g can be used because the impact of the standing developer on the photoreceptor can be reduced, which is advantageous for achieving high image quality. is preferred.
These may be used individually by 1 type, and may use 2 or more types together.

The volume average particle diameter of the core material is not particularly limited and can be appropriately selected depending on the intended purpose. When the volume average particle diameter is 10 μm or more, it is possible to prevent fine powder from increasing in the carrier and suppress the occurrence of scattering of the carrier due to a decrease in magnetization per particle. If it is 150 μm or less, it is possible to prevent the specific surface area from decreasing, suppress the occurrence of toner scattering, and particularly in full-color printing with many solid areas, it is possible to suppress the deterioration of the reproduction of solid areas. can.

When the toner is used in a two-component developer, it may be used by being mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected according to the purpose. Parts or less is preferable, and 93 parts by mass or more and 97 parts by mass or less is more preferable.

The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

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

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

For the amorphous silicon photoreceptor, for example, a support is heated to 50° C. to 400° C., and vacuum deposition, sputtering, ion plating, thermal CVD (Chemical Vapor Deposition) is performed on the support. ) method, photo-CVD method, plasma-enhanced CVD method and the like can be used. Among these, the plasma CVD method, that is, the method of decomposing a raw material gas by direct current, high frequency or microwave glow discharge to form an a-Si deposition film on a support is preferred.

The shape of the electrostatic latent image carrier is not particularly limited and can be appropriately selected depending on the intended purpose, but a cylindrical shape is preferred. The outer diameter of the cylindrical electrostatic latent image bearing member is not particularly limited and can be appropriately selected according to the purpose. 30 mm or less is particularly preferred.

<Electrostatic latent image forming means and electrostatic latent image forming step>
The electrostatic latent image forming means is not particularly limited as long as it forms an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. For example, means having at least a charging member for charging the surface of the electrostatic latent image carrier and an exposing member for imagewise exposing the surface of the electrostatic latent image carrier may be used.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. For example, after the surface of the electrostatic latent image carrier is charged, it can be imagewise exposed, and can be carried out using the electrostatic latent image forming means.

<<Charging member and charging>>
The charging member is not particularly limited and can be appropriately selected according to the purpose. For example, there are known contact chargers equipped with conductive or semi-conductive rollers, brushes, films, rubber blades, etc., and non-contact chargers using corona discharge such as corotrons and scorotrons.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.

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

<<Exposure member and exposure>>
The exposure member is not particularly limited as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed in an image-wise manner to be formed, and is appropriately selected according to the purpose. be able to. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
The light source used for the exposure member is not particularly limited and can be appropriately selected according to the purpose. For example, fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light-emitting diodes (LEDs), semiconductor lasers (LDs), electroluminescence (ELs), and other light-emitting materials in general can be used.

Moreover, 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 be used in order to irradiate only light in a desired wavelength range.
The exposure can be performed, for example, by imagewise exposing the surface of the electrostatic latent image carrier using the exposure member.
In addition, in the present invention, a light rear surface method in which imagewise exposure is performed from the rear surface side of the electrostatic latent image carrier may be employed.

<Developing means and developing process>
The developing means is not particularly limited as long as it is a developing means having toner for developing the electrostatic latent image formed on the electrostatic latent image bearing member to form a visible image, and may be selected according to the purpose. It can be selected as appropriate.
The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a visible image, depending on the purpose. For example, it can be carried out by the developing means.

The developing means may be of a dry developing system or may be of a wet developing system. Further, it may be a single-color developing means or a multi-color developing means.
The developing means includes a stirrer for frictionally stirring and charging the toner, and a magnetic field generating means fixed inside, and a rotatable developer carrying developer containing the toner on its surface. A developing device having a body is preferred.
In the developing means, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time and held in a bristling state on the surface of a rotating magnet roller to form a magnetic brush. . The magnet roller is arranged near the electrostatic latent image carrier. Therefore, part of the toner forming the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier due to the electric attractive force. As a result, the electrostatic latent image is developed with the toner to form a visible image with the toner on the surface of the electrostatic latent image carrier.

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

<<Transfer Means and Transfer Process>>
The transfer means is not particularly limited as long as it is a means for transferring a visible image onto a recording medium, and can be appropriately selected according to the purpose. Among them, an embodiment having primary transfer means for transferring a visible image onto an intermediate transfer body to form a composite transfer image and secondary transfer means for transferring the composite transfer image onto a recording medium is preferred.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. Among them, it is preferable that an intermediate transfer member is used, and after the visible image is primarily transferred onto the intermediate transfer member, the visible image is secondarily transferred onto the recording medium.

The transfer step can be performed, for example, by charging the visible image to the photoreceptor using a transfer charger, and can be performed by the transfer means.
Here, when the image to be secondarily transferred onto the recording medium is a color image made of toner of a plurality of colors, the transfer means sequentially superimposes the toners of each color on the intermediate transfer body to perform the intermediate transfer. An image may be formed on the medium, and the intermediate transfer means may secondary transfer the image on the intermediate transfer medium onto the recording medium all at once.
The intermediate transfer member is not particularly limited, and can be appropriately selected from known transfer members depending on the intended purpose. For example, a transfer belt is suitable.

It is preferable that the transfer means (the primary transfer means, the secondary transfer means) have at least a transfer device that separates and charges the visible image formed on the photoreceptor to the recording medium side. Examples of the transfer device include a corona transfer device using 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 is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base or the like can also be used.

<<Fixing Means and Fixing Process>>
The fixing means is not particularly limited as long as it is means for fixing the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose, but a known heating and pressurizing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, each color toner may be transferred each time it is transferred to the recording medium, or each color toner may be laminated and transferred at once.

The fixing step can be performed by the fixing means.
Heating in the heating and pressurizing member is preferably at 80° C. or higher and 200° C. or lower.
In addition, in the present invention, depending on the purpose, for example, a known optical fixing device may be used together with or in place of the fixing means.
The surface pressure in the fixing step is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 N/cm ² or more and 80 N/cm ² or less.

<<Cleaning means and cleaning process>>
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. Examples include magnetic brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, the cleaning means can be used.

<<static elimination means and static elimination process>>
The charge removing means is not particularly limited as long as it removes charges by applying a charge removing bias to the photoreceptor, and can be appropriately selected according to the purpose. For example, a static elimination lamp may be used.
The static elimination step is not particularly limited as long as it is a step of applying a static elimination bias to the photosensitive member to eliminate static electricity, and can be appropriately selected according to the purpose. .

<<Recycling means and recycling process>>
The recycling means is not particularly limited as long as it is a means for recycling the toner removed in the cleaning process to the developing device, and can be appropriately selected according to the purpose. mentioned.
The recycling step is not particularly limited as long as it is a step of recycling the toner removed in the cleaning step to the developing device, and can be appropriately selected according to the purpose. can be done.

<<Control Means and Control Process>>
The control means is not particularly limited as long as it can control the movement of each means, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.
The control process is not particularly limited as long as it can control the movement of each process, and can be appropriately selected according to the purpose. For example, it can be performed by the control means.

Next, one aspect of implementing the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. A color image forming apparatus 100A shown in FIG. It comprises an exposure device 30 as exposure means, a developing device 40 as the development means, an intermediate transfer body 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means. .

The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of the arrow by means of three rollers 51 arranged inside and stretched thereon. Some of the three rollers 51 also function as transfer bias rollers capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50 . A cleaning device 90 having a cleaning blade is arranged near the intermediate transfer member 50 . Further, in the vicinity of the intermediate transfer member 50, there is a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) the developed image (toner image) onto the transfer paper 95 as the recording medium. , are arranged to face the intermediate transfer member 50 . Around the intermediate transfer body 50 , a corona charger 58 for imparting electric charge to the toner image on the intermediate transfer body 50 is arranged so that the photoreceptor 10 and the intermediate transfer body 50 are in contact with each other in the rotation direction of the intermediate transfer body 50 . It is arranged between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95 .

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

In the color image forming apparatus 100A shown in FIG. 2, for example, the charging roller 20 uniformly charges the photosensitive drum 10. As shown in FIG. The exposure device 30 imagewise exposes the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred onto the transfer paper 95 (secondary transfer). As a result, a transfer image is formed on the transfer paper 95 . Toner remaining on the photoreceptor 10 is removed by the cleaning device 60 , and the charge on the photoreceptor 10 is temporarily removed by the charge removal lamp 70 .

FIG. 3 shows another example of the image forming apparatus of the present invention. The image forming apparatus 100B does not have a developing belt 41, and has a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C arranged around the photosensitive drum 10 so as to directly face each other. Except for this, it has the same configuration as the image forming apparatus 100A shown in FIG.

FIG. 4 shows another example of the image forming apparatus of the present invention. The image forming apparatus 100C shown in FIG.
An endless belt-shaped intermediate transfer member 50 is provided in the center of the copying apparatus main body 150 .
The intermediate transfer member 50 is stretched around support rollers 14, 15 and 16 and is rotatable clockwise in FIG. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is arranged near the support roller 15 . A tandem type in which four yellow, cyan, magenta, and black image forming means 18 are arranged facing each other along the conveying direction of the intermediate transfer body 50 stretched between the support rollers 14 and 15. A developing device 120 is arranged. In the vicinity of the tandem type developing device 120, the exposure device 21, which is the exposure member, is arranged. A secondary transfer device 22 is arranged on the side of the intermediate transfer member 50 opposite to the side where the tandem type developing device 120 is arranged. In the secondary transfer device 22, the secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. It is possible. In the vicinity of the secondary transfer device 22, a fixing device 25, which is the fixing means, is arranged. The fixing device 25 includes an endless fixing belt 26 and a pressure roller 27 pressed against the fixing belt 26 .
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper is arranged near the secondary transfer device 22 and the fixing device 25 to form images on both sides of the transfer paper. .

Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the document is set on the contact glass 32 of the scanner 300 by opening the automatic document feeder 400, and then the automatic document feeder is operated. Close 400.

When the start switch is pressed, when the document is set on the automatic document feeder 400, the document is conveyed and moved onto the contact glass 32. On the other hand, when the document is set on the contact glass 32, the document is immediately set. , the scanner 300 is driven. Then, the first running body 33 and the second running body 34 run. At this time, the light from the light source is irradiated by the first traveling member 33, and the reflected light from the surface of the document is reflected by the mirror of the second traveling member 34, and is received by the reading sensor 36 through the imaging lens 35, resulting in a color image. A document (color image) is read to obtain black, yellow, magenta, and cyan image information.

Then, each image information of black, yellow, magenta, and cyan is processed by each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 . forming means). Then, each image forming means forms black, yellow, magenta, and cyan toner images.

That is, each of the image forming units 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image forming unit) in the tandem type developing device 120 is static as shown in FIG. an electrostatic latent image carrier 10 (a black electrostatic latent image carrier 10K, a yellow electrostatic latent image carrier 10Y, a magenta electrostatic latent image carrier 10M, and a cyan electrostatic latent image carrier 10C); A charging device 160 which is the charging means for uniformly charging the electrostatic latent image carrier 10, and an imagewise exposure of the electrostatic latent image carrier 10 corresponding to each color image based on each color image information (FIG. 5). medium, L), an exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and an exposure device for forming the electrostatic latent image on each color toner (black toner, yellow toner, magenta toner); , and cyan toner) to form a toner image of each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, A cleaning device 63 and a static eliminator 64 are provided.

Each image forming unit 18 can form each monochromatic image (a black image, a yellow image, a magenta image, and a cyan image) based on the respective color image information. The black image, the yellow image, the magenta image and the cyan image thus formed are transferred onto an intermediate transfer member 50 which is rotationally moved by support rollers 14, 15 and 16, respectively. A black image formed on the top, a yellow image formed on the electrostatic latent image carrier 10Y for yellow, a magenta image formed on the electrostatic latent image carrier 10M for magenta, and an electrostatic latent image carrier for cyan. The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200 , one of the paper feed rollers 142 is selectively rotated to feed a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143 . The sheet is separated one by one by a separation roller 145 and sent to a paper feed path 146, conveyed by a conveying roller 147, guided to a paper feed path 148 in the main body 150 of the copying machine, and stopped by being abutted against a registration roller 49. be done. Alternatively, the sheet (recording paper) on the manual feed tray 54 is fed out by rotating the paper feed roller 142 , separated one by one by the separation roller 52 , put into the manual feed path 53 , and stopped by striking the registration roller 49 . . Although the registration roller 49 is generally grounded and used, it may be used with a bias applied to remove paper dust from the sheet.

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

The sheet (recording paper) on which the color image is transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25. In the fixing device 25, the composite color image (color image) is applied by heat and pressure. A transferred image) is fixed on the sheet (recording paper). After that, the sheet (recording paper) is switched by a switching claw 55 and discharged by a discharge roller 56 to be stacked on a paper discharge tray 57 . Alternatively, the sheet is switched by the switching claw 55, reversed by the sheet reversing device 28, and led to the transfer position again. be done.

(toner storage unit)
The toner containing unit in the present invention means a unit having a function of containing toner and containing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, a process cartridge, and the like.
A toner container is a container containing toner.
A developing device means a device having a means for storing and developing toner.
A process cartridge is a cartridge that integrates at least an image carrier and developing means, stores toner, and is detachable from an image forming apparatus. The process cartridge may further comprise at least one selected from charging means, exposure means and cleaning means.

By mounting the toner storage unit of the present invention on an image forming apparatus and forming an image, the image is formed using the toner of the present invention, so that both cleanability and low-temperature fixability can be achieved.

The toner storage container is not particularly limited, and can be appropriately selected from known ones. For example, one having a container body and a cap can be mentioned.

Moreover, the size, shape, structure, material, etc. of the container body are not particularly limited, and can be changed as appropriate.
The shape is preferably cylindrical or the like, and spiral unevenness is formed on the inner peripheral surface, and by rotating it, the developer, which is the content, can move to the discharge port side. It is particularly preferable that part or all of the spiral unevenness has a bellows function.

Furthermore, although the material is not particularly limited, it is preferable that the material has good dimensional accuracy. Examples thereof include resin materials such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.

Since the toner storage container is easy to store, transport, etc., and is excellent in handleability, it can be detachably attached to a process cartridge, an image forming apparatus, or the like, and used for replenishing toner.

An example of a process cartridge related to the present invention is an electrostatic latent image carrier that carries an electrostatic latent image and an electrostatic latent image carrier that is molded to be attachable to and detachable from various image forming apparatuses. It has at least developing means for developing the electrostatic latent image with the developer of the present invention to form a toner image. Incidentally, the process cartridge of the present invention may further have other means as required.

The developing means includes at least a developer storage container that stores the developer of the present invention and a developer carrier that carries and conveys the developer stored in the developer storage container. The developing means may further have a regulating member or the like for regulating the thickness of the developer to be carried.

FIG. 6 shows an example of a process cartridge relating to the present invention. The process cartridge 110 has a photosensitive drum 10 , a corona charger 58 , a developer 40 , a transfer roller 80 and a cleaning device 90 .

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. "Parts" means "mass parts" unless otherwise specified. "%" represents "% by mass" unless otherwise specified.

Each measured value in the following examples was measured by the method described in this specification. The Tg and molecular weight of amorphous polyester resin A, amorphous polyester resin B, crystalline polyester resin C, etc. were measured from each resin obtained in Production Examples.

(Production example 1)
<Synthesis of ketimine>
170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirring rod and a thermometer, and reacted at 50° C. for 5 hours to obtain [Ketimine Compound 1]. The amine value of [ketimine compound 1] was 418 mgKOH/g.

(Production Example A-1)
<Synthesis of amorphous polyester resin A-1>
-Synthesis of prepolymer A-1-
3-Methyl-1,5-pentanediol, isophthalic acid, and plant-derived sebacic acid were added to a reaction vessel equipped with a condenser, stirrer, and nitrogen inlet, and OH/OH, which is the molar ratio of hydroxyl groups to carboxyl groups. COOH is 1.1, the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol, the composition of the dicarboxylic acid component is 66 mol% of isophthalic acid and 34 mol% of sebacic acid, and Trimethylolpropane was introduced together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the amount of trimethylolpropane was 1.5 mol %. After that, the temperature was raised to 200° C. over about 4 hours, then to 230° C. over 2 hours, and the reaction was carried out until no water flowed out. After that, the mixture was further reacted under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester A-1].

Next, in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, the obtained [intermediate polyester A-1] and isophorone diisocyanate (IPDI) are added at a molar ratio (isocyanate group of IPDI/intermediate polyester The hydroxyl group of the polymer) was added at 2.0, diluted with ethyl acetate to give a 50% ethyl acetate solution, and reacted at 100° C. for 5 hours to obtain [prepolymer A-1].

-Synthesis of Amorphous Polyester Resin A-1-
The obtained [prepolymer A-1] is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen inlet tube, and further the amount of [ketimine compound 1] relative to the amount of isocyanate in [prepolymer A-1]. [Ketimine compound 1] was added dropwise to the reaction vessel in an amount such that the amount of the amine was equimolar. The obtained stretched prepolymer was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain [amorphous polyester resin A-1]. Table 1 shows the physical properties of this resin.

(Production Example A-2)
<Synthesis of amorphous polyester resin A-2>
-Synthesis of prepolymer A-2-
3-Methyl-1,5-pentanediol, isophthalic acid, and plant-derived sebacic acid were added to a reaction vessel equipped with a condenser, stirrer, and nitrogen inlet, and OH/OH, which is the molar ratio of hydroxyl groups to carboxyl groups. COOH is 1.1, the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol, the composition of the dicarboxylic acid component is 83 mol% of isophthalic acid and 17 mol% of sebacic acid, and Trimethylolpropane was introduced together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the amount of trimethylolpropane was 1.5 mol %. After that, the temperature was raised to 200° C. over about 4 hours, then to 230° C. over 2 hours, and the reaction was carried out until no water flowed out. After that, the mixture was further reacted under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate Polyester A-2].

Next, in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the obtained [intermediate polyester A-2] and isophorone diisocyanate (IPDI) are added at a molar ratio (isocyanate group of IPDI/intermediate polyester The hydroxyl group of the polymer) was added at 2.0, diluted with ethyl acetate to give a 50% ethyl acetate solution, and reacted at 100° C. for 5 hours to obtain [Prepolymer A-2].

-Synthesis of Amorphous Polyester Resin A-2-
The obtained [prepolymer A-2] is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen inlet tube, and further the amount of [ketimine compound 1] relative to the amount of isocyanate in [prepolymer A-2]. [Ketimine compound 1] was added dropwise to the reaction vessel in an amount such that the amount of the amine was equimolar. The obtained stretched prepolymer was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain [amorphous polyester resin A-2]. Table 1 shows the physical properties of this resin.

(Production Example A-3)
<Synthesis of amorphous polyester resin A-3>
-Synthesis of prepolymer A-3-
3-Methyl-1,5-pentanediol, isophthalic acid, and adipic acid were added to a reaction vessel equipped with a condenser, stirrer, and nitrogen inlet tube so that the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, was 1. .1, the composition of the diol component is 100 mol % of 3-methyl-1,5-pentanediol, the composition of the dicarboxylic acid component is 50 mol % of isophthalic acid and 50 mol % of adipic acid, and trimethylolpropane in all monomers was added together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the amount of was 1.5 mol %. After that, the temperature was raised to 200° C. over about 4 hours, then to 230° C. over 2 hours, and the reaction was carried out until no water flowed out. After that, the mixture was further reacted under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester A-3].

Next, in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, the obtained [intermediate polyester A-3] and isophorone diisocyanate (IPDI) are added at a molar ratio (isocyanate group of IPDI/intermediate polyester 2.0 of hydroxyl group), diluted with ethyl acetate to give a 50% ethyl acetate solution, and reacted at 100° C. for 5 hours to obtain [Prepolymer A-3].

-Synthesis of Amorphous Polyester Resin A-3-
The obtained [prepolymer A-3] is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen inlet tube, and further the amount of [ketimine compound 1] relative to the amount of isocyanate in [prepolymer A-3]. [Ketimine compound 1] was added dropwise to the reaction vessel in an amount such that the amount of the amine was equimolar. The obtained stretched prepolymer was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain [amorphous polyester resin A-3]. Table 1 shows the physical properties of this resin.

(Production Example B-1)
<Synthesis of Amorphous Polyester Resin B-1>
Plant-derived propylene glycol, terephthalic acid, and plant-derived succinic acid were added to a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, and the molar ratio of terephthalic acid to succinic acid (terephthalic acid / succinic acid) is 86/14, and it is charged so that the molar ratio of hydroxyl group to carboxyl group, OH/COOH, is 1.3, and titanium tetraisopropoxide (500 ppm relative to the resin component) , reacted at 230° C. for 8 hours, and further reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Then, trimellitic anhydride was added to the reaction vessel so as to be 1 mol % of the total resin components, and 180° C., normal pressure, 3 hours. to obtain [amorphous polyester resin B-1]. Table 2 shows the physical properties of this resin.

(Manufacturing Example B-2)
<Synthesis of amorphous polyester resin B-2>
Propylene glycol, 2 mol bisphenol A propylene oxide adduct, terephthalic acid, and plant-derived succinic acid were added to a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and propylene glycol and bisphenol A ethylene. Oxide 2 mol adduct has a molar ratio (propylene glycol/bisphenol A ethylene oxide 2 mol adduct) of 60/40, and terephthalic acid and succinic acid have a molar ratio (terephthalic acid/succinic acid) of 86/14. It is prepared so that the OH/COOH, which is the molar ratio between hydroxyl groups and carboxyl groups, is 1.3, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at normal pressure and 230 ° C. for 8 hours, After reacting for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg, trimellitic anhydride was added to the reaction vessel so as to be 1 mol% of the total resin component, and reacted at 180 ° C. at normal pressure for 3 hours to obtain [amorphous polyester Resin B-2] was obtained. Table 2 shows the physical properties of this resin.

(Production Example B-3)
<Synthesis of amorphous polyester resin B-3>
Bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct, terephthalic acid, and adipic acid were added to a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and bisphenol A propylene. The molar ratio of the oxide 2-mol adduct and the bisphenol A ethylene oxide 2-mol adduct (bisphenol A propylene oxide 2-mol adduct/bisphenol A ethylene oxide 2-mol adduct) was 60/40, and terephthalic acid and adipic acid is 97/3 in molar ratio (terephthalic acid/adipic acid), and OH/COOH, which is the molar ratio between hydroxyl group and carboxyl group, is 1.3. and 500 ppm) under normal pressure at 230°C for 8 hours, and further reacted at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours. , normal pressure for 3 hours to obtain [amorphous polyester resin B-3]. Table 2 shows the physical properties of this resin.

(Production Example C-1)
<Synthesis of crystalline polyester resin C-1>
Plant-derived sebacic acid and 1,6-hexanediol were added to a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and OH/ which is the molar ratio of hydroxyl groups to carboxyl groups. Prepared so that the COOH was 0.9, reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours. [Crystalline polyester resin C-1] was obtained by reaction for 2 hours at a pressure of 3 kPa. Table 3 shows the physical properties of this resin.

(Production example C2)
<Synthesis of crystalline polyester resin C-2>
[Crystalline polyester resin C-2] was obtained in the same manner as in the synthesis of [Crystalline polyester resin C-1], except that the dicarboxylic acid was replaced with plant-derived dodecanedioic acid. Physical property values are shown in Table 3.

(Production Example C-3)
<Synthesis of crystalline polyester resin C-3>
[Crystalline polyester resin C-3] was obtained in the same manner as in the synthesis of [Crystalline polyester resin C-1], except that the diol was replaced with plant-derived ethylene glycol. Physical property values are shown in Table 3.

(Production Example C-4)
<Synthesis of crystalline polyester resin C-4>
[Crystalline polyester resin C-4] was obtained in the same manner as in the synthesis of [Crystalline polyester resin C-1], except that the dicarboxylic acid was replaced with adipic acid. Physical property values are shown in Table 3.

(Production Example C-5)
<Synthesis of crystalline polyester resin C-5>
[Crystalline polyester resin C-5] was synthesized in the same manner as [Crystalline polyester resin C-1] except that the diol was replaced with 1,8-octanediol and the dicarboxylic acid was replaced with plant-derived tetradecanoic acid. got Physical property values are shown in Table 3.

<Preparation of masterbatch (MB)>
1,200 parts of water, 500 parts of carbon black (Printex 35, manufactured by Dexsa) [DBP oil absorption = 42 mL/100 mg, pH = 9.5], and 500 parts of [amorphous polyester resin B-1] were added, and Henschel After mixing with a mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), the mixture was kneaded at 150° C. for 30 minutes using two rolls, cooled by rolling and pulverized with a pulperizer to obtain [Masterbatch 1].

<Preparation of WAX dispersion liquid 1>
Into a container equipped with a stirring rod and a thermometer, 42 parts of carnauba wax (RN-5, vegetable wax manufactured by Celarica Noda, melting point 82° C.) as [releasing agent 1] and 420 parts of ethyl acetate are charged and stirred. After raising the temperature to 80° C. and keeping it at 80° C. for 5 hours, it was cooled to 30° C. in 1 hour, and a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) was used to feed the liquid at a rate of 1 kg/hr at a disk peripheral speed. [WAX Dispersion 1] was obtained by performing dispersion at 6 m/sec, filling 80% by volume of zirconia beads with a diameter of 0.5 mm, and performing 3 passes. The volume average particle diameter of the obtained wax particles was 420 nm, and the solid content concentration of the resin particles was 10%.

<Preparation of WAX dispersion liquid 2>
To 720 parts of ion-exchanged water, 180 parts of ester wax (manufactured by NOF Corporation, WE-11, synthetic wax of plant-derived monomers, melting point 67° C.) as [releasing agent 1], 17 parts of anionic surfactant as surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC, sodium dodecylbenzenesulfonate) was added. This was dispersed with a homogenizer while being heated to 90° C. to obtain [WAX Dispersion Liquid 2]. The volume average particle diameter of the obtained wax particles was 250 nm, and the solid content concentration of the resin particles was 25%.

<Preparation of WAX dispersion liquid 3>
50 parts of paraffin wax (manufactured by Nippon Seiro Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8) as [release agent 1] in a container equipped with a stirring rod and a thermometer, and 450 parts of ethyl acetate were charged, heated to 80°C with stirring, maintained at 80°C for 5 hours, then cooled to 30°C in 1 hour, and using a bead mill (Ultra Viscomil, manufactured by Imex), [WAX Dispersion 3] was obtained by carrying out dispersion under the conditions of a liquid feed rate of 1 kg/hr, a disk peripheral speed of 6 m/sec, a filling of 80% by volume of zirconia beads with a diameter of 0.5 mm, and three passes. The volume average particle diameter of the obtained wax particles was 350 nm, and the solid content concentration of the resin particles was 25%.
Table 4 shows the compositions and physical properties of WAX dispersions 1 to 3.

<Preparation of crystalline polyester resin dispersion liquid 1>
45 parts of [Crystalline Polyester Resin C-1] and 450 parts of ethyl acetate were placed in a vessel equipped with a stirring rod and a thermometer, heated to 80° C. with stirring, and maintained at 80° C. for 5 hours. Cooled to 30 ° C. in 1 hour, using a bead mill (Ultra Visco Mill, Aimex Co., Ltd.), a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, filled with 80% by volume of zirconia beads with a diameter of 0.5 mm, 3 Dispersion was carried out under pass conditions to obtain [Crystalline Polyester Resin Dispersion 1]. The volume average particle diameter of the obtained crystalline polyester resin particles was 350 nm, and the solid content concentration of the resin particles was 10%.

<Preparation of Crystalline Polyester Resin Dispersion Liquid 2>
45 parts of [Crystalline Polyester Resin C-2] and 450 parts of ethyl acetate were placed in a container equipped with a stirring rod and a thermometer, heated to 80° C. with stirring, and maintained at 80° C. for 5 hours. Cooled to 30 ° C. in 1 hour, using a bead mill (Ultra Visco Mill, Aimex Co., Ltd.), a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, filled with 80% by volume of zirconia beads with a diameter of 0.5 mm, 3 Dispersion was carried out under pass conditions to obtain [Crystalline Polyester Resin Dispersion 2]. The volume average particle diameter of the obtained crystalline polyester resin particles was 350 nm, and the solid content concentration of the resin particles was 10%.

<Preparation of Crystalline Polyester Resin Dispersion 3>
45 parts of [Crystalline Polyester Resin C-3] and 450 parts of ethyl acetate were placed in a vessel equipped with a stirring rod and a thermometer, heated to 80° C. while stirring, and maintained at 80° C. for 5 hours. Cooled to 30 ° C. in 1 hour, using a bead mill (Ultra Visco Mill, Aimex Co., Ltd.), a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, filled with 80% by volume of zirconia beads with a diameter of 0.5 mm, 3 Dispersion was carried out under pass conditions to obtain [Crystalline Polyester Resin Dispersion 3]. The volume average particle size of the obtained crystalline polyester resin particles was 360 nm, and the solid content concentration of the resin particles was 10%.

<Preparation of Crystalline Polyester Resin Dispersion 4>
[Crystalline polyester resin C-1] 350 parts, 210 parts of methyl ethyl ketone, and 61.8 parts of isopropyl alcohol are placed in a separable flask, thoroughly mixed at 40° C. and dissolved. Part dripped. The heating temperature is lowered to 65° C., and while stirring, ion-exchanged water is added dropwise using a liquid-sending pump at a liquid-sending rate of 8 g/min. After the liquid becomes uniformly cloudy, the liquid-sending rate is increased to 12 g/min. Dropping of ion-exchanged water was stopped when the liquid amount reached 1400 parts. Thereafter, the solvent was removed under reduced pressure to obtain [Crystalline Polyester Resin Dispersion 4]. The volume average particle size of the obtained crystalline polyester resin particles was 160 nm, and the solid content concentration of the resin particles was 30%.

<Preparation of Crystalline Polyester Resin Dispersion Liquid 5>
45 parts of [Crystalline polyester resin C-4] and 450 parts of ethyl acetate were placed in a vessel equipped with a stirring rod and a thermometer, heated to 80° C. while stirring, and maintained at 80° C. for 5 hours. Cooled to 30 ° C. in 1 hour, using a bead mill (Ultra Visco Mill, Aimex Co., Ltd.), a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, filled with 80% by volume of zirconia beads with a diameter of 0.5 mm, 3 Dispersion was carried out under pass conditions to obtain [Crystalline Polyester Resin Dispersion 5]. The obtained crystalline polyester resin particles had a volume average particle diameter of 340 nm and a solid content concentration of 10%.

<Preparation of Crystalline Polyester Resin Dispersion 6>
45 parts of [Crystalline Polyester Resin C-5] and 450 parts of ethyl acetate were placed in a vessel equipped with a stirring rod and a thermometer, heated to 80° C. while stirring, and maintained at 80° C. for 5 hours. Cooled to 30 ° C. in 1 hour, using a bead mill (Ultra Visco Mill, Aimex Co., Ltd.), a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, filled with 80% by volume of zirconia beads with a diameter of 0.5 mm, 3 Dispersion was carried out under pass conditions to obtain [Crystalline Polyester Resin Dispersion 6]. The obtained crystalline polyester resin particles had a volume average particle diameter of 340 nm and a solid content concentration of 10%.

(Example 1)
<Preparation of oil phase>
[WAX dispersion 1] 50 parts, [amorphous polyester resin A-1] 150 parts, [crystalline polyester resin dispersion 1] 50 parts, [amorphous polyester resin B-1] 750 parts, [masterbatch 1] 50 parts (pigment) were placed in a container and mixed at 5,000 rpm for 60 minutes with a TK homomixer (manufactured by Primix Co., Ltd.) to obtain [oil phase 1].
In addition, the said compounding quantity shows the compounding quantity of the solid content in each raw material.

<Preparation of aqueous phase>
990 parts of water, 20 parts of sodium dodecylsulfate and 90 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This was designated as [aqueous phase 1].

<Emulsification>
20 parts of 28% aqueous ammonia was added to 700 parts of [oil phase 1] while stirring at 8,000 rpm with a TK homomixer, and after mixing for 10 minutes, 1,200 parts of [aqueous phase 1] was gradually added dropwise. Then, [Emulsified slurry 1] was obtained.

<Solvent removal>
[Emulsified slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed for 180 minutes at 30°C to obtain [solvent-free slurry 1].

<aggregation>
100 parts of a 3% magnesium chloride solution was added dropwise to [Slurry 1 for removing the solvent], and the mixture was further stirred for 5 minutes. The aggregation step was terminated to obtain [aggregated slurry 1].

<fusion>
[Aggregated slurry 1] was heated to 70° C. while stirring, and cooled when it reached the desired average circularity of 0.957 to obtain [dispersed slurry 1].

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

<External additive treatment process>
2.0 parts of hydrophobic silica (HDK-2000, manufactured by Clariant Co., Ltd.) as an external additive is mixed with 100 parts of [Toner base particles 1] using a Henschel mixer, and passed through a 500-mesh sieve. , [Toner 1] was obtained.

(Example 2)
In <preparation of oil phase> of Example 1, [amorphous polyester resin A-1] was replaced with [amorphous polyester resin A-2], and [amorphous polyester resin B-1] was added to 800 parts. [Toner 2] was obtained in the same manner as in Example 1, except that [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 2].

(Example 3)
In <preparation of oil phase> of Example 1, [amorphous polyester resin A-1] was replaced with 0 parts, and [amorphous polyester resin B-1] was replaced with [amorphous polyester resin B-2]. Instead, [Crystalline polyester resin dispersion 1] is replaced with [Crystalline polyester resin dispersion 3], [WAX dispersion 1] is replaced with 0 parts, and in <aggregation>, first [WAX dispersion 2] [Toner 3] was obtained in the same manner as in Example 1, except that 40 parts of was added.

(Example 4)
[Toner 4 ] was obtained.

(Example 5)
In <preparation of oil phase> of Example 1, [amorphous polyester resin B-1] was replaced with [amorphous polyester resin B-3], and [crystalline polyester resin dispersion 1] was replaced with 0 parts. , [WAX dispersion 1] was replaced with 0 parts, and in <aggregation>, 50 parts of [crystalline polyester resin dispersion 4] and 50 parts of [WAX dispersion 2] were added. [Toner 5] was obtained in the same manner as above.

(Example 6)
In <preparation of oil phase> of Example 1, [amorphous polyester resin B-1] was replaced with [amorphous polyester resin B-3], and [crystalline polyester resin dispersion 1] was replaced with 100 parts. , [WAX Dispersion 1] was replaced with [WAX Dispersion 3] to obtain [Toner 6] in the same manner as in Example 1.

(Example 7)
In <preparation of oil phase> of Example 1, [amorphous polyester resin A-1] was replaced with [amorphous polyester resin A-3], and [amorphous polyester resin B-1] was replaced with [amorphous In the same manner as in Example 1, except that [WAX Dispersion 1] was replaced with 0 parts instead of [High Quality Polyester Resin B-3], and 50 parts of [WAX Dispersion 2] was first added in <aggregation>. , [Toner 7] was obtained.

(Example 8)
In <preparation of oil phase> of Example 1, [amorphous polyester resin A-1] was replaced with [amorphous polyester resin A-3], and [amorphous polyester resin B-1] was replaced with [amorphous The same as in Example 1, except that [Crystalline Polyester Resin Dispersion 1] was replaced with 130 parts, and [WAX Dispersion 1] was replaced with [WAX Dispersion 3]. to obtain [Toner 8].

(Example 9)
In <preparation of oil phase> of Example 1, [amorphous polyester resin A-1] was replaced with 300 parts, and [amorphous polyester resin B-1] was replaced with [amorphous polyester resin B-2]. Instead, [Crystalline polyester resin dispersion 1] is replaced with [Crystalline polyester resin dispersion 3] 100 parts, [WAX dispersion 1] is replaced with 0 parts, and in <aggregation>, first [WAX dispersion [Toner 9] was obtained in the same manner as in Example 1, except that 40 parts of [2] was added.

(Example 10)
In <preparation of oil phase> of Example 1, [amorphous polyester resin A-1] was replaced with [amorphous polyester resin A-3], and [amorphous polyester resin B-1] was replaced with [non- [Toner 10] was obtained in the same manner as in Example 1, except that the crystalline polyester resin B-2] was used.

(Comparative example 1)
[Toner 11] was prepared in the same manner as in Example 1, except that [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 6] in <Preparation of oil phase> in Example 1. Obtained.

(Comparative example 2)
In <preparation of oil phase> of Example 1, [amorphous polyester resin A-1] was replaced with [amorphous polyester resin A-3], and [amorphous polyester resin B-1] was replaced with [amorphous [Toner 12] was added in the same manner as in Example 1, except that [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 6] 20 parts instead of [Crystalline polyester resin B-3]. Obtained.

(Comparative Example 3)
In <preparation of oil phase> of Example 1, [crystalline polyester resin dispersion 1] was replaced with [crystalline polyester resin dispersion 6], and [WAX dispersion 1] was replaced with [WAX dispersion 3]. Except for this, [Toner 13] was obtained in the same manner as in Example 1.

(Comparative Example 4)
In <preparation of oil phase> of Example 1, [amorphous polyester resin B-1] was replaced with [amorphous polyester resin B-2], 700 parts were replaced with [crystalline polyester resin dispersion 1]. [Toner 14] was obtained in the same manner as in Example 1, except that [Crystalline polyester resin dispersion 5] was used.

(Comparative Example 5)
In <Preparation of Oil Phase> of Example 1, [Crystalline Polyester Resin Dispersion 1] was replaced with [Crystalline Polyester Resin Dispersion 5] 5 parts, and in <Fusing>, the temperature was changed from 70°C to 60°C. [Toner 15] was obtained in the same manner as in Example 1, except that the toner was changed.

(Comparative Example 6)
In <preparation of oil phase> of Example 1, [amorphous polyester resin A-1] was replaced with [amorphous polyester resin A-3], and [amorphous polyester resin B-1] was replaced with [amorphous [Crystalline polyester resin B-3], [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 5], and [WAX dispersion 1] was replaced with [WAX dispersion 3] , [Toner 16] was obtained in the same manner as in Example 1.

(Comparative Example 7)
In <preparation of oil phase> of Example 1, [amorphous polyester resin B-1] was replaced with [amorphous polyester resin B-3], and [crystalline polyester resin dispersion 1] was replaced with [crystalline polyester [Toner 17] was obtained in the same manner as in Example 1, except that [wax dispersion 1] was replaced with [wax dispersion 2] instead of resin dispersion 6].

(Comparative Example 8)
In <preparation of oil phase> of Example 1, [amorphous polyester resin A-1] was replaced with [amorphous polyester resin A-3], and [amorphous polyester resin B-1] was replaced with [amorphous [Crystalline polyester resin B-3], [Crystalline polyester resin dispersion 1] is replaced with 1 part, [WAX dispersion 1] is replaced with [WAX dispersion 3], and in <Fusing>, the temperature is set to 70 [Toner 18] was obtained in the same manner as in Example 1, except that the temperature was changed from °C to 25 °C.

(Comparative Example 9)
Instead of the <emulsification> step of Example 1, add 1,200 parts of [aqueous phase 1] to the container containing [oil phase 1], and mix with a TK homomixer at a rotation speed of 8,000 rpm for 20 minutes. [Emulsified slurry 2] was obtained.
Instead of the step of <solvent removal>, put [Emulsified slurry 2] into a container equipped with a stirrer and a thermometer, remove the solvent at 30°C for 8 hours, and then age at 45°C for 4 hours. , [dispersed slurry 2] was obtained.
No <aggregation> and <fusion> steps.
<Washing/Drying> [Toner 19] was obtained in the same manner as in Example 1.

Table 5 shows the composition of the oil phase components and the characteristics of the aggregation, emulsification, and desolvation steps in Examples and Comparative Examples.

Table 6 shows combinations of major diameter of crystalline polyester, aspect ratio, and ¹⁴ C concentration of radioactive isotope in each toner.

<Method for measuring average length and average aspect ratio of crystalline polyester>
The average major diameter and average aspect ratio of the crystalline polyester of the toner were measured according to the following methods.
The toner was embedded in a visible light curable embedding resin (D-800, manufactured by Nisshin EM), cut to a thickness of 60 nm using an ultrasonic ultramicrotome (EM5, manufactured by Leica), and subjected to a vacuum dyeing apparatus (Filgen). (manufactured) was used for Ru staining. After that, observation was performed with a transmission electron microscope (H7500, manufactured by Hitachi) at an accelerating voltage of 120 kV. As the toner to be observed, 50 particles having a weight average particle diameter within ±2.0 μm were selected and photographed. In the case of the configuration of the present invention, when RuO4 dyeing is performed, the shade of the polyester resin C in the toner is deep, and when wax is used, the wax is projected even darker. The average major diameter and average aspect ratio of the domains made of the polyester resin C can be determined from the observed image, but the average aspect ratio can be calculated using image processing software as necessary.

Image-Pro Plus 5.1J (manufactured by Media Cybernetics) was used as image processing software. A cross-sectional image of a toner particle photographed by the method described above is used. First, a toner particle portion is selected to separate the toner particles and the background portion in order to extract the toner particles for analysis. Select Image-Pro Plus 5.1J "Measurement" - "Count/Size". From the "Count/Size" window, select "Measurement" - "Measurements". Select "Diameter (minimum)" and "Diameter (maximum)" from the measurement items. In the "brightness range selection", it is necessary to adjust the brightness range so that only the polyester resin A is selected. Depending on the RuO ₄ dyeing conditions, the brightness range must be changed each time, but the polyester resin A can be easily distinguished from the above-mentioned difference in shade. Select "Count" to display the measurement results. After that, the obtained "diameter (minimum)" is taken as the minor axis, and the "diameter (maximum)" is taken as the major axis, and the aspect ratio (major axis/minor axis) can be obtained. From the data of the aspect ratio of one toner particle thus obtained, the average value of 10 points in descending order of the diameter (maximum) was obtained, and this was repeated for 10 toner particles to obtain the average value of the aspect ratio.

<Method for measuring radioisotope ¹⁴ C concentration>
The radiocarbon isotope ¹⁴ C concentration of the toner was determined by radiocarbon dating. The toner was burned to reduce its CO ₂ (carbon dioxide) to obtain C (graphite). The ¹⁴ C concentration of the C (graphite) was measured using AMS (Accelerator Mass Spectroscopy, Beta Analytic).

<Evaluation>
The obtained toner was evaluated as follows. The results are shown in Table 7.

<<Carbon Neutrality>>
Carbon neutrality was evaluated based on the radioactive isotope ¹⁴ C concentration of the toner.

〔Evaluation criteria〕
◎: 40.0 pMC or more ○: 20.0 pMC or more and less than 40.0 pMC △: 5.4 pMC or more and less than 20.0 pMC ×: less than 5.4 pMC

<<Low temperature fixability>>
[Developer 1] was obtained by mixing the carrier used in imagio MP C5503 (manufactured by Ricoh Co., Ltd.) and the toner obtained above so that the concentration of the toner was 5% by mass.
After putting [developer 1] into the unit of imagio MP C5503 (manufactured by Ricoh Co., Ltd.), a 2 cm x 15 cm rectangular solid image was applied to PPC paper type 6000 <70W> A4 T-th (manufactured by Ricoh Co., Ltd.). It was formed so that the adhesion amount was 0.40 mg/cm ² . At this time, the surface temperature of the fixing roller was changed to observe whether or not cold offset, in which the undeveloped image of the solid image was fixed in a place other than the desired place, occurred, and the low-temperature fixability was evaluated.

〔Evaluation criteria〕
◎: less than 110°C ○: 110°C or more and less than 120°C △: 120°C or more and less than 130°C ×: 130°C or more

<Cleanability evaluation>
The carrier used in imagio MP C5503 (manufactured by Ricoh Co., Ltd.) and the toner obtained above were mixed so that the concentration of the toner was 5% by mass, to obtain a developer. After the developer is put into a unit of imagio MP C5503 (manufactured by Ricoh Co., Ltd.), an image with an image area ratio of 30% is developed, transferred to transfer paper, and the residual toner remaining on the photoreceptor is cleaned with a cleaning blade. The copier was stopped during the cleaning process, and the residual toner on the photoreceptor that had passed through the cleaning process was transferred to blank paper with Scotch tape (manufactured by Sumitomo 3M Co., Ltd.). Then, the difference between the average value and the measurement result when the tape was simply pasted on the blank paper was obtained and evaluated according to the following criteria.
The cleaning blade used was after cleaning 20,000 sheets.

〔Evaluation criteria〕
◎: Difference is 0.010 or less ○: Difference is over 0.010 and is 0.012 or less △: Difference is over 0.012 and is 0.015 or less ×: Difference is over 0.015

Table 7 shows the evaluation results.

The present invention relates to the toner described in (1) below, and includes the following (2) to (15) as embodiments.
(1) Resin particles containing at least a crystalline polyester resin, an amorphous polyester resin, a release agent, and a colorant,
The acid component of the crystalline polyester resin is a plant-derived dicarboxylic acid having 12 or less carbon atoms,
The average major axis of the domains of the crystalline polyester resin is 2.0 μm or less, and the average aspect ratio (long axis/minor axis) of the domains is 4.0 or more,
A resin particle characterized by having a radioactive carbon isotope ¹⁴ C concentration of 5.4 pMC or more.
(2) The resin particle according to (1) above, which has a radioactive carbon isotope ¹⁴ C concentration of 20.0 pMC or more.
(3) The resin particles according to (1) or (2) above, which have a radioactive carbon isotope ¹⁴ C concentration of 40.0 pMC or more.
(4) The resin particles according to any one of (1) to (3) above, wherein the acid component of the amorphous polyester resin contains either plant-derived succinic acid or sebacic acid.
(5) The resin particles according to any one of (1) to (4) above, wherein the alcohol component of the crystalline polyester resin is a diol having 8 or less carbon atoms.
(6) Any one of (1) to (5) above, wherein the alcohol component of the crystalline polyester resin contains any one of 1,6-hexanediol, 1,8-octanediol, and plant-derived ethylene glycol. The resin particles according to .
(7) The resin particles according to any one of (1) to (6) above, wherein the release agent for the amorphous polyester resin is a plant wax or an ester wax made from a plant-derived material.
(8) Resin particles for toner containing the resin particles according to any one of (1) to (7) above.
(9) A toner containing the resin particles for toner according to (8) above.
(10) The toner according to (9) above, wherein an external additive is further added to the toner resin particles.
(11) a) Step of dissolving or dispersing at least a crystalline polyester resin, an amorphous polyester resin, and a colorant in an organic solvent to prepare an oil phase b) Adding water to the oil phase to obtain water-in-oil phase inversion from a dispersion to an oil-in-water dispersion; c) agglomerating particles of said oil-in-water dispersion;
The method for producing resin particles according to any one of (1) to (8) above, wherein a releasing agent is added in the step a) or the step c).
(12) a) step of preparing an oil phase by dissolving or dispersing at least an amorphous polyester resin and a colorant in an organic solvent; A step of phase inversion to an oil dispersion c) adding a crystalline polyester resin to the oil-in-water dispersion to aggregate the particles,
The method for producing resin particles according to any one of (1) to (8) above, wherein a release agent is added in the step a) or the step c).
(13) A method for producing a toner, which comprises adding an external additive to the resin particles obtained by the method for producing resin particles according to (11) or (12) above.
(14) A developer containing the toner described in (9) or (10) above.
(15) A toner containing unit containing the toner described in (9) or (10) above.
(16) An electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier. a developing means comprising toner for developing the image to form a visible image;
An image forming apparatus, wherein the toner is the toner described in (9) or (10) above.

10 Photoreceptor, photoreceptor drum, electrostatic latent image carrier 10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 support roller 15 support roller 16 support roller 17 intermediate transfer member cleaning device 18 image forming means 20 charging device (charging roller)
21 exposure device 22 secondary transfer device 23 roller 24 secondary transfer belt 25 fixing device 26 fixing belt 27 pressure roller 28 sheet reversing device 30 exposure device 32 contact glass 33 first traveling body 34 second traveling body 35 imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer accommodating portion 42Y Developer accommodating portion 42M Developer accommodating portion 42C Developer accommodating portion 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development Roller 44Y Developing roller 44M Developing roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection roller 57 Ejection tray 58 Corona charger 60 Cleaning device 61 Developing device 62 Transfer charger 63 Photoreceptor cleaning device 64 Eliminating device 70 Eliminating lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A, 100B, 100C Image forming device 110 Process Cartridge 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier body 160 Charging device 200 Paper feed table 300 Scanner 400 Automatic document Conveyor (ADF)
L exposure

Japanese Patent No. 3343635 Japanese Patent No. 2909873 Japanese Patent No. 5473252 Japanese Patent No. 5984528 JP 2018-072454 A

Claims (16)

Resin particles containing at least a crystalline polyester resin, an amorphous polyester resin, a release agent, and a colorant,
The acid component of the crystalline polyester resin is a plant-derived dicarboxylic acid having 12 or less carbon atoms,
The average major axis of the domains of the crystalline polyester resin is 2.0 μm or less, and the average aspect ratio (long axis/minor axis) of the domains is 4.0 or more,
A resin particle characterized by having a radioactive carbon isotope ¹⁴ C concentration of 5.4 pMC or more. 2. The resin particles according to claim 1, wherein the radioactive carbon isotope ^14C concentration is 20.0 pMC or more. 3. The resin particles according to claim 1, wherein the radioactive carbon isotope ¹⁴ C concentration is 40.0 pMC or more. 4. The resin particles according to any one of claims 1 to 3, wherein the acid component of the amorphous polyester resin contains either plant-derived succinic acid or sebacic acid. 5. The resin particles according to any one of claims 1 to 4, wherein the alcohol component of the crystalline polyester resin is a diol having 8 or less carbon atoms. 6. The resin particles according to any one of claims 1 to 5, wherein the alcohol component of the crystalline polyester resin contains any one of 1,6-hexanediol, 1,8-octanediol, and plant-derived ethylene glycol. 7. The resin particles according to any one of claims 1 to 6, wherein the releasing agent for the amorphous polyester resin is a plant wax or an ester wax made from a plant-derived material. Resin particles for a toner, comprising the resin particles according to claim 1 . A toner comprising the toner resin particles according to claim 8 . 10. The toner according to claim 9, wherein an external additive is further added to the toner resin particles. a) Step of preparing an oil phase by dissolving or dispersing at least a crystalline polyester resin, an amorphous polyester resin, and a colorant in an organic solvent b) Adding water to the oil phase to obtain a water-in-oil dispersion to an oil-in-water dispersion, c) agglomerating particles of the oil-in-water dispersion,
9. The method for producing resin particles according to any one of claims 1 to 8, wherein a release agent is added in said step a) or said step c). a) a step of preparing an oil phase by dissolving or dispersing at least an amorphous polyester resin and a colorant in an organic solvent; b) adding water to the oil phase to convert from a water-in-oil dispersion to an oil-in-water dispersion; c) adding a crystalline polyester resin to the oil-in-water dispersion to agglomerate the particles;
9. The method for producing resin particles according to any one of claims 1 to 8, wherein a release agent is added in said step a) or said step c). 13. A method for producing a toner, comprising adding an external additive to the resin particles obtained by the method for producing resin particles according to claim 11 or 12. A developer comprising the toner according to claim 9 or 10. A toner containing unit containing the toner according to claim 9 or 10. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and development of the electrostatic latent image formed on the electrostatic latent image carrier. a developing means comprising toner for forming a visible image;
An image forming apparatus, wherein the toner is the toner according to claim 9 or 10.

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