JP2021012241A - Method of manufacturing electrostatic image development toner - Google Patents

Abstract

To provide a method of manufacturing an electrostatic image development toner which offers high image density.SOLUTION: A method of manufacturing an electrostatic image development toner is provided, the method comprising a step of agglutinating and fusing binder resin particles, mold release agent particles, and colorant particles in an aqueous medium. The mold release agent particles contain a mold release agent and an amorphous polyester resin E comprising a constituent derived from a polyester resin F and a constituent derived from a modified polyisobutene polymer G having a reactive functional group, where the constituent derived from the polyester resin F and the constituent derived from the modified polyisobutene polymer G are linked together via a covalent bond.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a toner for developing an electrostatic charge image used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

In the field of electrophotographic, with the development of electrophotographic systems, the development of toners for electrophotographics corresponding to high image quality and high speed is required. As a method for obtaining toner having a narrow particle size distribution and a small particle size in response to higher image quality, a coagulation fusion method (emulsification) in which fine resin particles and the like are aggregated and fused in an aqueous medium to obtain toner. The so-called chemical toner is produced by the agglomeration method and the agglomeration union method).

A subject of Patent Document 1 is to provide a toner for electrostatic charge image development capable of obtaining a toner having a small amount of desorption of a release agent and excellent heat-resistant storage stability, and step (1): mold release. A step of mixing the agent and the aqueous dispersion of the resin particles (A) and emulsifying them to obtain an aqueous dispersion of the release agent particles, Step (2): The release agent particles obtained in the step (1). A step of mixing and aggregating the aqueous dispersion of the resin particles (B) and the aqueous dispersion of the resin particles (B) to obtain agglomerated particles, and a step (3): fusing the agglomerated particles obtained in the step (2). A method for producing static charge image developing toner, which comprises a step of obtaining fused particles, wherein the resin particles (A) contain a polyester resin (X), and the polyester resin (X) contains a hydroxyl group or a carboxy group. Manufacture of a toner for static charge image development, which is a polyester resin containing a constituent component derived from the hydrocarbon wax and has a volume average particle diameter (DV) of the resin particles (A) of 0.01 μm or more and 1.0 μm or less. The method is described.

Japanese Unexamined Patent Publication No. 2018-11986

With the toner for static charge image development described in Patent Document 1, it has been difficult to obtain a printed matter having excellent image density.
The present invention relates to a method for producing a toner for static charge image development, which can obtain a high image density.

The present inventors have provided mold release agent particles containing a mold release agent, an amorphous polyester resin E having a constituent site derived from the modified polyisobutene polymer G, and binder resin particles and colorant particles. It has been found that a static charge image developing toner capable of obtaining a high image density can be obtained by aggregating and fusing in an aqueous medium.
The present invention relates to the following [1].
[1] A method for producing a toner for static charge image development, which comprises a step of aggregating and fusing the binder resin particles, the release agent particles and the colorant particles in an aqueous medium, wherein the release agent particles are A modified polyisobutene polymer G containing a release agent and an amorphous polyester resin E, wherein the amorphous polyester resin E is derived from a constituent site derived from the polyester resin F and a reactive functional group. A method for producing a toner for static charge image development, which has a constituent portion, and the constituent portion derived from the polyester resin F and the constituent portion derived from the modified polyisobutene polymer G are connected via a covalent bond.

According to the present invention, there is provided a method for producing a toner for developing an electrostatic charge image, which can obtain a high image density.

[Manufacturing method of toner for static charge image development]
The method for producing a toner for static charge image development of the present invention (hereinafter, also simply referred to as “toner”) involves a step of aggregating and fusing binder resin particles, mold release agent particles, and colorant particles in an aqueous medium. Including.
The release agent particles contain a release agent and an amorphous polyester resin E (hereinafter, also simply referred to as "resin E"). The amorphous polyester resin E has a constituent portion derived from the polyester resin F and a constituent portion derived from the modified polyisobutene polymer G having a reactive functional group, and the constituent portion derived from the polyester resin F. And the constituent site derived from the modified polyisobutene polymer G are linked via a covalent bond.
By the above manufacturing method, a toner capable of obtaining a high image density can be obtained.

The detailed mechanism of action for obtaining the above effects is unknown, but some are thought to be as follows.
In the present invention, the amorphous polyester resin E having a polyisobutene moiety has a high affinity with the release agent, is easily adsorbed on the surface of the release agent, and the dispersion stability of the release agent particles in an aqueous medium. Is expected to improve. As a result, it is considered that the agglomeration of the release agent particles is suppressed, the dispersibility of the release agent in the toner is improved, and the release agent particles are finely dispersed. Since the colorant also has a relatively high affinity with the release agent, the pigment can be finely dispersed in the toner as the release agent is finely dispersed, and the dispersion stability in the toner is improved. Conceivable. As a result, it is considered that a toner having high coloring power can be obtained and a high image density can be obtained.
The above mechanism regarding the effect of the present invention is a presumption and is not limited to this.

Definitions of various terms in the present specification are shown below.
In the specification, the carboxylic acid component of the polyester resin includes not only the compound but also an anhydride that decomposes during the reaction to produce a carboxylic acid, and an alkyl ester of each carboxylic acid (alkyl group having 1 or more carbon atoms and 3 carbon atoms). The following) is also included.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (° C.) / maximum endothermic peak temperature (° C.)) in the measurement method described in Examples described later. The crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins have a crystallinity index of less than 0.6 or more than 1.4. The crystallinity index can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
With respect to hydrocarbon groups, the parenthesized statements "(iso or tertiary)" and "(iso)" mean both with and without these prefixes, and without these prefixes. If the case is normal.
"(Meta) acrylic acid" means at least one selected from acrylic acid and methacrylic acid.
"(Meta) acrylate" means at least one selected from acrylate and methacrylate.
"(Meta) acryloyl group" means at least one selected from acryloyl group and methacryloyl group.
"Styrene-based compound" means unsubstituted or substituted styrene.
The "main chain" means the relatively longest bound chain in the addition polymer.

The method for producing a toner according to an embodiment of the present invention is, for example, a step of aggregating binder resin particles, a mold release agent particle, and a colorant particle in an aqueous medium to obtain agglomerated particles (hereinafter, also referred to as “step 1”). ) And the step of fusing the agglomerated particles in an aqueous medium (hereinafter, also referred to as “step 2”).
including.
Further, in the present invention, before the step 1, the release agent and the aqueous dispersion of the amorphous polyester resin E are mixed and emulsified to obtain an aqueous dispersion of the release agent particles (hereinafter,). , Also referred to as “step 1-1”).
Hereinafter, the present invention will be described by taking the embodiment as an example.

<Process 1-1>
In the present invention, there is a step (step 1-1) of mixing the release agent and the aqueous dispersion of the amorphous polyester resin E and emulsifying them to obtain the aqueous dispersion of the release agent particles. preferable.
In step 1-1, the release agent is dispersed with the amorphous polyester resin E to obtain a release agent particle dispersion liquid. By preparing the release agent particles using the release agent and the particles of the amorphous polyester resin E, the release agent is stabilized by the amorphous polyester resin E particles, and no surfactant is used. However, the release agent can be stably dispersed in the aqueous medium. In the dispersion liquid of the release agent particles, the particles of the amorphous polyester resin E adhere to the periphery of the release agent, so that a large number of amorphous polyester resin E adheres to the surface of the release agent particles. Is considered to have.

(Release agent particles)
The release agent particles contain a release agent and an amorphous polyester resin E.
〔Release agent〕
Examples of the release agent include wax. Examples of the wax include hydrocarbon wax, ester wax, silicone wax, and fatty acid amide wax.
Examples of the hydrocarbon wax include minerals such as paraffin wax and Fishertropsh wax or petroleum-based hydrocarbon wax; synthetic hydrocarbon wax such as polyolefin wax such as polyethylene wax, polypropylene wax and polybutene wax.
Examples of the ester wax include minerals such as Montan wax or petroleum-based ester wax; plant-based ester wax such as carnauba wax, rice wax and candelilla wax; and animal-based ester wax such as beeswax.
Examples of the fatty acid amide wax include oleic acid amide and stearic acid amide.
Among these, from the viewpoint of toner releasability, at least one selected from hydrocarbon wax or ester wax, more preferably hydrocarbon wax, further preferably paraffin wax, Fishertropch wax, and polyolefin wax, further It is preferably at least one selected from paraffin wax and Fishertroph wax.

From the viewpoint of toner releasability, the melting point of the release agent is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C. or higher, and improves the low temperature fixability of the toner to fix it. From the viewpoint of widening the possible temperature range, it is preferably 100 ° C. or lower, more preferably 95 ° C. or lower. When two or more mold release agents are used in combination, the melting points of both are preferably 60 ° C. or higher and 100 ° C. or lower. That is, when two or more types of mold release agents are used in combination, it is preferable to contain at least two types of mold release agents having a melting point of 60 ° C. or higher and 100 ° C. or lower, and the melting point of each mold release agent is 65 ° C. or higher and 95 ° C. The following is more preferable.
In the present invention, the melting point of the release agent is determined by the method described in Examples. When two or more types of release agents are used in combination, the melting point of the release agent having the largest mass ratio among the release agents contained in the obtained toner is defined as the melting point of the release agent in the present invention. When all have the same mass ratio, the melting point of the release agent having the lowest melting point is defined as the melting point of the release agent in the present invention.

From the viewpoint of mold release property of the toner, the amount of the release agent used is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the resin in the toner. It is more preferably 8 parts by mass or more, and from the viewpoint of improving the dispersion stability of the release agent and improving the image density, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably. It is 12 parts by mass or less.

[Amorphous polyester resin E]
The amorphous polyester resin E (resin E) has a constituent portion derived from the polyester resin F and a constituent moiety derived from the modified polyisobutene polymer G having a reactive functional group, and the constituent moiety derived from the polyester resin F ( Hereinafter, the constituent site (also referred to as “constituent site F”) and the constituent site derived from the modified polyisobutene polymer G (hereinafter, also referred to as “constituting site G”) are linked via a covalent bond.
Examples of the covalent bond include an ester bond, an ether bond, an amide bond, a urethane bond, and a bond having these bonds and a linking group.
Examples of the linking group include a divalent or higher hydrocarbon group having 1 or more and 6 or less carbon atoms. Examples of the linking group include a methylene group, an ethylene group, a propylene group, a phenylene group and the like.
Among these, it is preferable that the constituent parts F and the constituent parts G are directly connected by an ester bond, and it is preferable that the constituent parts F and the constituent parts G are directly connected by an ester bond.

≪Polyester resin F≫
The amorphous polyester resin E has a constituent portion derived from the polyester resin F. Here, the "constituent portion derived from the polyester resin F" is derived from the polyester resin F in which a part of the polyester resin F in the amorphous polyester resin E is bonded to other atomic groups. It is a partial structure.
Examples of the polyester resin include a polyester resin and a modified polyester resin. Examples of the modified polyester resin include a urethane modified product of a polyester resin, an epoxy modified product of a polyester resin, and a composite resin containing a polyester resin segment and an addition polymerization resin segment. Among these, the polyester resin F is preferably a polyester resin, a composite resin, and more preferably a composite resin.
The composite resin is, for example, an alcohol having an aromatic group, preferably a polyester resin segment which is a polycondensate of an alcohol component containing an alkylene oxide addition of an aromatic diol and a carboxylic acid component, and a raw material monomer containing a styrene compound. It contains an addition polymerization resin segment which is an addition polymerization, and a structural unit derived from a bireactive monomer in which the polyester resin segment and the addition polymerization resin segment are bonded via a covalent bond.
The polyester resin F is preferably amorphous.

The polyester resin is, for example, a polycondensate of an alcohol component and a carboxylic acid component.
Examples of the alcohol component include an alkylene oxide adduct of an aromatic diol, a linear or branched aliphatic diol, an alicyclic diol, and a trihydric or higher polyhydric alcohol.
As the alkylene oxide adduct of the aromatic diol, the formula (I):

(In the formula, OR and RO are oxyalkylene groups, R is an ethylene or propylene group independently, and x and y indicate the average adduct number of alkylene oxides, which are positive numbers, respectively, x and y. The value of the sum of is 1 or more, preferably 1.5 or more, 16 or less, preferably 8 or less, more preferably 4 or less), and preferably contains an alkylene oxide adduct of bisphenol A. ..
Examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include a propylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane and an ethylene oxide of 2,2-bis (4-hydroxyphenyl) propane. Additives and the like can be mentioned. One or more of these may be used.
When an alkylene oxide adduct of bisphenol A represented by the formula (I) is used as the alcohol component, the content thereof is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 80 mol% or more in the alcohol component. Is 90 mol% or more, more preferably 95 mol% or more, and 100 mol% or less, still more preferably 100 mol%.

Examples of the linear or branched aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 2,3-Butanediol, 2,2-dimethyl-1,3-Propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1, , 12-Dodecanediol, neopentyl glycol, 1,4-butenediol. Among these, an aliphatic diol having 3 or 4 carbon atoms having a hydroxy group bonded to a secondary carbon atom is preferable. Specific examples thereof include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol. From the viewpoint of improving the image density, 1,2-propanediol is used. And 2,3-butanediol are preferred, and 1,2-propanediol is more preferred.
Examples of the alicyclic diol include hydrogenated bisphenol A [2,2-bis (4-hydroxycyclohexyl) propane] and alkylene oxide adducts having 2 or more and 4 or less carbon atoms of hydrogenated bisphenol A (average addition molar number 2). 12 or less).
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
As these alcohol components, one kind or two or more kinds may be used.
When the alkylene oxide adduct of bisphenol A represented by the formula (I) is not used as the alcohol component, the content of the linear or branched aliphatic diol is preferably 70 mol% or more in the alcohol component. It is more preferably 80 mol% or more, further preferably 90 mol% or more, further preferably 95 mol% or more, and 100 mol% or less, still more preferably 100 mol%.

Examples of the carboxylic acid component include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, and trivalent or higher carboxylic acid compounds.
Among these, the carboxylic acid component preferably contains an aromatic dicarboxylic acid compound from the viewpoint of further improving the image density.
Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, and terephthalic acid. Among these, at least one selected from terephthalic acid and isophthalic acid is more preferable, and terephthalic acid is further preferable, from the viewpoint of low-temperature fixability.
The content of the aromatic dicarboxylic acid compound is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 60 mol% or more, still more preferably 80 mol% or more in the carboxylic acid component from the viewpoint of low temperature fixability. % And less, and less than 100 mol%.

The aliphatic dicarboxylic acid compound may be substituted with, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Aliphatic dicarboxylic acids such as succinic acid and adipic acid can be mentioned.
Examples of the succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include octyl succinic acid and dodecenyl succinic acid (tetrapropenyl succinic acid).
Of these, fumaric acid is preferable.
The content of the aliphatic dicarboxylic acid compound is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, and 0 mol% or more in the carboxylic acid component from the viewpoint of image concentration. It is preferably 0 mol%.

Examples of the trivalent or higher valent carboxylic acid compound include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. Among these, trimellitic acid and its anhydride are preferable.
The content of the trivalent or higher carboxylic acid compound is preferably 60 mol% or less, more preferably 30 mol% or less, still more preferably 10 mol% or less from the viewpoint of mold release agent dispersibility in the carboxylic acid component. , 0 mol% or more.
The alcohol component may contain a monohydric alcohol, and the carboxylic acid component may appropriately contain a monovalent carboxylic acid compound.

The ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less. It is preferably 1.2 or less.

When the polyester resin F is a composite resin, the polyester resin segment is the above-mentioned polyester resin from the viewpoint of obtaining a toner having excellent image density.
When the polyester resin F is a composite resin, the addition polymerization resin segment is an addition polymerization of a raw material monomer containing a styrene compound from the viewpoint of improving the image density by improving the dispersibility of the release agent.
Examples of the styrene-based compound include unsubstituted or substituted styrene. Examples of the substituent substituted with styrene include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfo group or a salt thereof.
Examples of the styrene-based compound include styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or a salt thereof. Of these, styrene is preferable.
The content of the styrene-based compound in the raw material monomer of the addition polymerization resin segment is preferably 50% by mass or more, more preferably 65% by mass or more, further preferably 80% by mass or more, and 100% by mass or less. It is preferably 98% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.

Examples of raw material monomers other than styrene compounds include (meth) acrylic acid esters such as alkyl (meth) acrylate, benzyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate; ethylene, propylene, and butadiene. Olefins; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as vinyl methyl ether; vinylidene halide such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone. Be done. Among these, (meth) acrylic acid ester is preferable, and alkyl (meth) acrylic acid is more preferable.
The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 24 or less, from the viewpoint of obtaining a better image density. It is more preferably 18 or less, still more preferably 12 or less.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, and (meth). ) Acrylic acid (iso) amyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid ( Examples thereof include iso) dodecyl, (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, and (meth) acrylic acid (iso) behenyl. Among these, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate are preferable, and 2-ethylhexyl (meth) acrylate, (meth) acrylic acid. Dodecyl and stearyl (meth) acrylate are more preferable, 2-ethylhexyl (meth) acrylate is more preferable, and 2-ethylhexyl acrylate is even more preferable.

The content of the (meth) acrylic acid ester in the raw material monomer of the addition polymerization resin segment is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 50% by mass or more. It is mass% or less, more preferably 35 mass% or less, still more preferably 20 mass% or less.

The total amount of the styrene compound and the (meth) acrylic acid ester in the raw material monomer of the addition polymerization resin segment is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably. Is 100% by mass.

When the polyester resin F is a composite resin, the composite resin preferably has a structural unit derived from a bireactive monomer bonded to the polyester resin segment and the addition polymerization resin segment via a covalent bond.
The “constituent unit derived from a bireactive monomer” means a unit in which the functional group and the unsaturated bond site of the bireactive monomer have reacted.
Examples of the bireactive monomer include an addition-polymerizable monomer having at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule. .. Among these, from the viewpoint of reactivity, an addition-polymerizable monomer having at least one functional group selected from a hydroxyl group and a carboxy group is preferable, and an addition-polymerizable monomer having a carboxy group is more preferable.
Examples of the addition-polymerizable monomer having a carboxy group include acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable, from the viewpoint of reactivity of both the polycondensation reaction and the addition polymerization reaction.
The amount of the structural unit derived from both reactive monomers is preferably 1 mol part or more, more preferably 3 mol parts or more, still more preferably 5 mol parts or more, based on 100 mol parts of the alcohol component of the polyester resin segment of the composite resin. And preferably 30 mol parts or less, more preferably 20 mol parts or less, still more preferably 10 mol parts or less.

When the polyester resin F is a composite resin, the preferable range of the content of each component is as follows.
The content of the polyester resin segment in the composite resin is preferably 40% by mass or more, more preferably 55% by mass, based on the total amount of the polyester resin segment, the addition polymerization resin segment, and the structural units derived from the bireactive monomers. As mentioned above, it is more preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less.

The content of the addition polymerization resin segment in the composite resin is preferably 5% by mass or more, more preferably 10% by mass, based on the total amount of the polyester resin segment, the addition polymerization resin segment, and the structural units derived from the bireactive monomers. % Or more, more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 25% by mass or less.

The amount of the structural unit derived from the bireactive monomer in the composite resin is preferably 0.1% by mass or more with respect to the total amount of the structural unit derived from the polyester resin segment, the addition polymerized resin segment, and the bireactive monomer. It is more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

The total amount of the constituent units derived from the polyester resin segment, the addition polymerization resin segment and the bireactive monomer in the composite resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more. And, it is 100% by mass or less, and more preferably 100% by mass.

The above amount is calculated based on the ratio of the amounts of the polyester resin segment, the raw material monomer of the addition polymerization resin segment, the bireactive monomer, and the radical polymerization initiator, and excludes the amount of dehydration due to polycondensation in the polyester resin segment and the like. When a radical polymerization initiator is used, the mass of the radical polymerization initiator is included in the addition polymerization resin segment for calculation.

≪Modified polyisobutene polymer G≫
The amorphous polyester resin E has a constituent site derived from the modified polyisobutene polymer G.
In addition, polyisobutene is synonymous with polyisobutylene.
The modified polyisobutene polymer G has a reactive functional group. Examples of the reactive functional group include a carboxylic acid group, an anhydrous carboxylic acid group, a hydroxy group, an epoxy group, and an isocyanate group. Among these, a carboxylic acid group or an anhydrous carboxylic acid group is preferable. That is, the modified polyisobutene polymer G is at least one selected from a carboxylic acid-modified polyisobutene polymer and an anhydrous carboxylic acid-modified polyisobutene polymer (hereinafter, these are collectively referred to as “acid-modified polyisobutene polymer”). It is preferable to have.
As the modified polyisobutene polymer G, a random graft type acid-modified product obtained by randomly grafting and modifying an acid on the polyisobutene polymer may be used.
The acid-modified polyisobutene polymer is preferably an acid-modified product in which polyisobutene (preferably the main chain terminal of polyisobutene) is modified with a carboxylic acid compound, and the carboxylic acid compound includes maleic acid, fumaric acid, and itaconic acid. , Isocrotonic acid, their anhydrides, or alkyl esters having 1 or more and 3 or less carbon atoms in the alkyl group. Among these, as the carboxylic acid compound, maleic acid, itaconic acid, isocrotonic acid, and anhydrides thereof are preferable, and polyisobutene modified with maleic anhydride is more preferable.

The end-modified polyisobutene polymer is preferably one molecule modified with one (one-ended) or two (both-ended) acids per molecule of the polyisobutene polymer. For example, in the case of a one-terminal acid denatured product with maleic anhydride, when modified with maleic anhydride, the double bond of maleic anhydride changes to a single bond, so by measuring the spectral change, maleic anhydride can be obtained. You can confirm that it has been introduced. Further, since the connected portion of the polyisobutene polymer also undergoes a spectral change before and after the introduction of maleic anhydride, it may be defined by measuring this.
The one-terminal acid-modified product is obtained by subjecting a polyisobutene polymer having an unsaturated bond at one end to an Ene reaction with a carboxylic acid compound having an unsaturated bond or an anhydride thereof. A polyisobutene polymer having an unsaturated bond at one end can be obtained by a known method, and can be produced, for example, by using a vanadium-based catalyst, a titanium-based catalyst, a zirconium-based catalyst, or the like.

Among these, polyisobutene having one end modified with maleic anhydride is preferable from the viewpoint of reactivity. That is, the acid-modified polyisobutene polymer is preferably a maleic anhydride-modified polyisobutene polymer. By modifying polyisobutene having an unsaturated bond at one end with maleic anhydride, a polyisobutene polymer in which succinic anhydride is introduced at one end can be obtained.
When the succinic anhydride moiety is introduced by modifying the polyisobutene polymer with maleic anhydride, the constituent moieties derived from one or two polyester-based resin F can be linked via an ester bond. In particular, by using a maleic anhydride-terminated polyisobutene polymer, it has a structure in which one or two, preferably two polyester-based resin F-derived constituent portions are connected by the succinic anhydride moiety at the terminal of the polyisobutene polymer. It is considered that the amorphous polyester resin E can be obtained. Therefore, it is considered that the image density is further improved by using the polyisobutene polymer modified with maleic anhydride.

The acid value of the modified polyisobutene polymer G is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 100 mgKOH / g or less, still more preferably 80 mgKOH / g or less, from the viewpoint of further improving the image density. Yes, and preferably 0.1 mgKOH / g or more, more preferably 1 mgKOH / g or more, still more preferably 10 mgKOH / g or more, still more preferably 30 mgKOH / g or more.

The weight average molecular weight of the modified polyisobutene polymer G is preferably 300 or more, more preferably 500 or more, still more preferably 700 or more, and preferably 50,000 or less, more preferably, from the viewpoint of further improving the image density. Is 30,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less, still more preferably 8,000 or less.
The weight average molecular weight is measured by gel permeation chromatography using polystyrene as a standard sample.

The amount of the constituent part derived from the modified polyisobutene polymer G in the amorphous polyester resin E is an image with respect to a total of 100 parts by mass of the alcohol component and the carboxylic acid component forming the constituent part derived from the polyester resin F. From the viewpoint of further improving the concentration, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, further preferably 7 parts by mass or more, still more preferably 8 parts by mass or more, and It is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less.
Regarding the above amount, the amount of dehydration of the alcohol component and the carboxylic acid component shall not be considered.

<< Manufacturing method of amorphous polyester resin E >>
In the present invention, the amorphous polyester resin E is, for example,
(A) Obtained by polycondensing a raw material monomer containing an alcohol component and a carboxylic acid component in the presence of the modified polyisobutene polymer G, or (b) reacting the modified polyisobutene polymer G with the polyester resin F. can get.
Examples of the above reaction include dehydration condensation and transesterification reaction.
The reaction conditions are preferably conditions in which the carboxylic acid group or anhydrous carboxylic acid group of the modified polyisobutene polymer G is dehydrated and condensed or transesterified with an alcohol component, a carboxylic acid component, or the like.
More specifically, as a method for obtaining the amorphous polyester resin E, for example,
(I) The modified polyisobutene polymer G is present from the initial stage of the reaction, and the raw material monomer containing the alcohol component and the carboxylic acid component is polycondensed.
(Ii) A modified polyisobutene polymer G is allowed to exist from the middle of the reaction, and a raw material monomer containing an alcohol component and a carboxylic acid component is polycondensed.
(Iii) A modified polyisobutene polymer G is present after polycondensation of a raw material monomer containing an alcohol component and a carboxylic acid component.
(Iv) The polyester resin F is melted by heating to allow the modified polyisobutene polymer G to be present under the conditions of a temperature of 180 ° C. or higher and 250 ° C. or lower.
The method can be mentioned.
Among these, the method (ii) is preferable from the viewpoint of ease of manufacture.

The polycondensation of the alcohol component and the carboxylic acid component should be carried out in an inert gas atmosphere, for example, in the presence of an esterification catalyst, a polymerization inhibitor, etc., at a temperature of about 150 ° C. or higher and 250 ° C. or lower. Can be done.
Examples of the esterification catalyst include tin compounds such as dibutyl tin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropoxybis (triethanolaminate). Examples of the esterification co-catalyst that can be used together with the esterification catalyst include gallic acid.
The amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component which are the raw materials of the amorphous polyester resin F. It is more than parts by mass, and preferably 1 part by mass or less, more preferably 0.6 parts by mass or less.
The amount of the esterification co-catalyst used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.01 part by mass or more, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is 0.5 parts by mass or less, more preferably 0.1 parts by mass or less.
When a polyisobutene polymer whose terminal is modified with maleic anhydride is used, one or two, preferably two, polyester-based resin F-derived constituent sites can be linked via an ester bond. Therefore, the image density can be further improved.

When the polyester resin F is a composite resin, for example, a step a of performing a polycondensation reaction with an alcohol component and a carboxylic acid component, and a step b of performing an addition polymerization reaction with a raw material monomer and a bireactive monomer of an addition polymerization resin segment. It may be manufactured by a method including.
The step b may be performed after the step a, the step a may be performed after the step b, or the step a and the step b may be performed at the same time.
In step a, a part of the carboxylic acid component is subjected to a polycondensation reaction, then step b is carried out, and then the rest of the carboxylic acid component is added to the polymerization system, and the polycondensation reaction of step a and both reactions if necessary. A method of further advancing the reaction with the sex monomer is more preferable. Further, the modified polyisobutene polymer G may be added in any of the above steps, but in step a, a part of the carboxylic acid component is subjected to a polycondensation reaction, and then step b is carried out, and then the modified polyisobutene polymer G is added. A method of adding the isobutylene polymer G and further adding the rest of the carboxylic acid component to the polymerization system to further advance the polycondensation reaction and the like is preferable.

Examples of the polymerization initiator for the addition polymerization reaction include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile). Can be mentioned.
The amount of the polymerization initiator used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw material monomer of the addition polymerization resin segment.
The temperature of the addition polymerization reaction is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, further preferably 150 ° C. or higher, and preferably 280 ° C. or lower, more preferably 250 ° C. or lower, still more preferably 200 ° C. or higher. It is as follows.

≪Physical characteristics of amorphous polyester resin E≫
The softening point of the amorphous polyester resin E is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher, still more preferably 105 ° C. or higher, from the viewpoint of increasing the image density. Then, from the viewpoint of further improving the low temperature fixability, the temperature is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, and further preferably 115 ° C. or lower.

The glass transition temperature of the amorphous polyester resin E is preferably 40 ° C. or higher, more preferably 45 ° C. or higher from the viewpoint of further improving the storage stability, and preferably from the viewpoint of further improving the low temperature fixability. Is 75 ° C. or lower, more preferably 65 ° C. or lower, still more preferably 55 ° C. or lower.

The acid value of the amorphous polyester resin E is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, and preferably 60 mgKOH / g or less, more preferably 50 mgKOH or less. / G or less, more preferably 40 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the resin E can be appropriately adjusted according to the type and amount of the raw material monomer used, and the production conditions such as the reaction temperature, reaction time, and cooling rate, and their values. Is determined by the method described in the examples.
Regarding the above-mentioned physical properties of the amorphous polyester resin E, when the amorphous polyester resin E contains two or more kinds of amorphous polyester resins E, their weighted average values are within the above range. Is preferable.

<< Amorphous polyester resin E aqueous dispersion P and its manufacturing method >>
The aqueous dispersion P of the amorphous polyester resin E is a resin particle (E) containing the amorphous polyester resin E in which the resin containing the amorphous polyester resin E described above is dispersed in an aqueous medium. (Aqueous dispersion liquid P).
The water-based medium preferably contains water as a main component, and the content of water in the water-based medium is preferable from the viewpoint of improving the dispersion stability of the dispersion liquid of the resin particles (E) and from the viewpoint of environmental friendliness. Is 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and 100% by mass or less, still more preferably 100% by mass. As the water, deionized water or distilled water is preferable. Examples of components other than water that can be contained in the aqueous medium include alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 total carbon atoms such as acetone and methyl ethyl ketone; and water such as cyclic ethers such as tetrahydrofuran. Examples include soluble organic solvents. Among these, methyl ethyl ketone is preferable.

The dispersion can be carried out by a known method, but it is preferably dispersed by a phase inversion emulsification method. Examples of the phase inversion emulsification method include a method in which an aqueous medium is added to an organic solvent solution of a resin or a molten resin for phase inversion emulsification. A method of adding an aqueous medium to the organic solvent solution of the resin and transferring emulsification is preferable.
The organic solvent used for phase inversion emulsification is not particularly limited as long as the resin is dissolved, and examples thereof include methyl ethyl ketone.
It is preferable to add a neutralizing agent to the organic solvent solution. Examples of the neutralizing agent include basic substances. Examples of the basic substance include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine. Among these, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide are preferable.
The degree of neutralization of the resin contained in the resin particles (E) is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, still more preferably 40 mol% or more, and It is preferably 100 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less.
The degree of neutralization of the resin contained in the resin particles (E) can be calculated by the following formula.
Degree of neutralization (mol%) = [{mass added with neutralizing agent (g) / equivalent of neutralizing agent} / [{weighted average acid value (mgKOH / g) of resin constituting resin particles (E) x resin Mass of resin constituting particle (E) (g)} / (56 × 1000)]] × 100

While stirring the organic solvent solution or the molten resin, an aqueous medium is gradually added to invert the phase.
The temperature of the organic solvent solution when the aqueous medium is added is preferably equal to or higher than the glass transition temperature of the amorphous polyester resin E constituting the resin particles (E) from the viewpoint of improving the dispersion stability of the resin particles (E). , More preferably 60 ° C. or higher, still more preferably 65 ° C. or higher, further preferably 70 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower.

After the phase inversion emulsification, if necessary, the organic solvent may be removed from the obtained dispersion by distillation or the like. In this case, the residual amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably substantially 0% by mass in the dispersion liquid.

The volume median particle diameter D ₅₀ of the resin particles (E) in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, and is preferably 0.08 μm or more, from the viewpoint of obtaining a toner that can obtain a high-quality image. It is preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.3 μm or less.
The CV value of the resin particles (E) in the dispersion is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, from the viewpoint of obtaining a toner that can obtain a high-quality image. More preferably, it is 30% or less.

The solid content concentration of the aqueous dispersion P of the resin particles (E) is preferably 5 mass from the viewpoint of improving the productivity of the toner and improving the dispersion stability of the aqueous dispersion P of the resin particles (E). % Or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 25. It is mass% or less.
The solid content is the total amount of non-volatile components.

[Manufacture of release agent particle dispersion W]
The release agent particle dispersion W is, for example, a homogenizer or a high-pressure disperser in which the release agent, the aqueous dispersion P of the resin particles (E) and, if necessary, the aqueous medium are mixed at a temperature equal to or higher than the melting point of the release agent. , Obtained by dispersing using a disperser having a strong shearing force such as an ultrasonic disperser.
The heating temperature at the time of dispersion is preferably equal to or higher than the melting point of the release agent and 80 ° C. or higher, more preferably 85 ° C. or higher, further preferably 90 ° C. or higher, and preferably the resin contained in the resin particles (E). The temperature is lower than 10 ° C. and 100 ° C. or lower, more preferably 98 ° C. or lower, still more preferably 95 ° C. or lower.

From the viewpoint of improving the dispersion stability of the release agent particles, from the viewpoint of suppressing the desorption and exposure of the release agent, from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step, and in the toner even after heating in the fusion step. From the viewpoint of containing the release agent, the amount of the amorphous polyester resin E used is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass with respect to 100 parts by mass of the release agent. By mass or more, more preferably 30 parts by mass or more, further preferably 35 parts by mass or more, and preferably 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably. It is 50 parts by mass or less.

The volume median particle diameter D ₅₀ of the release agent particles is preferably 0.05 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, and from the viewpoint of obtaining uniform aggregated particles, and It is preferably 1 μm or less, more preferably 0.8 μm or less, still more preferably 0.6 μm or less.
The CV value of the release agent particles is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably 35% or less, still more preferably 30% or less.
Method of measuring the volume-median particle size D ₅₀ and CV value of the release agent particles by the method described in Example.
The ratio of the volume median particle diameter (D ₅₀ ) of the resin particles (E) to the volume median particle diameter (D ₅₀ ) of the mold release agent particles (resin particles (E) (D ₅₀ ) / mold release agent particles (D) ₅₀ )) is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.06 or more, still more preferably 0.06 or more, from the viewpoint of further stabilizing the dispersion of the release agent and obtaining a toner having excellent image density. Is 0.1 or more, and preferably 1.5 or less, more preferably 1.0 or less, still more preferably 0.8 or less, still more preferably 0.6 or less, still more preferably 0.4 or less, further It is preferably 0.25 or less.

<Step 1>
In step 1, the binder resin particles, the release agent particles, and the colorant particles are aggregated in an aqueous medium to obtain aggregated particles. In step 1, in addition to the binder resin particles, the release agent particles, and the colorant particles, other additives may be aggregated.
The amount of the release agent particles relative to 100 parts by mass of the total amount of the binder resin particles used in the step 1 is preferably 4 parts by mass or more from the viewpoint of more stabilizing the dispersion of the release agent and obtaining a toner having excellent image density. , More preferably 8 parts by mass or more, further preferably 12 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less.

(Bound resin particles)
In step 1, the binder resin particles preferably contain at least an amorphous resin A, and more preferably a crystalline resin C.
Examples of the binder resin particles include the binder resin particles X containing the amorphous resin A, the binder resin particles Y containing the crystalline resin C, and the amorphous resin A and the crystalline resin C in the same particles. Although any of the binder resin particles XY containing the above can be used, it is preferable to use the binder resin particles XY containing the amorphous resin A and the crystalline resin C.
The binder resin particles preferably contain at least an amorphous resin (resin A) from the viewpoint of obtaining a toner having excellent charge stability and image density, and the amorphous resin A is an amorphous polyester resin (resin A). It is more preferable to contain the resin A1).

[Amorphous polyester resin (resin A1)]
The amorphous polyester resin (resin A1) contains an amorphous polyester resin or an amorphous polyester segment which is a polycondensate of an alcohol component containing a diol compound and a carboxylic acid component containing a dicarboxylic acid compound.
Examples of the amorphous polyester resin include a polyester resin and a modified polyester resin. Examples of the modified polyester resin include a urethane modified product of a polyester resin, an epoxy modified product of a polyester resin, and a composite resin containing a polyester resin segment and an addition polymerization resin segment. Among these, a polyester resin, a composite resin, and more preferably a polyester resin are preferable.

As the alcohol component, the alcohol component of the constituent portion derived from the polyester resin F in the above-mentioned amorphous polyester resin E is exemplified, and the preferable range is also the same.

Examples of the carboxylic acid component include the carboxylic acid component exemplified in the polyester resin F, and specific examples thereof include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, and trivalent or higher valent carboxylic acid compounds.
The amount of the aromatic dicarboxylic acid is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol% or less, more preferably 90 mol% or more, in the carboxylic acid component. It is 80 mol% or less, more preferably 75 mol% or less.

The amount of the aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and preferably 50 mol% or less, more preferably 50 mol% or more, in the carboxylic acid component. It is 40 mol% or less.

When a trivalent or higher polyvalent carboxylic acid is contained, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% in the carboxylic acid component. The above, and preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less.
One kind or two or more kinds of these carboxylic acid components may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less. It is preferably 1.2 or less.

(Manufacturing method of resin A1)
The resin A1 may be produced, for example, by a method including a step a of performing a polycondensation reaction with an alcohol component and a carboxylic acid component.
In step a, an esterification catalyst and an esterification co-catalyst may be used, if necessary, and the preferred types and amounts of the esterification catalyst and esterification catalyst are the esters in the method for producing the amorphous polyester resin E. This is the same as the preferable range of the preferable type and amount of the chemical catalyst and the esterification auxiliary catalyst.
When a monomer having an unsaturated bond such as fumaric acid is used in the polycondensation reaction, it is preferably 0.001 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component, if necessary. A radical polymerization inhibitor of 0.5 parts by mass or more may be used. Examples of the radical polymerization inhibitor include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, and preferably 260 ° C. or lower, more preferably 250 ° C. or lower.

(Physical characteristics of resin A1)
The softening point of the resin A1 is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and preferably 140 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 125 ° C. or lower. Is.
The glass transition temperature of the resin A1 is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, further preferably 45 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 60 ° C. or higher. It is as follows.

The acid value of the resin A1 is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, further. It is preferably 25 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the resin A1 can be appropriately adjusted according to the type and amount of the raw material monomer used, and the production conditions such as the reaction temperature, reaction time, and cooling rate, and their values. Is determined by the method described in the examples.
When two or more kinds of resin A1 are used in combination, it is preferable that the softening point, the glass transition temperature and the acid value obtained as a mixture thereof are within the above ranges.

In the present invention, the binder resin particles preferably contain a crystalline resin (resin C) from the viewpoint of obtaining a toner having excellent charge stability and image density. As the crystalline resin, a crystalline polyester resin (resin C1) is preferable.
[Crystalline polyester resin (resin C1)]
Resin C1 is, for example, a polycondensate of an alcohol component and a carboxylic acid component.
The alcohol component preferably contains an α, ω-aliphatic diol.
The carbon number of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, further preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. is there.
Examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol Can be mentioned. Among these, 1,4-butanediol or 1,10-decanediol is preferable.

The amount of α, ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and more preferably 95 mol% or more in the alcohol component. It is 100 mol% or less, more preferably 100 mol%.

The alcohol component may contain other alcohol components different from the α, ω-aliphatic diol. Other alcohol components include, for example, aliphatic diols other than α, ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin and penta. Examples thereof include trihydric or higher alcohols such as erythritol and trimethylol propane. One or more of these alcohol components may be used.

The carboxylic acid component preferably contains an aliphatic dicarboxylic acid.
The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, further preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid, dodecanedioic acid, or tetradecanedioic acid is preferable, and sebacic acid is more preferable. One kind or two or more kinds of these carboxylic acid components may be used.

The amount of the aliphatic dicarboxylic acid is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol in the carboxylic acid component. % Or less, more preferably 100 mol%.

The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid. Examples of other carboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and polyvalent carboxylic acids having a trivalent or higher valence. These carboxylic acid components may be used alone or in combination of two or more.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less. It is preferably 1.2 or less.

(Physical characteristics of resin C1)
The softening point of the resin C1 is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, and preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower. Is.
The melting point of the resin C1 is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower. is there.

The acid value of the resin C1 is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less. ..

The softening point, melting point, and acid value of the resin C1 can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate. Those values are obtained by the method described in Examples described later. When two or more types of resin C1 are used in combination, it is preferable that the values of the softening point, melting point, and acid value obtained as a mixture thereof are within the above ranges.

Resin C1 is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. As the polycondensation condition, for example, the condition shown in the polycondensation in the resin A1 described above can be applied.

The mass ratio [C / A] of the resin C to the resin A is preferably 1/99 or more, more preferably 5/95 or more, still more preferably 10/90 or more, still more preferably 15/85 or more, and It is preferably 50/50 or less, more preferably 40/60 or less, and further preferably 30/70 or less.

In the resin component of the toner, the total content of the resin A and the resin C used as the binder resin is preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass or less. It is preferably 98% by mass or less.

[Manufacturing method of binder resin particles]
When the binding resin particles contain the resin A and the resin C, the binding resin particles contain the resin A and the resin C in the same or different binding resin particles. Here, in the following description, the binder resin particles XY containing the resin A and the resin C in the same particles will be described.
Examples of the aqueous medium are the same as those used for the aqueous dispersion P of the resin particles (E) in step 1-1, and the preferred range is also the same.
Further, the resin A and the resin C can be dispersed in the aqueous medium by the same method as the aqueous dispersion of the amorphous polyester resin E in step 1-1, and the binder resin particles XY are transferred by the transfer emulsification method. It is preferable to obtain an aqueous dispersion of.
Regarding the organic solvent used for transfer emulsification, neutralizing agent, degree of neutralization, conditions for adding the organic solvent solution of the resin to the aqueous medium, and removal of the organic solvent after phase inversion emulsification, the amorphous polyester in step 1-1 The conditions are the same as in the production of the aqueous dispersion P of the based resin E, and the preferable range is also the same.

The volume median particle diameter D ₅₀ of the binder resin particles XY in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, and is preferably 0.08 μm or more, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. It is preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.3 μm or less.
The CV value of the binder resin particles XY in the dispersion is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, from the viewpoint of obtaining a toner that can obtain a high-quality image. More preferably, it is 30% or less.
The volume median particle size D ₅₀ and the CV value are determined by the methods described in Examples described later.
Both the binder resin particles X containing the amorphous resin A and the binder resin particles Y containing the crystalline resin C can be produced according to the above-mentioned method. The preferred ranges of the volume median particle diameter D ₅₀ and the CV value of the binder resin particles X and the binder resin particles Y are the same as those described above.

(Colorant particles)
In step 1, a colorant is added to obtain aggregated particles. It is preferable to add the colorant particle dispersion liquid Z in which the colorant is dispersed in an aqueous medium in step 1 to obtain aggregated particles.
Pigments and dyes are used as the colorant, and pigments are preferable from the viewpoint of improving the image density of the toner.
Examples of the pigment include a cyan pigment, a yellow pigment, a magenta pigment, and a black pigment.
As the cyan pigment, a phthalocyanine pigment is preferable, and copper phthalocyanine is more preferable. The yellow pigment is preferably a monoazo pigment, an isoindolin pigment, or a benzimidazolone pigment, and the magenta pigment is preferably a soluble azo pigment such as a quinacridone pigment or a BONA lake pigment, or an insoluble azo pigment such as a naphthol AS pigment. The black pigment is preferably carbon black.
Examples of the dye include an acridin dye, an azo dye, a benzoquinone dye, an azine dye, an anthraquinone dye, an indigo dye, a phthalocyanine dye, and an aniline black dye.
The colorants can be used alone or in combination of two or more.

The colorant particle dispersion Z can be suitably produced by mixing a colorant and, if necessary, a surfactant with an aqueous medium. At this time, it is preferable to disperse using a homogenizer or the like. As the aqueous medium, those mentioned in the above-mentioned production of the aqueous dispersion of the resin particles (E) are preferable.
Dispersion of the colorant in an aqueous medium is preferably performed in the presence of a surfactant from the viewpoint of improving the dispersion stability of the colorant.

The surfactant used in the production of the colorant particle dispersion Z is preferably an anionic surfactant. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium lauryl ether sulfate, dipotassium alkenylsuccinate and the like, and sodium dodecylbenzenesulfonate is preferable.
The amount of the surfactant is preferably 5 parts by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving the dispersion stability of the colorant particles and suppressing the release and exposure of the release agent. It is more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, and preferably 40 parts by mass or less, more preferably 35 parts by mass or less, still more preferably 30 parts by mass or less.

The solid content and the colorant content in the colorant particle dispersion Z are preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, respectively, and It is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.

The volume median particle diameter (D ₅₀ ) of the colorant particles in the colorant particle dispersion Z is preferably 0.05 μm or more, more preferably 0.08 μm or more, still more preferably 0.10 μm or more, and It is preferably 0.30 μm or less, more preferably 0.20 μm or less, still more preferably 0.15 μm or less.
The CV value of the colorant particles in the colorant particle dispersion Z is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, and from the viewpoint of obtaining a toner having a better image density. From the viewpoint of obtaining a high-quality image, it is preferably 40% or less, more preferably 35% or less, still more preferably 30% or less.
Volume-median particle size D ₅₀ and CV value of the colorant particles can be measured by the method described in Examples.

The agglutination of the resin particles, the colorant particles, and the release agent particles may be performed in the presence of other additives.
Examples of other additives include charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, and cleanability improvers. ..

(Surfactant)
In step 1, when the dispersion liquid of each particle is mixed to prepare the mixed dispersion liquid, the presence of a surfactant is present from the viewpoint of improving the dispersion stability of the binder resin particles, the colorant particles, the release agent particles, and the like. You may go below. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers.
When a surfactant is used, the total amount used is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, still more preferably 0.3 parts by mass, based on 100 parts by mass of the total amount of the binder resin particles. It is 0.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less.

The above-mentioned binder resin particle dispersion liquid, mold release agent particle dispersion liquid, colorant particle dispersion liquid, and optional components are mixed by a conventional method. From the viewpoint of efficient aggregation, it is preferable to add a flocculant to the mixed dispersion obtained by the mixing.

[Coagulant]
Examples of the flocculant include a cationic surfactant such as a quaternary salt, an organic flocculant such as polyethyleneimine, and an inorganic flocculant. Examples of the inorganic flocculant include inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride and calcium nitrate; inorganic ammonium salts such as ammonium sulfate, ammonium chloride and ammonium nitrate; and divalent or higher valent metal complexes. ..
From the viewpoint of improving the cohesiveness and obtaining uniform agglomerated particles, an inorganic flocculant of monovalent or higher and pentavalent or less is preferable, an inorganic metal salt of monovalent or higher and divalent or lower, an inorganic ammonium salt is more preferable, and an inorganic ammonium salt is preferable. More preferably, ammonium sulfate is even more preferable.

Using a flocculant, for example, in a mixed dispersion containing binder resin particles at 0 ° C. or higher and 40 ° C. or lower, mold release agent particles, and colorant particles, 5 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the total amount of resin. A coagulant of less than a part is added, and the binder resin particles, the release agent particles, and the colorant particles are agglomerated in an aqueous medium to obtain agglomerated particles. Further, from the viewpoint of promoting aggregation, it is preferable to raise the temperature of the dispersion after adding the flocculant.

Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation inhibitor, a method of diluting the dispersion, and the like. From the viewpoint of surely preventing unnecessary aggregation, a method of adding an aggregation terminator to stop aggregation is preferable.

[Coagulation terminator]
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, polyoxyalkylene alkyl ether sulfate and the like. These may be used alone or in combination of two or more. The aggregation terminator may be added in an aqueous solution.
The amount of the aggregation terminator added is preferably 1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the resin in the binder resin particles, from the viewpoint of surely preventing unnecessary aggregation. From the viewpoint of reducing the residue on the toner, the amount is preferably 60 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less.

Volume-median particle size _{D 50} of the aggregate particles is preferably 2μm or more, more preferably 3μm or more, more preferably 4μm or more, and, preferably 10μm or less, more preferably 8μm or less, more preferably at 6μm or less is there. Volume-median particle size D ₅₀ of the aggregate particles is obtained by the method described in Examples set forth below.

In the present invention, after step 1 and before step 2, a binder resin containing an amorphous resin (preferably an amorphous polyester resin) in the agglomerated particles (aggregated particles 1) obtained in step 1. It may have a step (step 1') of attaching the particles X'to obtain the agglomerated particles 2.
Here, as the amorphous polyester resin used for the binder resin particles X', the above-mentioned amorphous polyester resin (resin A1) is exemplified. The binding resin particles X'are obtained by the same method as the binding resin particles XY described above.
When the toner manufacturing method includes step 1', it is preferable to stop the agglomeration when the agglomerated particles 2 grow to an appropriate particle size as toner particles in the step 1', and the above-mentioned agglomeration terminator is used. A method of adding to stop aggregation is preferable.

<Process 2>
In step 2, for example, the agglomerated particles are fused in an aqueous medium.
By fusion, each particle contained in the agglomerated particles is fused to obtain fused particles.
The volume median particle diameter D ₅₀ of the fused particles obtained by fusion is preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less. , More preferably 6 μm or less.

The circularity of the fused particles obtained by fusion is preferably 0.955 or more, more preferably 0.960 or more, and preferably 0.990 or less, more preferably 0.985 or less, still more preferably 0.985 or less. It is 0.980 or less.
The fusion is preferably completed after reaching the above-mentioned preferable circularity.
Circularity is measured by the method described in Examples.

<Post-treatment process>
A post-treatment step may be performed after step 2, and toner particles are obtained by isolating the fused particles. Since the fused particles obtained in step 2 are present in the aqueous medium, it is preferable to first perform solid-liquid separation. A suction filtration method or the like is preferably used for solid-liquid separation.
It is preferable to perform cleaning after solid-liquid separation. At this time, since it is preferable to remove the added surfactant as well, it is preferable to wash with an aqueous medium below the cloud point of the surfactant. The washing is preferably performed a plurality of times.
Next, it is preferable to perform drying. Examples of the drying method include a vacuum low temperature drying method, a vibration type fluid drying method, a spray drying method, a freeze drying method, and a flash jet method.

[Toner particles]
The volume medium particle size D ₅₀ of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, from the viewpoint of obtaining a high-quality image and further improving the cleanability of the toner. Then, it is preferably 10 μm or less, more preferably 8 μm or less, and further preferably 6 μm or less.

The CV value of the toner particles is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more from the viewpoint of improving the productivity of the toner, and from the viewpoint of obtaining a high-quality image. It is preferably 40% or less, more preferably 35% or less, still more preferably 30% or less.
The volume median particle diameter D ₅₀ and the CV value of the toner particles can be measured by the method described in Examples.

[Toner for static charge image development]
The toner for developing an electrostatic charge image of the present invention (hereinafter, also simply referred to as toner) contains toner particles.
Although the toner particles can be used as they are as the toner, it is preferable to use the toner particles obtained by adding a fluidizing agent or the like as an external agent to the surface of the toner particles.

[External agent]
Examples of the external additive include fine particles of an inorganic material such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Of these, hydrophobic silica is preferred. The external additive may be used alone or in combination of two or more. Further, two or more kinds of hydrophobic silica having different particle diameters may be used.
When the surface treatment of the toner particles is performed using an external additive, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 2 parts by mass or more with respect to 100 parts by mass of the toner particles. It is 3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and further preferably 4 parts by mass or less.

Toner is used for electrostatic charge image development in electrophotographic printing. The toner can be used, for example, as a one-component developer or mixed with a carrier as a two-component developer.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Each property value was measured and evaluated by the following method.
In the notation such as "alkylene oxide (X)", the numerical value X in parentheses means the average number of moles of alkylene oxide added.

[Measuring method]
[Acid value of resin]
The acid value of the resin was measured according to the neutralization titration method described in JIS K 0070: 1992. However, the measurement solvent was chloroform.

[Resin softening point, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1 g sample is heated at a heating rate of 6 ° C./min while a load of 1.96 MPa is applied by a plunger to give a diameter of 1.96 MPa. Extruded from a 1 mm, 1 mm long nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was used as the softening point.
(2) Crystallinity index Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of the sample into an aluminum pan and cool it to 0 ° C at a temperature lowering rate of 10 ° C / min. did. Next, the sample was allowed to stand still for 1 minute, and then the temperature was raised to 180 ° C. at a heating rate of 10 ° C./min to measure the amount of heat. Of the observed endothermic peaks, the temperature of the peak with the largest endothermic area is set as the maximum endothermic temperature (1), and (softening point (° C.)) / (maximum endothermic peak temperature (1) (° C.)). The crystallinity index was calculated.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample is weighed in an aluminum pan, and the temperature is raised to 200 ° C. It was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the temperature of the sample was raised at a heating rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the largest peak area was defined as the maximum endothermic peak temperature (2). In the case of crystalline resin, the peak temperature was taken as the melting point.
In the case of amorphous resin, when a peak is observed, the temperature of the peak is observed, and when a step is observed without a peak, a tangent line indicating the maximum inclination of the curve of the step portion and the step The temperature at the intersection with the extension of the baseline on the low temperature side was defined as the glass transition temperature.

[Weight average molecular weight of modified polyisobutene polymer G]
(1) Preparation of sample solution The sample was dissolved in tetrahydrofuran so that the concentration was 0.5 g / 100 mL. Next, this solution was filtered using a fluororesin filter "FP-200" (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 2 μm to remove insoluble components, and used as a sample solution.
(2) Measurement Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: GMHXL + G3000HXL (manufactured by Tosoh Corporation)
Eluent: tetrahydrofuran Flow rate: 1 mL / min
Column temperature: 40 ° C
The measurement was carried out by injecting 100 μL of the sample solution. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration lines at this time include several types of monodisperse polystyrene (A-500 (Mw: 5.0 × 10 ² ), A-1000 (Mw: 1.01 × 10 ³ ), A-2500 manufactured by Tosoh Corporation). (Mw: 2.63 × 10 ³ ), A-5000 (Mw: 5.97 × 10 ³ ), F-1 (Mw: 1.02 × 10 ⁴ ), F-2 (Mw: 1.81 × 10) ⁴ ), F-4 (Mw: 3.97 × 10 ⁴ ), F-10 (Mw: 9.64 × 10 ⁴ ), F-20 (Mw: 1.90 × 10 ⁵ ), F-40 (Mw) : 4.27 × 10 ⁵ ), F-80 (Mw: 7.06 × 10 ⁵ ), F-128 (Mw: 1.09 × 10 ⁶ )) were prepared as standard samples. The molecular weight is shown in parentheses.

[Melting point of mold release agent]
Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of a sample into an aluminum pan, raise the temperature to 200 ° C, and then lower the temperature from 200 ° C to 10 ° C / min. Was cooled to 0 ° C. Next, the sample was heated at a heating rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endotherm was taken as the melting point.

[Binder resin particles, colorant particles, and the volume-median particle size D ₅₀ and CV value of the release agent particles]
(1) Measuring device: Laser diffraction type particle size measuring machine "LA-920" (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: A sample dispersion was placed in a measurement cell, distilled water was added, and the volume median particle diameter D ₅₀ and the volume average particle diameter D _v were measured at concentrations at which the absorbance was within an appropriate range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size _Dv ) × 100

[Solid concentration of binder resin particle dispersion, colorant particle dispersion, and release agent particle dispersion]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Scientific Research Institute Co., Ltd.), a measurement sample of 5 g was dried at a drying temperature of 150 ° C., measurement mode 96 (monitoring time 2.5 minutes, fluctuation range of water content 0.05%). ), The water content (% by mass) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (mass%) = 100-moisture (mass%)

[Moisture content of toner particles]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.), dry 5 g of toner particles at a drying temperature of 150 ° C., measurement mode 96 (monitoring time 2.5 minutes, fluctuation range of moisture content 0.05%). ), The water content (mass%) was measured.

[Volume medium particle size D _{50 of} aggregated particles]
Volume-median particle size D of the aggregated particles ₅₀ is measured as follows.
-Measuring machine: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter Co., Ltd.)
・ Aperture diameter: 50 μm
-Analysis software: "Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter Co., Ltd.)
-Electrolytic solution: "Isoton (registered trademark) II" (manufactured by Beckman Coulter Co., Ltd.)
-Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured again and the particle size is measured. The volume median particle size D ₅₀ was determined from the distribution.

[Circularity of fused particles]
The circularity of the fused particles was measured under the following conditions.
-Measuring device: Flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation)
-Preparation of dispersion: The dispersion of fused particles was prepared by diluting with deionized water so that the solid content concentration was 0.001 to 0.05% by mass.
-Measurement mode: HPF measurement mode

[Volume-median particle size D ₅₀ and CV value of the toner particles]
A volume-median particle size D of the toner particles ₅₀ is measured as follows.
Measuring device, aperture diameter, analysis software, the electrolytic solution used was the same as that used in the measurement of the volume-median particle size D ₅₀ of the aggregated particles described above.
Dispersion: Polyoxyethylene lauryl ether "Emargen (registered trademark) 109P" (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) is dissolved in the electrolytic solution, and the concentration is 5% by mass. Got
Dispersion conditions: 10 mg of a sample to be measured of toner particles after drying is added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of the electrolytic solution is added, and further to an ultrasonic disperser. The mixture was dispersed for 1 minute to prepare a sample dispersion.
-Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size is measured. From the distribution, the volume median particle size D ₅₀ and the volume average particle size _DV were determined.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size _DV ) x 100

[Image density of printed matter]
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation) on high-quality A4 paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhered to the paper is 0.24 to A solid image of 0.26 mg / cm ² was output with a length of 50 mm without fixing, leaving a margin of 5 mm from the upper end of the high-quality A4 paper.
Next, the same printer in which the fixing device was modified to have a variable temperature was prepared, the temperature of the fixing device was set to 100 ° C., and toner was fixed at a speed of 2.0 seconds per sheet in the A4 vertical direction to obtain a printed matter.
In the same manner, the temperature of the fuser was raised by 5 ° C. to fix the toner, and a printed matter was obtained.
Lightly paste the mending tape "Scotch (registered trademark) Mending Tape 810" (manufactured by Sumitomo 3M Ltd., width 18 mm) cut to a length of 50 mm from the top margin on the printed matter to the solid image. After that, a 500 g cylindrical weight (contact area: 1963 mm ² ) was placed and pressed once back and forth at a speed of 10 mm / s. Then, the attached tape was peeled off from the lower end side at a peeling angle of 180 ° and a speed of 10 mm / s to obtain a printed matter after the tape was peeled off. 30 sheets of high-quality paper "Excellent White Paper A4 size" (manufactured by Oki Data Co., Ltd.) are laid under the printed matter before and after the tape is applied, and the reflected image density of the fixed image part before and after the tape is applied to each printed matter is measured. , Colorimeter "SpectroEye" (manufactured by GretagMacbeth, light emission conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and the fixation rate from each reflected image density according to the following formula. Was calculated.
Fixing rate (%) = (reflection image density after tape peeling / reflection image density before tape application) x 100
The lowest temperature at which the fixing rate was 90% or more was defined as the lowest fixing temperature.
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhered to the paper is 0.25 mg / cm. ^The solid image of ² was output without being fixed.
Next, the temperature of the fuser is set to the minimum fixing temperature + 10 ° C. obtained in the above low temperature fixability test, and the toner is fixed in the A4 vertical direction at a speed of 2.0 seconds per sheet to prepare the printed matter. Obtained.
30 sheets of high-quality paper "Excellent White Paper A4 size" (manufactured by Oki Data Co., Ltd.) are laid under the printed matter, and the reflected image density of the solid image part of the output printed matter is measured by the colorimeter "SpectroEye" (manufactured by GretagMacbeth). Irradiation conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard) were used for measurement, and the measured values of any 10 points on the image were averaged to obtain the image density. The larger the value, the better the image density.

[Manufacturing of resin]
[Manufacturing of amorphous polyester resin A]
Production Example A1 (Production of Resin A-1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3880 g of a propylene oxide (2.2) adduct of 2,2-bis (4-hydroxyphenyl) propane. , 1,544 g of ethylene oxide (2.2) adduct of 2,2-bis (4-hydroxyphenyl) propane, 1578 g of terephthalic acid, 694 g of adipic acid, 40 g of di (2-ethylhexanoic acid) tin (II), and gallic acid 4 .0 g was added, the temperature was raised to 235 ° C. with stirring under a nitrogen atmosphere, and the temperature was maintained at 235 ° C. for 6 hours, then the pressure in the flask was further reduced, and the temperature was maintained at 8.3 kPa for 1 hour. Then, after cooling to 215 ° C. and returning to atmospheric pressure, 304 g of trimellitic anhydride was added, the temperature was maintained at 215 ° C. for 1 hour, the pressure in the flask was further lowered, and the desired softening point was 8.3 kPa. The reaction was carried out to obtain resin A-1. Table 1 shows the physical characteristics of the obtained resin.

[Manufacturing of crystalline polyester resin C]
Production Example C1 (Production of Resin C-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3471 g of 1,10-decanediol and 4029 g of sebacic acid were added, and while stirring, 135 The temperature was raised to ° C., held at 135 ° C. for 3 hours, and then raised from 135 ° C. to 200 ° C. over 10 hours. Then, 15 g of di (2-ethylhexanoic acid) tin (II) was added, and the mixture was further held at 200 ° C. for 1 hour, the pressure inside the flask was lowered, and the mixture was held under a reduced pressure of 8 kPa for 1 hour. I got 1. The physical characteristics are shown in Table 2.

[Manufacturing of amorphous polyester resin (resin for dispersing mold release agent) E]
Production Example E1 (Production of Resin E-1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3991 g of a propylene oxide (2.2) adduct of 2,2-bis (4-hydroxyphenyl) propane. , 1588 g of ethylene oxide (2.2) adduct of 2,2-bis (4-hydroxyphenyl) propane, 2299 g of terephthalic acid, 39 g of di (2-ethylhexanoic acid) tin (II), and 3.9 g of gallic acid. The temperature was raised to 235 ° C. while stirring under a nitrogen atmosphere, and the temperature was maintained at 235 ° C. for 10 hours, then the pressure inside the flask was further reduced, and the temperature was maintained at 8.3 kPa for 1 hour. Then, after cooling to 160 ° C. and returning to atmospheric pressure, 738 g of polyisobutene succinic anhydride was added, the temperature was raised to 235 ° C., the temperature was maintained at 235 ° C. for 5 hours, and then the pressure inside the flask was further lowered to 8.3 kPa. The reaction was carried out to a desired softening point to obtain resin E-1. Table 3 shows the physical characteristics of the obtained resin.

Production Example E2 (Production of Resin E-2)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and propylene oxide (2.2) of 2,2-bis (4-hydroxyphenyl) propane was used. ) Additives 3122 g, ethylene oxide (2.2) adducts of 2,2-bis (4-hydroxyphenyl) propane 1243 g, terephthalic acid 1904 g, di (2-ethylhexanoic acid) tin (II) 32 g, and gallic acid 3 .2 g was added, the temperature was raised to 235 ° C. with stirring under a nitrogen atmosphere, the temperature was maintained at 235 ° C. for 10 hours, the pressure in the flask was lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 1170 g of styrene, 223 g of 2-ethylhexyl acrylate, 64 g of acrylic acid, and 84 g of dibutyl peroxide was added dropwise over 1 hour. did. Then, after holding at 160 ° C. for 30 minutes, 738 g of polyisobutene succinic anhydride was added, the temperature was raised to 235 ° C., the temperature was kept at 235 ° C. for 5 hours, the pressure in the flask was further lowered, and the desired temperature was 8.3 kPa. The reaction was carried out to the softening point to obtain resin E-2. Table 3 shows the physical characteristics of the obtained resin.

Production example E81 (Production of resin E-81)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3880 g of a propylene oxide (2.2) adduct of 2,2-bis (4-hydroxyphenyl) propane. , 1544 g of ethylene oxide (2.2) adduct of 2,2-bis (4-hydroxyphenyl) propane, 2497 g of terephthalic acid, 40 g of di (2-ethylhexanoic acid) tin (II), and 4.0 g of gallic acid. The temperature was raised to 235 ° C. while stirring under a nitrogen atmosphere, and the temperature was maintained at 235 ° C. for 10 hours, then the pressure inside the flask was further reduced, and the temperature was maintained at 8.3 kPa for 1 hour. Then, after cooling to 160 ° C. and returning to atmospheric pressure, 738 g of Paracol 6490 was added, the temperature was raised to 235 ° C., the temperature was maintained at 235 ° C. for 5 hours, and then the pressure inside the flask was further lowered to 8.3 kPa. The reaction was carried out to a desired softening point to obtain resin E-81. Table 3 shows the physical characteristics of the obtained resin.

[Manufacturing of binder resin particle dispersion]
Production Example XY1 (Production of Bundling Resin Particle Dispersion Liquid XY-1)
240 g of resin A-1, 60 g of resin C-1, 360 g of methyl ethyl ketone, and 59 g of deionized water are placed in a container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube. , The resin was dissolved at 73 ° C. for 2 hours. A 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so as to have a neutralization degree of 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 280 r / min (peripheral speed 88 m / min) for phase inversion emulsification. While continuously maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass, thereby forming a binder resin. A particle dispersion XY-1 was obtained. Volume-median particle size D ₅₀ and CV value of the obtained binder resin particles shown in Table 4.

Production Example P1 (Production of Resin Particle Dispersion Liquid P-1)
200 g of resin E-1 and 200 g of methyl ethyl ketone were placed in a container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introduction tube, and the resin was dissolved at 73 ° C. for 2 hours. It was. A 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so as to have a neutralization degree of 60 mol% with respect to the acid value of the resin E-1, and the mixture was stirred for 30 minutes.
Then, 700 g of deionized water was added over 50 minutes while stirring at 280 r / min (peripheral speed 88 m / min) while maintaining the temperature at 73 ° C. for phase inversion emulsification. Methyl ethyl ketone was distilled off under reduced pressure while the temperature was continuously maintained at 73 ° C. to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid P-1 was obtained. Volume-median particle size D ₅₀ and CV value of the obtained resin particles shown in Table 4.

Production Examples P2 and P81 (Production of resin particle dispersions P-2 and P-81)
Resin particle dispersions P-2 and P-81 were obtained in the same manner as in Production Example P1 except that the resin used was changed to Table 4. Volume-median particle size D ₅₀ and CV value of the obtained resin particles shown in Table 4.

[Manufacture of release agent particle dispersion W]
Production Example W1 (Production of release agent particle dispersion W-1)
120 g of deionized water, 86 g of resin particle dispersion P-1 and 40 g of paraffin wax "HNP-9" (manufactured by Nippon Seiwa Co., Ltd., melting point 75 ° C.) were added to a beaker having an internal volume of 1 L, and 95 to 98 ° C. The mixture was melted at a temperature maintained at the same temperature and stirred to obtain a molten mixture.
The obtained molten mixture was further dispersed at 95 to 98 ° C. using an ultrasonic homogenizer "US-600T" (manufactured by Nissei Tokyo Office Co., Ltd.) for 20 minutes and then up to room temperature (20 ° C.). Cooled. Deionized water was added to adjust the solid content concentration to 20% by mass to obtain a release agent particle dispersion W-1. Release agent volume-median particle size D ₅₀ and CV value of the particle in the resulting dispersion are shown in Table 5.

Production Examples W2, W3, W81 (Production of release agent particle dispersion W-2, W-3, W-81)
The release agent particle dispersions W-2, W-3, and W-81 were prepared in the same manner as in Production Example W1 except that the types of the release agent and the resin particle dispersion used were changed as shown in Table 5. Obtained. Release agent volume-median particle size D ₅₀ and CV value of the particle in the resulting dispersion are shown in Table 5.

Production Example W82 (Production of release agent particle dispersion W-82)
To a beaker with an internal volume of 1 L, add 100 g of deionized water and 67 g of a 15 mass% sodium dodecylbenzene sulfonate aqueous solution "Neoperex G-15" (manufactured by Kao Co., Ltd., an anionic surfactant) to 95 to 98 ° C. The mixture was melted at a temperature and stirred to obtain a molten mixture.
The obtained molten mixture was further dispersed at 95 to 98 ° C. using an ultrasonic homogenizer "US-600T" (manufactured by Nissei Tokyo Office Co., Ltd.) for 20 minutes and then up to room temperature (20 ° C.). Cooled. Deionized water was added to adjust the solid content concentration to 20% by mass to obtain a release agent particle dispersion W-82. Release agent volume-median particle size D ₅₀ and CV value of the particle in the resulting dispersion are shown in Table 5.

Production Example Z1 (Production of colorant particle dispersion Z-1)
In a beaker with an internal volume of 1 L, 100 g of copper phthalocyanine pigment "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd.), 15 mass% sodium dodecylbenzene sulfonate aqueous solution "Neoperex G-15" (manufactured by Kao Co., Ltd., anionic) 167 g of surfactant) and 102 g of deionized water are mixed, and the rotation speed of the stirring blade is 8000 r / min at 20 ° C. using a homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Primix Co., Ltd.). After dispersion for 1 hour, a homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics) was used for 15-pass treatment at a pressure of 150 MPa. Then, the colorant particle dispersion liquid Z-1 was obtained by passing through a 200 mesh filter and adding deionized water so that the solid content concentration became 20% by mass. The volume median particle diameter D ₅₀ of the obtained colorant particles was 0.13 μm, and the CV value was 24%.

[Manufacturing of toner]
Example 1 (Manufacturing of Toner 1)
500 g of binder resin particle dispersion XY-1, 82 g of release agent particle dispersion W-1, colorant particle dispersion in a 4-neck flask with an internal volume of 3 L equipped with a dehydration tube, agitator and thermocouple. 81 g of Z-1, 3 g of 10 mass% aqueous solution of polyoxyethylene (50) lauryl ether "Emargen 150" (manufactured by Kao Co., Ltd., nonionic surfactant), and 15 mass% sodium dodecylbenzene sulfonate aqueous solution "Neo" 3 g of "Perex G-15" (manufactured by Kao Co., Ltd., anionic surfactant) was mixed at a temperature of 25 ° C. Next, while stirring the mixture, a solution prepared by adding a 4.8 mass% potassium hydroxide aqueous solution to an aqueous solution prepared by dissolving 43 g of ammonium sulfate in 580 g of deionized water to adjust the pH to 8.6 was applied at 25 ° C. for 10 minutes. The temperature was raised to 62 ° C. over 2 hours, and the temperature was maintained at 62 ° C. until the volume median particle diameter D _{50 of} the agglomerated particles reached 5.2 μm to obtain a dispersion of the agglomerated particles.
To the obtained dispersion of agglomerated particles, 48 g of polyoxyethylene lauryl ether sulfate sodium "Emar E-27C" (manufactured by Kao Corporation, anionic surfactant, effective concentration 27% by mass), 600 g of deionized water, and 0 An aqueous solution mixed with 70 g of a 1 mol / L sulfuric acid aqueous solution was added. Then, the temperature was raised to 80 ° C. over 1 hour and held at 80 ° C. for 30 minutes, 15 g of a 0.1 mol / L sulfuric acid aqueous solution was added, and the mixture was further held at 80 ° C. for 15 minutes. Then, 15 g of a 0.1 mol / L sulfuric acid aqueous solution was added again, and the mixture was kept at 80 ° C. until the circularity became 0.970 to obtain a dispersion of fused particles in which aggregated particles were fused.
The obtained fused particle dispersion was cooled to 30 ° C., the dispersion was suction-filtered to separate solids, washed with deionized water at 25 ° C., and suction-filtered at 25 ° C. for 2 hours. Then, using a vacuum constant temperature dryer "DRV622DA" (manufactured by ADVANTEC), vacuum drying was performed at 33 ° C. for 24 hours to obtain toner particles having a water content of 0.5% by mass or less. Table 6 shows the physical characteristics of the obtained toner particles.
100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica "Cabosil (registered trademark) TS720" (Cabot Japan Co., Ltd.) Company-made, number average particle size; 0.012 μm) 1.0 part by mass was placed in a Henschel mixer and stirred, and passed through a 150 mesh sieve to obtain toner 1. The evaluation results of the obtained toner are shown in Table 6.

Examples 2 and 3 and Comparative Examples 1 and 2 (manufacturing of toners 2, 3, 81 and 82)
Toners 2, 3, 81, and 82 were prepared in the same manner as in Example 1 except that the type of the release agent particle dispersion liquid used was changed as shown in Table 6. Table 6 shows the physical characteristics of the obtained toner particles and the evaluation results of the toner.

As shown in Table 6, according to the present invention, a toner having an excellent image density of printed matter can be obtained by using a release agent particle dispersion liquid containing a specific amorphous polyester resin E and a release agent. Be done.
On the other hand, Comparative Example 1 in which an amorphous polyester resin having no structural unit derived from the modified polybutadiene polymer G was used instead of the amorphous polyester resin E, and a comparison in which an anionic surfactant was used. In Example 2, a high image density was not obtained.

Claims (9)

A method for producing a toner for static charge image development, which comprises a step of aggregating and fusing the binder resin particles, the release agent particles, and the colorant particles in an aqueous medium.
The release agent particles contain the release agent and the amorphous polyester resin E.
The amorphous polyester resin E has a constituent portion derived from the polyester resin F and a constituent portion derived from the modified polyisobutene polymer G having a reactive functional group, and the constituent portion derived from the polyester resin F and the above. The constituent sites derived from the modified polyisobutene polymer G are linked via a covalent bond.
A method for manufacturing a toner for developing an electrostatic charge image. The modified polyisobutene polymer G is the polyisobutene in which polyisobutene is modified with maleic acid, succinic acid, fumaric acid, itaconic acid, and at least one acid selected from these acid anhydrides, according to claim 1. A method for manufacturing a toner for developing an electrostatic anhydride image. The method for producing a toner for static charge image development according to claim 1 or 2, wherein the acid value of the modified polyisobutene polymer G is 0.1 mgKOH / g or more and 200 mgKOH / g or less. The amount of the constituent part derived from the modified polyisobutene polymer G in the amorphous polyester resin E is 1 with respect to 100 parts by mass of the total of the alcohol component and the carboxylic acid component forming the constituent part derived from the polyester resin F. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the amount is not less than parts by mass and not more than 60 parts by mass. The method for producing a toner for static charge image development according to any one of claims 1 to 4, wherein the modified polyisobutene polymer G has a weight average molecular weight of 300 or more and 50,000 or less. The method for producing a toner for static charge image development according to any one of claims 1 to 5, wherein the binder resin particles contain a crystalline polyester resin. The polyester resin F is a polyester resin segment which is a polycondensate of an alcohol component and a carboxylic acid component, an addition polymerization resin segment which is an addition polymerization of a raw material monomer containing a styrene compound, and the polyester resin segment and the above. The method for producing an electrostatic charge image developing toner according to any one of claims 1 to 6, which comprises a structural unit derived from a bireactive monomer in which an addition polymerization resin segment is covalently bonded. Before the step of aggregating and fusing the binder resin particles, mold release agent particles and colorant particles in an aqueous medium,
The method according to any one of claims 1 to 7, further comprising a step of mixing the release agent and the aqueous dispersion of the amorphous polyester resin E and emulsifying them to obtain the aqueous dispersion of the release agent particles. A method for manufacturing a toner for developing an electrostatic charge image. The electrostatic charge image development according to any one of claims 1 to 8, wherein the content of the amorphous polyester resin E with respect to 100 parts by mass of the release agent in the release agent particles is 5 parts by mass or more and 100 parts by mass or less. Manufacturing method of toner for mold.