JP2018084705A - Method for manufacturing toner particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing toner particles having a sharp particle size distribution.SOLUTION: A method for manufacturing toner particles includes: a step (a) of mixing binder resin A, colorant, polymeric dispersant P, solid fine particles Q, organic solvent, and dispersion medium to form droplets each have a surface covered by the polymeric dispersant P and composite fine particles having the polymeric dispersant P adsorbed on the solid fine particles Q, and containing the binder resin A, colorant, and organic solvent; and a step (b) of removing the organic solvent contained in the droplets.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing toner particles used in electrophotography, electrostatic recording, and toner jet recording.

  2. Description of the Related Art In recent years, there has been a demand for image quality enhancement using toner in an electrophotographic apparatus, and there has been a demand for an electrophotographic apparatus that can obtain an image that does not deteriorate image quality even with a large number of prints. In order to improve image quality with toner, it is required to suppress variation in performance of each toner particle. For this purpose, it is effective to sharpen the particle size distribution with uniform toner particle size. As a method that can achieve the sharpening of the particle size distribution of the toner relatively easily, there is a “dissolution suspension method”.

  Furthermore, in recent years, a production method using liquid or supercritical carbon dioxide as a dispersion medium has been developed. According to this method, compared with the conventional method using an aqueous dispersion medium, there is an advantage that energy can be saved by omitting a washing step and a drying step in the production of toner particles. In the preparation of toner particles in the dissolution suspension method, it is effective to use a dispersant. Examples of the dispersant include a surfactant, a polymer dispersant, and a fine particle dispersant.

  In general, a dispersant (surfactant, polymer dispersant) used in a state dissolved in a dispersion medium is stably dispersed from a fine droplet to a coarse droplet regardless of the particle size of the droplet. On the other hand, the fine particle dispersant is said to be advantageous for the purpose of sharpening the particle size distribution of toner particles because it does not stabilize minute droplets. On the other hand, solid fine particles such as silica generally used as a fine particle dispersant often have low surface activity, and depending on the material, there is a concern of affecting the coarsening of resin particles. In order to eliminate this concern, there has been proposed a method for producing resin particles that supplements the surface activity by supplementarily using a polymer dispersant in addition to the fine particle dispersant.

  In Patent Document 1, resin particles obtained by using a polymer dispersant having at least one of a dimethylsiloxane group and a functional group containing fluorine and inorganic or organic fine particles as a fine particle dispersant in a dissolution suspension method There has been proposed a manufacturing method for producing the above.

JP 2007-277511 A

  However, when the present inventors applied the method of Patent Document 1 to toner particles and evaluated toner particles produced according to this method, it was found that the particle size distribution was not necessarily sharp. The present inventors consider that the reason is that the polymer dispersant and the fine particle dispersant contribute to the dispersion stability of the droplets by different mechanisms. As a result of the stable dispersion of the polymer dispersant from minute droplets to coarse droplets regardless of the particle size of the droplets, it was considered that the particle size distribution was broadened. In addition, since general inorganic or organic fine particles having a small surface activity were used as the fine particle dispersant, it was considered that the coarsening of the toner particles could not be sufficiently suppressed.

  An object of the present invention has been made in view of the above problems, and is to provide a method for producing toner particles having a sharp particle size distribution.

The present invention is a method for producing toner particles, the production method comprising:
a) A binder resin A, a colorant, a polymer dispersant P, solid fine particles Q, an organic solvent, and a dispersion medium are mixed, and the surface is the polymer dispersant P, and the polymer dispersant P is the solid fine particles. A step of forming a droplet containing the binder resin A, the colorant, and the organic solvent covered with the composite fine particles adsorbed on Q; and b) removing the organic solvent contained in the droplet. Process,
The present invention relates to a method for producing toner particles.

  According to the present invention, a method for producing toner particles having a sharp particle size distribution can be provided.

It is a figure explaining the calculation method of the adsorption rate of the polymer dispersing agent P with respect to the solid fine particle Q. It is a figure explaining the structure of the polymer dispersing agent P. FIG. It is the schematic which shows an example of the manufacturing apparatus of the toner particle in the manufacturing method of this invention.

The present invention is a method for producing toner particles, comprising the following steps.
a) The binder resin A, the colorant, the polymer dispersant P, the solid fine particles Q, the organic solvent, and the dispersion medium are mixed, and the polymer dispersant P and the polymer dispersant P are adsorbed on the solid fine particles Q. Forming a droplet containing the binder resin A, the colorant, and the organic solvent covered with the composite fine particles,
b) A step of removing the organic solvent contained in the droplets.

  One feature of the present invention is that, when obtaining toner particles by the dissolution suspension method, composite fine particles formed by adsorbing the polymer dispersant P on the solid fine particles Q are used as the dispersant. Since the composite fine particles have a surface activity derived from the polymer dispersant P, it is possible to disperse and stabilize droplets formed by a combination of various materials. In addition, since the fine composite particles are fine particle dispersants, the minute droplets are not stabilized, which is extremely advantageous for the purpose of sharpening the particle size distribution of the toner particles.

In order to form composite fine particles in which the polymer dispersant P is adsorbed on the solid fine particles Q, the adsorption rate of the polymer dispersant P on the solid fine particles Q is preferably 15.0% or more. This adsorption rate is calculated by the following formula (I).
Adsorption rate (%) = (1−S2 / S1) × 100 Formula (I)

  S1 and S2 in the formula (I) will be described with reference to FIG. S1 indicates a peak area derived from the polymer dispersant P by GPC measurement of a solution obtained by dissolving 0.1 g of the polymer dispersant P in 20.0 g of an organic solvent. In S2, first, 1.0 g of the solid fine particles Q and 30.0 g of glass beads are mixed in a solution obtained by dissolving 0.1 g of the polymer dispersant P in 20.0 g of an organic solvent. For 4 hours. After dispersion, the supernatant obtained by centrifuging the obtained dispersion is subjected to GPC measurement, and the peak area derived from the polymer dispersant P is defined as S2.

  When the adsorption rate satisfies 15.0% or more, the polymer dispersant P is favorably adsorbed to the solid fine particles Q, which is advantageous in obtaining composite fine particles. In addition, stable dispersion from minute droplets to coarse droplets is suppressed regardless of the particle size of the droplets, and the particle size distribution of the toner particles tends to be sharper.

  A more preferable range of the adsorption rate is 20.0% or more, and a more preferable range is 30.0% or more. The upper limit of the adsorption rate is not particularly limited, but it is difficult to adsorb the entire amount of the polymer dispersant P to the solid fine particles Q in the above method, and the upper limit is 90.0%.

  The polymer dispersant P of the present invention will be described. The polymer dispersant P is a polymer having a partial structure X and a partial structure Y, the partial structure X has an organic polysiloxane structure represented by the following formula (1), and the partial structure X and the partial structure Y are the following: It is preferable to satisfy the formula (2).

（式（Ｉ）中、Ｒ^１およびＲ^２は、それぞれ独立に、炭素数１から３のアルキル基を表し、ｎは２以上１５０以下である。）

(In formula (I), R ¹ and R ² each independently represents an alkyl group having 1 to 3 carbon atoms, and n is 2 or more and 150 or less.)

3.0 ≦ SP (Y) −SP (X) (2)
(In Formula (2), SP (X) represents the solubility parameter of the partial structure X, and SP (Y) represents the solubility parameter of the partial structure Y.)

  The partial structure X has an organic polysiloxane structure and plays a role of developing affinity for the dispersion medium, and the partial structure Y plays a role of developing affinity for the binder resin A. By coexisting such two partial structures, high surface activity can be obtained, and the dispersion stability of the droplets can be further improved.

  The structure represented by formula (1) exhibits high hydrophobicity, and when a low-polarity medium such as liquid or supercritical carbon dioxide is used as a dispersion medium, the affinity for the dispersion medium is increased. The chain can be greatly expanded. At this time, the polymer dispersant P including the structure of the formula (1) not only has a surface activity, but also exhibits an excluded volume effect that suppresses collisions between the droplets, thereby further improving the dispersion stability of the droplets. Is possible. In addition, the toner particles obtained using the polymer dispersant P having the structure of the formula (1) can also have an effect of being excellent in environmental stability.

  The solubility parameter is also called an SP value, and is a solubility index indicating how much a certain substance is dissolved in a certain substance. Those having close SP values have high solubility, and those having SP values apart have low solubility. That is, it is an index indicating the affinity between different substances, and those having close SP values have high affinity, and those that are separated from each other have low affinity. The SP value can be calculated using solubility parameter calculation software (Hansen Solubility Parameters in Practice).

  By satisfying the above formula (2), the solubility parameter of the partial structure X becomes a sufficiently small value as compared with the partial structure Y. Thereby, the polymer dispersant P has a sufficient surface activity and can contribute to the dispersion stabilization of the droplets.

  The weight average molecular weight (Mw) of the polymer dispersant P is preferably 50,000 or more and 500,000 or less. When Mw is within this range, the polymer dispersant P exhibits the above-described excluded volume effect, and can further enhance the dispersion stability of the droplets. When the Mw is 50,000 or more, the excluded volume effect can be sufficiently exhibited. Moreover, it becomes easy to control the adsorption rate of Formula (I) within the above range. On the other hand, when the Mw is 500,000 or less, it is easy to suppress a drop in the dispersion stability of the droplets due to cross-linking aggregation caused by the adsorption of the single polymer dispersant P between the droplets. A more preferable range of Mw of the polymer dispersant P is 80,000 or more and 350,000 or less.

  The partial structure Y of the polymer dispersant P is, for example, a polyester structure, a polyether structure, or a monomer composition containing at least one monomer selected from the group consisting of styrene, styrene derivatives, acrylates, and methacrylates. The polymer can be Among these, polyester having a polyester structure is preferable because the polyester has a high cohesive energy density, and thus an effect of increasing the adsorption rate of the formula (I) can be expected. As the polyester structure, either crystalline polyester or amorphous polyester can be used.

  The crystalline polyester means a resin having a structure in which polymer molecular chains are regularly arranged. Such a resin shows a clear melting point peak in differential scanning calorimetry using a differential scanning calorimeter (DSC), hardly softens in a temperature range lower than the melting point, and melts rapidly when the melting point is exceeded. Has sharp melt properties. Therefore, the toner using the crystalline polyester for the partial structure Y of the polymer dispersant P can achieve good low-temperature fixability. The melting point of the crystalline polyester is preferably 50 ° C. or higher and 120 ° C. or lower in view of solvent resistance to an organic solvent or a dispersion medium, and considering that the toner melts at a fixing temperature, it may be 50 ° C. or higher and 90 ° C. or lower. More preferred.

  The crystalline polyester that can be used as the partial structure Y of the polymer dispersant P is a polyester resin obtained by ring-opening polymerization of an aliphatic lactone, or obtained by reacting an aliphatic diol with an aliphatic dicarboxylic acid. The polyester resin which can be mentioned can be mentioned. Examples of the aliphatic lactone include δ-hexalanolactone, δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, β-methyl-δ-valerolactone, glycolide, and lactide. Etc. Among these, ε-caprolactone is preferable from the viewpoints of reactivity and availability. As the aliphatic diol, an aliphatic diol having 2 to 20 carbon atoms is preferable, and a linear aliphatic diol is more preferable from the viewpoint of crystallinity.

  Examples of the linear aliphatic diol having 2 to 20 carbon atoms include the following compounds. 1,2-ethanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1 , 10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol and 1,20-eicosanediol. These may be used alone or in combination of two or more. An aliphatic diol having a double bond can also be used. Examples of the aliphatic diol having a double bond include the following compounds. 2-butene-1,4-diol, 3-hexene-1,6-diol and 4-octene-1,8-diol.

  The aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, and a linear aliphatic dicarboxylic acid is more preferable from the viewpoint of crystallinity. Examples of the linear aliphatic dicarboxylic acid having 2 to 20 carbon atoms include the following compounds. Succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid and 1,18-octadecanedicarboxylic acid, or their lower alkyl esters and acid anhydrides object. These may be used alone or in combination of two or more. Aromatic dicarboxylic acids can also be used. Examples of the aromatic dicarboxylic acid include the following compounds. Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-biphenyldicarboxylic acid.

  There is no restriction | limiting in particular as a manufacturing method of crystalline polyester resin, It can manufacture by the polymerization method of the general polyester resin which makes a carboxylic acid component and an alcohol component react.

  As the polyester structure which is a preferable structure of the partial structure Y, amorphous polyester can also be used. The amorphous polyester is not particularly limited, and examples thereof include a polymer obtained by condensing a conventionally known divalent or trivalent or higher carboxylic acid and a divalent or trivalent or higher alcohol. Specific examples of these monomers include the following.

  Examples of the divalent carboxylic acid include the following compounds. Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenyl succinic acid, and anhydrides or lower alkyl esters thereof, and maleic acid, fumaric acid, Aliphatic unsaturated dicarboxylic acids such as itaconic acid and citraconic acid. Examples of the trivalent or higher carboxylic acid include the following compounds. 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and anhydrides or lower alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the divalent alcohol include the following compounds. Alkylene glycol (ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol); alkylene ether glycol (polyethylene glycol and polypropylene glycol); alicyclic diol (1,4-cyclohexanedimethanol); bisphenols (bisphenol) A); an alkylene oxide (ethylene oxide and propylene oxide) adduct of an alicyclic diol. The alkyl part of alkylene glycol and alkylene ether glycol may be linear or branched.

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

  For the purpose of adjusting the acid value and the hydroxyl value, monovalent acids such as acetic acid and benzoic acid, and monovalent alcohols such as cyclohexanol and benzyl alcohol can be used as necessary. The method for synthesizing the amorphous polyester resin is not particularly limited, and a conventionally known method can be used.

  The case where the partial structure Y of the polymer dispersant P is a polyether structure will be described. The polyether structure is represented, for example, by the following formula (3).

In formula (3), m is an integer of 1 or more and 3 or less, and x is 0 or 1. R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. p is an integer of 1 or more.

  Specific examples include the following formulas (4) to (8). If the above formula (3) is satisfied, a plurality of types may be used in combination.

In formulas (4) to (8), R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. p is an integer of 1 or more.

  The case where the partial structure Y of the polymer dispersant P is a polymer structure of a monomer composition containing at least one monomer selected from the group consisting of styrene, styrene derivatives, acrylates, and methacrylates will be described. . Examples of styrene and styrene derivatives include o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene. As acrylate and methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate , Acrylic esters such as 2-chloroethyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate Methacrylic acid esters such as 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

  In addition to the above monomers, using a radical polymerizable monomer having a plurality of radical polymerizable unsaturated groups in the compound, such as divinylbenzene, 1,6 hexane diacrylate, 1,6 hexane dimethacrylate, etc. Also good.

  The polymer of the monomer composition containing at least one monomer selected from the group consisting of styrene, styrene derivatives, acrylates, and methacrylates can be obtained by ordinary radical polymerization.

  A preferred structure of the polymer dispersant P will be described with reference to FIG. As shown in FIG. 2A, the polymer dispersant P (010) is a co-polymer having a partial structure X (030) and a partial structure Y (040) in the side chain with respect to the main chain (020). It is a coalescence. With such a structure, the mutual functions of the partial structure X (030) and the partial structure Y (040) are not hindered, so that the affinity for the dispersion medium and the droplets can be sufficiently exhibited.

  The polymer dispersant P (010) can be produced by radical copolymerization of a radical polymerizable monomer E having a partial structure X (030) and a radical polymerizable monomer F having a partial structure Y (040). is there. Specifically, the radical polymerizable monomer E, the radical polymerizable monomer F, and the polymerization initiator are dissolved in an organic solvent, and then sufficiently deoxygenated by nitrogen bubbling or the like. Thereafter, the polymerization is started by heating or the like. When the predetermined time has elapsed, the reaction is stopped by cooling. The polymer dispersant P can be obtained by dissolving the reaction solution in a good solvent for the obtained polymer, and then depositing, washing (reprecipitation) using a poor solvent for the polymer, and purifying. In addition, in the method for producing the polymer dispersant P, in addition to the radical polymerizable monomer E and the radical polymerizable monomer F, other radical polymerizable monomers such as styrene, acrylic acid, and methacrylic acid are used. The body may be used in combination. However, other radical polymerizable monomers used in combination with the radical polymerizable monomer E and the radical polymerizable monomer F are not limited to these.

  Examples of the polymerization initiator that can be used for radical polymerization include the following. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide-based polymerization initiators such as peroxide, lauroyl peroxide, tert-butyl-peroxypivalate. The amount of these polymerization initiators used is generally 0.1 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. The kind of the polymerization initiator is used alone or in combination with reference to the 10-hour half-life temperature. The polymer dispersant P can also be obtained by living radical polymerization such as atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), nitroxide-mediated radical polymerization (NMP).

  The radical polymerizable monomer E is a compound having a polymerizable unsaturated group at one end of the partial structure X (010). An example of the radical polymerizable monomer E is shown in Formula (9).

In Formula (9), R ¹ , R ² , R ^{5 to} R ⁹ represent an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkylene group having 1 to 10 carbon atoms, and R ¹⁰ represents a hydrogen atom or Represents a methyl group, and n is 2 or more and 150 or less.

  Examples of the method for synthesizing the compound of the formula (9) include a reaction by dehydrochlorination of carbinol-modified polysiloxane and acrylic acid chloride or methacrylic acid chloride.

  The radical polymerizable monomer F is a compound having a polymerizable unsaturated group at one end of the partial structure Y (040). In the radical polymerizable monomer F, an example of a monomer in which the partial structure Y is a polyester structure is shown in formulas (10) and (11).

In the above formulas (10) and (11), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents an alkylene group. R ¹³ represents an alkyl group. R ¹⁴ and R ¹⁵ represent an alkylene group or a substituted or unsubstituted arylene group. R ¹⁶ represents an alkyl group, a hydrogen atom, or a group obtained by substituting one of the hydrogen atoms of the alkyl group with a hydroxyl group. q and r indicate the degree of polymerization.

  The following method is mentioned as a manufacturing method of the compound which has a polymerizable unsaturated group in the one terminal of Formula (10) and (11). For the above formula (10), a method of coupling a polyester prepared by ring-opening polymerization of a lactone ring and a radically polymerizable compound. For the above formula (11), a method of coupling a crystalline polyester or amorphous polyester synthesized by polycondensation of a dicarboxylic acid and a diol and a radically polymerizable compound.

  Examples of the method for producing the monomer of the formula (10) include the following methods.

  (10-1) A method in which a polyester having a hydroxyl group at a terminal obtained by ring-opening polymerization of an aliphatic lactone and a radically polymerizable compound having a carboxyl group and a polymerizable unsaturated group are coupled by a condensation reaction.

  (10-2) A method of coupling a polyester having a hydroxyl group at the terminal obtained by ring-opening polymerization of an aliphatic lactone and an acid halide by a dehydrochlorination reaction.

  Examples of the radical polymerizable compound having a carboxyl group and a polymerizable unsaturated group used in the method (10-1) include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 2-methacryloxyethyl succinic acid, and 2 -Methacryloxyethyl hexahydrophthalic acid, 2-methacryloxyethyl glutarate; dicarboxylic acids such as (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid and the anhydrides; monomethylmaleic acid, monoethylmaleic acid, mono Dicarboxylic acids such as butyl maleic acid, monooctyl maleic acid, monomethyl fumaric acid, monoethyl fumaric acid, monobutyl fumaric acid, monooctyl fumaric acid, monomethyl itaconic acid, monoethyl itaconic acid, monobutyl itaconic acid, monooctyl itaconic acid Monoalkyl esters of acids, etc. It is. More preferred are acrylic acid and methacrylic acid. This radically polymerizable compound may be used alone or in combination of two or more.

  Examples of the acid halide used in the method of (10-2) include acrylic acid chloride and methacrylic acid chloride as carboxylic acid chlorides.

  Examples of the method for producing the monomer of the formula (11) include the following methods. In the coupling, a radically polymerizable compound containing a functional group capable of reacting with the terminal functional group of the polyester may be directly coupled. Further, the terminal of the polyester may be modified and coupled with a binder so that the reaction with the functional group contained in the radical polymerizable compound is possible. Specifically, the following methods are mentioned.

  (11-1) A method of coupling a polyester having a carboxyl group at a terminal and a radically polymerizable compound having a hydroxyl group and a polymerizable unsaturated group by a condensation reaction.

  (11-2) A method of coupling a polyester having a hydroxyl group at a terminal and a radical polymerizable compound having an isocyanate group and a polymerizable unsaturated group by a urethanization reaction.

  (11-3) A method of coupling a polyester having a hydroxyl group at a terminal and a radical polymerizable compound having a hydroxyl group and a polymerizable unsaturated group by a urethanization reaction using a diisocyanate as a binder.

  Examples of the radical polymerizable compound having a hydroxyl group and a polymerizable unsaturated group include hydroxystyrene, N-methylolacrylamide, N-methylolmethacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol mono Acrylate, polyethylene glycol monomethacrylate, allyl alcohol, methallyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl Examples include alcohol, 2-hydroxyethylpropenyl ether, and sucrose allyl ether. Of these, preferred are hydroxyethyl acrylate and hydroxyethyl methacrylate.

  Examples of the radical polymerizable compound having an isocyanate group include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, 2-[( 3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate. Among these, particularly preferred are 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.

  Examples of the diisocyanate include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, And modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, and oxazolidone group-containing modified products (hereinafter also referred to as modified diisocyanates). .

  Examples of the aromatic diisocyanate include the following. m- and / or p-xylylene diisocyanate (XDI), α, α, α ', α'-tetramethylxylylene diisocyanate. Examples of the aliphatic diisocyanate include the following. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate. Examples of the alicyclic diisocyanate include the following. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate. Among these, XDI, HDI, and IPDI are preferable.

  In the radical polymerizable monomer F, specific examples of the monomer in which the partial structure Y is a polyether structure are shown in the following formulas (12) to (16).

In formulas (12) to (16), R ¹⁷ represents a hydrogen atom or a methyl group. R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. p is preferably an integer of 1 or more.

  As a method for producing a radical polymerizable monomer having a polyether structure, a method for producing a radical polymerizable monomer having a polyester structure is the same as the method described in (11-2) or (11-3). A method is mentioned. At this time, the polyester having a hydroxyl group at the terminal in the method described in (11-2) or (11-3) is changed to a polyether having a hydroxyl group at the terminal.

  Another preferred structure of the polymer dispersant P will be described with reference to FIG. In the polymer dispersant P (100), as shown in FIG. 2B, the segment (110) having the partial structure X as a stem portion and the segment (120) having the partial structure Y as a stem portion are combined. It is a copolymer. With such a structure, inhibition of the mutual functions of the partial structure X (110) and the partial structure Y (120) is suppressed, and the affinity to the dispersion medium and droplets can be sufficiently exerted. become.

  Examples of the method for producing the polymer dispersant P (100) shown in FIG. 2B include the following methods. A step of preparing a macroinitiator having a partial structure X containing formula (I) and a functional group capable of generating free radicals, using the macroinitiator as a polymerization initiator, and other radical polymerizable monomers such as styrene and methacrylic acid. It can be manufactured by a step of copolymerizing a monomer. At this time, the radical polymerizable monomer is not limited to these as long as it can form the partial structure Y by polymerization.

  The functional group that generates free radicals is a functional group that can be decomposed by heat or light, generate free radicals at the decomposition site, and start polymerization from that site when a monomer is present. For example, an azo functional group having an —N═N— structure, a peroxide functional group having an —O—O— structure, and a dihalogen functional group having a halogen-halogen bond can be given.

  A macroinitiator is a compound that has a functional group that generates the above-mentioned free radicals and also has a partial structure X or a partial structure Y in the molecule. When radically polymerizing a monomer in the presence of this macroinitiator, the polymerization is first started from the functional group site that generates the free radical of the macroinitiator, and the monomer is added and extended sequentially. . As a result, as a copolymer in which a segment derived from a macroinitiator containing a partial structure X and a segment composed of a polymer containing a partial structure Y obtained by polymerizing a radical polymerizable monomer are combined. A molecular dispersant P is obtained. Alternatively, a polymer as a copolymer in which a segment derived from a macroinitiator containing a partial structure Y and a segment composed of a polymer containing a partial structure X obtained by polymerizing a radical polymerizable monomer are combined. Dispersant P can be obtained.

  As the macroinitiator, a commercially available macroinitiator may be used, or it may be produced and used. As a commercially available macroinitiator containing the partial structure X, VPS-1001 (made by Wako Pure Chemical Industries, Ltd.) can be mentioned.

When manufacturing the macroinitiator containing the partial structure X, the method of (17)-(19) shown below is mentioned, for example.
(17) A method in which a compound containing a hydroxyl group and a partial structure X is coupled to a compound having a carboxyl group and a functional group that generates a free radical by esterification.
(18) A method in which a compound containing a carboxyl group and a partial structure X is coupled to a compound having a hydroxyl group and a functional group that generates a free radical by esterification.
(19) Esterification of a compound containing any one of acid halide, acid anhydride, lower carboxylic acid ester and partial structure X with a compound having a hydroxyl group and a functional group capable of generating a free radical How to couple by.

  In the methods (17) and (18), in order to esterify the hydroxyl group and the carboxyl group, use of a dehydration condensing agent can be mentioned. Examples of the dehydrating condensing agent include, but are not particularly limited to, carbodiimide, imidazole, triazine, phosphonium, uronium, and haloronium condensing agents.

  Another preferred structure of the polymer dispersant P will be described with reference to FIG. The polymer dispersant P (200) includes a segment (210) having a partial structure X as a trunk site and a segment (220) including a graft polymer having a partial structure Y (240) as a branch site with respect to the main chain (230). ) And a copolymer. With such a structure, each segment does not easily interfere with each other's functions, and can fully exhibit the affinity to the dispersion medium and droplets.

  The production method of the polymer dispersant P (200) shown in FIG. 2 (c) uses, for example, a step of preparing a macroinitiator having a partial structure X and a functional group that generates free radicals, using a macroinitiator, A method of radical polymerization of the radical polymerizable monomer F may be mentioned. At this time, other radical polymerizable monomers such as styrene and methacrylic acid may be copolymerized.

  Another preferred structure of the polymer dispersant P will be described with reference to FIG. The polymer dispersant P (300) includes a segment (310) having a partial structure Y as a trunk site and a segment (320) made of a graft polymer having the partial structure X as a branch site with respect to the main chain (330). A bonded copolymer. With such a structure, each segment does not easily interfere with each other's functions, and can fully exhibit the affinity to the dispersion medium and droplets.

  The production method of the polymer dispersant P (300) as shown in FIG. 2D is, for example, a step of preparing a macroinitiator having a partial structure Y and a functional group that generates free radicals, using a macroinitiator. And a method of radical polymerization of the radical polymerizable monomer E. At this time, other radical polymerizable monomers such as styrene and methacrylic acid may be copolymerized.

When manufacturing the macroinitiator containing the partial structure Y, the method of (20)-(22) shown below is mentioned, for example.
(20) A method in which a compound having a hydroxyl group and a partial structure Y is coupled to a compound having a carboxyl group and a functional group that generates a free radical by esterification.
(21) A method of coupling a compound having a carboxyl group and a partial structure Y by esterifying a compound having a hydroxyl group and a functional group that generates a free radical.
(22) Esterification of a compound containing any one of acid halide, acid anhydride, lower carboxylic acid ester and partial structure Y, and a compound having a hydroxyl group and a functional group capable of generating a free radical How to couple by.

  In the methods (20) and (21), in order to esterify the hydroxyl group and the carboxyl group, use of a dehydration condensing agent can be mentioned. Examples of the dehydrating condensing agent include those similar to the dehydrating condensing agent used in the above methods (17) and (18).

  The partial structure X is preferably contained in an amount of 10.0% by mass to 60.0% by mass with respect to the polymer dispersant P. More preferably, they are 15.0 mass% or more and 50.0 mass% or less. When the partial structure X is 10.0% by mass or more, the polymer dispersant P exhibits sufficient surface activity. Further, when the partial structure X contained in the polymer dispersant P is 60.0% by mass or less, the adsorption rate of the polymer dispersant P with respect to the solid dispersant Q is further improved, and the formula (I) is controlled. It becomes easy.

  The partial structure Y is preferably contained in the polymer dispersant P in an amount of 30.0% by mass to 70.0% by mass. More preferably, it is 40.0 mass% or more and 60.0 mass% or less. When the partial structure Y is 30.0% by mass or more, the adsorption rate of the polymer dispersant P with respect to the solid dispersant Q is further improved, and the formula (I) is easily controlled. When the partial structure Y is 70.0% by mass or less, the polymer dispersant P exhibits sufficient surface activity.

  The mass ratio of the polymer dispersant P to the solid fine particles Q is preferably 0.3 or more and 3.0 or less. More preferably, it is 0.8 or more and 2.0 or less. When the mass ratio is 0.3 or more, the surface activity of the composite fine particles is further improved, and the toner particles can be prevented from being coarsened. When the mass ratio is 3.0 or less, the polymer dispersant P is sufficiently adsorbed on the solid fine particles Q, and can be stably dispersed from a fine droplet to a coarse droplet regardless of the particle size of the droplet. The toner particle size distribution tends to be sharper.

  The total mass ratio of the polymer dispersant P and the solid fine particles Q to the binder resin A is preferably 0.08 or more and 0.30 or less. More preferably, it is 0.12 or more and 0.20 or less. When the total amount of the polymer dispersant P and the solid fine particles Q is in this range, the ratio of the composite fine particles to the droplet surface becomes an appropriate amount, which is advantageous for achieving a particle size equivalent to the toner particles. It is easy to become. When the mass ratio is 0.08 or more, the amount of dispersant used is sufficient, and sufficient dispersion stability can be imparted to the droplets. As a result, the resulting toner particles are prevented from becoming coarse and the particle size distribution tends to be sharper. When the mass ratio is 0.30 or less, the amount of the composite fine particles formed by adsorbing the polymer dispersant P on the solid fine particles Q becomes an appropriate amount, and aggregation of the composite fine particles is difficult to occur.

  The solid fine particles Q will be described. As the solid fine particles Q, resin fine particles or inorganic fine particles can be used. From the viewpoint of improving the adsorption rate, the solid fine particles Q are preferably resin fine particles. When the solid fine particles Q are resin fine particles, a crystalline resin and an amorphous resin can be used as the resin constituting the resin fine particles. When the solid fine particles Q are composed of a crystalline resin, the melting point of the crystalline resin is preferably 50 ° C. or more and 120 ° C. or less in consideration of solvent resistance to an organic solvent or a dispersion medium, and considering melting at a fixing temperature as a toner. Then, 50 degreeC or more and 90 degrees C or less are more preferable. When the solid fine particles Q are composed of an amorphous resin, the glass transition temperature of the amorphous resin is preferably 50 ° C. or higher and 130 ° C. or lower from the viewpoint of solvent resistance to an organic solvent or a dispersion medium. From the viewpoint of melting at the fixing temperature, 50 ° C. or higher and 100 ° C. or lower is preferable. For the purpose of giving the resin fine particles solvent resistance to an organic solvent or a dispersion medium, the molecular weight of the resin constituting the resin fine particles may be adjusted, or a crosslinked structure or a polar group may be introduced into the resin.

  It is preferable to use crystalline polyester, crystalline alkyl, or the like as the crystalline resin constituting the resin fine particles in order to impart solvent resistance to the organic solvent and the dispersion medium. As the crystalline polyester, those similar to the crystalline polyester described in the description of the partial structure Y of the polymer dispersant P can be used.

  The crystalline alkyl resin is a vinyl resin obtained by polymerizing an alkyl acrylate having 12 to 30 carbon atoms and an alkyl methacrylate for expressing crystallinity. Specifically, the following can be mentioned. Lauryl acrylate, lauryl methacrylate, myristyl acrylate, myristyl methacrylate, cetyl acrylate, cetyl methacrylate, stearyl acrylate, stearyl methacrylate, eicosyl acrylate, eicosyl methacrylate, behenyl acrylate, behenyl methacrylate. Further, when other vinyl monomers are copolymerized to such an extent that the crystallinity is not impaired, it can be regarded as a crystalline alkyl resin.

  Examples of the amorphous resin that can be used for the resin fine particles include vinyl resins such as polyurethane, polyester, styrene acrylic resin, and polystyrene. As the amorphous resin, a resin subjected to urethane modification, urea modification, or epoxy modification may be used.

  Polyurethane as an amorphous resin is a reaction product of a diol component and a diisocyanate component, and a resin having various functions can be obtained by adjusting the diol component and the diisocyanate component.

  As the diisocyanate component, the same diisocyanate component as described in the explanation of the partial structure Y of the polymer dispersant P can be used.

  Examples of the diol component include the following. Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol), alkylene ether glycol (polyethylene glycol, polypropylene glycol) alicyclic diol (1,4-cyclohexanedimethanol), bisphenols (bisphenol A) ), An alkylene oxide (ethylene oxide, propylene oxide) adduct of the alicyclic diol. The alkyl part of the alkylene glycol and alkylene ether glycol may be linear or branched.

  When the amorphous resin constituting the resin fine particles is an amorphous polyester, the amorphous polyester is the same as the amorphous polyester described in the description of the partial structure Y of the polymer dispersant P. be able to.

  The resin constituting the resin fine particles is more preferably a crystalline polyester or an amorphous polyester. Polyester is effective as a means for increasing the adsorption rate of formula (I) because of its high cohesive energy density.

  The case where the solid fine particles Q are inorganic fine particles will be described. Examples of the inorganic fine particles include fine particles such as silica, alumina, titania, and composite oxide fine particles thereof, and silica fine particles are preferable.

  As a method for producing silica fine particles, a combustion method obtained by burning a silane compound (that is, a method for producing fumed silica), a deflagration method obtained by explosively burning metal silicon powder, and sodium silicate and mineral acid Examples thereof include a wet method obtained by a neutralization reaction and a sol-gel method (so-called Stöber method) obtained by hydrolysis of an alkoxysilane of hydrocarbyloxysila. Among them, a sol-gel method that can sharpen the particle size distribution as compared with other methods is preferable as a method for obtaining silica fine particles having a number average diameter of primary particles of the present invention.

  The adsorption rate of the formula (I) can be controlled by subjecting the inorganic fine particles to a hydrophobic treatment. Examples of the hydrophobic treatment agent for inorganic fine particles include the following. Chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, t-butyldimethylchlorosilane, vinyltrichlorosilane; tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane , Diphenyldimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, Dodecyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltrieth Sisilane, diphenyldiethoxysilane, i-butyltriethoxysilane, decyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Dimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ -Alkoxysilanes such as (2-aminoethyl) aminopropylmethyldimethoxysilane; hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, hexabutyldisilazane, hexapentyl Silazanes such as silazane, hexahexyldisilazane, hexacyclohexyldisilazane, hexaphenyldisilazane, divinyltetramethyldisilazane, dimethyltetravinyldisilazane; dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, alkyl modified Silicone oil, chloroalkyl-modified silicone oil, chlorophenyl-modified silicone oil, fatty acid-modified silicone oil, polyether-modified silicone oil, alkoxy-modified silicone oil, carbinol-modified silicone oil, amino-modified silicone oil, fluorine-modified silicone oil, and terminal reaction -Based silicone oils: hexamethylcyclotrisiloxane, octamethylcyclotetra Siloxanes such as siloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane; fatty acids and metal salts thereof such as undecyl acid, lauric acid, tridecyl acid, dodecyl acid, myristic acid, palmitic acid, pentadecylic acid, Long chain fatty acids such as stearic acid, heptadecylic acid, arachidic acid, montanic acid, oleic acid, linoleic acid and arachidonic acid, and salts of the fatty acids with metals such as zinc, iron, magnesium, aluminum, calcium, sodium and lithium. Among these, alkoxysilanes, silazanes, and straight silicone oils are preferably used because they can be easily subjected to a hydrophobic treatment. Such hydrophobizing agents can be used alone or in admixture of two or more. The method for hydrophobizing the inorganic fine particles is not particularly limited, and a conventionally known method can be used.

  The number average particle size of the solid fine particles Q is preferably 40 nm or more and 200 nm or less. More preferably, it is 60 nm or more and 150 nm or less. When composite fine particles obtained using solid fine particles Q having a number average particle size of 40 nm or more are used as the fine particle dispersant, the particle size of the composite fine particles becomes appropriately large, and the droplets can be further stabilized. This makes it easier to sharpen the particle size distribution of the toner particles obtained. When the number average particle diameter of the solid fine particles Q is 200 nm or less, the specific surface area becomes appropriate, the adsorption rate of the polymer dispersant P to the solid fine particles Q is improved, and the formula (I) is easily controlled. .

  The amount of the solid fine particles Q used is preferably 2.0% by mass or more and 20.0% by mass or less with respect to the binder resin A. When the amount of the solid fine particles Q used is within this range, the ratio of the solid fine particles Q covering the droplet surface becomes an appropriate amount, and it becomes easy to achieve a particle size equivalent to the toner particles.

  The binder resin A will be described. In the present invention, the binder resin A is, for example, a polymer of a monomer composition containing at least one monomer selected from the group consisting of styrene, styrene derivatives, acrylates, and methacrylates, or Polyester is preferred.

  About the polymer of the monomer composition containing at least one monomer selected from the group consisting of styrene, styrene derivatives, acrylates, and methacrylates, an example of the partial structure Y contained in the polymer dispersant P A polymer obtained by polymerizing the radically polymerizable monomer described can be used.

  As for the polyester, the crystalline polyester or amorphous polyester described in the explanation of the polymer dispersant P and the solid fine particles Q can be used.

  The toner particles contain a colorant. Examples of the colorant include organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic particles. In addition, colorants used in conventional toner particles can be used.

  Examples of the colorant for yellow include the following. Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180 are preferably used.

  Examples of the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 are preferably used.

  Examples of the colorant for cyan include the following. Copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 are preferably used.

  The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in toner particles. The colorant is preferably used in an amount of 1.0 to 20.0 parts by mass with respect to 100.0 parts by mass of the binder resin. When magnetic particles are used as the colorant, the amount added is preferably 40.0 parts by mass or more and 150.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

  The organic solvent is not particularly limited as long as it dissolves the binder resin A and the polymer dispersant P and does not dissolve the solid fine particles Q. Examples thereof include the following. Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and di-n-butyl ketone; ester solvents such as ethyl acetate, butyl acetate and methoxybutyl acetate; ether solvents such as tetrahydrofuran, dioxane, ethyl cellosolve and butyl cellosolve; dimethylformamide Amide solvents such as dimethylacetamide; aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene.

  As the dispersion medium, when the compound of the formula (1) is used as the partial structure X of the polymer dispersant P, it is preferable to use a low-polarity dispersion medium. By using a low-polarity dispersion medium, spreading into the dispersion medium of the formula (1) is promoted, and the polymer dispersant P not only exhibits a surface activity, but also exhibits an excluded volume effect, The dispersion stability of the droplets can be improved. The low polarity dispersion medium means a dispersion medium having a polarity lower than that of the organic solvent, and examples thereof include the following. Hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, hexadecane, and cyclohexane; silicone solvents such as polydimethylsiloxane, carbon dioxide. From the viewpoint of energy saving during the production of toner particles, it is particularly preferable to use carbon dioxide in a liquid state or a supercritical state.

  Hereinafter, in the production method of the present invention, a toner production method in the case where carbon dioxide in a liquid state or a supercritical state is used as a dispersion medium will be described in detail.

  In the step a), first, the binder resin A, the colorant, the polymer dispersant P, the solid fine particles Q, the organic solvent, and the dispersion medium are mixed. The mixing order of these materials will be exemplified below for two typical mixing orders, but the present invention is not limited to these.

  As a first mixing order, first, a mixed liquid 1 comprising a binder resin A, a colorant, a polymer dispersant P, solid fine particles Q, and an organic solvent is prepared. At this time, the polymer dispersant P is adsorbed on the solid fine particles Q to form composite fine particles. In preparing the mixed liquid 1, a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser can be used as necessary. Next, when the mixed liquid 1 is put into a pressure vessel and a predetermined amount of high-pressure carbon dioxide is added under stirring conditions, liquid / liquid phase separation occurs in the mixed liquid 1, and the binder resin A, Droplets containing a colorant and an organic solvent are formed. Since the surface of this droplet is covered with the composite fine particles having surface activity and the polymer dispersant P, the dispersed state can be maintained.

  As the second mixing order, first, a mixed liquid 2 comprising a binder resin A, a colorant, and an organic solvent is prepared. Separately, a mixed liquid 3 composed of the polymer dispersant P, the solid fine particles Q, and the organic solvent is prepared. At this time, the polymer dispersant P is adsorbed on the solid fine particles Q to form composite fine particles. In preparing the mixed liquid 2 and the mixed liquid 3, a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser can be used as necessary. Next, the mixed liquid 2 is put into a pressure vessel, a predetermined amount of high-pressure carbon dioxide is added thereto under stirring conditions, and the mixed liquid 3 is further added at the timing when liquid / liquid separation occurs in the mixed liquid 2. It puts into a pressure-resistant container and makes it the mixture 3. In the mixture 3, droplets containing the binder resin A, the colorant, and the organic solvent are formed. Since the surface of this droplet is covered with the composite fine particles having surface activity and the polymer dispersant P, the dispersed state can be maintained. In the second mixing order, a high-pressure pump can be used as a method for introducing the mixed liquid 3 into the pressure vessel. Further, carbon dioxide having a pressure higher than that of the pressure vessel can be mixed with the mixed liquid 3 to use a differential pressure with respect to the pressure vessel.

  Subsequently, in step b), the organic solvent contained in the droplets is removed to obtain toner particles. This is a process of obtaining toner particles by performing so-called desolvation, in which pressurized carbon dioxide is circulated in the pressure vessel and the organic solvent contained in the droplets is removed from the pressure vessel together with carbon dioxide. . When the replacement with carbon dioxide is insufficient and the organic solvent remains in the pressure vessel, the toner particles may be dissolved or the toner particles may be aggregated when the obtained toner particles are recovered. There is. Therefore, the replacement with carbon dioxide is preferably performed until the organic solvent is completely removed. When the toner particles are taken out as a powder, the inside of the pressure vessel may be depressurized. At this time, the pressure may be released to room temperature and normal pressure all at once, but the pressure may be released stepwise by providing multiple pressure-controlled containers. The depressurization speed is preferably set within a range where the toner particles do not foam. In addition, the organic solvent and carbon dioxide to be used can be recycled.

  It is also a preferred form that the toner particles contain a wax. The wax is not particularly limited, and examples thereof include the following. Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax Waxes based on fatty acid esters such as aliphatic hydrocarbon ester waxes; and partially or fully deoxidized fatty acid esters such as deoxidized carnauba wax; fatty acids such as behenic monoglyceride A partially esterified product of a monohydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  Of these, aliphatic hydrocarbon waxes and ester waxes are preferred. The ester wax used in the present invention is preferably a tri- or higher functional ester wax, more preferably a tetra-functional or higher ester wax, and particularly preferably a hexa-functional or higher functional ester wax. A tri- or higher functional ester wax is obtained, for example, by condensation of a tri- or higher valent acid and a long-chain linear saturated alcohol, or a tri- or higher-valent alcohol and a long-chain linear saturated fatty acid.

  Examples of the trivalent or higher alcohol include glycerin, trimethylolpropane, erythritol, pentaerythritol, and sorbitol. Moreover, as these condensates, diglycerin condensed with glycerin, triglycerin, tetraglycerin, hexaglycerin and decaglycerin, etc. Examples thereof include condensed dipentaerythritol and trispentaerythritol. Among these, a structure having a branched structure is preferable, pentaerythritol or dipentaerythritol is more preferable, and dipentaerythritol is particularly preferable.

The long-chain linear saturated fatty acid is represented by C _n H _{2n + 1} COOH, and n is preferably 5 or more and 28 or less. Examples include caproic acid, caprylic acid, octylic acid, nonylic acid, decanoic acid, dodecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and behenic acid. From the viewpoint of the melting point of the wax, myristic acid, palmitic acid, stearic acid, and behenic acid are preferred.

  Examples of the trivalent or higher acid include trimellitic acid and butanetetracarboxylic acid.

The long-chain linear saturated alcohol is represented by C _n H _{2n + 1} OH, and n is preferably 5 or more and 28 or less. Examples include capryl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol. From the viewpoint of the melting point of the wax, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol are preferable.

  The content of the wax in the toner particles is preferably 1.0% by mass or more and 20.0% by mass or less, more preferably 2.0% by mass or more and 15.0% by mass. The wax preferably has a maximum endothermic peak at 60 ° C. or higher and 120 ° C. or lower as measured by a differential scanning calorimeter (DSC). More preferably, it is 60 degreeC or more and 90 degrees C or less.

  The toner particles may contain a charge control agent as necessary. Further, the toner particles may be externally added. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system. As the charge control agent, known ones can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable.

  Examples of the charge control agent that control toner particles to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Examples of controlling the toner particles to be positively charged include the following. Examples include nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganotin borates, guanidine compounds and imidazole compounds.

  A preferable blending amount of the charge control agent is 0.01 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles.

  It is preferable to add inorganic fine particles to the toner particles as a fluidity improver. Examples of the inorganic fine particles added to the toner particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, or double oxide fine particles thereof. Of the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferable.

Examples of the silica fine particles include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. Of these, dry silica is preferable because it has few silanol groups on the surface and inside of the silica fine particles, and has few Na ₂ O and SO ₃ ²⁻ . The dry silica may be composite fine particles of silica and another metal oxide produced by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process.

  The inorganic fine particles are preferably externally added to the toner particles in order to improve the fluidity of the toner and make the toner charge uniform. In addition, hydrophobic treatment of the inorganic fine particles can achieve adjustment of the charge amount of the toner, improvement of environmental stability, and improvement of characteristics in a high humidity environment. More preferably, it is used. When the inorganic fine particles added to the toner particles absorb moisture, the charge amount as the toner is lowered, and the developability and transferability tend to be lowered.

  As treatment agents for hydrophobic treatment of inorganic fine particles, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, organotitanium compounds Is mentioned. These treatment agents may be used alone or in combination.

  The addition amount of the inorganic fine particles is preferably 0.1 parts by mass or more and 4.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles. More preferably, it is 0.2 to 3.5 parts by mass.

  Measurement methods for various physical properties of the toner particles and the like of the present invention will be described below.

<Method for Measuring Particle Diameter of Solid Fine Particle Q, Wax Particle, and Colorant Particle>
The particle diameter of each fine particle such as the solid fine particle Q, the wax particle, and the colorant particle is measured using a microtrack particle size distribution measuring apparatus HRA (X-100) (manufactured by Nikkiso Co., Ltd.). The measurement range is set to 0.001 μm to 10 μm, and the number average particle diameter (μm or nm) or the volume average particle diameter (μm or nm) is measured. Note that water or acetone is selected as the dilution solvent.

<Method of measuring number average molecular weight (Mn) and weight average molecular weight (Mw)>
The molecular weight (Mn, Mw) of the THF soluble part of each polymer used in the present invention is measured by gel permeation chromatography (GPC) as follows.

  First, a sample is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is prepared so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.

Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Method for Measuring Adsorption Rate of Polymer Dispersant P on Solid Fine Particle Q>
The adsorption rate (%) of the polymer dispersant P with respect to the solid fine particles Q is measured by gel permeation chromatography (GPC) as follows.

  First, 0.1 g of the polymer dispersant P is dissolved in 20.0 g of acetone (organic solvent) at room temperature to prepare a solution. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mishori Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution before adsorption in which the polymer dispersant P is dissolved. A sample solution for GPC measurement is collected from the sample solution before adsorption. The pre-adsorption sample solution has a polymer dispersant P concentration of about 0.5% by mass.

Next, 20.1 g of the pre-adsorption sample solution, 1.0 g of solid fine particles Q, and 30.0 g of glass beads are put into a heat-resistant glass container and dispersed for 4 hours with a paint shaker (manufactured by Toyo Seiki). Glass beads are removed from the obtained dispersion with a nylon mesh to obtain a dispersion of solid fine particles Q in which the polymer dispersant P is adsorbed on the surface. Further, the solid fine particles Q adsorbing the polymer dispersant P contained in the dispersion of the solid fine particles Q are separated by a centrifuge, and the supernatant liquid is filtered in the same manner as the sample solution before the adsorption, so that the post-adsorption Obtain a sample solution. The conditions for centrifugation are shown below.
・ Centrifuge: H-9R (manufactured by KOKUSAN)
・ Rotor: B _N1 rotor (manufactured by KOKUSAN)
・ Set temperature in equipment: 4 ℃
・ Rotation speed: 14500 rpm
・ Time: 20 minutes

The obtained pre-adsorption sample solution and post-adsorption sample solution were measured by the GPC used in the above-described method for measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw), and the area derived from the polymer dispersant P was determined. Each is calculated | required and adsorption rate (%) is calculated | required by using a following formula. The peak area derived from the polymer dispersant P obtained by GPC measurement of the sample solution before adsorption is S1, and the peak area derived from the polymer dispersant P obtained by GPC measurement of the sample solution after adsorption is S2. And In order to obtain the area ratio between S1 and S2, the GPC chart for obtaining the peak areas S1 and S2 is a GPC chart using the vertical axis and the horizontal axis of the same scale.
Adsorption rate (%) = (1-S2 / S1) × 100

<Weight average particle diameter (D4), number average particle diameter (D1) and particle size distribution (D4 / D1) of toner particles>
The weight average particle diameter (D4), number average particle diameter (D1), and particle size distribution (D4 / D1) are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software is set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman・ Set the value obtained using Coulter). By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm. A specific measurement method is shown below.
(1) About 200 ml of the electrolytic solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with a phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which toner particles are dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1). Further, D4 / D1 is a particle size distribution.

<Measurement method of fine particle ratio of toner particles>
The fine particle ratio of the toner particles is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.

The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The particle image is picked up by a CCD camera, and the picked-up image is image-processed at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted. Then, the maximum length (D _max ), the maximum vertical length (D _v-max ), and the projected area (S) of the particle image are measured.

The equivalent circle diameter is obtained using the projected area S. The equivalent circle diameter is a diameter of a circle having the same area as the projected area of the particle image, and is calculated by the following equation (23).
Equivalent circle diameter (μm) = 2 × (π × S) ^1/2 (23)

Next, the fine powder ratio is obtained using the number of toner particles (N _s ) having an equivalent circle diameter less than 1.985 μm and the number of all toner particles (N _all ). The fine powder is defined as particles having an equivalent circle diameter of less than 1.985 μm. The fine powder rate is calculated by the following equation (24).
Fine powder ratio (number%) = N _s / N _all × 100 (24)

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids have been removed in advance is placed in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervo Creer)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

The flow type particle image analyzer equipped with a standard objective lens (10 ×) is used for measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion liquid prepared according to the procedure is introduced into a flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the maximum length (D _max ) and maximum length vertical length (D _v-max ) and the projected area (S) are obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles ("RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

  EXAMPLES Hereinafter, although a manufacture example and an Example demonstrate this invention concretely, these do not limit this invention at all. All parts and% in the following formulations are based on mass unless otherwise specified.

<Binder Resin A: Synthesis of Binder Resin A1>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-Styrene 52.0 parts-Butyl acrylate 38.0 parts-Methacrylic acid 10.0 parts-Toluene 130.0 parts-N, N-dimethylformamide 50.0 parts After heating up said monomer solution to 70 degreeC Then, 0.9 part of tertiary butyl peroxypivalate as a polymerization initiator was mixed and stirred at 70 ° C. for 6 hours. Further, while continuing stirring, the temperature was raised to 80 ° C., held for 1 hour, and then air-cooled to stop the reaction. After reprecipitating in methanol, the filtrate separated by filtration was dried to obtain Binder Resin A1. The number average molecular weight (Mn) of the binder resin A1 was 25,000, and the weight average molecular weight (Mw) was 40,000. Further, the solubility parameter SP (a) of the binder resin A1 was calculated with calculation software. The results are shown in Table 1.

<Binder Resin A: Synthesis of Binder Resin A2>
The following raw materials were charged while introducing nitrogen into a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple.
・ Bisfer A ethylene oxide adduct (2.0 mol addition) 100.0 parts ・ Bisfer A propylene oxide adduct (2.3 mol addition) 38.4 parts ・ Isosorbide 25.5 parts ・ Terephthalic acid 37.3 parts ・31.1 parts of isophthalic acid and 1.3 parts of di (2-ethylhexanoic acid) tin In a nitrogen atmosphere, the mixture containing the above raw materials was reacted at 200 ° C. for 6 hours. Further, 8.3 parts of trimellitic anhydride was added at 210 ° C., and the reaction was carried out under a reduced pressure of 40 mmHg for 7 hours, followed by air cooling to stop the reaction. After reprecipitating in methanol, the filtered residue was dried to obtain a binder resin A2. The number average molecular weight (Mn) of the binder resin A2 was 7300, and the weight average molecular weight (Mw) was 16,200. Further, the solubility parameter SP (a) of the polymer a2 constituting the binder resin A2 was calculated with calculation software. The results are shown in Table 1 above.

<Preparation of Binder Resin A1 and A2 Solution>
In a beaker equipped with a stirrer, 500.0 parts of acetone and 500.0 parts of binder resins A1 and A2 were added, and stirring was continued until the solution was completely dissolved at a temperature of 40 ° C. % Binder resin A1 and A2 solutions were prepared.

<Preparation of radical polymerizable monomer E1>
In the present invention, X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula (9) was used as the monomer E1 having the partial structure X as a part of the compound. Here, R ¹ , R ² , R ^{5 to} R ⁹ are methyl groups, R ⁴ is a propylene group, and R ¹⁰ is a methyl group. The value of n is 60 and the molecular weight is 4600. Further, the solubility parameter SP (X) of the radical polymerizable monomer E1 was calculated by calculation software and found to be 13.5 (J / cm ³ ) ^1/2 .

<Synthesis of radical polymerizable monomer F1>
First, the crystalline polyester 1 was synthesized. The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-1,6-Hexanediol 76.0 parts-Sebacic acid 124.0 parts The system was purged with nitrogen by depressurization, and then stirred at 180 ° C for 6 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing the stirring, and the temperature was further maintained for 2 hours. Crystalline polyester 1 was synthesize | combined by air-cooling when it became a viscous state and stopping reaction.

  Next, 150.0 parts of tetrahydrofuran was added and dissolved in 200.0 parts of the obtained crystalline polyester 1, and 25.9 parts of triethylamine was added. Thereafter, 6.0 parts of acrylic acid chloride was slowly added dropwise in an ice bath. After completion of dropping, the mixture was stirred for 3 hours in an ice bath and further stirred at room temperature for 2 hours. The radical polymerizable monomer F1 having the partial structure Y as a part of the compound was synthesized by performing solvent distillation and reprecipitation with methanol. Table 2 shows the results obtained by measuring the weight average molecular weight Mw of the radical polymerizable monomer F1 and calculating the solubility parameter SP (Y) for the partial structure Y by calculation software.

<Synthesis of radical polymerizable monomer F2>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-Ε-Caprolactone 200.0 parts-Stearyl alcohol 28.1 parts-Dibutyltin oxide 0.1 parts The system was purged with nitrogen by a vacuum operation, and then stirred at 180 ° C for 2 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing the stirring, and the temperature was further maintained for 2 hours. When it became viscous, it was air-cooled to stop the reaction, thereby synthesizing a polyester having a hydroxy group at one end. Thereafter, 150.0 parts of tetrahydrofuran was added and dissolved, and 25.9 parts of triethylamine was added. Then, 38.8 parts of acrylic acid chloride was slowly added dropwise in an ice bath. After completion of dropping, the mixture was stirred for 3 hours in an ice bath and further stirred at room temperature for 2 hours. The solvent was distilled off, and reprecipitation with methanol was performed to obtain a radical polymerizable monomer F2 having the partial structure Y as a part of the compound. Table 2 shows the results of measuring the weight average molecular weight Mw of the radical polymerizable monomer F2 and calculating the solubility parameter SP (Y) for the partial structure Y with calculation software.

<Preparation of radical polymerizable monomer F3>
As the radical polymerizable monomer F3 having a polyether-based partial structure Y, a monomer represented by the following formula (25) (trade name: Light Ester 041MA, manufactured by Kyoeisha Chemical Co., Ltd.) was used. Table 2 shows the results obtained by measuring the weight average molecular weight Mw of the radical polymerizable monomer F3 and calculating the solubility parameter SP (Y) for the partial structure Y using calculation software.

<Synthesis of Polymer Dispersant P1 (Polymer Having Partial Structure X and Partial Structure Y in Side Chain)>
The following raw materials were charged into a reaction vessel equipped with a stirrer and a thermometer as shown in Table 3 while substituting with nitrogen.
-30.0 parts of radical polymerizable monomer E1-50.0 parts of radical polymerizable monomer F1-10.0 parts of styrene-10.0 parts of methacrylic acid-Azobisisobutyronitrile (initiator) 0. 20 parts / toluene 200.0 parts The above mixture was heated to 80 ° C. and reacted for 5 hours. After cooling to room temperature, the reaction solution was dissolved in tetrahydrofuran, poured into methanol, precipitated, and washed to obtain a polymer dispersant P1. Table 4 shows the physical properties of the obtained polymer dispersant P1. The ratio of the partial structure X and the partial structure Y to the polymer dispersant P was determined by 1H-NMR measurement. 1H-NMR measurement was performed by measuring a solution obtained by dissolving the obtained polymer dispersant P1 in chloroform deuterated.

<Synthesis of Polymer Dispersants P2 to P13 (Polymer Having Partial Structure X and Partial Structure Y in Side Chain)>
In the synthesis of the polymer dispersant P1, polymer dispersants P2 to P13 were synthesized in the same manner except that the types of raw materials to be used, the charged amount, the reaction temperature, and the reaction time were changed as shown in Table 3 above. The physical properties of the polymer dispersants P2 to P13 are shown in Table 4 above.

<Preparation of Polymer Dispersant P1 Solution to P13 Solution>
In a beaker equipped with a stirrer, 50.0 parts of acetone and 50.0 parts of polymer dispersants P1 to P13 are charged, and stirring is continued until the solution is completely dissolved at a temperature of 40 ° C., so that the solid content is 50.0. Mass% polymer dispersants P1 to P13 solutions were prepared.

<Preparation of solid fine particle Q1 dispersion>
・ Crystalline polyester 1 16.7 parts ・ Acetone 150.0 parts ・ Glass beads (1 mm) 300.0 parts The above materials are put into a heat-resistant glass container and dispersed for 4 hours in a paint shaker (manufactured by Toyo Seiki). Went. From this dispersion, glass beads were removed with a nylon mesh to obtain a solid fine particle Q1 dispersion having a solid content of 10.0% by mass. Next, the above-mentioned solid fine particle Q1 dispersion was further dispersed using a desktop wet ultra-high pressure fine particle experiment apparatus Nanovaida (manufactured by Yoshida Kikai Kogyo Co., Ltd.). The pressure when discharging the dispersion liquid to the nozzle was set to 190 MPa, and the entire amount of the solid fine particle Q1 dispersion liquid was circulated for 30 cycles to pass. The number average particle diameter of the obtained solid fine particle Q1 dispersion was measured and found to be 120 nm.

<Preparation of solid fine particle Q2 and Q3 dispersion>
As shown in Table 5, solid fine particles Q2 and Q3 dispersions were obtained in the same manner as the preparation method of the solid fine particle Q1 dispersion except that the type of the solid fine particles Q was changed. Table 5 shows the measurement results of the number average particle diameters of the solid fine particles Q2 and Q3.

<Preparation of solid fine particle Q4 dispersion>
In the preparation of the solid fine particle Q1 dispersion, the entire amount of the solid fine particle Q1 dispersion was the same except that it was passed through 80 cycles using a desktop wet ultrahigh pressure fine particle experiment apparatus Nanovaida (manufactured by Yoshida Kikai Kogyo Co., Ltd.). By performing the preparation, a solid fine particle Q4 dispersion was obtained. The results of measuring the number average particle size of the solid fine particle Q4 dispersion are shown in Table 5 above.

<Preparation of solid fine particle Q5 dispersion>
Except that the total amount of the solid fine particle Q1 dispersion liquid when the solid fine particle Q1 dispersion liquid was prepared was passed through 15 cycles using a desktop wet ultra-high pressure atomization experimental device Nanovaida (manufactured by Yoshida Kikai Kogyo Co., Ltd.). A solid fine particle Q5 dispersion was obtained. The results of measuring the number average particle size of the solid fine particle Q5 dispersion are shown in Table 5 above.

<Preparation of colorant dispersion>
・ C. I. Pigment Blue 15: 3 100.0 parts Acetone 150.0 parts Glass beads (1 mm) 300.0 parts The above materials are put into a heat-resistant glass container and dispersed for 5 hours in a paint shaker (manufactured by Toyo Seiki). The glass beads were removed with a nylon mesh to obtain a colorant dispersion having a number average particle size of 200 nm and a solid content of 40.0% by mass.

<Preparation of wax dispersion>
Dipentaerythritol palmitate ester wax 16.0 parts Wax dispersant 8.0 parts (in the presence of polyethylene 15.0 parts, styrene 50.0 parts, n-butyl acrylate 25.0 parts, acrylonitrile 10.0 parts Copolymer having a peak molecular weight of 8,500)
Acetone 76.0 parts The above was put into a glass beaker (made by IWAKI glass) with a stirring blade, and the system was heated to 50 ° C to dissolve the wax in acetone. Next, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid. This solution was put into a heat-resistant container together with 20.0 parts of 1 mm glass beads, dispersed for 3 hours with a paint shaker, glass beads were removed with a nylon mesh, the number average particle size was 270 nm, solid A wax dispersion having an amount of 24.0% by mass was obtained.

<Example 1>
(Manufacture of toner particles 1)
-200.0 parts of binder resin A1 solution-12.0 parts of colorant dispersion liquid-20.0 parts of wax dispersion liquid are put into a container and stirred at 1000 rpm for 1 minute using a disper (manufactured by Tokushu Kika Co., Ltd.). Thus, a resin composition 1 was obtained.

  In the apparatus shown in FIG. 3, the resin composition 1 was charged into the granulation tank t1 with the valves V1, V2 and the pressure adjustment valve V3 closed, and the temperature was adjusted to 30 ° C. While stirring the inside of the granulation tank t1 at a rotational speed of 300 rpm, the valve V1 is opened and carbon dioxide (purity 99.99%) is introduced from the cylinder B1 into the granulation tank t1, and the internal pressure at this time is 2.0 MPa. When the pressure reached the valve V1, the valve V1 was closed. The mass of the introduced carbon dioxide was 250.0 parts as measured using a mass flow meter.

  Next, 20.0 parts of the polymer dispersant P1 solution and 66.0 parts of the solid fine particle Q1 dispersion were charged into the dispersant introduction tank t2, and then the internal temperature was adjusted to 30 ° C. After the valve V4 was opened and the internal pressure of the dispersant introduction tank t2 was 2.5 MPa, the valve V4 was closed. While opening the valve V2 and stirring the inside of the granulation tank t1 at 1000 rpm, the polymer dispersant P1 solution and the solid fine particle Q1 dispersion in the dispersant introduction tank t2 are all put into the granulation tank t1 using the pump P2. Introduced. When all of the mixed liquid was introduced, the valve V2 was closed and the pump P2 was stopped. After the introduction, the internal pressure of the granulation tank t1 was 2.2 MPa. The total mass of carbon dioxide introduced was 285.0 parts as measured using a mass flow meter. After confirming that the temperature in the granulation tank t1 was 30.0 ° C., granulation was performed by stirring for 10 minutes at a rotational speed of 1000 rpm to prepare droplets.

  Next, the rotational speed was reduced to 300 rpm, the valve V1 was opened, the pressure in the granulation tank t1 was set to 5.0 MPa, and then the valve V1 was closed. After 5 minutes, the valve V1 was opened, and carbon dioxide was introduced from the cylinder B1 into the granulation tank t1 using the pump P1. At this time, the pressure adjusting valve V3 was set to 8.0 MPa, and carbon dioxide was further circulated while maintaining the internal pressure of the granulation tank t1 at 8.0 MPa. By this operation, carbon dioxide containing the organic solvent (acetone) extracted from the granulated droplets was discharged to the solvent recovery tank t3, and the organic solvent and carbon dioxide were separated.

  After 1 hour, the pump P1 is stopped, the valve V1 is closed, the pressure adjusting valve V3 is opened little by little, and the internal pressure of the granulation tank t1 is reduced to atmospheric pressure, thereby collecting the toner particles 1 captured by the filter. did.

<Examples 2-29 and Comparative Examples 1-6>
In Example 1, toner particles 2 to 29 and comparative toner particles 1 to 6 were obtained in the same manner as in Example 1 except that the types of raw materials used and the amounts charged were changed as shown in Table 6.

  Table 6 shows the adsorption rate obtained by the above-described method in the combination of the polymer dispersant P and the solid fine particles Q used as the raw materials of Examples 1 to 29 and Comparative Examples 1 to 6. The mass ratio of the polymer dispersant P to the solid fine particles Q, the total mass ratio of the polymer dispersant P and the solid fine particles Q to the binder resin A, and the values of SP (Y) -SP (X) are also shown in Table 6. Shown in

  In Table 6, “mass ratio of the polymer dispersant P” means the mass ratio of the polymer dispersant P to the solid fine particles Q. Further, “the total mass ratio of the polymer dispersant P and the solid fine particles Q” means the total mass ratio of the polymer dispersant P and the solid fine particles Q to the binder resin A.

(Evaluation method of toner particles)
The obtained toner particles were evaluated by measuring the particle size, particle size distribution, and the ratio of fine powder in the toner particles. Table 7 shows the evaluation results. The evaluation criteria are as follows.
(I) Particle size distribution D4 / D1
A: D4 / D1 value is less than 1.15 B: D4 / D1 value is 1.15 or more and less than 1.20 C: D4 / D1 value is 1.20 or more and less than 1.30 D: D4 / D1 value is 1. 30 to less than 1.40 E: D4 / D1 value is 1.40 or more (ii) Fine powder ratio of toner particles Fine powder ratio (%) of 2.0 μm or less
A: Less than 5.0% B: 5.0% or more and less than 10.0% C: 10.0% or more and less than 15.0% D: 15.0% or more and less than 20.0%

010 Polymer dispersant P
020 Main chain 030 Partial structure X
040 Partial structure Y
100 Polymer dispersant P
110 Segment with Partial Structure X as Stem Part 120 Segment with Partial Structure Y as Stem Part 200 Polymer Dispersant P
210 Segment with Partial Structure X as Trunk Site 220 Segment Made of Graft Polymer Having Partial Structure Y as Branch Site 230 Main Chain 240 Partial Structure Y
300 Polymer Dispersant P
310 Segment having partial structure Y as trunk site 320 Segment made of graft polymer having partial structure X as branch site 330 Main chain 340 Partial structure X
t1 granulation tank t2 dispersant introduction tank t3 solvent recovery tank B1 cylinder P1 pump P2 pump V1 valve V2 valve V4 valve V3 pressure regulating valve

Claims (13)

A method for producing toner particles, the production method comprising:
a) A binder resin A, a colorant, a polymer dispersant P, solid fine particles Q, an organic solvent, and a dispersion medium are mixed, and the surface is the polymer dispersant P, and the polymer dispersant P is the solid fine particles. A step of forming a droplet containing the binder resin A, the colorant, and the organic solvent covered with the composite fine particles adsorbed on Q; and b) removing the organic solvent contained in the droplet. Process,
A method for producing toner particles, comprising:   The method for producing toner particles according to claim 1, wherein an adsorption rate of the polymer dispersant P to the solid fine particles Q is 15.0% or more. The polymer dispersant P is a polymer having a partial structure X and a partial structure Y,
The partial structure X has an organic polysiloxane structure represented by the following formula (1):

(In formula (I), R ¹ and R ² each independently represents an alkyl group having 1 to 3 carbon atoms, and n is 2 or more and 150 or less.)
The method for producing toner particles according to claim 1 or 2, wherein the solubility parameter SP (X) of the partial structure X and the solubility parameter SP (Y) of the partial structure Y satisfy the following formula (2).
3.0 ≦ SP (Y) −SP (X) (2)   The method for producing toner particles according to claim 3, wherein the polymer dispersant P contains the partial structure Y in an amount of 30.0 mass% to 70.0 mass%.   The method for producing toner particles according to claim 3, wherein the partial structure Y has a polyester structure.   The method for producing toner particles according to claim 1, wherein the polymer dispersant P has a weight average molecular weight of 50,000 or more and 500,000 or less.   The method for producing toner particles according to claim 1, wherein the solid fine particles Q are resin fine particles.   The method for producing toner particles according to claim 7, wherein the resin constituting the resin fine particles is polyester.   The method for producing toner particles according to claim 1, wherein the solid fine particles Q have a number average particle diameter of 40 nm to 200 nm. The binder resin A is
A polymer of a monomer composition comprising at least one monomer selected from the group consisting of styrene, styrene derivatives, acrylates, and methacrylates, or polyester,
The method for producing toner particles according to claim 1, comprising:   The method for producing toner particles according to claim 1, wherein a mass ratio of the polymer dispersant P to the solid fine particles Q is 0.3 or more and 3.0 or less.   12. The toner particles according to claim 1, wherein a total mass ratio of the polymer dispersant P and the solid fine particles Q to the binder resin A is 0.08 or more and 0.30 or less. Production method. The method for producing toner particles according to claim 1, wherein the dispersion medium contains carbon dioxide in a liquid state or a supercritical state.

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