JP2017044932A - Manufacturing method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a toner that has a sharp particle size distribution, the method capable of reducing power consumption during the manufacture.SOLUTION: There is provided a manufacturing method of a toner including the steps of: (a) stirring a mixture of a binder resin, colorant, organic solvent that can dissolve the binder resin, vinyl resin P, fine particles Q, and dispersion medium to form droplets containing the binder resin, the colorant, and the organic solvent; and (b) removing the organic solvent included in the droplets to obtain toner particles, wherein the binder resin contains crystalline polyester; the vinyl resin P is a resin obtained by polymerizing a compound 1 and a compound 2 having a specific structure; the volume average molecular weight (Mw) of the vinyl resin P is 10,000 or more and 50,000 or less; the mole fraction of a structural unit derived from the compound 1 in the vinyl resin P to the vinyl resin P is 0.40 or more and 0.95 or less; the ratio of the average value L2 of the lengths of the side chains of the structural unit derived from the compound 2 to the average value L1 of the lengths of the side chains of the structural unit derived from the compound 1 in the vinyl resin P (L2/L1) is 1.0 or more and 4.0 or less; the number average particle diameter (D1) of primary particles of the fine particles Q is 40 nm or more and 200 nm or less.SELECTED DRAWING: None

Description

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

  In recent years, energy saving has been considered as a technical problem in electrophotographic apparatuses, and a drastic reduction in the amount of heat applied to a fixing apparatus has been studied. Accordingly, there is a growing need for so-called “low-temperature fixability” that can fix toner with lower energy. In addition, there is a demand for an electrophotographic apparatus that can obtain an image with high image quality and no deterioration in image quality even when a large number of copies or prints are made. Therefore, in addition to the low-temperature fixability, the toner is required to achieve both high image quality and high durability.

  In order to improve image quality with toner, it is necessary to suppress variation in performance of each toner. For this purpose, it is effective to make the toner particles equal in particle size, that is, to sharpen the particle size distribution. As a method for producing a toner with relatively easy particle size distribution, a resin solution in which a resin is dissolved in an organic solvent is dispersed in a dispersion medium in the presence of a dispersant to form droplets of the resin solution. Then, the “dissolution suspension method” is known in which the organic solvent is removed to obtain resin particles. In particular, in a method using a low-polarity medium as a dispersion medium, a low-polarity dispersant can be used as compared with a method using water as a dispersion medium, and toner particles having excellent electrical stability can be obtained. This is advantageous. Another feature is that inorganic fine particles can be used as a dispersant.

  Patent Documents 1 and 2 propose a production method in which resin particles are produced using liquid or supercritical carbon dioxide as a dispersion medium and silica particles that are inorganic fine particles as a dispersant.

  On the other hand, energy saving is considered as a major technical problem in toner production. The solution suspension method using liquid or supercritical carbon dioxide as the dispersion medium does not require washing and drying steps for toner removal compared to the aqueous solution suspension method, so it can reduce power consumption. There is.

JP 2007-277511 A JP 2010-168522 A

  When the present inventors examined the methods described in Patent Documents 1 and 2, it was found that resin particles having a good particle size distribution were not necessarily obtained. The reason is that the number average diameter of the primary particles of the silica particles used is as small as about 15 nm, so that the formed droplets are easily united. Therefore, there has been a problem in further sharpening the particle size distribution.

  The present invention has been made in view of the above problems, and provides a toner production method that has a sharp particle size distribution and can further reduce power consumption during production.

The present invention is a method for producing a toner having toner particles containing a binder resin, a colorant, and a vinyl resin P,
The manufacturing method is
a) A mixture of the binder resin, the colorant, the organic solvent, the vinyl resin P, the fine particles Q, and the dispersion medium is stirred to form droplets containing the binder resin, the colorant, and the organic solvent. The process of
b) removing the organic solvent contained in the droplets to obtain toner particles;
Have
The binder resin contains crystalline polyester;
The vinyl resin P is a resin obtained by polymerizing the compound 1 represented by the following formula (1) and the compound 2 represented by the following formula (2),
The vinyl resin P has a weight average molecular weight (Mw) of 10,000 or more and 50,000 or less,
The molar fraction of the structural unit derived from the compound 1 with respect to the vinyl resin P is 0.40 or more and 0.95 or less,
The ratio L2 / L1 between the average value L1 of the side chain length of the structural unit derived from the compound 1 and the average value L2 of the side chain length of the structural unit derived from the compound 2 is 1.0 or more and 4.0 or less. Yes,
The number average diameter (D1) of primary particles of the fine particles Q is 40 nm to 200 nm.

（式（１）中、Ｒ¹は水素原子またはメチル基を表す。Ｒ²からＲ⁶はそれぞれ独立して炭素数１以上３以下のアルキル基を表す。Ａは１以上３以下の整数であり、Ｂは括弧内の構造の繰り返し数を示し、化合物１における重合度は、１以上である。）

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² to R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms. A is an integer of 1 to 3) And B represents the number of repetitions of the structure in parentheses, and the degree of polymerization in Compound 1 is 1 or more.

（式（２）中、Ｒ⁷は水素原子またはメチル基を表す。ｎは１以上３以下の整数であり、Ｘは０または１である。Ｒ⁸は水素又は炭素数１以上３以下のアルキル基を表す。Ｄは１以上の整数である。）

(In the formula (2), R ⁷ represents a hydrogen atom or a methyl group. N is an integer of 1 to 3 and X is 0 or 1. R ⁸ is hydrogen or an alkyl having 1 to 3 carbon atoms. Represents a group, D is an integer of 1 or more.)

  According to the present invention, it is possible to provide a production method capable of producing a toner having a sharp particle size distribution and further reducing power consumption during production.

It is a figure which shows an example of the manufacturing apparatus of the manufacturing method of the toner of this invention.

The present invention is a method for producing a toner having toner particles containing a binder resin, a colorant, and a vinyl resin P,
a) A mixture of the binder resin, the colorant, the organic solvent, the vinyl resin P, the fine particles Q, and the dispersion medium is agitated to form droplets containing the binder resin, the colorant, and the organic solvent. Forming step,
b) removing the organic solvent contained in the droplets to obtain toner particles;
Have
The binder resin contains crystalline polyester;
The vinyl resin P is a resin obtained by polymerizing a compound 1 represented by the following formula (1) and a compound 2 represented by the following formula (2),
The vinyl resin P has a weight average molecular weight (Mw) of 10,000 or more and 50,000 or less,
The molar fraction of the structural unit derived from the compound 1 in the vinyl resin P with respect to the vinyl resin P is 0.40 or more and 0.95 or less,
The ratio L2 / L1 between the average value L1 of the side chain length of the structural unit derived from the compound 1 in the vinyl resin P and the average value L2 of the side chain length of the structural unit derived from the compound 2 is 1.0. Is 4.0 or less,
The number average diameter (D1) of primary particles of the fine particles Q is 40 nm or more and 200 nm or less.

  The steps a) and b) are hereinafter referred to as a droplet formation step and a solvent removal step, respectively.

  In the droplet forming step in the present invention, the binder resin, the colorant, and the material contained in the toner particles are mixed with the binder resin in an organic solvent to obtain a resin solution, and the resin solution and dispersion are obtained. A stirring step of mixing and stirring the medium; The vinyl resin P and the fine particles Q may be mixed in a resin solution or in a dispersion medium. It is also possible to add the vinyl resin P and fine particles Q after mixing the resin solution and the dispersion medium.

  By passing through the dissolution and dispersion step and the stirring step, droplets containing a binder resin, a colorant and an organic solvent can be obtained.

  The binder resin used in the production method of the present invention contains a crystalline polyester. In general, crystalline polyester hardly softens to near the melting point, melts from near the melting point, and softens rapidly. Such a resin exhibits a clear melting point peak in differential scanning calorimetry using a differential scanning calorimeter (DSC). Therefore, the crystalline polyester is likely to exhibit good low-temperature fixability due to the low viscosity after melting.

  In the present invention, the organic solvent is preferably an organic solvent capable of dissolving a resin containing a crystalline polyester. That is, it is preferable to use an organic solvent having an affinity for polyester. Examples of the organic solvent 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 An amide solvent such as dimethylformamide and dimethylacetamide; an aromatic hydrocarbon solvent such as toluene, xylene and ethylbenzene;

  In the dissolution and dispersion step, additives other than the binder resin are preferably dissolved or finely dispersed in an organic solvent. The binder resin and the colorant and other additives can be dissolved or dispersed by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser.

  As the dispersion medium, an aqueous medium is generally used, but in the present invention, it is preferable to use a low-polarity dispersion medium. A low-polarity dispersion medium means a dispersion medium whose polarity is lower than that of an organic solvent. Examples of the dispersion medium include the following. Hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, hexadecane and cyclohexane; silicone solvents such as polydimethylsiloxane.

  Moreover, it is also one of the preferable forms to use a carbon dioxide as a dispersion medium. Carbon dioxide may be used alone as a dispersion medium, and an organic solvent may be contained as another component. In this case, it is preferable that carbon dioxide and the organic solvent form a homogeneous phase. Moreover, it is preferable that content of the carbon dioxide in a dispersion medium is 50 mass% or more.

  In the solvent removal step of the present invention, toner particles are obtained by removing the organic solvent contained in the droplets. The method for removing the organic solvent is not particularly limited, but a method in which the organic solvent is distilled off while heating under reduced pressure, and the organic solvent is removed together with the inert gas while flowing an inert gas such as nitrogen. And a method of adding a dispersion medium and gradually removing the organic solvent transferred from the droplets into the dispersion medium.

  The production method of the present invention is characterized in that, in the droplet forming step, a vinyl resin P having affinity for both the resin solution and the dispersion medium is used as a dispersant. In addition to the vinyl resin P, the fine particles Q are further used as a dispersant.

  When the vinyl resin P is used alone, the stability of the droplets in the droplet forming step can be obtained, but the stability is lost before the toner particles are taken out through the solvent removal step, and the particle size is increased. Or particle size distribution may increase. This is thought to be due to the following. The vinyl resin P functions in a liquid state at the time of granulation, lowers the interfacial energy of the droplets, and can realize the formation of fine particles in the droplet forming step, but the coalescence prevention ability is not always sufficient. In the solvent removal step, the composition of the resin solution that forms the droplets changes as the solvent is removed, and the viscosity of the droplets increases. In particular, in a production method using carbon dioxide as a dispersion medium, this tendency becomes more prominent because it may be necessary to increase the amount of carbon dioxide introduced during the transition from the droplet formation step to the solvent removal step. As a result, the coalescence due to the collision between the droplets cannot be suppressed and the particle size is increased and the particle size distribution is increased. Increasing the molecular weight of the vinyl-based resin P is an effective means to suppress this, but if the molecular weight is too large, the stirring power during shearing in the droplet formation process increases, increasing the manufacturing cost. It is not preferable because it leads to.

  As a result of investigations by the present inventors, by adding fine particles Q in addition to vinyl resin P, it is possible to obtain particles having a uniform particle size even with respect to the composition variation of the resin solution in the solvent removal step. It became. This is because, when the fine particles Q have an appropriate particle diameter and are present on the surface of the droplets, they act as steric hindrance and can suppress coalescence of droplets sheared by stirring.

(Vinyl resin P)
The vinyl resin P used in the production method of the present invention will be described in detail.

  The vinyl resin P is a resin obtained by polymerizing the compound 1 represented by the following formula (1) and the compound 2 represented by the following formula (2).

  Compound 1 is a vinyl monomer containing a silicone group.

In the formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² to R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms. A is an integer of 1 or more and 3 or less, B represents the number of repetitions of the structure in parentheses, and the polymerization degree of B in Compound 1 is 1 or more. Furthermore, the polymerization degree of B is preferably 1 or more and 500 or less, and more preferably 3 or more and 200 or less.

  Compound 1 has an affinity for a low polarity dispersion medium. Moreover, the affinity with the binder resin, crystalline polyester, and organic solvent contained in the resin solution is low. Therefore, it acts as an affinity group for the dispersion medium.

  On the other hand, Compound 2 is a vinyl monomer containing a polyether group.

In the formula (2), R ⁷ represents a hydrogen atom or a methyl group. n is an integer of 1 to 3, and X is 0 or 1. R ⁸ represents hydrogen or an alkyl group having 1 to 3 carbon atoms. D is an integer of 1 or more. Furthermore, D is preferably 1 or more and 500 or less, and more preferably 3 or more and 200 or less.

  Compound 2 has an affinity for crystalline polyester. In addition, the affinity with the dispersion medium is low.

  Therefore, it acts as an affinity group for the droplets of the resin solution.

  Further, examples of a preferable structure of the compound 2 include the following formulas (3) to (7).

  Furthermore, since the compound 1 and the compound 2 have high affinity with an organic solvent, the vinyl resin P can also be kept in a liquid state during granulation. That is, the vinyl resin P has a function as an amphiphilic dispersant having an affinity group for the dispersion medium and an affinity group for the droplets of the resin solution.

  In the present invention, regarding the identification of the structure, compound 1 is determined from the structure identification by NMR, and compound 2 is determined from the manufacturer's catalog.

  The weight average molecular weight (Mw) of the vinyl resin P is 10,000 or more and 50,000 or less. When the weight average molecular weight (Mw) is 10,000 or more, sufficient adsorptivity to the droplet derived from the mobility of the polymer chain, which is a characteristic of the vinyl resin P, can be obtained, and the droplet can be used for a long time. It can be stabilized. On the other hand, when the weight average molecular weight (Mw) exceeds 50,000, the stirring power at the time of shearing in the droplet forming process increases, and the production cost increases. More preferably, the weight average molecular weight (Mw) is 15,000 or more and 40,000 or less.

  The molar fraction of the structural unit derived from the compound 1 in the vinyl resin P with respect to the vinyl resin P is 0.40 or more and 0.95 or less. If the content mole fraction of Compound 1 is 0.40 or more, it can effectively act as an affinity group for the dispersion medium. On the other hand, when the content molar fraction of the monomer of compound 1 is larger than 0.95, the amount acting as a parent dispersion group with the crystalline polyester is small, so that it is difficult to adsorb to the crystalline polyester, and the polymer dispersion It becomes difficult to function as an agent.

  A more preferable range of the mole fraction of monomer of compound 1 is 0.60 or more and 0.90 or less. Within this range, the dispersion effect of the compound 1 on the dispersion medium can be further enhanced, and at the same time, the adsorptivity to the resin solution by the compound 2 can be enhanced. It can have a function as an agent.

  In the present invention, the ratio L2 / L1 between the average value L1 of the side chain length of the structural unit derived from the compound 1 in the vinyl resin and the average value L2 of the side chain length of the structural unit derived from the compound 2 is 1.0. It is necessary to be 4.0 or more. The side chain length indicates the extended chain length from the carbonyl carbon of the side chain to the end of the side chain in the formulas (1) and (2), and the bond angle is calculated as 180 °. Moreover, when it has a branch in a side chain, let the longest bond length among the branched length be a side chain length. The method for calculating the side chain length is the sum of the covalent bond radii of each element.

  The side chain length ratio L2 / L1 corresponds to the ratio of the length when the side chains of compound 1 and compound 2 are most extended, and therefore compound 1 and compound 2 interact with the dispersion medium and the dispersoid, respectively. Related parameters. The side chain length ratio L2 / L1 is 1.0 or more is a case where the side chain length of the compound 1 and the side chain length of the compound 2 have a side chain length equal to or greater than that. With such a combination, it is possible to act without blocking the dispersoid adsorption effect of the side chain of compound 2 by the side chain of compound 1. Further, when the side chain length ratio L2 / L1 is 4.0 or less, the combination can act without inhibiting the dispersion effect of the side chain of Compound 1 on the dispersion medium by the side chain of Compound 2. it can.

  A more preferable range of the side chain length ratio L2 / L1 is 1.2 or more and 3.0 or less. Within this range, the adsorption action to the dispersoid by the compound 2 becomes more effective, and at the same time, the inhibition of the compound 2 by the compound 2 is limited, so that the function as a polymer dispersant having a higher dispersion stabilizing effect is achieved. Can be obtained.

  In this invention, it is preferable that the usage-amount of vinyl resin P is 5.0 to 50.0 mass% with respect to binder resin. By being in this range, the ratio of the vinyl resin P to the droplet surface in the droplet formation step becomes appropriate, and the droplet stabilization effect at the time of toner production can be effectively exhibited. In addition, it is more preferable that the amount of the vinyl resin P used is 50.0% by mass or less with respect to the binder resin because the particle size distribution of the obtained toner particles becomes small (sharp).

  The vinyl resin P may be any of a random copolymer, an alternating copolymer, and a block copolymer composed of at least compound 1 and compound 2.

  Further, Compound 1 may be a mixture of a plurality of compounds as long as Compound 1 satisfies Formula 1 and Compound 2 satisfies Formula 2.

  In addition to the compound 1 and the compound 2, the vinyl resin P may be copolymerized with another vinyl compound as long as the liquid state can be maintained during granulation. In this case, it is preferable that the constituent parts of the compound 1 and the compound 2 become the main component of the vinyl resin P. More preferably, the constituent parts of Compound 1 and Compound 2 are contained in an amount of 70 mol% or more based on the total number of moles of the vinyl resin P. More preferably, it is 90 mol% or more.

  The vinyl resin P can be obtained by radical polymerization from a mixed solution containing the compound 1 and the compound 2.

  Specifically, compound 1 and compound 2 are dissolved in a general organic solvent, and if necessary, other vinyl compounds and radical polymerization initiators are dissolved and heated after degassing to contain compound 1 and compound 2. A copolymer can be obtained.

  In the present invention, conventionally known radical polymerization initiators can be applied. Among these, an oil-soluble radical polymerization initiator that is soluble in an organic solvent that dissolves Compound 1 and Compound 2 is preferable. Specifically, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2-methylpropanenitrile), 2,2′-azobis- (2,4-dimethylpentanenitrile), 2 , 2′-azobis- (2-methylbutanenitrile), 1,1′-azobis- (cyclohexanecarbonitrile), 2,2′-azobis- (2,4-dimethyl-4-methoxyvaleronitrile), 2, 2′-azobis- (2,4-dimethylvaleronitrile) azo polymerization initiator, dibenzoyl peroxide, cumene hydroperoxide, di-2-ethylhexyl peroxydicarbonate, di-sec-butylperoxydi Carbonate, acetyl peroxide, peracid ester (t-butylperoctate, α-cumylperoxypivalate and t-butylperoxide It can be exemplified an organic peroxide-based polymerization initiator Tate). An acetophenone-based or ketal-based radical photopolymerization initiator is also applicable.

  In the present invention, examples of the polymerization solvent include general organic solvents such as toluene, benzene, chloroform, and ethyl acetate, but are not limited thereto. It is also possible to use two or more organic solvents.

  The vinyl resin P can also be obtained by living radical polymerization of atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), or nitroxide-mediated radical polymerization (NMP).

(Fine particle Q)
The fine particles Q used in the present invention are adsorbed on the surface of the droplets by the resin solution at the time of granulation, thereby preventing the coalescence of the droplets and improving the dispersion stability. Therefore, it is necessary to use fine particles Q that are somewhat large. Further, when the fine particles Q remain on the surface of the toner particles, it is possible to provide a function as a spacer for suppressing deterioration of the external additive of the toner, like the large particle size external additive.

  The number average diameter (D1) of the primary particles of the fine particles Q needs to be 40 nm or more and 200 nm or less.

  When the number average diameter of the primary particles of the fine particles Q is smaller than 40 nm, the effect of preventing the droplets from being coalesced cannot be exhibited, and the particle size distribution of the toner particles becomes wide. When it is larger than 200 nm, it is difficult to perform uniform surface coating, and it becomes difficult to obtain toner particles having a particle diameter suitable as a toner. A more preferable range of the number average diameter of the primary particles of the fine particles Q is 60 nm or more and 150 nm or less.

  In the present invention, the amount of fine particles Q used is preferably 1.0% by mass or more and 10.0% by mass or less with respect to the binder resin. By being in this range, the ratio of the fine particles Q to the droplet surface becomes appropriate, and the steric hindrance effect for preventing the coalescence of the droplets can be effectively exhibited. In addition, it is more preferable that the amount of the fine particles Q used is 10.0% by mass or less with respect to the binder resin because the fine particle ratio of the obtained toner particles becomes small.

  In the present invention, the fine particles Q can be inorganic fine particles or resin fine particles.

  Hereinafter, the inorganic fine particles will be described in detail.

  Examples of the inorganic fine particles include fine particles such as silica, alumina, titania, and composite oxide fine particles thereof. 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.

  Furthermore, the inorganic fine particles are preferably subjected to a hydrophobic treatment. By being hydrophobized, the inorganic fine particles are likely to be located at the interface between the droplet and the hydrophobic dispersion medium, and the dispersion stability of the droplet is easily improved.

  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; salts of said 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 known method can be used.

  When the inorganic fine particles are left on the toner particle surface, the surface coverage of the inorganic fine particles with respect to the toner particles is preferably 10% or more and 50% or less. When the surface coverage is in the above range, the spacer effect for suppressing the deterioration of the external additive of the toner can be more effectively expressed, and the durability can be improved. That is, when the surface coverage is 10% or more, the area where the inorganic fine particles are not present on the toner particle surface is reduced, and as a result, the spacer effect is easily exhibited. When the surface coverage is 50% or less, the low temperature fixability is not inhibited by the inorganic fine particles.

  Next, resin fine particles will be described.

  As the resin constituting the resin fine particles, either a crystalline resin or an amorphous resin can be used.

  The resin fine particles are preferably present in a solid state from the droplet forming step to the toner particles through the solvent removal step. Therefore, it is preferable to use a resin whose solubility in an organic solvent is suppressed by adjusting the molecular weight or introducing a crosslinked structure, a polar group or a nonpolar group.

  Examples of the crystalline resin that can be used for the resin fine particles include crystalline polyester and crystalline alkyl resin.

  As the crystalline polyester, it is preferable to use an aliphatic diol having 4 to 20 carbon atoms and a polyvalent carboxylic acid as raw materials. Furthermore, it is desirable that the aliphatic diol is linear.

  Although the following can be mentioned as a linear aliphatic diol used suitably by this invention, It is not limited to this. Depending on the case, it is also possible to use a mixture. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol. Among these, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferable from the viewpoint of the melting point.

  As the polyvalent carboxylic acid, an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid are preferable. Among them, an aliphatic dicarboxylic acid is preferable, and a linear aliphatic dicarboxylic acid is particularly preferable.

  Examples of the aliphatic dicarboxylic acid include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. 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, 1,18-octadecanedicarboxylic acid. Or its lower alkyl ester and acid anhydride. Of these, sebacic acid, adipic acid, 1,10-decanedicarboxylic acid or its lower alkyl ester and acid anhydride are preferred.

  Examples of the aromatic dicarboxylic acid include the following. Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid.

  There is no restriction | limiting in particular as a manufacturing method of crystalline polyester, It can manufacture by the general polyester polymerization method which makes an acid monomer and an alcohol monomer react. The direct polycondensation and transesterification methods are used according to the type of monomer.

  The production of the crystalline polyester is preferably performed at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower, and the reaction system is preferably subjected to a reaction while reducing the pressure in the reaction system and removing water and alcohol generated during condensation. . When the monomer is not dissolved or compatible at the reaction temperature, it is preferable to dissolve it by adding an organic solvent having a high boiling point as a solubilizing agent. In the polycondensation reaction, the dissolution aid is distilled off. In the case where a monomer having poor compatibility exists in the copolymerization reaction, it is preferable to condense the monomer having poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance and then polycondense together with the main component.

  Examples of the catalyst that can be used in the production of the crystalline polyester include the following. Titanium catalyst of titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide. Tin catalyst of dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide.

  The melting point of the crystalline polyester is preferably 50 ° C. or higher and 120 ° C. or lower, and more preferably 50 ° C. or higher and 90 ° C. or lower in consideration of melting at the fixing temperature.

  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. 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, but are not limited to, vinyl resins such as polyurethane resins, polyester resins, styrene acrylic resins, and polystyrene. These resins may be modified with urethane, urea, or epoxy.

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

  Examples of the diisocyanate component include the following. Aromatic diisocyanates having 6 to 20 carbon atoms, aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and diisocyanates thereof (excluding carbon in the NCO group, the same shall apply hereinafter) Modified product (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product, hereinafter also referred to as modified diisocyanate), and two or more of these Mixture of.

  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.

  Aromatic diisocyanates include the following. m- and / or p-xylylene diisocyanate (XDI), α, α, α ', α'-tetramethylxylylene diisocyanate.

  Of these, preferred are HDI, IPDI, and XDI.

  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.

  The polyester resin as the amorphous resin will be described. An amorphous polyester can be produced by a condensation reaction of a polyhydric alcohol and a polyvalent carboxylic acid.

  Examples of the monomer used in the polyester resin as the amorphous resin include the following compounds. Divalent carboxylic acids include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenyl succinic acid dibasic acid, anhydrides thereof and lower alkyl esters thereof, maleic acid , Fumaric acid, itaconic acid, citraconic acid aliphatic unsaturated dicarboxylic acid. Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, anhydrides thereof, and 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. Bisphenol A, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, propylene glycol. Examples of the trivalent or higher alcohol include the following compounds. Glycerin, trimethylol ethane, trimethylol propane, pentaerythritol. These may be used individually by 1 type and may use 2 or more types together. If necessary, a monovalent acid such as acetic acid or benzoic acid, or a monovalent alcohol such as cyclohexanol or benzyl alcohol can be used for the purpose of adjusting the acid value or the hydroxyl value.

  The polyester resin as the amorphous resin contains a trivalent or higher polyvalent monomer, that is, a trihydric or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound from the viewpoint of solvent solubility. Preferably it is. By containing these polyvalent monomers, it becomes possible for the polyester resin to have a crosslinked structure and to impart insolubility to an organic solvent.

  The glass transition temperature (Tg) of the amorphous resin in the resin fine particles of the present invention is preferably 50 ° C. or higher and 130 ° C. or lower. More preferably, it is 50 degreeC or more and 100 degrees C or less.

  Moreover, it is preferable that resin which comprises the resin fine particle of this invention is resin which contains the organic polysiloxane structure shown by following formula (8) in molecular structure.

The organic polysiloxane structure is a structure having a repeating unit of SiO bond and further having two alkyl groups bonded to the Si. In the formula, R ⁹ represents an alkyl group. The alkyl group preferably has 1 to 3 carbon atoms, and more preferably R ⁹ has 1 carbon atom. N is the degree of polymerization and is an integer of 2 or more.

  In the present invention, the degree of polymerization n of the organic polysiloxane structure is preferably an integer of 2 or more and 100 or less. When the degree of polymerization n is 100 or less, the resin fine particles are difficult to soften, and the durability of the toner is further improved. More preferably, it is an integer of 2 or more and 15 or less.

  The content of the organic polysiloxane structure in the resin constituting the resin fine particles is preferably 5.0% by mass or more and 30.0% by mass or less, and more preferably 5. 5% by mass or less with respect to the resin constituting the resin fine particles. It is 0 mass% or more and 20.0 mass% or less.

  The method of introducing the organic polysiloxane structure into the molecular structure is not particularly limited, and examples thereof include a method of copolymerizing the vinyl monomer containing the organic polysiloxane structure with another vinyl monomer.

  As the other vinyl monomer, a monomer of an ordinary resin material can be used. Although illustrated below, this is not restrictive.

  Aliphatic vinyl hydrocarbons: alkenes, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins; alkadienes, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene and 1,7-octadiene.

  Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes, cyclohexene, cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene; terpenes, pinene, limonene, indene.

  Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene , Phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene; and vinylnaphthalene.

  Carboxyl group-containing vinyl monomer and metal salt thereof: unsaturated monocarboxylic acid having 3 to 30 carbon atoms, unsaturated dicarboxylic acid and anhydride and monoalkyl (1 to 27 carbon atoms) ester, acrylic acid, methacrylic acid Acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester Cinnamic acid carboxyl group-containing vinyl monomer.

  Vinyl esters: vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, vinyl methoxy Acetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl acrylate and alkyl methacrylate having 1 to 11 carbon atoms (linear or branched) (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl) Methacrylate, butyl acrylate, butyl methacrylate, 2-ethyl Xyl acrylate, 2-ethylhexyl methacrylate, dialkyl fumarate (dialkyl fumarate) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl Maleate (maleic acid dialkyl ester) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), polyallyloxyalkanes (diallyloxyethane) , Triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane), vinyl monomers having a polyalkylene glycol chain (polyethylene glycol (molecular weight 300) monoacrylate, polyethylene glycol ( 300 molecular weight monomethacrylate, poly Propylene glycol (molecular weight 500) monoacrylate, polypropylene glycol (molecular weight 500) monomethacrylate, methyl alcohol ethylene oxide (ethylene oxide is hereinafter abbreviated as EO) 10 mol adduct acrylate, methyl alcohol ethylene oxide (ethylene oxide is abbreviated as EO hereinafter) 10 mol adduct methacrylate, lauryl alcohol EO 30 mol adduct acrylate lauryl alcohol EO 30 mol adduct methacrylate), polyacrylates and polymethacrylates (polyacrylates and polymethacrylates of polyhydric alcohols: ethylene glycol diacrylate, ethylene glycol) Dimethacrylate, propylene glycol diacrylate, propylene glycol dimethac Rate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyethylene glycol diacrylate. Polyethylene glycol dimethacrylate.

  Among these, styrene and methacrylic acid are preferably copolymerized as other vinyl monomers.

  Furthermore, as another vinyl monomer, it is one of preferred modes to use a vinyl monomer having a polyester portion capable of taking a crystal structure. The polyester part that can take the crystal structure means a part that regularly arranges and expresses crystallinity when a large number of polyester parts are aggregated, that is, a crystalline polyester component. The crystalline polyester described above can be used as the crystalline polyester component.

  As a method for producing a vinyl monomer having the crystalline polyester component, radical polymerization can be performed on a polyester chain by urethanizing the crystalline polyester component and a hydroxyl group-containing vinyl monomer with a diisocyanate as a binder. Examples thereof include a method for producing a monomer having an urethane group by introducing an unsaturated group. For this reason, the crystalline polyester component is preferably alcohol-terminated. Therefore, in the preparation of the crystalline polyester component, the molar ratio of the acid component to the alcohol component (alcohol component / carboxylic acid component) is preferably 1.02 or more and 1.20 or less.

  As the diisocyanate, the above-described diisocyanate component is preferably used.

  As the hydroxyl group-containing vinyl monomer, hydroxystyrene, N-methylolacrylamide, N-methylolmethacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol monoacrylate, 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 alcohol, 2-hydroxyethylpropenyl ether Sucrose allyl ether. Of these, preferred are hydroxyethyl acrylate and hydroxyethyl methacrylate.

  In the present invention, a preferable range of the copolymerization ratio of the vinyl monomer having the crystalline polyester portion in the resin fine particles is 15.0% by mass or more and 50.0% by mass or less with respect to 100% by mass of all monomers. By being in this range, it becomes easy to express good low-temperature fixability.

  The weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the resin fine particles in the present invention is preferably 20,000 or more and 80,000 or less. By being in this range, the shell phase has an appropriate hardness and durability is improved. That is, if it is 20,000 or more, the durability is improved, and if it is 80,000 or less, the fixing property is not lowered.

(Binder resin)
The binder resin used in the present invention will be described. The binder resin in the present invention contains a crystalline polyester that is a crystalline resin in order to facilitate the development of good low-temperature fixability. The crystalline resin means a resin having a structure in which polymer molecular chains are regularly arranged. Therefore, it hardly softens to the vicinity of the melting point, but melts from the vicinity of the melting point and softens rapidly. Such a resin exhibits a clear melting point peak in differential scanning calorimetry using a differential scanning calorimeter (DSC).

  The crystalline polyester that can be used as the binder resin will be described.

  As the monomer used for the crystalline polyester, a monomer that can be used for the resin fine particles described above is preferably used.

  An aliphatic diol having a double bond can also be used as the aliphatic diol. Examples of the aliphatic diol having a double bond include the following compounds. 2-butene-1,4-diol, 3-hexene-1,6-diol, 4-octene-1,8-diol. Furthermore, a dicarboxylic acid having a double bond can also be used. Such dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters and acid anhydrides are also included. Among these, fumaric acid and maleic acid are preferable in terms of cost.

  The melting point of the crystalline resin contained in the binder resin used in the present invention is preferably 50 ° C. or higher and 90 ° C. or lower. Within this range, the viscosity tends to decrease during fixing, and good low-temperature fixing properties can be easily obtained. When the temperature is lower than 50 ° C., the storage stability may be deteriorated. When the temperature is higher than 90 ° C., the viscosity at the time of fixing is hardly reduced, and good low-temperature fixability is hardly obtained.

  Further, when the crystalline resin is used for the fine particles Q, the melting point of the binder resin is desirably set to be the same or lower than the melting point of the crystalline resin fine particles. By doing so, the binder resin having a low viscosity at the time of fixing can more easily enter between the fibers of the paper, and the low-temperature fixability can be further improved.

  The binder resin used in the present invention may contain an amorphous resin.

  The amorphous resin that can be contained in the binder resin will be described. Examples of the amorphous resin include, but are not limited to, vinyl resins such as polyurethane resins, polyester resins, styrene acrylic resins, and polystyrene. These resins may be modified with urethane, urea, or epoxy. Among these, from the viewpoint of maintaining elasticity, the polyester resin and the polyurethane resin are preferably used.

  The polyester resin as the amorphous resin is preferably a resin that can be used as the resin fine particles described above. As the polyurethane resin as the amorphous resin, a resin that can be used for the resin fine particles described above is preferably used.

  The glass transition temperature (Tg) of the amorphous resin in the binder resin is preferably 50 ° C. or higher and 130 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower. By being in this range, the elasticity in the fixing region is easily maintained.

  In the present invention, when the amorphous resin is contained, the ratio of the crystalline resin and the amorphous resin in the binder resin is preferably 30% by mass or more and 85% by mass or less of the crystalline resin. . When the crystalline resin is 30% by mass or more, the viscosity at the time of melting the toner tends to be low, and as a result, the effect of suppressing the toner peeling from the fixed image is easily obtained. On the other hand, when it is 85% by mass or less, the elasticity after the toner is melted is easily maintained, and the fixing region is hardly narrowed. More preferably, it is 50 mass% or more.

  Furthermore, in the present invention, it is also one of preferred embodiments that the binder resin is a block polymer in which a crystalline polyester and an amorphous resin component are chemically bonded.

  The block polymer is composed of an AB type diblock polymer, an ABA type triblock polymer, a BAB type triblock polymer, an ABAB... Type multi of the crystalline resin component (A) and the amorphous resin component (B). Any form of block polymer can be used.

  In the present invention, as the method for preparing the block polymer, the crystalline polyester and the amorphous resin component are separately prepared, and the two are combined (two-stage method), the crystalline polyester, and the amorphous A method (one-step method) in which the raw materials for the resin component are simultaneously charged and prepared at one time can be used.

  The block polymer in the present invention can be selected from various methods in consideration of the reactivity of each terminal functional group to be the block polymer.

  When the amorphous resin component is a polyester resin, it can be prepared by preparing each component separately and then using a binder. In particular, when the acid value of one polyester is high and the hydroxyl value of the other polyester is high, the reaction proceeds easily. The reaction temperature is preferably about 200 ° C.

  When the binder is used, the following binders are exemplified. Polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, polyfunctional epoxy, polyhydric acid anhydride. These binders can be used for synthesis by dehydration reaction or addition reaction.

  On the other hand, in the case where the amorphous resin component is the polyurethane resin, each component is prepared separately and then prepared by urethanating the alcohol terminal of the crystalline polyester and the isocyanate terminal of the polyurethane. The synthesis can also be performed by mixing and heating the crystalline polyester having an alcohol terminal and the diol and diisocyanate constituting the polyurethane resin. At the initial stage of the reaction when the diol and diisocyanate concentrations are high, the diol and diisocyanate react selectively to form a polyurethane resin, and after the molecular weight has increased to some extent, the urethanization reaction between the isocyanate terminal of the polyurethane resin and the alcohol terminal of the crystalline polyester occurs. The block polymer can be used.

  The ratio of the crystalline resin component in the block polymer is preferably 30.0% by mass or more and 85.0% by mass or less.

(Coloring agent)
The toner obtained by the production method of the present invention contains a colorant. Examples of the colorant preferably used in the present invention include organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic powder. In addition, it is possible to use colorants conventionally used in toners. I can do it.

  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, anthraquinones, 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 toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The colorant is preferably used by adding 1.0% by mass or more and 20.0% by mass or less to the toner particles. When magnetic powder is used as the colorant, the amount added is preferably 25.0 mass% or more and 60.0 mass% or less with respect to the toner particles.

(wax)
The toner obtained by the production method of the present invention preferably contains a wax. The wax is not particularly limited, but includes 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; fat A wax mainly composed of a fatty acid ester such as an aromatic hydrocarbon ester wax; and a partially or completely deoxidized fatty acid ester such as a deoxidized carnauba wax; a partial ester of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  Waxes particularly preferably used in the present invention are aliphatic hydrocarbon waxes and ester waxes. 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 can be obtained by condensation of a tri- or higher functional acid and a long-chain linear saturated alcohol, or synthesis of a tri- or higher-functional alcohol and a long-chain linear saturated fatty acid.

  Examples of the trifunctional or higher functional alcohol that can be used in the present invention include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. Glycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitol. Also, as these condensates, diglycerin condensed with glycerin, triglycerin, tetraglycerin, hexaglycerin and decaglycerin so-called polyglycerin, condensed trimethylolpropane condensed with tritrimethylolpropane, tristrimethylolpropane and pentaerythritol. And 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 that can be used in the present invention is represented by the general formula C _n H _{2n + 1} COOH, and those in which n is 5 or more and 28 or less are preferably used.

  Although the following can be mentioned, it is not limited to this. Depending on the case, it is also possible to use a mixture. 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 trifunctional or higher functional acid that can be used in the present invention include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. Trimellitic acid, butanetetracarboxylic acid.

The long-chain linear saturated alcohol that can be used in the present invention is represented by C _n H _{2n + 1} OH, and those having n of 5 or more and 28 or less are preferably used.

  Although the following can be mentioned, it is not limited to this. Depending on the case, it is also possible to use a mixture. 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.

  In the present invention, the amount of wax added to 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.

  In the present invention, 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.

(Charge control agent)
In the toner of the present invention, a charge control agent may be contained in the toner particles 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.

  A known charge control agent can be used as the charge control agent, and in particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable.

  Examples of the charge control agent that control the toner 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 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% by mass or more and 20.0% by mass or less, and more preferably 0.5% by mass or more and 10.0% by mass or less with respect to the toner particles.

(Method for producing toner particles)
The production method of the present invention is particularly preferably a method using high-pressure carbon dioxide as a dispersion medium.

  In the present invention, a resin solution in which a binder resin, a colorant, and a vinyl resin P are dissolved or dispersed in an organic solvent capable of dissolving the binder resin is added to a high-pressure state dioxide dioxide containing fine particles Q. Particularly preferred is a production method in which toner particles are formed by dispersing in a dispersion medium containing carbon and removing the organic solvent from the resulting dispersion.

  Here, the high-pressure carbon dioxide is preferably carbon dioxide having a pressure of 1.5 MPa or more. Further, liquid or supercritical carbon dioxide may be used alone as a dispersion medium, and an organic solvent may be contained as another component. In this case, it is preferable that the high-pressure carbon dioxide and the organic solvent form a homogeneous phase.

  Hereinafter, a method for producing toner particles using a dispersion medium containing carbon dioxide in a high-pressure state suitable for the production method of the present invention will be described as an example.

  First, in the dissolution and dispersion step of obtaining a resin solution, a colorant, vinyl resin P and, if necessary, wax and other additives are added to an organic solvent capable of dissolving the binder resin, and a homogenizer, ball mill, colloid It is uniformly dissolved or dispersed by a disperser such as a mill or an ultrasonic disperser.

  Next, in the stirring step, the resin solution thus obtained and high-pressure carbon dioxide are mixed to form droplets of the resin solution.

  At this time, it is preferable to disperse the fine particles Q in a dispersion medium containing carbon dioxide in a high pressure state. In addition to the fine particles Q, the vinyl resin P and other components may be mixed and used in the dispersion medium.

  In the present invention, any method may be used as a method of dispersing the fine particles Q in a dispersion medium containing carbon dioxide in a high pressure state. Specific examples include a method in which a dispersion medium containing the dispersant and high-pressure carbon dioxide is charged into a container and directly dispersed by stirring or ultrasonic irradiation. Another example is a method in which a dispersion liquid in which the dispersant is dispersed in an organic solvent is introduced into a container charged with a dispersion medium containing carbon dioxide in a high-pressure state using a high-pressure pump.

  In the present invention, it is important that the dispersion medium containing carbon dioxide in a high-pressure state is a single phase. When granulating by dispersing the resin composition in carbon dioxide in a high pressure state, a part of the organic solvent in the droplets moves into the dispersion. At this time, it is not preferable that the carbon dioxide phase and the organic solvent phase exist in a separated state, which causes a drop in the stability of the droplets. Therefore, it is preferable to adjust the temperature and pressure of the dispersion medium and the amount of the resin composition with respect to the high-pressure carbon dioxide within a range in which the carbon dioxide and the organic solvent can form a homogeneous phase.

  In addition, regarding the temperature and pressure of the dispersion medium, attention should be paid to granulation properties (ease of forming droplets) and solubility of constituent components in the resin composition in the dispersion medium. The binder resin and wax in the resin composition may be dissolved in the dispersion medium depending on temperature conditions and pressure conditions. Usually, the lower the temperature and the lower the pressure, the more the solubility of the above components in the dispersion medium is suppressed, but the formed droplets are likely to agglomerate and coalesce, and the granulation property is lowered. On the other hand, although the granulation property is improved as the temperature and pressure are increased, the component tends to be easily dissolved in the dispersion medium. Therefore, in the production of the toner particles of the present invention, the temperature of the dispersion medium is preferably in the temperature range of 10 ° C. or higher and 40 ° C. or lower.

  Further, the pressure in the container forming the dispersion medium is preferably 1.5 MPa or more and 20.0 MPa or less, and more preferably 2.0 MPa or more and 15.0 MPa or less. In addition, the pressure in this invention shows the total pressure, when components other than a carbon dioxide are contained in a dispersion medium.

  After granulation is completed in this way, in the solvent removal step, the organic solvent remaining in the droplets is removed through a dispersion medium of carbon dioxide in a high pressure state. Specifically, carbon dioxide in a high-pressure state is further mixed with the dispersion medium in which droplets are dispersed, and the remaining organic solvent is extracted into a carbon dioxide phase. By replacing with carbon dioxide in the state.

  In the mixing of the dispersion medium and the high-pressure carbon dioxide, carbon dioxide having a higher pressure may be added to the dispersion medium, and the dispersion medium may be added to carbon dioxide having a lower pressure. Also good.

  And as a method of substituting the carbon dioxide containing an organic solvent with the carbon dioxide of a high pressure state, the method of distribute | circulating a high pressure carbon dioxide is mentioned, keeping the pressure in a container constant. At this time, the toner particles formed are captured while being captured by a filter.

  When the replacement with carbon dioxide in the high-pressure state was not sufficient and the organic solvent remained in the dispersion medium, it was dissolved in the dispersion medium when the container was decompressed to recover the obtained toner particles. In some cases, the organic solvent may condense and the toner particles may be redissolved or the toner particles may coalesce. Therefore, the replacement with carbon dioxide in the high pressure state needs to be performed until the organic solvent is completely removed. The amount of high-pressure carbon dioxide to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, and most preferably 1 to 30 times the volume of the dispersion medium.

  When removing the toner particles from the dispersion containing high-pressure carbon dioxide in which the toner particles are dispersed, the container may be decompressed to room temperature and normal pressure at once. The pressure may be reduced stepwise by providing. The decompression speed is preferably set within a range where the toner particles do not foam.

  The organic solvent and carbon dioxide used in the present invention can be recycled.

(External additive)
In the present invention, an inorganic fine powder is preferably added to the toner particles as a fluidity improver. Examples of the inorganic fine powder to be added to the toner particles include fine powder such as silica fine powder, titanium oxide fine powder, alumina fine powder, or double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.

Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less Na ₂ O and SO ₃ ²⁻ is preferable. The dry silica may be a composite fine powder 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 powder is preferably externally added to the toner particles in order to improve the fluidity of the toner and to make the toner uniform. In addition, the hydrophobic treatment of the inorganic fine powder makes it possible to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics in a high-humidity environment. More preferably, the body is used. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner is reduced, and the developability and transferability are easily lowered.

  Treatment agents for hydrophobizing inorganic fine powder include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organic titanium. Compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the hydrophobicity-treated inorganic fine powder treated with silicone oil treated with silicone oil simultaneously or after the hydrophobic treatment of the inorganic fine powder with a coupling agent increases the charge amount of the toner particles even in a high humidity environment. It is good for maintaining high and reducing selective developability.

  The amount of the hydrophobized powder treated with silicone oil treated with silicone oil at the same time or after the hydrophobizing treatment of the inorganic fine particles with a coupling agent is 0.1% with respect to 100 parts by mass of toner particles. It is preferable that it is not less than 4.0 parts by mass and more preferably not less than 0.2 parts by mass and not more than 3.5 parts by mass.

  The toner particles of the present invention preferably have a weight average particle diameter (D1) of 3.00 μm or more and less than 6.50 μm. More preferably, it is less than 6.00 μm, more preferably 3.00 μm or more and less than 5.50 μm. It is preferable to use toner particles having such a weight average particle diameter (D1) in order to sufficiently satisfy the dot reproducibility while improving the handleability.

  The toner of the present invention has a number average molecular weight (Mn) of 8,000 to 40,000 and a weight average molecular weight (Mw) of 15,0 in gel permeation chromatography (GPC) measurement of tetrahydrofuran (THF) solubles. It is preferably from 000 to 60,000. By being in this range, it is possible to impart appropriate viscoelasticity to the toner. That is, when Mn is 8,000 and Mw is 15,000 or more, the toner does not become too soft, the heat-resistant storage stability does not deteriorate, and the toner does not peel from the fixed image. When Mn is 40,000 and Mw is 60,000 or less, the toner does not become too hard and the fixing property is not deteriorated. A more preferable range of Mn is 10,000 or more and 20,000 or less, and a more preferable range of Mw is 20,000 or more and 50,000 or less. Furthermore, it is desirable that Mw / Mn is 6 or less. A more preferable range of Mw / Mn is 3 or less.

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

<Measurement Method of Degree of Polymerization B in Compound 1>
The degree of polymerization B in compound 1 is measured by ¹ H-NMR under the following conditions.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times Measurement temperature: 30 ° C
Sample: 50 mg of compound 1 to be measured is placed in a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. to prepare.

From the obtained ¹ H-NMR chart, an integrated value S ₁ of a peak (about 0.0 ppm) attributed to hydrogen bonded to carbon bonded to silicon is calculated. Similarly, an integral value S ₂ of a peak (about 6.0 ppm) attributed to one of the terminal hydrogens of the vinyl group is calculated. The degree of polymerization B is determined as follows using the integral value S ₁ and the integral value S ₂ . Here, n ₁ in the formula (8) is a total value of the number of hydrogen bonded to carbons of R ² and R ^{3 in} the formula (1), and when R ² and R ³ are each a methyl group, n 1 ₁ becomes 6, and n ₁ becomes 4 when each is an ethyl group or more. N ₂ is the total value of the number of hydrogen bonded to the carbons of R ⁴ , R ⁵ and R ⁶ in formula (1).
Degree of polymerization B = {(S ₁ −n ₂ ) / n ₁ } / S ₂ (8)

<Method of measuring number average molecular weight (Mn) and weight average molecular weight (Mw)>
In the present invention, the molecular weight (Mn, Mw) of the tetrahydrofuran (THF) soluble matter of the vinyl resin P, the crystalline polyester, and the block polymer is measured by GPC as follows.

First, a sample is dissolved in THF at room temperature for 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 adjusted 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 (trade names “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.

<Measuring method of number average diameter of primary particles of fine particles Q>
The number average diameter of the primary particles of the inorganic fine particles A and the resin fine particles B is observed using a scanning electron microscope S4700 (manufactured by Hitachi, Ltd.), and the particle size of 100 particles is measured. Was the number average diameter.

<Measurement method of particle diameter of colorant particles and wax particles>
The particle diameters of the colorant particles and the wax particles are measured using a Microtrac particle size distribution measuring device HRA (X-100) (manufactured by Nikkiso Co., Ltd.) in the range of 0.001 μm to 10 μm, and the volume average particle diameter (μm Or nm). In addition, acetone was selected as a dilution solvent.

<Measuring method of melting point of crystalline polyester, block polymer, and wax>
Melting | fusing point of crystalline polyester, block polymer, and wax was measured on condition of the following using DSC Q1000 (made by TA Instruments).
Temperature increase rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 200 ° C

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 2 mg of a sample is precisely weighed, placed in a silver pan, and measured using an empty silver pan as a reference. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 20 ° C., and then heated again. In the case of crystalline polyester and block polymer, the peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 20 ° C. to 200 ° C. is measured in the first temperature increase process in the case of wax and in the second temperature increase process in the case of wax. The melting point of polyester, block polymer, and wax.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1) of toner particles>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner particles 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, “ISOTON II” (manufactured by Beckman Coulter, Inc.) obtained by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass 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.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed 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 aqueous 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 incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) 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 (1) installed in the sample stand, the electrolyte solution (5) in which the 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).

<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 sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted, The maximum length (D _max ), the maximum length vertical length (D _v-max ), and the projected area (S) are measured.

The equivalent circle diameter is determined using the 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 (9).
Equivalent circle diameter (μm) = 2 × (π × S) ^1/2 (9)

Next, the fine powder ratio is determined using the number of toner particles having an equivalent circle diameter of less than 1.985 μm (N _s ) 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 ratio is calculated by the following equation (10).
Fine powder ratio (number%) = N _s / N _all × 100 (10)

  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 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the 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 ("DISE Scientific AND RESPARTIC AND TEST PARTILES Latex Microsphere Suspensions 5200A" 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.

<Measurement Method of Viscosity of Resin Solution, Vinyl Resin P, Fine Particle Q Mixed Resin Solution Liquid>
The resin solution composition whose liquid temperature was adjusted to 40 ± 1 ° C. was measured under the following conditions using a Viscocoater VT550 (manufactured by HAAKE).
Sensor: MV-DIN
Shear rate: 1.075 (1 / s) <1 min> → 1.29 (1 / s) <1 min> → 4.3 (1 / s) <1 min> → 12.9 (1 / s) <1 min> → 21.5 (1 / s) <1 min>

  In addition, the measured value when 1 min passed at a shear rate of 12.9 (1 / s) was taken as the representative viscosity.

<Method for measuring motor load during stirring>
The load of the motor during stirring in the stirring step was determined by measuring the driving voltage and current of the motor. The drive current of the agitation drive motor was 200V, where the input current to the motor coil was monitored with an AC clamp meter.

  The measurement of the motor load at the time of stirring is the value in the step of granulating by stirring at 1000 rpm for 3 minutes after the introduction of the contents of the tank Ta1 described in the following example into the tank Ta2. It calculated | required by calculation from the average of the electric current value of 1 minute from the start 1 minute.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way.

<Synthesis of crystalline polyester 1>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-Sebacic acid 124.0 parts by mass-1,6-hexanediol 76.0 parts by mass-Dibutyltin oxide 0.1 part by mass 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 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. The melting point of the crystalline polyester 1 was 73 ° C., Mn was 5,800, and Mw was 11,800.

<Synthesis of crystalline polyester 2>
In the synthesis of crystalline polyester 1, the same procedure was followed except that the amount of sebacic acid charged was changed to 121.0 parts by mass and the amount of 1,6-hexanediol charged was changed to 79.0 parts by mass. Got. The melting point of the crystalline polyester 2 was 73 ° C., Mn was 2,500, and Mw was 4,600.

<Synthesis of block polymer>
Crystalline polyester 1 180.0 parts by mass Xylylene diisocyanate (XDI) 73.0 parts by mass Cyclohexanedimethanol (CHDM) 47.0 parts by mass Tetrahydrofuran (THF) 300.0 parts by mass A stirrer and a thermometer The above was charged into a reaction vessel equipped with nitrogen substitution. The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours. The solvent THF was distilled off to obtain a block polymer. The melting point of the block polymer was 65 ° C., Mn was 12,300, and Mw was 30,400.

<Preparation of block polymer solution>
A beaker equipped with a stirrer was charged with 500.0 parts by mass of acetone and 500.0 parts by mass of a block polymer, and stirring was continued until the solution was completely dissolved at a temperature of 40 ° C. to prepare a block polymer solution.

<Production of vinyl resin P1>
As a compound 1, 134.0 g of siloxane monomer 1 (X-22-42475 manufactured by Shin-Etsu Kogyo Co., Ltd.) and 66.0 g of ether monomer 1 (light acrylate 130A manufactured by Kyoeisha Chemical Co., Ltd.) as a polymerization initiator 1.0 g of AIBN was dissolved in 100.0 g of toluene as a solvent and introduced into a three-necked flask equipped with a condenser. After bubbling with 200 ccm of nitrogen for 30 minutes, polymerization was carried out by heating to 70 ° C. while stirring with a stirrer. After 4 hours, the heating was stopped and the flask was opened to the atmosphere to complete the polymerization. The vinyl resin P1 was obtained by removing unreacted monomer from the obtained sample by methanol reprecipitation.

  The characteristics of Compound 1 used in Examples and Comparative Examples are shown in Table 1, and the characteristics of Compound 2 are shown in Table 2. Table 3 shows the mole fraction of vinyl resin P1 derived from compound 1, the side chain length ratio L2 / L1, and the molecular weight of vinyl resin P1.

<Preparation of vinyl resins P2 to P19>
Vinyl resins P2 to P7 were obtained in the same manner except that the types and addition amounts of compound 1 and compound 2 and the types and addition amounts of initiator in the production of vinyl resin P1 were changed to the conditions shown in Table 3. It was. Table 3 shows the physical properties of the obtained vinyl resins P2 to P19.

<Preparation of fine particles Q1>
In a 3 L glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 577.2 parts by mass of methanol, 42.0 parts by mass of pure water and 47.1 parts by mass of 28% by mass ammonia water were mixed. The obtained solution was adjusted to 35 ° C., and 1100.0 parts by mass of tetramethoxysilane and 395.2 parts by mass of 5.4% by mass ammonia water were begun simultaneously with stirring. Tetramethoxysilane was added dropwise over 7 hours and ammonia water over 6 hours. After completion of the dropwise addition, the mixture was further stirred for 0.2 hours for hydrolysis. Thereafter, the dispersion was sufficiently dried at 80 ° C. under reduced pressure to obtain silica fine particles 1 by a sol-gel method.

  Subsequently, 100.0 parts by mass of silica fine particles 1 by a sol-gel method are put into a reaction vessel, and 7.6 parts by mass of silicone oil (KF-96, 50 cs: manufactured by Shin-Etsu Chemical Co., Ltd.) is stirred with stirring in a nitrogen atmosphere. A solution diluted with 6 parts by mass of normal hexane was sprayed. Thereafter, this mixture was stirred at 300 ° C. for 60 minutes under a nitrogen stream, dried and cooled to obtain hydrophobized fine particles Q1. The number average diameter of the primary particles of the fine particles Q1 was 80 nm. Table 4 shows the physical properties of the resulting fine particles Q1.

<Preparation of fine particles Q2 to Q7>
Fine particles Q2 to Q7 were obtained in the same manner except that the amount of methanol added and the treatment conditions for the silicone oil treatment in the production of fine particles Q1 were changed to the conditions shown in Table 4. Table 4 shows the physical properties of the obtained fine particles Q2 to Q7.

<Preparation of fine particle Q1 dispersion to Q7 dispersion>
In a container charged with 800.0 parts by mass of acetone, 200.0 parts by mass of the fine particles Q1 to Q7 are added with stirring, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Machine Bios) is used. By dispersing for 5 minutes, fine particle Q1 dispersion to Q7 dispersion were obtained.

<Synthesis of vinyl-modified polyester monomer>
In a reaction vessel with a stir bar and thermometer set,
-Xylylene diisocyanate (XDI) 59.0 parts by mass was charged, 41.0 parts by mass of 2-hydroxyethyl methacrylate was added dropwise, and reacted at 55 ° C for 4 hours to obtain a vinyl-modified monomer intermediate.

Next, in a reaction vessel with a stir bar and thermometer set,
-Crystalline polyester 2 83.0 parts by mass-THF 100.0 parts by mass were charged and dissolved at 50 ° C. Thereafter, 10.0 parts by mass of the vinyl-modified monomer intermediate was dropped and reacted at 50 ° C. for 4 hours to obtain a vinyl-modified polyester monomer solution. The solvent, THF, was distilled off to obtain a vinyl-modified polyester monomer.

<Preparation of fine particle Q8 dispersion>
Siloxane monomer 1 15.0 parts by mass (X-22-2475: Degree of polymerization B = 3, manufactured by Shin-Etsu Chemical Co., Ltd.)
-Vinyl-modified polyester monomer 40.0 parts by mass-Styrene (St) 35.0 parts by mass-Methacrylic acid (MAA) 10.0 parts by mass-Azobismethoxydimethylvaleronitrile 0.3 parts by mass-THF 50.0 Part by mass A beaker was charged with the above, stirred and mixed at 20 ° C. to prepare a monomer solution, which was introduced into a dripping funnel that had been heated and dried in advance. Separately from this, 100.0 parts by mass of THF was charged into a heat-dried two-necked flask. After substituting with nitrogen, a dropping funnel was attached, and the monomer solution was added dropwise at 70 ° C. for 1 hour in a sealed state. Stirring was continued for 3 hours from the end of the dropping, and a mixture of 0.3 parts by mass of azobismethoxydimethylvaleronitrile and 20.0 parts by mass of THF was added again, followed by stirring at 70 ° C. for 3 hours to obtain a polymer solution. It was.

  Subsequently, this polymer solution was added dropwise over 10 minutes to 400.0 parts by mass of acetone adjusted to 20 ° C. while stirring at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika). A dispersion of coalesced fine particles was obtained. A part of the resulting dispersion of polymer fine particles was dried, and the number average diameter of the primary particles was measured. As a result, it was 110 nm. The polymer fine particle dispersion was prepared by adding acetone so that the solid content concentration of the polymer fine particle dispersion was 20% by mass to obtain a resin fine particle Q8 dispersion.

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

<Preparation of wax dispersion>
Paraffin wax HNP10 (melting point: 75 ° C., Nippon Seiwa Co., Ltd.) 17.0 parts by mass Wax dispersant 8.0 parts by mass (in the presence of 15.0 parts by mass of polyethylene, 50.0 parts by mass of styrene, n -Copolymer having a peak molecular weight of 8,500 obtained by copolymerizing 25.0 parts by mass of butyl acrylate and 10.0 parts by mass of acrylonitrile)
Acetone 76.0 parts by mass The above was put into a glass beaker (made by IWAKI glass) with a stirring blade, and the system was heated to 70 ° C. to dissolve paraffin wax in acetone.

  Then, 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 is put into a heat-resistant container together with 20 parts by weight of 1 mm glass beads, dispersed for 3 hours with a paint shaker, and a wax dispersion having a volume average particle size of 270 nm and a wax solid content of 17.0% by mass is obtained. Obtained.

[Example 1]
(Manufacture of toner particles 1)
A glass beaker was charged with materials having the following composition.
Block polymer solution 173.0 parts by mass Wax dispersion 30.0 parts by mass Colorant dispersion 12.0 parts by mass Vinyl resin P1 15.0 parts by mass Acetone 15.0 parts by mass The mixture was heated to 0 ° C. and dispersed for 5 minutes using an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios Co., Ltd.) to dissolve the vinyl resin P1 and obtain a resin solution composition . It was 112 mPa * s as a result of measuring the viscosity in 40 degreeC of this resin solution composition according to the measuring method of the said viscosity.

  In the apparatus shown in FIG. 1, with the valves V1, V2, and V3 closed, the resin solution composition was charged into the tank Ta1, and the internal temperature was adjusted to 50 ° C. Next, while stirring the inside of the tank Ta1 at a rotational speed of 300 rpm, the valve V1 is opened, carbon dioxide (purity 99.99%) is introduced into the tank Ta1 from the cylinder B1, and the internal pressure reaches 3.0 MPa. Valve V1 was closed.

  Next, 10.0 parts by mass of the fine particle Q1 dispersion is charged into a pressure-resistant granulation tank Ta2 equipped with a filter and a stirring mechanism for capturing toner particles, the pressure adjustment valve V4 is closed, and the internal temperature is adjusted to 20 ° C. did.

  Next, the valve V3 was opened, carbon dioxide was introduced from the cylinder B1 into the granulation tank Ta2, and the valve V3 was closed when the internal pressure reached 1.0 MPa.

  Next, the valve V2 is opened, and the contents of Ta1 are introduced into the granulation tank Ta2 using the pump Pu2 while stirring the inside of the granulation tank Ta2 at a rotational speed of 1000 rpm. Closed. Thereafter, the valve V3 was opened, carbon dioxide was further introduced from the cylinder B1 using the pump Pu1, and the valve V3 was closed. After the introduction, the temperature of the granulation tank Ta2 was 25 ° C., and the internal pressure was 5.0 MPa. The mass of the total carbon dioxide introduced was measured using a mass flow meter and was 280.0 parts by mass.

  Thereafter, the inside of the granulation tank Ta2 was stirred for 10 minutes at a rotational speed of 1000 rpm for dispersion. The load applied to the motor during stirring at this time was measured by the above-described measurement method.

  Next, the valve V3 was opened, and carbon dioxide was introduced into the granulation tank Ta2 from the cylinder B1 using the pump Pu1. At this time, the pressure adjusting valve V4 was set to 10.0 MPa, and carbon dioxide was further circulated for 1 hour at a flow rate of 50 g / min while maintaining the internal pressure of the granulation tank Ta1 at 10.0 MPa. By this operation, carbon dioxide containing the organic solvent (mainly acetone) extracted from the granulated droplets was discharged to the organic solvent recovery tank Ta3, and the organic solvent and carbon dioxide were separated.

  Finally, the pressure regulating valve V4 was opened little by little, and the internal pressure of the granulation tank Ta2 was reduced to atmospheric pressure, whereby the toner particles 1 were recovered.

<Evaluation of number average particle diameter (D1) and weight average particle diameter (D4) / number average particle diameter (D1)>
The values of number average particle diameter (D1) and weight average particle diameter (D4) / number average particle diameter (D1) were evaluated according to the following criteria.
-Weight average particle diameter (D1)
A: Number average particle diameter (D1) is less than 5.50 μm B: Number average particle diameter (D1) is 5.50 μm or more and less than 6.00 μm C: Number average particle diameter (D1) is 6.00 μm or more and less than 6.50 μm D: Number average particle diameter (D1) is 6.50 μm or more. Weight average particle diameter (D4) / Number average particle diameter (D1)
A: The value of weight average particle size (D4) / number average particle size (D1) is less than 1.15 B: The value of weight average particle size (D4) / number average particle size (D1) is 1.15 or more. Less than 20 C: The value of weight average particle diameter (D4) / number average particle diameter (D1) is 1.20 or more and less than 1.25 D: The value of weight average particle diameter (D4) / number average particle diameter (D1) is 1.30 or more

<Evaluation of fine powder ratio>
The value of the fine powder rate was evaluated according to the following criteria.
A: The value of the fine powder ratio is less than 5.0% B: The value of the fine powder ratio is 5.0% or more and less than 10.0% C: The value of the fine powder ratio is 10.0% or more and less than 15.0% D: The fine powder ratio The value of 15.0% or more

<Evaluation of motor load during stirring>
The motor load during stirring was evaluated according to the following criteria.
A: Motor load power is less than 30 W B: Motor load power fine powder ratio is 30 W or more and less than 40 W C: Motor load power fine powder ratio is 40 W or more and less than 50 W D: Motor load power fine powder ratio is 50W or more

  The properties of the obtained toner particles are shown in Table 6.

[Comparative Example 1]
In Example 1, toner particles 2 for comparison were obtained in the same manner as in Example 1 except that the vinyl resin P1 was not used in the production process of the toner particles 1. Table 6 shows the properties of the toner particles 2 thus obtained.

[Comparative Example 2]
In Example 1, toner particles 3 were obtained in the same manner as in Example 1, except that the fine particles Q1 were not used in the production process of the toner particles 1. Table 6 shows the properties of the obtained toner particles 3.

[Comparative Examples 3 to 10]
In Example 1, the toner particles 4 for comparison are the same as in Example 1 except that the types and amounts of the vinyl resin P and the fine particles Q in the production process of the toner particles 1 are changed to those shown in Table 5. Thru 11 were obtained. Table 6 shows the characteristics of the obtained toner particles 4 to 11.

[Examples 2 to 28]
In Example 1, the toner particles 12 of the present invention are the same as in Example 1 except that the types and amounts of the vinyl-based resin P and the fine particles Q in the manufacturing process of the toner particles 1 are changed to those shown in Table 5. Thru 38 were obtained. Table 6 shows the characteristics of the obtained toner particles 12 to 38.

  Ta1: tank, Ta2: granulation tank, Ta3: solvent recovery tank, B1: container (carbon dioxide cylinder), Pu1, Pu2: pump (compression pump), V1, V2, V3: valve, V4: pressure regulating valve

Claims (9)

A method for producing a toner having toner particles containing a binder resin, a colorant, and a vinyl resin P,
The manufacturing method is
a) A mixture of the binder resin, the colorant, the organic solvent, the vinyl resin P, the fine particles Q, and the dispersion medium is stirred to form droplets containing the binder resin, the colorant, and the organic solvent. The process of
b) removing the organic solvent contained in the droplets to obtain toner particles;
Have
The binder resin contains crystalline polyester;
The vinyl resin P is a resin obtained by polymerizing the compound 1 represented by the following formula (1) and the compound 2 represented by the following formula (2),
The vinyl resin P has a weight average molecular weight (Mw) of 10,000 or more and 50,000 or less,
The molar fraction of the structural unit derived from the compound 1 with respect to the vinyl resin P is 0.40 or more and 0.95 or less,
The ratio L2 / L1 between the average value L1 of the side chain length of the structural unit derived from the compound 1 and the average value L2 of the side chain length of the structural unit derived from the compound 2 is 1.0 or more and 4.0 or less. Yes,
The toner production method, wherein the number average diameter (D1) of primary particles of the fine particles Q is 40 nm or more and 200 nm or less.

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² to R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms. A is an integer of 1 to 3) , B represents the number of repetitions of the structure in parentheses, and the polymerization degree of B in compound 1 is 1 or more.)

(In formula (2), R ⁷ represents a hydrogen atom or a methyl group. N is an integer of 1 or more and 3 or less, and X is 0 or 1. R ⁸ is a hydrogen atom or a carbon number of 1 or more and 3 or less. Represents an alkyl group, D is an integer of 1 or more.) The addition amount of the vinyl resin P in the step a) is 5.0% by mass or more and 50.0% by mass or less with respect to the binder resin.
2. The toner manufacturing method according to claim 1, wherein the amount of the fine particles Q added in the step a) is 1.0% by mass or more and 10.0% by mass or less with respect to the binder resin.   The toner production method according to claim 1, wherein L2 / L1 is 1.2 or more and 3.0 or less.   4. The method for producing a toner according to claim 1, wherein a molar fraction of the structural unit derived from the compound 1 with respect to the vinyl resin P is 0.60 or more and 0.90 or less. 5.   The method for producing a toner according to claim 1, wherein the fine particles Q are inorganic fine particles.   The toner manufacturing method according to claim 5, wherein the inorganic fine particles are inorganic fine particles that have been subjected to a hydrophobic treatment.   The toner production method according to claim 1, wherein the fine particles Q are resin fine particles.   The toner manufacturing method according to claim 7, wherein the resin fine particles contain a resin including an organic polysiloxane structure in a molecular structure.   The method for producing a toner according to claim 1, wherein the dispersion medium contains carbon dioxide.

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