JP7023762B2 - Toner and toner manufacturing method - Google Patents

Description

The present invention relates to a toner used in an electrophotographic method and a method for producing the toner.

In recent years, printers and copiers are required to have high image quality and high durability, and in particular, printers are widely required to be smaller and lighter.
The printer must be adapted to various business situations such as a network printer used by a large number of people and a personal printer used in SOHO or the like via a network. Further, in an office or SOHO environment, good handling of the process cartridge is strongly desired. Therefore, there is a strong demand for space saving, that is, miniaturization and weight reduction of the printer.
Regarding the miniaturization and weight reduction of the printer, it is mainly effective to miniaturize the fixing device and the process cartridge. In particular, the process cartridge occupies most of the volume of the printer, and the miniaturization of the process cartridge can greatly contribute to the miniaturization of the printer. Regarding the miniaturization of the process cartridge, it is effective to miniaturize the developing device and the cleaning device.
There are two-component development method and one-component development method as the development method of electrophotographic, but the one-component development method is suitable when focusing on the miniaturization of the developing apparatus. This is because members such as carriers are not used. Further, it can be said that spherical toner having good development efficiency and transfer efficiency is suitable for miniaturization of the developing apparatus because less toner is stored in the developing container.

Focusing on the cleaning device, if a spherical toner with a small amount of residual transfer toner is used, the amount of waste toner collected in the cleaning container is reduced, so that the spherical toner is also suitable for downsizing the cleaning device. I can say.
However, there are also unique problems with cleaning using spherical toner.
Due to the shape of the spherical toner, it is easy for it to slip through in the cleaning section, and cleaning defects are likely to be noticeable even under normal temperature and humidity. Usually, in the cleaning portion, particularly at the tip of the edge, the additive adhering to the surface of the toner particles is accumulated to form a blocking layer for preventing the toner from slipping through. Further, a retention layer in which the transfer residual toner is accumulated is formed on the immediate front side (upstream side) of the blocking layer. When the adhesive force between the spherical toner and the photoconductor becomes large, the toner in the retention layer destroys the blocking layer, and the toner slips through the destroyed portion, resulting in poor cleaning.

On the other hand, in order to reduce the electrostatic adhesion between the spherical toner and the photoconductor, it has been proposed to form a convex portion on the surface of the toner particles by using organic-inorganic composite fine particles (for example, Patent Document 1).
Further, in order to reduce the adhesive force between the spherical toner and the photoconductor, it is one of the means to increase the degree of hydrophobicity of the toner. The degree of hydrophobicity of the toner can be increased by adding a monoester wack having a low melting point. Many proposals have been made for toners that are spherical toners and contain monoester waxes having a low melting point (Patent Document 2 and the like).

Japanese Unexamined Patent Publication No. 2015-45862 International Publication No. 14/157424

In the invention of Patent Document 1, although a certain effect can be seen in improving the developing efficiency and the transfer efficiency and further reducing the adhesion between the toner and the photoconductor, both the developability, the transferability and the cleaning property at a high level are compatible. There is still room for consideration in terms of trying to achieve this. Further, in Patent Document 2, there is still room for study in terms of achieving both developability, transferability, and cleaning property at a high level.
An object of the present invention is to obtain a toner having good developability and transferability under various environments and having good cleaning property, and a method for producing the toner.

The present invention is a toner having toner particles containing a binder resin, a colorant, and a crystalline material.
The crystalline material contains a monoester compound and
The theoretical surface area obtained from the number average particle size, particle size distribution, and true density of the toner particles is A (m ² / g), and the specific surface area of the toner particles measured by the BET method is B (m ² / g). Then, the A and the B satisfy the following formula (1), and the following formula (1) is satisfied.
1.00 ≦ B / A ≦ 1.15 ・ ・ ・ (1)
The adhesive force F (nN) of the toner with the polycarbonate flat plate satisfies the following formula (2).
15.0 ≤ F ≤ 45.0 ... (2)
It relates to a toner characterized by that.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a toner having good developability and transferability under various environments and having good cleaning property, and a method for producing the toner.

Schematic diagram showing an example of an image forming apparatus Schematic diagram of a device for measuring adhesive force F

In the present invention, the description of "○○ or more and XX or less" and "○○ to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
Hereinafter, embodiments for carrying out the present invention will be described in detail.
The present invention is a toner having toner particles containing a binder resin, a colorant, and a crystalline material.
The theoretical surface area obtained from the number average particle size, particle size distribution, and true density of the toner particles is A (m ² / g).
When the specific surface area of the toner particles measured by the BET method is B (m ² / g),
The A and B satisfy the following formula (1),
1.00 ≦ B / A ≦ 1.15 ・ ・ ・ (1)
The toner is characterized in that the adhesive force F (nN) of the toner with the polycarbonate flat plate satisfies the following formula (2).
15.0 ≤ F ≤ 45.0 ... (2)

In the present invention, the value of B / A (hereinafter referred to as surface unevenness index B / A) is 1.00 or more and 1.15 or less. It is preferably 1.05 or more and 1.15 or less, and more preferably 1.05 or more and 1.10 or less.
This surface unevenness index B / A is a value that approaches 1.00 as much as possible when the toner particles are in a smooth state with no irregularities on the surface of the toner particles. When the surface unevenness index B / A is in this range, the development efficiency is high in the developing process, and the variation in the charge amount distribution is also the smallest, so that the toner is developed on the white background caused by poor charging or the like (a phenomenon). Hereinafter referred to as fog) is less likely to occur. Further, in the transfer step, the transfer efficiency is high, the amount of toner remaining on the transfer is the smallest, and the amount of waste toner in the cleaner container can be reduced.

Further, the toner of the present invention has an adhesive force F with a polycarbonate flat plate of 15.0 nN or more and 45.0 nN or less. The polycarbonate flat plate imitates the typical surface layer of the photoconductor, and it has been confirmed that there is a correlation even when the surface layer material of the photoconductor is changed to the conventionally used photoconductor. When the adhesive force F is in this range, it is possible to prevent the toner retention layer in the cleaning portion from rushing into the blocking layer following the photoconductor and destroying the blocking layer. On the other hand, the movement of the retention layer becomes excessive and the blocking layer is not destroyed, so that the toner can be effectively prevented from slipping through.

When the surface unevenness index B / A exceeds 1.15, even if both the development efficiency and the transfer efficiency are good at the initial stage in the developing process and the transfer process, fog is likely to occur after durable use and the transfer residual concentration decreases. It's easy to do.
The surface unevenness index B / A can be controlled by the granulation conditions at the time of toner production. Specifically, it will be described later.

When the adhesive force F is less than 15.0 nN, the movement of the toner retention layer in the cleaning portion becomes excessive, the blocking layer may be destroyed, and the toner slips out easily.
On the other hand, when the adhesive force F exceeds 45.0 nN, the toner retention layer in the cleaning portion may follow the photoconductor and enter the blocking layer, destroying the blocking layer, and toner slipping out occurs. It will be easier.
The adhesive force F is preferably 18 nN or more and 40 nN or less. The adhesive force F can be controlled by controlling the type and content of the crystalline material and the state of existence of the crystalline material in the toner, for example, quenching conditions and annealing conditions.

Next, the toner material and the manufacturing method of the present invention will be described.
First, toner particles and toner will be described.
For the production of the toner particles, any known production method such as a dry method, an emulsion polymerization method, a dissolution suspension method, and a suspension polymerization method can be used. In a cleanerless system, it is preferable that the toner is spherical, so that it is preferable to perform a surface modification treatment such as a thermal spheroidization treatment in the dry method, and a suspension polymerization method is preferable in the polymerization method. Particularly preferably, in an aqueous medium, a polymerizable monomer composition containing a polymerizable monomer, a colorant, a crystalline material and, if necessary, other additives capable of producing a binder resin is granulated. , A suspension polymerization method for forming toner particles by polymerizing a polymerizable monomer contained in the polymerizable monomer composition.

Hereinafter, the suspension polymerization method will be described.
As the polymerizable monomer, a vinyl-based monomer capable of radical polymerization is preferable. For example, a monofunctional monomer or a polyfunctional monomer can be used. As the monofunctional monomer, styrene; α-methylstyrene, β-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methylstyrene. , P-methoxystyrene, styrene derivatives such as p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Acrylate-based polymerizable monomers such as; methacrylic-based polymerizable monomers such as methyl methacrylate, ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl such as vinyl propionate. Esters; vinyl ethers such as vinyl methyl ethers, vinyl ethyl ethers, vinyl isobutyl ethers; vinyl ketones such as vinyl methyl ketones, vinyl hexyl ketones, vinyl isopropyl ketones.
Among the above, the polymerizable monomer preferably contains styrene or a styrene derivative.

Examples of the polyfunctional monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tetramethylolmethanetetramethacrylate, divinylbenzene, and divinyl ether.
The monofunctional monomer may be used alone or in combination of two or more, or the monofunctional monomer and the polyfunctional monomer may be used in combination. The polyfunctional monomer can also be used as a cross-linking agent.

A polymerization initiator may be used in the suspension polymerization method. As the polymerization initiator, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. Further, when the polymerization reaction is carried out with an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum value between 10,000 and 100,000 in molecular weight is usually obtained, which is appropriate. It is preferable because toner particles having a high strength and melting characteristics can be obtained.
Examples of the polymerization initiator include the following 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 1,1'-azobis (cyclohexane-1-carbo). Azo-based or diazo-based polymerization initiators such as nitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2- Ethylhexanoate, t-butylperoxypivalate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, methylethylketone peroxide, diisopropylperoxycarbonate, cumenehydroperoxide, 2,4- Examples thereof include peroxide-based polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide.
In order to control the degree of polymerization of the polymerizable monomer, it is also possible to further add and use a known chain transfer agent, polymerization inhibitor and the like.

The toner particles may contain a polyester resin. In the case of the suspension polymerization method, the polyester resin can be contained in the polymerizable monomer composition. Amorphous polyester resin is preferable.
The polyester resin can be obtained, for example, by polycondensation of a divalent acid component and a divalent alcohol component.
Examples of the divalent acid component include the following dicarboxylic acids or derivatives thereof. Benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or its anhydrides or lower alkyl esters thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or its anhydrides or The lower alkyl ester; an alkenyl succinic acid or an alkyl succinic acid such as n-dodecenyl succinic acid, n-dodecyl succinic acid, or an anhydride thereof or a lower alkyl ester thereof; such as fumaric acid, maleic acid, citraconic acid, itaconic acid. Unsaturated dicarboxylic acids or anhydrides thereof or lower alkyl esters thereof.
Examples of the divalent alcohol component include the following. Ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol (CHDM), hydride bisphenol A, formula (1) ) And its derivatives:

(In the formula, R is an ethylene or propylene group, x and y are integers of 0 or more, respectively, and the average value of x + y is 0 to 10.)
The polyester resin is selected from a monovalent carboxylic acid compound, a monovalent alcohol compound, a trivalent or higher carboxylic acid compound, and a trivalent or higher alcohol compound in addition to the above-mentioned divalent acid component and divalent alcohol component. At least one of the above may be contained as a constituent component.
Examples of the monovalent carboxylic acid compound include aromatic carboxylic acids having 30 or less carbon atoms such as benzoic acid and p-methylbenzoic acid, and aliphatic carboxylic acids having 30 or less carbon atoms such as stearic acid and behenic acid. ..
Examples of the monohydric alcohol compound include aromatic alcohols having 30 or less carbon atoms such as benzyl alcohol, and fatty alcohols having 30 or less carbon atoms such as lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol. Be done.

The carboxylic acid compound having a trivalent or higher valence is not particularly limited, and examples thereof include trimellitic acid, trimellitic anhydride, and pyromellitic acid.
Examples of the trihydric or higher alcohol compound include trimethylolpropane, pentaerythritol, and glycerin.
The method for producing the polyester resin is not particularly limited, and a known method can be used.
The content of the polyester resin (preferably amorphous polyester resin) in the toner particles is preferably 0.5 to 10% by mass.

The crystalline material is not particularly limited, but preferably contains a crystalline polyester. The crystalline material means a material showing a clear melting point in differential scanning calorimetry.
As the alcohol component used in the raw material monomer of the crystalline polyester, it is preferable to use an aliphatic diol having 6 or more and 18 or less carbon atoms from the viewpoint of enhancing crystallinity. From the viewpoint of fixability and heat stability, an aliphatic diol having 6 or more and 12 or less carbon atoms is more preferable.
Aliphatic diols include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1, Examples thereof include 12-dodecanediol. The content of the aliphatic diol is preferably 80.0 mol% or more and 100.0 mol% or less in the alcohol component from the viewpoint of further enhancing the crystallinity of the crystalline polyester.

As the alcohol component for obtaining the crystalline polyester, a polyhydric alcohol component other than the above-mentioned aliphatic diol may be contained. For example, it is represented by the above formula (1) containing a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, a polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane, and the like. Aromatic diols such as alkylene oxide adducts of bisphenol A; trihydric or higher alcohols such as glycerin, pentaerythritol and trimethylolpropane.

As the carboxylic acid component used in the raw material monomer of the crystalline polyester resin, it is preferable to use an aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms. From the viewpoint of toner fixability and heat stability, an aliphatic dicarboxylic acid compound having 6 or more and 12 or less carbon atoms is more preferable.
Examples of the aliphatic dicarboxylic acid compound include octanedioic acid, nonanedioic acid, decanedioic acid, undecanedioic acid, and dodecanedioic acid. The content of the aliphatic dicarboxylic acid compound having 6 or more and 18 or less carbon atoms is preferably 80.0 mol% or more and 100.0 mol% or less in the carboxylic acid component.

The carboxylic acid component for obtaining the crystalline polyester may contain a carboxylic acid component other than the above-mentioned aliphatic dicarboxylic acid compound. For example, an aromatic dicarboxylic acid compound, a trivalent or higher aromatic polyvalent carboxylic acid compound, and the like can be mentioned, but the present invention is not particularly limited thereto. Aromatic dicarboxylic acid compounds also include aromatic dicarboxylic acid derivatives.
Specific examples of the aromatic dicarboxylic acid compound include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, anhydrides of these acids, and alkyl (1 to 3 carbon atoms) esters thereof. .. Examples of the alkyl group in the alkyl ester include a methyl group, an ethyl group, a propyl group and an isopropyl group.
Examples of the trivalent or higher polyvalent carboxylic acid compound include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid and pyromellitic acid, and these. Examples thereof include derivatives such as acid anhydrides and alkyl (1 or more and 3 or less carbon atoms) esters.
The content of the crystalline polyester is preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 7 parts by mass with respect to 100 parts by mass of the binder resin.

The crystalline material may contain wax.
As the wax, hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, and fatty acid esters are preferable from the viewpoint of high releasability. If necessary, two or more kinds of wax may be used together.

Specific examples of the wax include the following. Viscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Kasei Kogyo Co., Ltd.), High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals Co., Ltd.) ), Sazole H1, H2, C80, C105, C77 (Schumann Sazole), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seikan Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unisid (registered trademark) 350, 425, 550, 700 (Toyo Adre Co., Ltd.), wood wax, beeswax, rice wax, candelilla wax, carnauba wax (Co., Ltd.) Ceralica NODA).
In the present invention, when a wax containing a fatty acid ester as a main component (hereinafter referred to as ester wax) is used as a mold release agent, the binder resin is easily plasticized and the low temperature fixability is easily improved. Further, in a specific production method, it is preferable because it is easy to form a microdomain and it is easy to control it into a suitable shape of the present invention.

In the present invention, it is preferable that the crystalline material contains a monoester compound. The monoester compound means an ester compound in which the number of ester groups contained in one molecule is one.
The melting point of the monoester compound is preferably 60 ° C. or higher and 72 ° C. or lower. When the melting point is in the above range, it is possible to effectively improve the low temperature fixability of the toner. Further, it becomes easy to control the degree of hydrophobicity of the toner within a predetermined range, and it becomes easy to control the adhesive force F.

Examples of the aliphatic alcohol that can be used for the monoester compound include the following. 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, undecyl alcohol, lauryl alcohol, myristyl alcohol, 1-hexadecanol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol.
On the other hand, examples of aliphatic carboxylic acids include pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid. Can be mentioned.
The carbon number of one molecule of the monoester compound is preferably 36 or more and 42 or less. Since the monoester compound having 36 or more carbon atoms has a relatively long alkyl chain, the electric conductivity of the lamellar structure tends to be high. Further, if the monoester compound has 42 or less carbon atoms, the monoester compound easily sufficiently plasticizes the binder resin when the toner receives heat.

As the monoester compound, a condensate of an aliphatic alcohol having 6 to 24 carbon atoms and a long-chain carboxylic acid, or a condensate of an aliphatic carboxylic acid having 4 to 24 carbon atoms and a long-chain alcohol can be used. Here, any long-chain carboxylic acid or long-chain alcohol can be used, but a combination capable of satisfying the above melting point is preferable.
The content of the monoester compound is preferably 1 to 30 parts by mass, and more preferably 2 to 25 parts by mass with respect to 100 parts by mass of the binder resin.

In the DSC curve obtained in the process of raising the temperature to 180 ° C and then lowering the temperature by the differential scanning calorimetry DSC of the toner, the maximum exothermic peak temperature of the monoester compound alone obtained by the measurement under the same conditions is in the region of ± 5 ° C. When the calorific value is C and the calorific value in the region of the maximum heat generation peak temperature + 5 ° C. or higher and the maximum heat generation peak temperature + 15 ° C. or lower is D, the D / C is preferably 0.5 or more and 4.0 or less. .. More preferably, it is 0.5 or more and 3.5 or less. The D / C can be controlled by the type and content of the monoester compound, and the quenching conditions and annealing conditions at the time of toner production.
The fact that the D / C is in the above range indicates that the crystallization of the monoester compound in the toner and the binder resin is controlled to some extent.
When the D / C is 0.5 or more, the monoester compound is appropriately crystallized together with the binder resin, so that good fixability can be obtained. When the D / C exceeds 4.0, the thermal strength of the toner becomes good, and the development stability, particularly the durability, is improved.

In the cross section of the toner particles observed by a transmission electron microscope, microdomains of the crystalline material are present, and the number average value of the major axis of the microdomains is preferably 50 nm or more and 350 nm or less, preferably 100 nm or more and 300 nm or less. It is more preferable to have. The major axis of the microdomain can be controlled by the type and content of the crystalline material, and the quenching conditions and annealing conditions at the time of toner production.
When the number average value of the major axis of the microdomain is 50 nm or more, the amount of crystallization of the crystalline material in the toner is appropriate, the thermal strength as the toner is high, and the development stability, especially the durability is good. Become. On the other hand, when it is 350 nm or less, the exposure of the domain to the surface of the toner particles can be suppressed, and the chargeability and fusion to other members can be suppressed.
The cross section of the toner particles is dyed so that the crystalline material can be easily observed, and the region having the lamellar structure confirmed by the transmission electron microscope TEM observation of the cross section is defined as the domain of the crystalline material. Further, a domain having a domain major axis of 10 nm or more and 1000 nm or less is referred to as a microdomain in the present invention. Further, a domain having a major axis of more than 1000 nm is called a large domain. The detailed measurement method of the micro domain will be described later.

From the viewpoint of controlling the formation of the microdomain, it is preferable that the crystalline material contains a hydrocarbon wax.
Hydrocarbon wax is known to crystallize in the form of stacked linear hydrocarbon chain portions, and examples thereof include paraffin wax and Fischer-Tropsch wax.
In the suspension polymerization method, the hydrocarbon wax tends to form a large domain near the center of the toner particles. Therefore, the minute domains are likely to be locally unevenly distributed near the surface of the toner particles.
The content of the hydrocarbon wax is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the binder resin.

The content of the crystalline material is preferably 5 parts by mass or more and 45 parts by mass or less, and more preferably 15 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the binder resin.

The degree of hydrophobicity of the toner particles in the methanol wettability test is preferably 25 to 60% by mass of methanol, and more preferably 35 to 60% by mass of methanol.
Within the above range, the adhesive force between the toner and the photoconductor is controlled to the optimum range, and the toner slips through the cleaning portion and the destruction of the blocking layer is suppressed.

Further, the toner particles may be magnetic toner particles or non-magnetic toner particles.
In the case of magnetic toner particles, it is preferable to use magnetic iron oxide. As the magnetic iron oxide, iron oxide such as magnetite, maghematite, and ferrite is used. The amount of magnetic iron oxide contained in the toner is preferably 25.0 parts by mass or more and 100.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

When producing non-magnetic toner particles, carbon black or other known pigments or dyes can be used as the colorant. Further, only one kind of pigment or dye may be used, or two or more kinds may be used in combination. The content of the colorant is preferably 0.1 parts by mass or more and 60.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 50.0 parts by mass or less with respect to 100 parts by mass of the binder resin. Is.
In the method for producing toner particles by the suspension polymerization method, in addition to the above-mentioned materials, known charge control agents, conductivity-imparting agents, lubricants, abrasives and the like may be added.

The method for producing toner particles by the suspension polymerization method preferably uniformly dissolves or disperses a polymerizable monomer, a colorant, a crystalline material and, if necessary, other additives capable of producing a binder resin. To obtain a polymerizable monomer composition,
A granulation step of dispersing and granulating this polymerizable monomer composition in an aqueous medium containing a dispersion stabilizer A using an appropriate stirrer, and the polymerizable property contained in the polymerizable monomer composition. Polymerization step of obtaining toner particles by polymerizing a monomer,
Have.
Even if the polymerization step is followed by a cooling step that can control the location and size of the microdomains of the crystalline material, and a holding (annealing) step that controls the crystallinity of the crystalline material, if necessary. good.

In the dissolution step, the necessary materials are uniformly dissolved or dispersed using a disperser such as a ball mill or an ultrasonic disperser to prepare a polymerizable monomer composition.
In the granulation step, the obtained polymerizable monomer composition is put into an aqueous medium containing the dispersion stabilizer A, and the polymerizable monomer composition is prepared by, for example, a stirrer or a disperser having a high shear force. A droplet of material is formed to the size of the desired toner particles. In the granulation step, it is preferable to carry out an emulsification / dispersion treatment for about 20 to 200 minutes by an emulsification / disperser such as Cavitron (Eurotech) before granulation with a stirrer or a disperser.
After the granulation step, the temperature is preferably set to 50 to 90 ° C. to carry out the polymerization reaction of the polymerizable monomer contained in the polymerizable monomer composition. At this time, a polymerization initiator may be added as needed. The polymerization initiator can be added in any step, for example, it may be added in the dissolution step or it may be added in the dispersion step.

In the method for producing toner particles by the suspension polymerization method, the aqueous medium containing the dispersion stabilizer A (hereinafter, also referred to as the first aqueous medium) is 0.2% by mass with respect to 100 parts by mass of the polymerizable monomer composition. It is preferable to contain sodium chloride in an amount of 3 parts or more and 3.0 parts by mass or less in order to control the surface unevenness index of the toner particles. More preferably, it is 0.4 parts by mass or more and 2.0 parts by mass or less.
The sodium chloride concentration in the aqueous medium containing the dispersion stabilizer A is preferably 1.5 to 4.0% by mass, more preferably 1.5 to 2.5% by mass.
Further, by containing a predetermined sodium chloride in the aqueous medium, it is possible to prevent the polymerizable monomer from being dissolved in the aqueous medium from the particles of the polymerizable monomer composition due to the salting out effect thereof. When the polymerizable monomer is dissolved in the aqueous medium, the dispersion stabilizer may adhere to the polymerizable monomer to generate fine particles such as so-called emulsified particles. Further, the particles of the polymerizable monomer composition having a desired particle size may be adhered to each other starting from the emulsified particles to generate coalesced particles.

Therefore, the content of sodium chloride is preferably 0.2 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer composition. Dispersion stabilizers usually produce by-products in aqueous media. However, the content of this by-product salt alone is small in order to control the surface unevenness index B / A of the toner and to exhibit the salting out effect during production. On the other hand, if the amount of the dispersion stabilizer added is large, it becomes difficult to obtain toner particles having a desired particle size, so it is preferable to add sodium chloride. The amount of sodium chloride added in addition to the by-product salt is preferably 0.15 parts by mass or more and 2.25 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer composition.

Further, in the present invention, it is preferable to have a step of granulating the polymerizable monomer composition in the granulation step and then mixing the obtained dispersion with a second aqueous medium containing the dispersion stabilizer B. The content of the dispersion stabilizer B in the aqueous medium is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the dispersion stabilizer A in the first aqueous medium.
By containing the above amount of the dispersion stabilizer B in the second aqueous medium, it is possible to supplement the dispersion stabilizer deficient at the time of granulation and obtain toner particles having a smooth surface shape. When the content of the dispersion stabilizer B is 5 parts by mass or more, the surface unevenness index B / A can be easily controlled within the range of the present invention. On the other hand, when it is 60 parts by mass or less, it is possible to suppress the excessive dispersion stabilizer B from adhering to the polymerizable monomer during polymerization, and it is possible to suppress the generation of fine particles.

In the production of toner particles, it is preferable to adjust the content of sodium chloride in the primary aqueous medium by adding sodium chloride to the primary aqueous medium as described above.
The dispersion stabilizers A and B are not particularly limited, and known dispersion stabilizers can be used. For example, magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, etc. may be used. Can be done.
The dispersion stabilizer A or B is preferably prepared by mixing an aqueous solution of calcium chloride and an aqueous solution of sodium phosphate. As shown in the following formula (1), hydroxyapatite and sodium chloride, which is a by-product salt, are produced from calcium chloride and calcium phosphate. Hydroxyapatite is a preferred dispersion stabilizer for stabilizing the particles of the polymerizable monomer composition. In addition, since sodium chloride is produced as a by-product salt, it is also preferable for exhibiting a salting out effect that suppresses fine particles.
6Na ₃ PO ₄ + 10CaCl ₂ + 2H ₂ O → [Ca ₃ (PO ₄ ) ₂ ] ₃ Ca (OH) ₂ + 18 NaCl + 2HCl… Equation (1)

After obtaining the toner particles by the polymerization step, it is preferable to perform the following operations in the subsequent cooling step in order to control the existence position and size of the fine domain of the crystalline material. Specifically, it is preferable to cool the aqueous medium to a temperature equal to or lower than the glass transition of the binder resin at a cooling rate of 5 ° C./min or more, more preferably to a cooling rate of 20 ° C./min or more, and a cooling rate of 50. It is more preferable to cool at ° C./min or higher. The upper limit of the cooling rate is not particularly limited, but is preferably 500 ° C./min or less.

After cooling at the above cooling rate, it is preferable to hold the material at a temperature of 45 to 65 ° C. for 30 minutes or more in order to control the crystallinity of the crystalline material. The holding time is more preferably 60 minutes or more, further preferably 120 minutes or more. The upper limit of the holding time is about 24 hours or less in relation to manufacturing efficiency.

The toner particles obtained as described above are filtered, washed, and dried by a known method, and if necessary, an inorganic fine powder as a fluidity improver is mixed and adhered to the surface to obtain a toner. Can be done.
As the inorganic fine powder, known ones can be used. Preferred are silica fine particles such as titania fine particles, wet manufacturing silica, and dry silica, and inorganic fine powder obtained by surface-treating the silica with a silane coupling agent, a titanium coupling agent, silicone oil, or the like. The surface-treated inorganic fine powder preferably has a hydrophobicity of 30 or more and 98 or less titrated by the methanol wettability test.
The amount of the inorganic fine powder added is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the toner particles.

Next, the image forming apparatus will be described.
FIG. 1 is a schematic diagram showing an example of an image forming apparatus.
The electrostatic latent image carrier 100 is charged by a roller-shaped charging member (charging roller) 117, and is exposed by being irradiated with a laser beam 123 by a laser generator 121. An electrostatic latent image corresponding to the target image is formed on the surface. The electrostatic latent image carrier 100 and the toner carrier 102 rotate in the directions of arrows, respectively. The toner is housed in the developing device 140 and is supplied to the toner carrier 102 by the toner stirring member 141. The supplied toner is regulated by the nip portion between the toner carrier 102 and the toner regulating member 142, and is conveyed to the developing region where the electrostatic latent image carrier 100 and the toner carrier 102 face each other for development.
The developed toner image is conveyed to the transfer region where the electrostatic latent image carrier 100 and the transfer member 114 face each other, transferred to the transfer material P, and heat-fixed by the fixing device 126. Further, the toner that is not transferred and remains on the electrostatic latent image carrier 100 is conveyed to the cleaning region where the electrostatic latent image carrier 100 and the cleaning member 116 face each other, and is scraped off by a cleaning blade or the like.

In the charging step, the electrostatic latent image carrier 100 and the charging roller 117 form a contact portion and come into contact with each other, and a predetermined charging bias is applied to the charging roller 117 to determine the surface of the electrostatic latent image carrier 100. It is preferable to use a contact charging method in which the polarity and potential of the above are charged. By performing contact charging in this way, stable and uniform charging can be performed, and the generation of ozone and the like can be reduced. Further, in order to maintain uniform contact with the electrostatic latent image carrier 100 and perform uniform charging, it is more preferable to use a charging roller 117 that rotates in the same direction as the electrostatic latent image carrier 100.
As a preferable process condition when the charging roller is used, a case where the contact pressure of the charging roller is 4.9 to 490.0 N / m and a DC voltage or an AC voltage is superimposed on the DC voltage can be exemplified. It is preferable that the AC voltage is 0.5 to 5.0 kVpp, the AC frequency is 50 to 5 kHz, and the absolute value of the DC voltage is 400 to 1,700 V. Further, the peripheral speed difference of the charging roller with respect to the electrostatic latent image carrier is preferably 100 to 150%.

Examples of the material of the charging roller include, but are not limited to, the following as the material of the elastic layer.
A rubber material in which a conductive substance such as carbon black or metal oxide is dispersed in order to adjust the electric resistance in ethylene-propylene-diene polyethylene (EPDM), urethane, butadiene acrylonitrile rubber (NBR), silicone rubber, isoprene rubber, etc. , Also foamed from these. It is also possible to adjust the electrical resistance using an ionic conductive material without dispersing the conductive material or in combination with the conductive material.
Examples of the core metal used for the charging roller include aluminum and SUS. The charging roller is disposed by being pressed against the charged body as the electrostatic latent image carrier with a predetermined pressing force against elasticity, and is a contact portion between the charging roller and the electrostatic latent image carrier. A charged contact portion is formed.

In the developing step, the electrostatic latent image carrier and the toner carrier form a contact portion and come into contact with each other, and a predetermined development bias is applied to the toner carrier to apply an electrostatic latent image on the electrostatic latent image carrier. It is preferable to use a contact development method in which the image is a toner image. By performing such contact development, a high-definition toner image can be obtained, and a high-quality output image can be obtained. Further, since it is contact development, it is preferable that the toner carrier has an elastic layer on the surface of the substrate.
Further, in the developing step, it is preferable to apply a developing bias to the toner carrier and use the electrostatic latent image on the electrostatic latent image carrier as a toner image, and the applied developing bias is a DC voltage or a DC voltage. It may be a voltage on which an alternating electric field is superimposed.
As the waveform of the alternating electric field, a sine wave, a rectangular wave, a triangular wave, or the like can be appropriately used. Further, it may be a pulse wave formed by periodically turning on / off the DC power supply. As described above, as the waveform of the alternating electric field, a bias in which the voltage value changes periodically can be used.

Further, in the developing process, when magnetic toner is used, it is necessary to arrange a magnet inside the toner carrier. In this case, the toner carrier preferably has a fixed magnet having multiple poles inside, and preferably has 3 to 10 poles as magnetic poles.
Further, in the developing step, it is preferable that the toner regulating member abuts on the toner carrier via the toner to regulate the toner layer thickness on the toner carrier. By doing so, high image quality without fog can be obtained. As the toner regulating member that comes into contact with the toner carrier, a regulating blade is generally used, and can be suitably used in the present invention.

As the regulation blade, a rubber elastic body such as silicone rubber, urethane rubber, or NBR; a synthetic resin elastic body such as polyethylene terephthalate, or a metal elastic body such as a phosphor bronze plate or a SUS plate can be used, and a composite thereof. It may be a body. Further, for the purpose of controlling the chargeability of the toner on an elastic support such as rubber, synthetic resin, or metal elastic body, a charge control substance such as resin, rubber, metal oxide, or metal is applied to the toner carrier contact portion. You may use the one attached so as to hit. Among these, those in which resin and rubber are bonded to the metal elastic body so as to hit the contact portion of the toner carrier are particularly preferable.
As the material of the member to be bonded to the metal elastic body, a material such as urethane rubber, urethane resin, polyamide resin, and nylon resin, which is easily charged with a positive electrode property, is preferable.

The base portion on the upper side of the regulated blade is fixedly held on the developing device side, and the lower side is bent in the forward or reverse direction of the toner carrier against the elastic force of the blade to bend the toner carrier. The surface is brought into contact with an appropriate elastic pressing force.
The contact pressure between the regulation blade and the toner carrier is preferably 1.30 to 245.0 N / m, more preferably 4.9 to 118.0 N / m as the linear pressure in the direction of the toner carrier bus. When the contact pressure is 1.30 N / m or more, uniform application of toner is easy, and fog and scattering are less likely to occur. When the contact pressure is 245.0 N / m or less, it is difficult to apply a large pressure to the toner and it is difficult to cause deterioration of the toner.

As the transfer step, a contact transfer method using a transfer member such as a transfer roller is preferable. In the contact transfer method, the electrostatic latent image carrier electrostatically transfers the toner image to the recording medium while contacting the transfer member to which a voltage of opposite polarity is applied to the toner via the recording medium. The contact pressure of the transfer member is preferably a linear pressure of 2.9 N / m or more, and more preferably 19.6 N / m or more. When the linear pressure as the contact pressure is 2.9 N / m or more, the transfer deviation of the recording medium and the occurrence of transfer defects are unlikely to occur.

As the cleaning step, a blade cleaning method having a cleaning blade is preferable. The cleaning blade is held at the tip of a support, usually made of sheet metal. The cleaning blade has one end side in the lateral direction fixed to the tip of the support so that its longitudinal direction is substantially parallel to the longitudinal direction of the electrostatic latent image carrier, and the other end in the lateral direction. The free end, which is a portion, is arranged so as to abut against the electrostatic latent image carrier in the counter direction.
As the material of the cleaning blade, a rubber material is suitable from the viewpoint of the ability to follow the surface of the electrostatic latent image carrier and the difficulty of scratching the surface of the electrostatic latent image carrier. Among them, polyurethane rubber is the most suitable in terms of physical characteristics and chemical durability. The rubber hardness of the rubber material constituting the cleaning blade is preferably 60 degrees or more and 90 degrees or less in terms of international rubber hardness (IRHD) from the viewpoint of stability in cleaning toner from the electrostatic latent image carrier.

The cleanability is greatly affected by the contact angle of the cleaning blade and the setting of the contact line pressure. As a method of contacting the cleaning blade, the rubber blade is fixed to a support tilted at 15 ° or more and 45 ° or less with respect to the tangent line of the electrostatic latent image carrier at the contact position of the cleaning blade, and the rubber blade is in contact with the counter. Is preferable.
The contact line pressure of the cleaning blade is preferably set to about 10 N / m or more and 100 N / m or less from the viewpoint of preventing the toner from slipping through. The contact line pressure can be measured by providing a load transducer (load cell) at the portion where the cleaning blade is fixed. As a measuring method, a load converter may be installed by modifying the cleaning device inside the image forming apparatus main body, but a HEIDON friction tester (Tribostation TYPE32 modified machine) manufactured by Shinto Kagaku Co., Ltd. may be used.
As the fixing step, a known fixing method can be used. When a heated fixing member is used, a halogen heater, an IH heater, or the like is preferably used as a heat source. Further, the shape of the fixing member may be a roller shape or an endless belt shape.

Next, the method for measuring the physical properties of the toner particles, the toner, and the toner carrier is as shown below. In the examples described later, the physical property values are measured based on these methods.
<Measurement of resin glass transition temperature Tg>
The Tg of the resin is measured according to ASTM D3418-82 using a differential scanning calorimetry apparatus "Q2000" (manufactured by TA Instruments). The melting point of indium and zinc is used for temperature correction of the device detection unit, and the heat of fusion of indium is used for the correction of calorific value.
Specifically, about 2 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rise rate is 10 in the measurement temperature range of 30 to 200 ° C. Measure at ° C / min. In the measurement, the temperature is raised to 200 ° C., then lowered to 30 ° C., and then raised again. The specific heat change can be obtained in the temperature range of 40 ° C. to 100 ° C. in the second temperature raising process. The intersection of the line at the midpoint of the baseline before and after the specific heat change at this time and the differential thermal curve is defined as the glass transition temperature Tg of the resin.

<Measurement of softening point of resin>
The softening point of the resin is measured by using a constant load extrusion type thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) and following the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with a piston,
The temperature of the measurement sample filled in the cylinder is raised to melt it, and the melted measurement sample is extruded from the die at the bottom of the cylinder, and a flow curve showing the relationship between the amount of piston drop and the temperature at this time can be obtained.
The softening point is the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation device flow tester CFT-500D". The melting temperature in the 1/2 method is calculated as follows. First, 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time when the outflow starts is obtained (this is defined as X. X = (Smax-Smin) /. 2). The temperature of the flow curve when the amount of descent of the piston is the sum of X and Smin in the flow curve is the melting temperature in the 1/2 method.
As the measurement sample, about 1.0 g of the sample was compression-molded in an environment of 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) at about 10 MPa for about 60 seconds. Use a columnar one with a diameter of about 8 mm.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rise method Temperature rise rate: 4 ° C / min
Starting temperature: 50 ° C
Reaching temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature rise rate: 4.0 ° C / min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0 mm

<Measuring method of weight average particle size (D4) and number average particle size (D1)>
The weight average particle size (D4) and the number average particle size (D1) of the toner particles are the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, Beckman) by the pore electric resistance method equipped with an aperture tube of 100 μm. -Using Coulter) and the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (Beckman Coulter) for setting measurement conditions and analyzing measurement data, the number of effective measurement channels is 25. It was measured in 1000 channels, and the measurement data was analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, one in which special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.
Before performing the measurement and analysis, the dedicated software was set as follows.
In the dedicated software "Change standard measurement method (SOM) screen", set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). The value obtained by using (manufactured by) is set. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement.
In the dedicated software "Pulse to particle size conversion setting screen", set the bin spacing to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

The specific measurement method is as follows.
1. 1. About 200 ml of the electrolytic aqueous solution is placed in a 250 ml round bottom beaker made of glass dedicated to the Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "flash of the aperture tube" function of the dedicated software.
2. 2. Approximately 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat-bottomed beaker made of glass, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder) is used as a dispersant for cleaning a precision measuring instrument at pH 7. Add about 0.3 ml of a diluted solution obtained by diluting a 10% by mass aqueous solution of a neutral detergent (manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass.
3. 3. Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and a predetermined amount of ions are contained in the water tank of the ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. Add exchange water, and add about 2 ml of the Contaminone N to this water tank.
4. 2. Is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic solution in the beaker is maximized.
5. 4. In a state where the electrolytic aqueous solution in the beaker is irradiated with ultrasonic waves, about 10 mg of toner particles are added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. For ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
6. The above 1. installed in the sample stand. Toner particles were dispersed in a round-bottomed beaker using a pipette. The electrolytic aqueous solution of No. 1 is added dropwise to adjust the measured concentration to about 5%. Then, the measurement is performed until the number of measured particles reaches 50,000.
7. The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) and the number average particle size (D1) are calculated. In addition, when the graph / number% and graph / volume% are set by the dedicated software, the "arithmetic diameter" on the analysis / number statistic (arithmetic mean) and analysis / volume statistic (arithmetic mean) screens is the number average. The particle size (D1) and the weight average particle size (D4).

<Calculation method of surface unevenness index B / A>
The surface unevenness index is obtained from the theoretical surface area A per unit mass of the toner particles and the BET specific surface area B (= B / A). When measuring the surface unevenness index of toner particles in a toner in which an external additive is added to the toner particles, it is necessary to remove the external additive. Specific methods include, for example, the following methods. Can be mentioned.
-For magnetic toner (1) Put 45 mg of magnetic toner in a sample bottle and add 10 mL of methanol.
(2) Disperse the sample for 1 minute with an ultrasonic cleaner to separate the external additive.
(3) Suction filtration (10 μm membrane filter) is performed to separate the magnetic toner particles and the external additive. Alternatively, a magnet may be placed on the bottom of the sample bottle to fix the magnetic toner particles and separate only the supernatant liquid.
(4) The above (2) and (3) are performed a total of three times, and the obtained magnetic toner particles are sufficiently dried in a vacuum dryer at room temperature. The magnetic toner particles from which the external additive has been removed can be observed with a scanning electron microscope, and it can be confirmed that the external additive has disappeared. If the external additive has not been sufficiently removed, repeat steps (2) and (3) until the external additive is sufficiently removed. As another method for removing the external additive instead of the above (2) and (3), there is a method of dissolving the external additive with an alkaline solution. As the alkali, an aqueous solution of sodium hydroxide is preferable.
-For non-magnetic toner Add 160 g of sucrose (manufactured by Kishida Chemical) to 100 mL of ion-exchanged water and dissolve while using a hot water sink to prepare a sucrose concentrate. 31 g of the sucrose concentrate and 6 mL of Contaminone N are placed in a centrifuge tube to prepare a dispersion. 1 g of toner is added to this dispersion, and the toner lumps are loosened with a spatula or the like.
The centrifuge tube is shaken with the shaker for 20 minutes under the condition of 350 reciprocations per minute. After shaking, the solution is replaced with a glass tube for a swing rotor (50 mL), and centrifugation is performed at 3500 rpm for 30 minutes with a centrifuge. In the glass tube after centrifugation, toner particles are present in the uppermost layer and silica fine particles are present on the aqueous solution side of the lower layer, so that only the toner particles in the uppermost layer are recovered.
If the external additive has not been sufficiently removed, centrifugation is repeated as necessary, and after sufficient separation, the toner solution is dried and toner particles are collected.
Each calculation method is as follows.

<< Calculation method of theoretical surface area A per unit weight of toner particles >>
After obtaining the number average particle size (D1), use the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) to analyze the measurement data from 2.0 μm to 32. Dividing up to 0.0 μm into 12 channels (2.000 to 2.520 μm, 2.520 to 3.175 μm, 3.175 to 4.000 μm, 4.000 to 5.040 μm, 5.040 to 6.350 μm, 6.350 to 8,000 μm, 8,000 to 10.079 μm, 10.079 to 12.699 μm, 12.699 to 16.000 μm, 16.000 to 20.159 μm, 20.159 to 25.398 μm, 25. 398 to 32.000 μm), the number ratio of toner particles in each particle size range is determined.
Then, using the median value of each channel (for example, if it is 2.000 to 2.520 μm, the median value is 2.260 μm), it is assumed that the toner particles at the median value of each channel are true spheres. The theoretical surface area (= 4 × π × (median value of each channel) ² ) is obtained. By multiplying the theoretical surface area by the number ratio of the particles belonging to each channel obtained above, the average theoretical surface area (a) of the toner particles assuming that the measured toner particles are true spheres is obtained.
Next, the theoretical weight (= 4/3 × π × (= 4/3 × π ×) when it is assumed that the toner particles at the median value of each channel are true spheres from the median value of each channel and the true density of the measured toner particles in the same manner. Find the median) ³ x true density of each channel. The average theoretical weight (b) of the toner particles is obtained from the theoretical weight and the ratio of the number of particles belonging to each channel obtained above.
The true density of the toner particles is measured by a dry automatic densitometer Auto Pycnometer (manufactured by Yuasa Ionics Co., Ltd.). The conditions are as follows.
Cell SM cell (10 mL)
Sample amount 2.0g
This measuring device measures the true density of solids and liquids based on the gas phase replacement method. Similar to the liquid phase replacement method, it is based on Archimedes' principle, but the accuracy is high because gas (argon gas) is used as the replacement medium.
As described above, the average theoretical surface area A (= a / b) per unit weight of the measured toner particles is calculated from the average theoretical surface area and the average theoretical weight of the toner particles.

<< Measurement method of BET specific surface area B of toner particles >>
The BET specific surface area of the toner particles can be determined by a low temperature gas adsorption method based on a dynamic constant pressure method according to the BET multipoint method. BET specific surface area (m ² ) by adsorbing nitrogen gas on the sample surface using the specific surface area measuring device "Gemini 2375 Ver.5.0" (manufactured by Shimadzu Corporation) and measuring using the BET multipoint method. / G) is calculated. Specifically, the measurement is performed by the following procedure.
After measuring the mass of the empty sample cell, the sample cell is filled with 1.0 g of the measurement sample. Further, a sample cell filled with a sample is set in the degassing device, and degassing is performed at room temperature for 7 hours. After degassing, the mass of the entire sample cell is measured, and the exact mass of the sample is calculated from the difference from the empty sample cell.
Next, empty sample cells are set in the balance port and analysis port of the BET measuring device. A dewar bottle containing liquid nitrogen is set in a predetermined position, and P0 is measured by a saturated vapor pressure (P0) measurement command. After the P0 measurement is completed, the degassed sample cell is set in the analysis port, the sample mass and P0 are input, and then the measurement is started by the BET measurement command. After that, the BET specific surface area is automatically calculated.

<Measurement method of adhesive force F (nN) between toner and polycarbonate flat plate>
For the measurement of the adhesive force, a vibration type electrostatic adhesive force measuring device reported at KONICA MINOLTA TECHNOLOGY REPORT VOL1 (2004) and the 1st Study Group on Image Formation Technology (2012) is used.
As an outline of the apparatus, toner mixed with a magnetic carrier and triboelectricly charged is developed on a sample table by a two-component developing method and electrostatically adhered. The sample table is coated with polycarbonate, which is also used for the surface of the photoconductor. The sample table is mounted on a vibration unit in which a horn for amplitude amplification is connected to the piezoelectric vibrator, and the vibrator is vibrated to give vibration acceleration to the toner. The vibration acceleration is given by dividing 0 to 2 Mm / sec ² into 24 parts. The state in which the toner is detached from the sample electrode is observed by the CCD, and the vibration acceleration when the toner is detached by 50% in area ratio from the initial state is calculated.
Here, assuming that the vibration amplitude is A, the vibration angular velocity of the vibrator is ω, and the mass of the toner is m, the inertial force acting on the toner is given by F = mAω ² . The gravity of the toner is sufficiently small with respect to the adhesive force and can be ignored. Since the inertial force when the toner is detached is equal to the adhesive force of the toner, the calculation was performed from the above formula. At this time, the mass m of the toner is calculated from m = π / 6 × r ³ × ρ from the number average particle size r of the toner and the true density ρ of the toner.
The outline of the measuring device is shown in FIG. 3 g of toner is put into the developer 1, and the developing sleeve 1-1 is rotated to coat the toner on the sleeve 1-1. At this time, the toner coated on the sleeve 1-1 is visually confirmed, and if the coating amount needs to be adjusted, between the developing blade (not shown in the figure) provided in the developing device and the sleeve 1-1. Make adjustments at the distance of.
The vibration unit 2 is composed of a vibrator 2-1, a horn 2-2, and a sample table 2-3, and a polycarbonate resin (bisphenol Z type, trade name: Upiron Z200, Mitsubishi Gas Chemical) is on the surface of the sample table 2-3. A thin film of (manufactured by) was adhered. While rotating the developing sleeve 1-1, the vibration unit 2 was moved so as to pass over the sleeve 1-1 (developing position). At that time, the sleeve 1-1 was passed so that the rotation speed was 0.1 m / sec and the moving speed of the vibration unit 2 was 0.001 m / sec. Further, when the vibration unit 2 passes over the sleeve 1-1, a voltage is applied between the sleeve 1-1 and the sample table 2-3 to develop (fly) the toner on the sample table 2-3. The electric field strength at this time can be adjusted by the voltage applied between the sleeve 1-1 and the sample table 2-3 and the gap thereof, depending on the amount of triboelectric charge of the toner and the like. As a guide, the electric field strength is 0.5 V / m.
After developing the toner on the sample table 2-3, the vibration unit 2 is moved to the vibration position, and the adhesion state of the toner is confirmed by the CCD3-3 equipped with the objective lens 3-1 and the lens barrel 3-2. As for the performance of the detection unit 3, the lens 3-1 and the CCD 3-3 are selected so that the resolution is 0.22 μm and the field of view is 570 μm × 427 μm. Here, the toner adhered state is performed in a state where one or two layers of toner are laminated over the entire visual field. The state is determined by using the image from the detection unit 3 and the presence of toner particles in the entire visual field after the development before and after the development.
After the toner is attached to the sample table 2-3, the sample table 2-3 is vibrated by the vibrator 2-1. The sample table 2-3 is vibrated by being amplified from the transmitter 4 via the oscillator 2-1 and the horn 2-2. The vibration acceleration (= Aω ² ) is divided into 24 from 0 to 2 × 10 ⁶ m / sec ² so that the sample table 2-3 can be vibrated intermittently. By the way, at the time of vibration, the toner separated from the sample table 2-3 is sucked by the vacuum cleaner 5.
The state of adhesion of the toner is such that after applying vibration acceleration to the sample table 2-3, the toner is taken in from the CCD 3-3 to the personal computer 3-4 in synchronization. After applying vibration acceleration up to 2 × 10 ⁶ m / sec ² , the state of the toner is image-processed with image processing software (manufactured by Photoshop). Specifically, when the obtained image is binarized, the portion to which the toner adheres is converted to black. When the vibration acceleration is not applied, the toner is present in the entire field of view, so that the area ratio of the black converted portion is close to 100%. When the vibration acceleration is increased from there, when the toner separates from the sample table 2-3 at a certain vibration acceleration, the area ratio of the portion converted to black decreases. The toner inertial force (= adhesive force F) is obtained from the vibration acceleration given when the area ratio becomes 50% by the above formula.

<Method of calculating the number average particle size of the major axis of the fine domain of crystalline material>
The number average diameter of the major axis of the microdomain of the crystalline material is the number average diameter obtained from the major axis of the domain of the crystalline material based on the cross-sectional image of the toner particles observed by a transmission electron microscope (TEM). means.
The toner cross section observed with a transmission electron microscope (TEM) is prepared as follows.
When the toner is stained with ruthenium, the crystalline material is not stained, so that the domain of the crystalline material appears black when TEM-observed, thus identifying the domain. In calculating the domain diameter, observe the cross section of 100 toner particles. All domains with a major axis of 10 nm or more and 1000 nm or less are measured, and the number average diameter is calculated. The obtained number average diameter is defined as the number average diameter of the major axis of the microdomain of the crystalline material.
A cross-sectional image of the toner particles can be obtained as follows.
Using an osmium plasma coater (filgen, OPC80T), an Os film (5 nm) and a naphthalene film (20 nm) were applied to the toner as a protective film, and the toner was embedded in a photocurable resin D800 (JEOL Ltd.) and then ultra-supercharged. A toner particle cross section having a film thickness of 60 nm (or 70 nm) is produced at a cutting speed of 1 mm / s by an ultrasonic ultramicrotome (Leica, UC7).
The obtained cross section was subjected to RuO ₄ gas 5 using a vacuum electron staining device (filgen, VSC4R1H).
Staining was performed in a 00 Pa atmosphere for 15 minutes, and STEM observation was performed using the STEM function of TEM (JEOL, JEM2800). The probe size of STEM is 1 nm, and the image size is 1024 x 1024 pixels.
For the obtained image, the major axis of the domain is obtained using the image processing software "Image-Pro Plus (manufactured by Media Cybernetics)".

<Calculation method of calorific value ratio D / C in DSC>
The calorific value ratio D / C is measured according to ASTM D3418-82 using a differential scanning calorimeter analyzer "Q2000" (manufactured by TA Instruments). The melting point of indium and zinc is used for temperature correction of the device detection unit, and the heat of fusion of indium is used for the correction of calorific value.
Specifically, about 2 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rise rate is 10 in the measurement temperature range of 30 to 180 ° C. Measure at ° C / min. In the measurement, the temperature is once raised to 180 ° C. at 10 ° C./min, and then to 30 ° C. at a temperature lowering rate of 10 ° C./min.
In the DSC curve obtained in this temperature lowering process, the calorific value in the region of ± 5 ° C. with respect to the maximum exothermic peak temperature obtained by using the monoester compound alone in the measurement under the same conditions is defined as C [J / g], and the maximum is said. The calorific value in the region of the exothermic peak temperature + 5 ° C. or higher and the maximum exothermic peak temperature + 15 ° C. or lower is D [J / g] to obtain the calorific value ratio D / C.

<Measurement of hydrophobicity by methanol wettability test>
For the methanol wettability test, a powder wettability tester WET-100P manufactured by Resuka Co., Ltd. is used, and the methanol dropping transmittance curve measured by the following conditions and procedures is used.
First, 50 ml of pure water (methanol concentration 0% by mass) is placed in a flask and the transmittance is measured. At this time, the transmittance is set to 100%, and the state in which no light is transmitted is set to 0%, and the transmittance is measured. That is, when methanol is added to the pure water and the transmitted light intensity becomes half of the transmitted light intensity of pure water (methanol concentration 0% by mass), the degree of hydrophobicity according to the methanol wettability test is 1% by mass of methanol. And.
The transmittance is measured as follows.
Place the magnetic stirrer in a beaker containing 50 ml of pure water (methanol concentration 0% by mass). Then, 0.1 g of inorganic fine powder or toner particles sifted with a mesh having an opening of 150 μm is precisely weighed and placed in the flask. Next, stirring is started by a magnetic stirrer at a stirring speed of 300 rpm (5 rpm), and methanol is continuously added to the measurement sample solution by a glass tube at an addition rate of 1.3 ml / min. The transmittance of light having a wavelength of 780 nm is measured, and a methanol dropping transmittance curve is created. At this time, methanol was used as the titration solvent because the influence of elution of dyes, pigments, charge control agents and the like contained in the toner is small, and the surface state of the toner can be observed more accurately.
In this measurement, a glass beaker having a diameter of 5 cm is used, and a magnetic stirrer having a length of 25 mm and a maximum diameter of 8 mm and having a Teflon (registered trademark) coating is used.

Hereinafter, examples will be shown. In the following description, parts are based on mass unless otherwise specified.

<Manufacturing example of magnetic material A>
In ferrous sulfate aqueous solution, 1.00 to 1.10 equivalents of caustic soda solution with respect to iron element, P ₂ O ₅ with an amount of 0.15% by mass in terms of phosphorus element with respect to iron element, to iron element On the other hand, SiO ₂ in an amount of 0.50% by mass in terms of elemental silicon was mixed to prepare an aqueous solution containing ferrous hydroxide. The pH of the aqueous solution was set to 8.0, and an oxidation reaction was carried out at 85 ° C. while blowing air to prepare a slurry liquid having seed crystals.
Next, a ferrous sulfate aqueous solution was added to this slurry liquid so that the amount was 0.90 to 1.20 equivalents with respect to the initial alkali amount (sodium component of caustic soda), and then the slurry liquid was maintained at pH 7.6. The oxidation reaction was promoted while blowing air to obtain a slurry liquid containing magnetic iron oxide. After filtering and washing, this water-containing slurry liquid was once taken out. At this time, a small amount of water-containing sample was taken and the water content was measured.
Next, this water-containing sample was put into another aqueous medium without being dried, and the slurry was redistributed with a pin mill while stirring and circulating the slurry to adjust the pH of the redispersed liquid to about 4.8. Then, while stirring, 1.4 parts of the n-hexyltrimethoxysilane coupling agent was added to 100 parts of magnetic iron oxide (the amount of magnetic iron oxide was calculated as the value obtained by subtracting the water content from the water content sample), and water was added. Disassembly was performed. After that, the mixture was sufficiently stirred to adjust the pH of the dispersion to 8.6, and surface treatment was performed.
The generated hydrophobic magnetic material is filtered with a filter press, washed with a large amount of water, dried at 100 ° C. for 2 hours, and the obtained particles are crushed to obtain a magnetic material having a volume average particle size of 0.26 μm. I got A.

<Production example of amorphous polyester resin B>
40 mol% of terephthalic acid, 10 mol% of trimellitic acid, and 50 mol% of bisphenol A-propylene oxide (PO) 2 mol adduct were placed in a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and then a catalyst. As a result, 1.5 parts of dibutyltin oxide was added to 100 parts of the total amount of the monomer.
Then, after rapidly raising the temperature to 180 ° C. under normal pressure under a nitrogen atmosphere, water was distilled off while heating at a rate of 10 ° C./hour from 180 ° C. to 210 ° C. to carry out polycondensation. After reaching 210 ° C., the pressure inside the reaction vessel was reduced to 5 kPa or less, and polycondensation was performed under the conditions of 210 ° C. and 5 kPa or less to obtain an amorphous polyester resin B. At that time, the polymerization time was adjusted so that the softening point of the obtained polyester resin was 120 ° C.

<Production example of crystalline polyester C1>
After putting 49 mol% of 1,9-nonanediol, 49 mol% of 1,10-decanedioic acid and 2 mol% of n-octadecanoic acid in a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, As a catalyst, 1 part of tin dioctylate was added to 100 parts of the total amount of the monomer, and the mixture was heated to 140 ° C. under a nitrogen atmosphere and reacted for 6 hours while distilling off water under normal pressure. Next, the reaction was carried out while raising the temperature to 200 ° C. at 10 ° C./hour, and after reaching 200 ° C., the reaction was carried out for 2 hours. Sexual polyester C1 was obtained.

<Production example of crystalline polyester C2>
Crystalline polyester C2 was obtained in the same manner as in the production example of crystalline polyester C1 except that the alcohol monomer was changed to 1,6-hexanediol 49 mol% and the acid monomer was changed to 1,12-dodecane diic acid.

<Manufacturing example of toner 1>
Toner particles and toner were manufactured by the following procedure.
(Adjustment of the first aqueous medium)
After adding 2.9 parts of sodium chloride dodecahydrate to 353.8 parts of ion-exchanged water and heating to 60 ° C. with stirring using a TK homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.). , A calcium chloride aqueous solution containing 1.7 parts of calcium chloride dihydrate added to 11.7 parts of ion-exchanged water and a sodium chloride aqueous solution containing 1.5 parts of sodium chloride added to 15.0 parts of ion-exchanged water were added. Stirring proceeded to obtain a first aqueous medium containing the dispersion stabilizer A.
(Preparation of polymerizable monomer composition)
・ Styrene 75.0 parts ・ n-butyl acrylate 25.0 parts ・ 1-6 hexanediol diacrylate 0.5 parts ・ Colorant: Magnetic material A 90.0 parts ・ Polyester resin B 5.0 parts ・ Crystalline polyester C1 5.0 parts After uniformly dispersing and mixing the above materials using an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.), the mixture was heated to 60 ° C., and behenyl wax stearate (melting point 68 ° C.) 20. 0 part and 10.0 part of paraffin wax (melting point: 78 ° C.) were added and mixed and dissolved to obtain a polymerizable monomer composition.

(Adjustment of the second water-based medium)
0.6 part of sodium phosphate dodecahydrate was added to 166.8 parts of ion-exchanged water and heated to 60 ° C. while stirring using a paddle stirring blade, and then 2.3 parts of ion-exchanged water was filled with calcium chloride. An aqueous calcium chloride solution containing 0.3 part of dihydrate was added and stirring was advanced to obtain a second aqueous medium containing the dispersion stabilizer B.
(Granulation)
The polymerizable monomer composition is put into the first aqueous medium, and the granulation solution is treated with Cavitron (manufactured by Eurotech) at a peripheral speed of the rotor at 35 m / s for 1 hour. Was performed, and the mixture was uniformly dispersed and mixed. Further, 7.0 parts of t-butylperoxypivalate was added as a polymerization initiator, and the mixture was stirred at 12000 rpm for 10 minutes with a TK homomixer (Special Machinery Chemical Industry Co., Ltd.) at 60 ° C. under an _N2 atmosphere. While granulating, a granulating solution containing droplets of the polymerizable monomer composition was obtained.

(Polymerization / Distillation / Drying / External)
The granulation liquid was put into the second aqueous medium and reacted at 74 ° C. for 3 hours while stirring with a paddle stirring blade. After completion of the reaction, the temperature was raised to 98 ° C. and distillation was performed for 3 hours to obtain a reaction slurry. Then, as a cooling step, water at 0 ° C. was added to the reaction slurry, the reaction slurry was cooled from 98 ° C. to 45 ° C. at a rate of 100 ° C./min, then further heated and held at 50 ° C. for 3 hours. Then, it was allowed to cool to 25 ° C. at room temperature. The allowed-cooled reaction slurry was washed by adding hydrochloric acid, filtered and dried to obtain toner particles having a weight average particle size of 7.6 μm. The surface unevenness index B / A of the obtained toner particles was 1.05, and the degree of hydrophobicity by the methanol wettability test was 50% by mass.
The following materials were mixed with 100 parts of the obtained toner particles with a Henschel mixer (FM-10 type manufactured by Mitsui Miike Machinery Co., Ltd.) to obtain toner 1. The temperature of the Henschel mixer jacket was adjusted to 45 ° C.
-Number of primary particles surface-treated with 25% by mass of hexamethyldisilazane 0.5 parts of hydrophobic silica fine particles with an average particle size of 20 nm-Number of primary particles surface-treated with 15% by mass of hexamethyldisilazane Average particle size of 40 nm 0.5 parts of hydrophobic silica fine particles The adhesive force F of the obtained toner 1 is 22.0 (nN), the calorific value ratio D / C of DSC is 3.0, and the average particle size of the number of microdomains is 220 (nm). Met.

<Manufacturing example of toners 2 to 4>
Toners 2 to 4 were obtained in the same manner as in the production example of toner 1, except that the material composition was as shown in Table 1. Table 1 shows the physical characteristics of the obtained toner.

<Manufacturing example of toner 5>
Toner 5 was obtained in the same manner as in the production example of toner 1 except that the cooling rate of the reaction slurry was changed to 150 ° C./min. Table 1 shows the physical characteristics of the obtained toner.

<Manufacturing example of toner 6>
Toner 6 was obtained in the same manner as in the production example of toner 5, except that the time for holding the reaction slurry at 50 ° C. was changed to 1 hour. Table 1 shows the physical characteristics of the obtained toner.

<Manufacturing example of toner 7>
Toner 7 was obtained in the same manner as in the production example of toner 1 except that the cooling rate of the reaction slurry was changed to 50 ° C./min. Table 1 shows the physical characteristics of the obtained toner.

<Manufacturing example of toner 8>
Toner 8 was obtained in the same manner as in the production example of toner 7, except that the time for holding the reaction slurry at 50 ° C. was changed to 5 hours. Table 1 shows the physical characteristics of the obtained toner.

<Manufacturing example of toners 9 to 14>
Toners 9 to 14 were obtained in the same manner as in the production example of toner 1, except that the material composition was as shown in Table 1. Table 1 shows the physical characteristics of the obtained toner.

<Manufacturing example of toner 15>
Toner 1 except that the material composition was as shown in Table 1 and the sodium phosphate dodecahydrate used for preparing the secondary aqueous medium was changed to 1.2 parts and calcium chloride dihydrate was changed to 0.6 parts. The toner 15 was obtained in the same manner as in the production example of. Table 1 shows the physical characteristics of the obtained toner.

<Manufacturing example of toner 16>
The toner 16 was obtained in the same manner as in the production example of the toner 1 except that the material composition was as shown in Table 1 and the second aqueous medium was not used. Table 1 shows the physical characteristics of the obtained toner.

<Manufacturing example of toner 17>
The toner 17 was obtained in the same manner as in the production example of the toner 1 except that the material composition was as shown in Table 1 and 90.0 parts of the magnetic material A as a colorant was changed to 7.0 parts of carbon black. Table 1 shows the physical characteristics of the obtained toner.

<Manufacturing example of toner 18>
The toner 18 was obtained in the same manner as in the production example of the toner 16 except that the material composition was as shown in Table 1 and the Cavitron in the granulation step was not used. Table 1 shows the physical characteristics of the obtained toner.

<Manufacturing examples of toners 19 and 20>
Toners 19 and 20 were obtained in the same manner as in the production example of toner 1, except that the material composition was as shown in Table 1. Table 1 shows the physical characteristics of the obtained toner.

Next, the evaluation using the obtained toner will be described.
<Example 1>
A commercially available laser printer LaserJet Enterprise M506 (manufactured by Hewlett-Packard Co., Ltd.) was used for the image drawing evaluation of the examples. The cartridge was taken out from the main body, the product toner was taken out from the cartridge, and 300 g of toner 1 was filled. The cartridge was modified so that the cleaning blade was tilted by + 10 ° C in the vertical direction with respect to the photosensitive drum, and the main body and cartridge were left for 24 hours in each environment where the temperature and humidity were controlled when evaluating each image. After that, the image drawing evaluation was performed. Regarding the image output evaluation, the following evaluation was performed and the judgment was made using the following indicators. The evaluation results are shown in Table 2.

(1) Measurement of fog after passing 10,000 sheets of durable paper under high temperature and high humidity environment (H / H) (32.5 ° C, 85% RH) After passing 10,000 sheets of horizontal line image with a printing ratio of 1%, solid white The fog density (%) was calculated from the difference between the white background of the image and the white background of the non-passing paper. For fog measurement, TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.) was used, and the average value of 5 points was used as the fog concentration (%), and the determination was made using the following index. As the durability evaluation paper, businessss 4200 (manufactured by Xerox) having a basis weight of 75 g / m ² was used.
A: Less than 1.5% B: 1.5% or more and less than 2.0% C: 2.0% or more and less than 2.5% D: 2.5% or more and less than 3.0% E: 3.0% or more

(2) Evaluation of transfer residual density after 10000 sheets of durable paper under low temperature and low humidity environment (L / L) (15 ° C, 10% RH) After 10000 sheets of horizontal line image with printing ratio of 1%, solid black image Immediately after the transfer of the above, the transfer residual toner on the photoconductor was taped. The taped tape was attached to a blank sheet, and the difference in concentration from the tape without taping was defined as the transfer residual concentration (%). TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.) was used to measure the residual transfer concentration, and the average value of 5 points was used as the residual transfer concentration (%), and the determination was made using the following index. As the durability evaluation paper, businessss 4200 (manufactured by Xerox) having a basis weight of 75 g / m ² was used.
A: Less than 1.0% B: 1.0% or more and less than 2.0% C: 2.0% or more and less than 3.0% D: 3.0% or more and less than 4.0% E: 4.0% or more

(3) Evaluation of cleaning performance in a low temperature environment (7.5 ° C, 30% RH) After passing 5000 sheets of horizontal line images with a printing ratio of 1%, check all the images to find out where cleaning defects have occurred. It was identified visually and judged by the following indicators. As the durability evaluation paper, businessss 4200 (manufactured by Xerox) having a basis weight of 75 g / m ² was used.
A: 0/5000 B: 1-5 / 5000 C: 6-10 / 5000 D: 11-20 / 5000 E: 21 or more / 5000

(4) Fixability evaluation under normal temperature and humidity environment (N / N) (23 ° C. 50% RH) The output images are solid images on Canon A4 size OceRedLabel paper (basis weight 80 g / m ² ), left and right. Adjust so that the margins are 80 mm each and 10 mm above and below each. Using this image, while changing the set temperature control every 5 ° C in the fixing temperature range from 170 ° C to 190 ° C, the presence or absence of white spots at each temperature control temperature was visually confirmed and judged by the following index.
A: Does not occur at 175 ° C (white spots occur at 170 ° C)
B: Does not occur at 180 ° C (white spots occur at 175 ° C)
C: Does not occur at 185 ° C (white spots occur at 180 ° C)
D: Does not occur at 190 ° C (white spots occur at 185 ° C)

<Examples 2 to 16, Comparative Examples 1 to 3>
The evaluation was performed in the same manner as in Example 1 except that the toner was changed as shown in Table 2. The evaluation results are shown in Table 2.

<Example 17>
The evaluation machine was a commercially available color laser printer ColorLaserJetEnterprise M553 (manufactured by Hulett Packard), modified in the same manner as in Example 1, and imaged and evaluated using a black cartridge. The evaluation results are shown in Table 2.

100: Electrostatic latent image carrier (photoreceptor), 102: Toner carrier, 114: Transfer member (transfer roller), 116: Cleaning member (cleaning blade), 117: Charging member (charging roller), 121: Laser generation Device (latent image forming means, exposure device), 123: laser, 124: pickup roller, 125: conveyor belt, 126: fixing device, 140: developing device, 141: toner stirring member, 142: toner regulating member 1: developing device , 1-1: Development sleeve, 2: Vibration unit, 2-1: Oscillator, 2-2: Horn, 2-3: Sample stand, 3-1: Objective lens, 3-2: Toner cylinder, 3-3 : CCD, 3: Detector, 4: Transmitter, 3-4: Personal computer

Claims (8)

A toner having toner particles containing a binder resin, a colorant, and a crystalline material.
The crystalline material contains a monoester compound and
The theoretical surface area obtained from the number average particle size, particle size distribution, and true density of the toner particles is A (m ² / g), and the specific surface area of the toner particles measured by the BET method is B (m ² / g). Then, the A and the B satisfy the following formula (1), and the following formula (1) is satisfied.
1.00 ≦ B / A ≦ 1.15 ・ ・ ・ (1)
The adhesive force F (nN) of the toner with the polycarbonate flat plate satisfies the following formula (2).
15.0 ≤ F ≤ 45.0 ... (2)
Toner characterized by that. The toner according to claim 1, wherein A and B satisfy the following formula (3).
1.05 ≤ B / A ≤ 1.15 ... (3) The toner according to claim 1 or 2, wherein the crystalline material further contains a crystalline polyester. In the DSC curve obtained in the process of raising the temperature to 180 ° C and then lowering the temperature by the differential scanning calorimetry DSC of the toner, the region of the maximum exothermic peak temperature ± 5 ° C of the monoester compound alone obtained by the measurement under the same conditions. When the calorific value of is C and the calorific value in the region of the maximum heat generation peak temperature + 5 ° C. or higher and the maximum heat generation peak temperature + 15 ° C. or lower is D , the D / C is 0.5 or more and 4.0 or less. The toner according to any one of Items 1 to 3 . In the cross section of the toner particles observed by a transmission electron microscope, microdomains of the crystalline material are present.
The toner according to any one of claims 1 to 4 , wherein the number average value of the major axis of the microdomain is 50 nm or more and 350 nm or less. The toner according to any one of claims 1 to 5 , wherein the crystalline material further contains a hydrocarbon wax. The method for manufacturing a toner according to any one of claims 1 to 6 .
The manufacturing method is
A dissolution step of uniformly dissolving or dispersing the polymerizable monomer capable of producing the binder resin, the colorant, and the crystalline material to obtain a polymerizable monomer composition.
A granulation step of dispersing and granulating the polymerizable monomer composition in an aqueous medium containing a dispersion stabilizer A, and a granulation step.
A polymerization step of obtaining the toner particles by carrying out a polymerization reaction of the polymerizable monomer contained in the polymerizable monomer composition.
A method for manufacturing toner having. The aqueous medium containing the dispersion stabilizer A contains 0.2 parts by mass or more and 3.0 parts by mass or less of sodium chloride with respect to 100 parts by mass of the polymerizable monomer composition.
The production method includes a step of mixing a second aqueous medium containing the dispersion stabilizer B with the dispersion liquid obtained in the granulation step.
The method for producing a toner according to claim 7 , wherein the content of the dispersion stabilizer B in the second aqueous medium is 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the dispersion stabilizer A.

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