JP2018045004A - Toner and method for manufacturing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that satisfies high image quality and high durability even when used in a printer employing a high-speed one-component developing system, and a method for manufacturing toner.SOLUTION: A toner includes toner particles each containing a binder resin and colorant, and fine particles A present on the surface of the toner particle. The fine particles A are (i) fixed or adhered to the surface of the toner particle, (ii) fine particles containing a charge control agent in its surface, and (iii) in a particle size distribution based on the number of the fine particles A, have a half-value width of the maximum peak in a range of 1 μm or less of 200 nm or less, where the toner has a wall surface frictional angle θ calculated from the following formula (1) of 16° or less; the toner has a force between two particles of 2.0×10N or less; the ratio of the fine particles A adhered to the surface of the toner is 50 mass% or more. Formula (1): θ=τ/3.0, wherein τ represents a shearing stress obtained when a disc is rotated (π/36)rad revolutions at (π/10)rad/min, while causing the disc to enter, at a vertical load of 3.0 kPa, a toner powder layer formed by applying a vertical load of 9.0kPa.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic image forming method for developing an electrostatic image, and a toner manufacturing method.

In general electrophotography, a latent image is formed on an image carrier (photosensitive drum), toner is supplied to the latent image to make a visible image, and the toner image is transferred to a transfer material such as paper. A method of fixing a toner image on a transfer material by heat / pressure to obtain a copy is known. Among them, printers using a high-speed one-component development method are used because of demands for miniaturization, high speed, and high stability. Since the one-component development method has fewer opportunities for contact between the toner and the charging member than the two-component development method using a carrier, it is necessary to obtain a charge amount by applying a relatively high stress to the toner. Is big.
The toner contains an inorganic fine particle powder such as a metal oxide in order to obtain stable chargeability even during long-term use. Some conventional external additives have been proposed in which a charge control agent is treated on the surface of the external additive in order to obtain stable chargeability even during long-term use.
For example, a toner containing a toner additive composed of a composition containing a charge control agent and a fluidizing agent has been proposed (Patent Document 1). The toner is obtained by adding 4 parts by weight of toner or 4 parts by weight of toner particles of a comparative sample to 96 parts by weight of carrier (reduced iron powder) and using a tumbler mixer under conditions of a temperature of 20 ° C. and a humidity of 45% RH. After mixing for a certain period of time and tribocharging, the charge amount was measured with a blow-off powder charge amount measuring device. As a result, the charge rise rate and charge stabilization rate were excellent.
However, the toner additive is in a state where it is mechanically mixed with toner particles, and the toner additive is expected to be able to migrate from the toner. When used in the printer used, there is a concern that the additive of the toner may be transferred to other toner, a development carrier, a toner container, or the like, and the stable charge imparting function may be impaired. In that case, there is a case where the demand for high speed and high stability cannot be satisfied.
The toner includes a plurality of external additives, and at least one of the external additives is selected from the group consisting of calixarene compound-containing metal azo dyes, salicylic acid metal salts, metal salts of salicylic acid derivatives, and boron complexes. Proposed is a toner whose surface is treated with a charge control agent and whose adhesion strength between the toner base and the surface of the external additive is 60% or more (see FIG. Patent Document 2). The toner has a good charge amount and charge distribution before and after the endurance, and the roller filming also gives good results.
However, since the proposed toner has a broad particle size distribution of the externally added fine particles that are surface-treated with the added charge control agent, when used in a printer using a high-speed one-component development system, In some cases, the adhesion between the toners becomes uneven, and the demand for high speed and high stability cannot be satisfied.

JP 2007-65373 A Japanese Patent Laid-Open No. 2007-249088

  The problem to be solved by the present invention is to provide a high-quality output product that is free from image defects such as fogging and ghosting even when used for a long time with a printer using a high-speed one-component development system. .

The above object is achieved by the present invention described below. That is, the present invention is a toner having toner particles containing a binder resin and a colorant, and fine particles A present on the surface of the toner particles,
The fine particles A are
(I) is attached or fixed to the toner particle surface;
(Ii) fine particles having a charge control agent on the surface;
(Iii) In the number-based particle size distribution of the fine particles A, the full width at half maximum of the maximum peak in the range of 1 μm or less is 200 nm or less,
The wall friction angle θ calculated from the following formula (1) of the toner is 16 ° or less,
Toner force between two particles Fp is 2.0 × 10 ⁻⁸ N or less,
The toner is characterized in that the adhesion rate of the fine particles A on the surface of the toner is 50% by mass or more.
θ = τ / 3.0 Formula (1)
(However, τ indicates that the disk-shaped disk is (π / 10) while allowing the disk-shaped disk to enter the toner powder layer formed by applying a vertical load of 9.0 kPa with a vertical load of 3.0 kPa. ) In rad / min, represents the shear stress obtained when (π / 36) rad rotation.
Further, the present invention is a method for producing a toner having the above-described configuration, and includes a step of processing an object to be processed including the toner particles and the fine particles A using a toner processing apparatus.
The toner processing apparatus includes a processing chamber that accommodates the object to be processed, and a rotating body that is provided inside the processing chamber so as to be rotatable around a drive shaft.
The rotating body is
(I) a rotating body body;
(Ii) A processing surface that collides with the object to be processed by the rotation of the rotating body and processes the object to be processed, extends radially outward from the outer peripheral surface of the main body of the rotating body, and the processing A processing unit having a processing surface formed such that a region of the surface that is away from the rotating body main body is positioned on the downstream side in the rotation direction of the rotating body from an area closer to the rotating body main body than the region. When,
A method for producing a toner.
Furthermore, the present invention is a toner having toner particles containing a binder resin and a colorant, and fine particles A present on the surface of the toner particles,
The fine particles A are
(I) is attached or fixed to the toner particle surface;
(Ii) Aromatic carboxylic acid metal compound, azo dye or azo pigment metal compound, polymer having sulfonic acid group or carboxylic acid group, quaternary ammonium salt, polymer having quaternary ammonium salt, guanidine compound, nigrosine Fine particles having on the surface a compound selected from the group consisting of a compound and an imidazole compound,
(Iii) In the number-based particle size distribution of the fine particles A, the full width at half maximum of the maximum peak in the range of 1 μm or less is 200 nm or less,
The wall friction angle θ calculated from the above formula (1) of the toner is 16 ° or less,
Toner force between two particles Fp is 2.0 × 10 ⁻⁸ N or less,
The toner is characterized in that the adhesion rate of the fine particles A on the surface of the toner is 50% by mass or more.

  According to the present invention, a toner that can provide a high-quality output product that is free from image problems such as fogging and ghosting in a low-temperature and low-humidity environment even when used for a long time in a printer that uses a high-speed one-component development system, and A toner production method can be provided.

1 is a schematic configuration diagram of a toner processing apparatus of the present invention. It is the schematic of the processing tank of this invention. It is the schematic of the rotary body of this invention. It is explanatory drawing of the cross-sectional shape of the process part of this invention. It is shape explanatory drawing of the process part of this invention. It is explanatory drawing of the relationship with the to-be-processed object in the process part of this invention. It is explanatory drawing of the angle of the process part of this invention. It is explanatory drawing of the angle of the process part of this invention. It is the schematic of the flow means of this invention. It is explanatory drawing of the propeller type | mold blade in a powder fluidity | liquidity analyzer. It is explanatory drawing of the disk shaped disk for measuring wall surface friction angle (theta).

The present invention is a toner obtained by fixing the fine particles A surface-treated with a charge control agent to a toner particle surface containing a binder resin and a colorant at a fixing ratio of 50% by mass or more, In the particle size distribution based on the number of the fine particles A, the full width at half maximum of the maximum peak in the range of 1 μm or less is 200 nm or less, the wall friction angle θ calculated from the following formula (1) of the toner is 16 ° or less, and the toner The toner has a two-particle force Fp of 2.0 × 10 ⁻⁸ N or less. This toner has the excellent effect of providing a high-quality output product that is free from image defects such as fogging and ghosting under low-temperature and low-humidity environments even when used for a long time with a printer that uses a high-speed one-component development system. It can be demonstrated.
θ = τ / 3.0 Formula (1)
(However, τ indicates that the disk-shaped disk is (π / 10) while allowing the disk-shaped disk to enter the toner powder layer formed by applying a vertical load of 9.0 kPa with a vertical load of 3.0 kPa. ) In rad / min, represents the shear stress obtained when (π / 36) rad rotation.

  In general, when a large number of copying operations are performed in a one-component development system, the toner is compressed by the stress applied between the developer carrier and the developer regulating blade or between the developer carrier and the photosensitive drum. The fluidity is lowered due to the embedding of the additive. When toner fluidity deteriorates, the amount of toner supplied to the developer carrier becomes non-uniform, and the amount of toner passing between the developer carrier and the regulating blade varies, resulting in a wide toner charge amount distribution. Become. As a result, fogging due to low-charged toner may occur.

  In the one-component development system, it is expected that the toner exists as a toner layer corresponding to two to three toners between the developer carrier and the regulating blade. Among them, it is expected that the toner moves on the surface of the developer carrying member while rolling or not rolling. As described above, when the toner is compressed and the fluidity of the toner is deteriorated, the toner movement between the developer carrier and the regulating blade becomes non-uniform, and the toner charging performed between the developer carrier and the regulating blade is performed. Becomes uneven. Therefore, a ghost image derived from non-uniform charging may occur.

  One of the major features of the present invention is that the amount of toner supplied to the developer carrying member can be uniformly controlled even when a printer using a high-speed one-component developing system is used in a severe low-temperature and low-humidity environment. In addition, it is one of the features of the present invention to uniformly control the movement of the toner between the developer carrying member and the regulating blade. With these synergistic effects, it is the present invention that fog and ghost can be effectively suppressed even in the low temperature and low humidity environment, even if the single component development system of high speed process has high durability.

In order to obtain such an effect, the present inventors have conducted intensive studies. As a result, the toner of the present invention has a particle size distribution in a certain region (the number-based particle size distribution has a half-width of the maximum peak in a range of 1 μm or less. The fine particles A having a surface of 200 nm or less and having a charge control agent on the surface need to be adhered or fixed to the toner particle surface (fixing rate is 50 mass% or more). As a result, the toner of the present invention has a wall surface friction angle θ calculated from the following formula (1) of 16 ° or less, and the two-particle force Fp of the toner is 2.0 × 10 ⁻⁸ N or less.
θ = τ / 3.0 Formula (1)
(However, τ indicates that the disk-shaped disk is (π / 10) while allowing the disk-shaped disk to enter the toner powder layer formed by applying a vertical load of 9.0 kPa with a vertical load of 3.0 kPa. ) In rad / min, represents the shear stress obtained when (π / 36) rad rotation.

  The present inventors have a particle size distribution in a certain region on the toner particle surface (the half-width of the maximum peak in the range of 1 μm or less in the number-based particle size distribution is 200 nm or less), and the fine particles A surface-treated with a charge control agent. In the toner fixed in a fixing ratio of 50% by mass or more, it was found that the adhesive force Fp between the two particles of the toner is kept low and the fluidity can be stabilized through long-term use. As a result, no toner stayed between the developer carrying member and the regulating blade, and the developability could be improved.

  The details are not clear, but they are considered as follows.

  As a premise, in the one-component development method, it is required that the toner pass between the developer carrier and the regulating blade in a uniform fluid state over a long period of use. If fine particles that have been surface-treated with a charge control agent are fixed on the surface of the toner particles, toner particles collected in the vicinity of the developer carrier due to the rotation of the developer carrier are smoothly applied to the surface of the developer carrier. -Will be transported. Furthermore, since the force acting between the two toner particles is reduced, the rolling speed of the toner is uniform when passing between the developer carrier and the regulating blade, so that the toner passes between the developer carrier and the regulating blade. It is considered that the charge applied to the toner becomes uniform.

  As described above, it is considered that the fluidity can be stabilized and the developability can be improved through long-term use even if the process speed is increased by the two actions.

  In order to achieve the range of the wall friction angle shown above, it is necessary to use an external additive having a charge control agent (surface treatment agent) on the surface. In particular, it is preferable to coat the surface of the external additive with a charge control agent by surface treatment. The reason is not clear, but it is considered as follows.

  In general, it is known that a substance having an atom having a large electronegativity has a small friction coefficient. This can be understood by considering the definition of van der Waals forces. The van der Waals force is an attractive force caused by the fluctuation of electrons generated when two atoms approach each other. For this reason, the van der Waals force is small for substances that have a high electronegativity and are unlikely to cause electron fluctuations. Therefore, the friction coefficient is also reduced.

  The present invention is characterized by having a charge control agent on the surface of the external additive, and since the polar substituent has a high affinity with moisture in the air, it is considered that the surface direction is easily oriented. Since the substituent having such polarity is composed of atoms having a high electronegativity, it is considered that the substituent is easily brought into contact with the partner substance and exhibits low friction characteristics.

  In addition, since the compound used as the charge control agent in the toner particles is effective for the surface treatment of the fine particles A, the compound used for the surface treatment is referred to as a “charge control agent”. Is not using.

  When the particle size distribution of the fine particles A is broad (in the number-based particle size distribution, the full width at half maximum of the maximum peak in the range of 1 μm or less is greater than 200 nm), When used, the toner particle surface may be embedded in the toner. As a result, the adhesion between the two toner particles increases, the toner fluidity changes, and the toner is regulated by the developer carrier and developer. The effect of keeping the toner rolling speed uniform between the blades is reduced, and image defects may occur during long-term use.

  When the surface of the fine particles A of the present invention is not surface-treated with the charge control agent, the adhesion force between the two toner particles is increased, the fluidity of the toner is changed, and the toner is a developer carrier and a developer regulating blade. In this case, the effect of keeping the toner rolling speed uniform is reduced, and an image defect may occur during long-term use.

  When the adhesion rate of the fine particles A is less than 50% by mass, the fine particles A existing on the toner surface may migrate to other toners, a developer carrier, a toner container, or the like during long-term use. As a result, rotation of the developer carrying member makes it difficult for the toner group collected near the developer carrying member to be smoothly transported to the surface of the developer carrying member, and image defects are likely to occur. There is a case.

  When the wall surface friction angle θ of the toner is larger than 16 °, the fluidity of the toner changes during long-term use, and it becomes difficult for the toner to be smoothly conveyed from the toner group near the developer carrier to the surface of the developer carrier. For this reason, the uniformity of toner supply to the developer carrying member is lowered, and as a result, the toner is non-uniformly charged and fog may be deteriorated.

When the interparticle force Fp of the toner is greater than 2.0 × 10 ⁻⁸ N, the fluidity of the toner changes during long-term use, and the adhesive force between the toner particles increases. Since the rolling speed of the toner passing between the blades becomes non-uniform, as a result, the toner charge distribution becomes broad and a ghost image may occur.

  The fine particles A of the present invention are more preferably one type or two or more types of fine particles selected from silica, titanium oxide, or alumina. When particles of the above components are used, it is possible to impart fluidity to the toner and further stabilize the chargeability. Furthermore, it becomes easy to control the wall surface friction angle θ of the toner to be low, and to control the force Fp between the two particles of the toner to be low.

The two-particle adhesion force Fp of the toner of the present invention is more preferably 1.0 × 10 ⁻⁸ N or less. Even if the wall surface friction angle θ of the toner is the same, if the adhesion force Fp between the two particles of the toner is kept low, the rolling speed of the toner passing between the developer carrier and the regulating blade can be further increased even during long-term use. It is thought to stabilize, the charge distribution becomes sharp, and it becomes easy to obtain a high-quality output product.

  The number average particle size of the fine particles A is more preferably 100 nm or more and 300 nm or less. When the number average particle size of the fine particles A is in this range, the toner wall surface friction angle θ and the toner adhesion force Fp between the two particles are controlled within the range of the present invention while maintaining the fluidity of the toner. Can do. A more preferable range is 100 nm or more and 200 nm or less.

  The coating amount of the charge control agent on the fine particles A is preferably 1% by mass or more and 20% by mass or less. When the coating amount of the charge control agent is within this range, the surface of the fine particles A can be uniformly coated. As a result, the wall surface friction angle θ of the toner and the adhesion force Fp between the two particles of the toner can be controlled within the range of the present invention, and an output product with high image quality can be easily obtained.

  The amount of the fine particles A added to the toner is preferably 0.2% by mass or more and 3.0% by mass or less in order to exhibit the effect of the present invention.

  The average circularity of the toner of the present invention is preferably 0.970 or more. When the average circularity of the toner is within this range, the toner shape approaches a sphere, so when used in a printer using a one-component development system, the toner when passing between the developer carrier and the regulating blade is used. The rolling speed is easily stabilized. Thereby, the charge distribution becomes sharp and it becomes easy to obtain an output product with high image quality. Furthermore, when a toner image is transferred from the photosensitive drum to a transfer agent such as paper, the contact area of the toner with the photosensitive member is reduced, and thus the transferability is easily improved.

  Further, the present invention is a method for producing a toner including a step of externally adding toner particles and fine particles A using a toner processing apparatus described below.

The toner processing apparatus includes a process of processing an object to be processed including the toner particles and the fine particles A using the toner processing apparatus, and the toner processing apparatus stores the object to be processed. And a rotator provided rotatably around the drive shaft inside the processing chamber, the rotator comprising:
(I) a rotating body body;
(Ii) A processing surface that collides with the object to be processed by the rotation of the rotating body and processes the object to be processed, extends radially outward from the outer peripheral surface of the main body of the rotating body, and the processing Of the surface, the region away from the rotating body is
And a processing unit having a processing surface formed so as to be positioned on the downstream side in the rotation direction of the rotating body from an area closer to the rotating body main body than the area.

  By using the toner processing apparatus, the present inventors were able to more firmly fix the fine particles A to the toner particle surfaces when the toner particles and the fine particles A were externally added. As a result, the characteristics of the toner of the present invention described above could be achieved.

  This reason is considered as follows. By using the toner processing apparatus, the fine particles A existing on the surface of the toner particles efficiently collide with the processing surface in the processing apparatus, so that the effect of fixing the fine particles A to the surface of the toner particles is considered to be increased. .

  The fine particles A of the present invention will be described. The fine particles A have a charge control agent on the particle surface. The type of the charge control agent is not limited, and conventional charge control agents for black toner and color toner can be used.

  For example, as a negative charge control agent, salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, metal compounds of aromatic carboxylic acids such as naphthoic acid, dicarboxylic acids, monoazo metal compounds such as metal salts or metal complexes of azo dyes or azo pigments, Examples thereof include a polymer having a sulfonic acid group or a carboxylic acid group, a urea compound, and a calixarene. Examples of the positive charge control agent include quaternary ammonium salts, polymers having a quaternary ammonium salt, guanidine compounds, nigrosine compounds, and imidazole compounds. In the present invention, from the viewpoint of easy treatment on the surface of the external additive, a polymer type charge control agent (charge control resin) is preferable, and a polymer having a sulfonic acid group is preferably used. Moreover, it is more preferable that the weight average molecular weight (Mw) of this polymer is 1,000 or more and 300,000 or less because the surface of the external additive can be treated uniformly. More preferably, it is 3000 or more and 50000 or less.

  Examples of the polymer having a sulfonic acid group include resins derived from styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), vinyl sulfonic acid, methacryl sulfonic acid, a maleimide derivative, or a styrene derivative, A maleic acid amide derivative of the formula (3) can be exemplified, and a resin having a partial structure derived from 2-acrylamido-2-methylpropanesulfonic acid is particularly preferable. The content of the partial structure derived from 2-acrylamido-2-methylpropanesulfonic acid in the charge control resin is preferably 0.3% by mass or more and 20.0% by mass or less.

  Examples of the polymer having a carboxy group and the polymer having a salicylic acid group include 3-vinyl salicylic acid, 4-vinyl salicylic acid, 5-vinyl salicylic acid, 6-vinyl salicylic acid, 3-vinyl-5-isopropyl salicylic acid, and 3-vinyl-5. Examples include -t-butylsalicylic acid, 4-vinyl-6-t-butylsalicylic acid, and polymer A having a monovalent group a represented by the following formula (4), and in particular, a monovalent compound represented by the following formula (4). Polymer A having the group a is preferred.

（式中、Ｒ¹は、それぞれ独立して、ヒドロキシ基、カルボキシ基、炭素数が１以上１８以下のアルキル基、又は、炭素数が１以上１８以下のアルコキシ基を示し、Ｒ²は水素原子、ヒドロキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を示し、ｇは１以上３以下の整数であり、ｈは０以上３以下の整数である。）

(In the formula, each R ¹ independently represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydrogen atom. , A hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, g is an integer of 1 to 3 and h is an integer of 0 to 3; )

Examples of the alkyl group in R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. Examples of the alkoxy group Includes a methoxy group, an ethoxy group, a propoxy group, and the like.
The main chain structure of the polymer A is not particularly limited.

  Examples thereof include vinyl polymers, polyester polymers, polyamide polymers, polyurethane polymers, polyether polymers, and the like. Moreover, the hybrid type polymer which combined these 2 or more types is also mentioned. Among these, a vinyl polymer is preferable in consideration of adhesion to the toner base particles. The content of the monovalent group in the polymer A is preferably 0.3% by mass or more and 30% by mass or less.

  The polymer A can be synthesized, for example, by using a compound having a polymerizable functional group such as a vinyl group at the substitution position of the group represented by the formula (4) as a monomer. In that case, the polymer A having a monovalent group a is represented by the following formula (4-2).

  The charge control resin preferably has an acid value of 15 mgKOH / mg or more and 35 mgKOH / mg or less. The wall friction reducing effect in the present invention is considered to be manifested by a polar substituent. Therefore, when the acid value is 15 mgKOH / mg or more, a good friction reducing effect can be exhibited. However, when the acid value is 35 mgKOH / mg or less, the moisture adsorption amount is hardly increased, and the wall friction reducing effect is easily exhibited. The acid value can be controlled by the type of monomer used and the monomer ratio.

  Further, the base of the fine particles A needs to be fine particles in which the charge control agent adheres to the surface of the raw material. For example, fine powder silica such as wet process silica and dry process silica, fine powder unoxidized titanium oxide Inorganic powders such as fine powder unalumina are used. The inorganic powder may be silica, titania, alumina, a composite oxide composed of two or more of these, or a powder obtained by mixing two or more of these.

  In the case of titanium oxide fine powder, fine particles of titanium oxide obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of sulfuric acid method, chlorine method, volatile titanium compounds such as titanium alkoxide, titanium halide, titanium acetylacetonate are used. . As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.

  And if it is alumina fine powder, alumina obtained by the buyer method, improved buyer method, ethylene chlorohydrin method, underwater spark discharge method, organoaluminum hydrolysis method, aluminum alum pyrolysis method, ammonium aluminum carbonate pyrolysis method Any fine powder can be used.

  For example, as a preferred fluidizing agent, so-called dry process silica or fumed silica produced by vapor phase oxidation of a silicon halide is used. Further, dry titania, dry alumina produced by vapor phase oxidation of a metal halide, or a mixed oxide thereof can be used. These are produced, for example, by utilizing a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame.

In the fine particles A according to the present invention, the following (a) and (b) may be used as the mode of containing the active substance of the fine particles A and the charge control agent.
(B) A composition comprising a mixture of a fine particle A raw material made of inorganic powder and a charge control agent insoluble or hardly soluble in water and an organic solvent.
(B) Containing a composition of fine particles A made of inorganic powder, and having the inorganic powder surface-treated with a dissolved charge control agent.

  In the composition (a), the charge control agent that is insoluble or hardly soluble in water and an organic solvent may be dry-mixed with the active substance of the fine particles A in a powder state. Can be manufactured.

  The composition (b) uses a charge control agent that is soluble in water or an organic solvent, and sprays this solution on the base of the fine particle A or mixes it with the base of the fine particle A and heat-treats it. The fluidizing agent powder may be surface-treated by volatilizing and removing water or an organic solvent. By this surface treatment, fine particles A having a charge control agent supported on the surface can be obtained.

  In the particle size distribution of the fine particles A of the present invention, the half width of the maximum peak in the range of 1 μm or less in the number-based particle size distribution of the fine particles A is 200 nm or less. As a method for achieving this particle size distribution, for example, in a method for obtaining particles having a sharp particle size distribution by a production method such as a sol-gel method, or a method for producing a so-called dry method silica produced by vapor phase oxidation of a silicon halide, A method of changing the heat treatment conditions is mentioned.

  A method for measuring the particle size distribution of the fine particles A of the present invention will be described below.

  As a method for measuring the particle size distribution of the fine particles A, SEM observation of the fine particles A was performed. The method of SEM observation is as follows. This was performed using images taken with a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). The image capturing conditions of S-4800 are as follows.

(1) Sample preparation A conductive paste is thinly applied to a sample stage (aluminum sample stage 15 mm × 6 mm), and then a fine mixer A and resin fine particles (polystyrene monodisperse particles) having a number average particle size of 10 μm are supermixed by Piccolo (Kawata). And spray the treated particles at 3000 rpm for 5 minutes. Further, air is blown to remove excess fine particles from the sample stage, and then platinum deposition is performed at 15 mA for 30 seconds. The sample stage is set on the sample holder, and the height of the sample stage is adjusted to 36 mm by the sample height gauge.

(2) S-4800 observation condition setting Liquid nitrogen is poured into the anti-contamination trap attached to the S-4800 body until it overflows, and is placed for 30 minutes. The “PC-SEM” of S-4800 is activated and flushing (cleaning of the FE chip as an electron source) is performed. Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2 and execute. Confirm that the emission current by flashing is 20-40 μA. Insert the sample holder into the sample chamber of the S-4800 mirror. Press [Origin] on the control panel to move the sample holder to the observation position.

  Click the acceleration voltage display section to open the HV setting dialog, and set the acceleration voltage to [0.8 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select the SE detector [Up (U)] and [+ SE], and set the mode to observe the secondary electron image. . Similarly, in the [Basic] tab of the operation panel, the probe current of the electron optical system condition block is set to [Normal], the focus mode is set to [UHR], and the WD is set to [8.0 mm]. Press the [ON] button in the acceleration voltage display section of the control panel to apply the acceleration voltage.

(3) Focus adjustment Drag within the magnification display section of the control panel to set the magnification to 5000 (5k). The focus knob [COARSE] on the operation panel is rotated, and the aperture alignment is adjusted when the focus is achieved to some extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. The STIGMA / ALIGNMENT knob (X, Y) on the operation panel is rotated to move the displayed beam to the center of the concentric circle. Next, [Aperture] is selected, and the STIGMA / ALIGNMENT knobs (X, Y) are turned one by one to stop the movement of the image or adjust the movement to the minimum. Close the aperture dialog and focus with auto focus. Repeat this operation two more times to focus. In the state where the midpoint of the maximum diameter of the observation particle is aligned with the center of the measurement screen, the magnification is set to 10,000 (10k) by dragging within the magnification display section of the control panel. The focus knob [COARSE] on the operation panel is rotated, and the aperture alignment is adjusted when the focus is achieved to some extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. The STIGMA / ALIGNMENT knob (X, Y) on the operation panel is rotated to move the displayed beam to the center of the concentric circle. Next, [Aperture] is selected, and the STIGMA / ALIGNMENT knobs (X, Y) are turned one by one to stop the movement of the image or adjust the movement to the minimum. Close the aperture dialog and focus with auto focus. Thereafter, the magnification is set to 50000 (50k), focus adjustment is performed using the focus knob and the STIGMA / ALIGNMENT knob in the same manner as described above, and the focus is again adjusted by autofocus. Repeat this operation again to focus.

(4) Image storage Brightness adjustment is performed in the ABC mode, and a photograph is taken with a size of 640 × 480 pixels and stored.

  From the observation result of the obtained SEM, the particle size distribution of 5000 fine particles A was calculated by image processing (image J). From the measurement results, the full width at half maximum of the maximum peak in the range of 1 μm or less was measured in the number average particle diameter (D1) of the fine particles A and the particle size distribution based on the number of the fine particles A.

  As a method for controlling the fixing rate of the fine particles A on the surface of the toner of the present invention, FM mixer, COMPOSI (manufactured by Nippon Coke Industries Co., Ltd.), Super, which is a mixer for externally adding an external additive to toner particles. Examples include a mixer (manufactured by Kawata), nobilta (manufactured by Hosokawa Micron), and a hybridizer (manufactured by Nara Machinery Co., Ltd.). Among these, Nobilta and COMPOSI are preferable in order to control the fixing rate of the external additive and to coat the external additive uniformly. Alternatively, the toner processing apparatus shown in FIGS. 1 to 9 is particularly preferable.

  Hereinafter, the toner processing apparatus will be described in detail. However, these are examples, and are not limited to these.

[Toner Processing Device]
FIG. 1 is a schematic view of a toner processing apparatus applicable to the present invention.

  The toner processing apparatus 100 includes a processing tank 110 serving as a processing chamber for storing an object to be processed including toner particles having a binder resin and a colorant and fine particles A, and a flow means provided rotatably at the bottom of the processing tank 110. A stirring blade 120 may be provided. Furthermore, it is comprised with the process blade | wing 140 as a rotary body provided so that it could rotate upwards rather than the stirring blade | wing 120. FIG. Furthermore, a deflector fixed to the processing tank 110 may be provided above the processing blade 140 as necessary.

[Processing room]
FIG. 2 shows a schematic diagram of the treatment tank 110.

  The processing tank 110 is a cylindrical container having a flat bottom, and is provided with a drive shaft 111 for attaching the stirring blade 120 and the processing blade 140 at substantially the center of the bottom. The treatment tank 110 is preferably made of metal such as iron or SUS from the viewpoint of strength, and the inner surface is preferably made of a conductive material or the inner surface is subjected to conductive processing.

[Rotating body]
In the present invention, the processing blade 140 is to collide with a flowing object to be processed and process the object to be processed. FIG. 3 shows an example of a schematic diagram of the processing blade 140. 3A is a top view and FIG. 3B is a side view.

  The processing blade 140 includes an annular rotator main body 141 and a processing unit 142 extending radially outward from the outer peripheral surface of the rotator main body 141. With such a configuration, it is considered that the object to be processed and the processing blade 140 collide efficiently, and the effect of fixing the fine particles A on the surface of the toner particles is increased.

  On the other hand, when the processing unit 142 extends vertically upward from the rotator main body 141, the collision frequency between the object to be processed and the processing unit 142 decreases, so that sufficient fixing performance cannot be obtained.

  A perspective view of the processing unit 142 is shown in FIG. Of the processing unit 142, a processing surface that mainly collides with an object to be processed is indicated by hatching. The processing surface of the present invention has a configuration in which the upper and lower ends of the processing surface have curvature as shown in (A) of the AA ′ cross-sectional view of FIG. 4, and the processing surface is driven as shown in (B) and (C). A configuration having an angle with respect to the shaft 111, and a shape curved in the vertical direction as shown in (D) and (E). In order to obtain sufficient fixing properties, the treatment surface is preferably a flat surface. The plane mentioned here has a portion having no curvature as shown in (A), (B), and (C).

  The cross-sectional area of the processing surface shown in the shaded area in FIG. 4 affects the flow of the object to be processed if the cross-sectional area is too large, which may increase the drive torque or raise the temperature of the object to be processed. The desired processing capacity cannot be obtained.

  Therefore, the cross-sectional area of the processing unit is appropriately designed according to the size and operating conditions of the toner processing apparatus, the amount of the object to be processed, and the specific gravity.

  The treatment blade 140 is preferably made of metal such as iron or SUS from the viewpoint of strength, and may be plated or coated for wear resistance as necessary.

[Rotating body size]
The size of the processing blade 140 will be described with reference to FIGS.

  When ½ of the inner diameter of the processing tank 110 is d2 (mm) and the radius of the rotation trajectory is d1 (mm), the length d1 is 80% or more and less than 100% of d2, that is, FIG. It is preferable that it is outside of 0.8L. More preferably, it is 90% or more, that is, outside of 0.9L in FIG. 5, and 95% or more is most preferable.

  The length of the processing unit 142 can be set in a range where the processing unit 142 does not contact the inner peripheral surface of the processing tank 110.

  In the present invention, the upper limit of d1 is considered to be 96% of d2 in view of tolerances in manufacturing the device.

  With such a structure, as shown in FIG. 6A, when the processing surface is long in the radial direction and the processing surface has the same height, the processing area becomes large. Can be processed many times. Moreover, since the processing surface is rotating, the peripheral speed of the tip portion of the processing surface becomes faster as the processing surface is separated from the drive shaft 111. As the peripheral speed increases, the impact force on the object to be processed increases, so that it is considered that the effect of fixing the object to be processed increases.

  On the other hand, as shown in FIG. 6B, when the length of the processing surface is short, the probability of colliding with the object to be processed is considered to be low.

  Further, as described above, since there is no processing surface in a region with a high peripheral speed away from the drive shaft 111, it is considered that the effect of processing the workpiece is reduced.

[Angle of processing surface]
The angle of the processing surface with respect to the rotation direction of the processing blade 140 will be described with reference to FIGS. A locus located at 80% of d2 from the drive shaft 111 is shown as 0.8L in FIG.

  The angle formed by the line connecting the part closest to the rotating body main body of the processing surface and the second part intersecting with 0.8L in FIG. 7 and the tangent to the processing surface of the circle of 0.8L in FIG. It is desirable that the angle is greater than 90 degrees. That is, the region away from the rotator main body 141 is located on the downstream side in the rotation direction of the processing blade 140 from the region closer to the rotator main body 141 than the region.

  The angle (θ) on the downstream side in the rotation direction is greater than 90 degrees and preferably 130 degrees or less, and more preferably, θ is greater than 90 degrees and 121 degrees or less.

  If the workpiece is turning in the circumferential direction of the concentric circle with the rotation of the processing blade 140, the flow direction of the workpiece is considered to be the tangential direction of the concentric circle with the rotation of the processing blade 140. The angle at which the workpiece and the processing surface collide is considered to be the angle between the tangential direction of the circle at a certain radius around the drive axis and the processing surface.

  It is considered that the object to be processed swirls in the rotation direction of the processing blade 140 and at the same time leaves the drive shaft side by centrifugal force and flows in the direction toward the inner wall of the processing tank 110.

  As shown in FIG. 8B, it is considered that the object to be processed flowing in the direction of the inner wall of the processing tank 110 effectively collides with the processing surface by setting the value of θ to be larger than 90 degrees. As shown in FIG. 8A, when θ is 90 degrees or less, it is considered that an object to be processed flowing in the direction of the inner wall of the processing tank 110 does not easily collide with the processing surface. This is not preferable because the tip peripheral speed of the processing surface is high and becomes remarkable on the tip side where the processing effect is high.

[Number of processing units]
The present invention has a basic configuration in which a processing unit 142 is provided on a processing blade 140 as a rotating body, and optimizing the number of processing units 142 to be installed according to the size and peripheral speed of the processing blade 140 has an effect of fixing. More preferred for obtaining.

[Flowing means]
FIG. 9 shows a schematic diagram of the stirring blade 120. FIG. 9A is a top view and FIG. 9B is a side view.

  In the present invention, the stirring blade 120 is preferably provided with a material for flowing (raising) the object to be processed in the processing tank 110.

  The stirring blade 120 has a blade portion extending from the center toward the outside, and is shaped so that the tip of the blade portion rises up the workpiece. The shape of the blade can be appropriately designed according to the size and operating conditions of the toner processing apparatus, the amount of the object to be processed, and the specific gravity.

  The stirring blade 120 is preferably made of metal such as iron or SUS from the viewpoint of strength, and may be plated or coated for wear resistance as necessary.

  The stirring blade 120 is fixed to the drive shaft 111 at the bottom of the processing tank 110 and rotates clockwise as viewed from above. Due to the rotation of the stirring blade 120, the object to be treated rises while rotating clockwise in the treatment tank 110, and eventually descends due to gravity, so that it is considered that the object to be treated can be mixed uniformly.

<Measuring method of adhesion rate of fine particles A>
160 g of sucrose (manufactured by Kishida Chemical) is added to 100 mL of ion-exchanged water, and dissolved with a hot water bath to prepare a sucrose concentrate. 31 g of the above sucrose concentrate in a centrifuge tube, and 10% by weight aqueous solution of neutral detergent for cleaning a precision measuring instrument having a pH of 7, comprising non-ionic surfactant, anionic surfactant and organic builder, 6 mL of Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. 1 g of toner (toner particles and fine particles A are treated) is added to this dispersion, and the mass of toner is loosened with a spatula or the like.

  Shake the centrifuge tube on a shaker at 350 spm for 20 min. After shaking, the solution is replaced with a glass tube for swing rotor (50 mL) and separated by a centrifuge at 3500 rpm for 30 min. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the toner separated in the uppermost layer is collected with a spatula or the like. The collected aqueous solution containing the toner is filtered with a vacuum filter and then dried with a dryer for 1 hour or more. The dried product is crushed with a spatula, and the amount of the external additive is measured with fluorescent X-rays (diameter aluminum ring 10 mm). The fixing rate is calculated from the amount of fine particles A of the toner after washing with water and the initial toner.

  The measurement of the fluorescent X-ray of each element of the fine particles A conforms to JIS K 0119-1969, and is specifically as follows.

  As a measuring device, a wavelength dispersion type fluorescent X-ray analyzer “Axios” (manufactured by PANalytical) and attached dedicated software “SuperQ ver. 4.0F” (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).

  As a measurement sample, about 1 g of the toner after washing with water and the initial toner are put in a dedicated aluminum ring for press and flattened, and a tablet molding compressor “BRE-32” (manufactured by Maekawa Test Instruments Co., Ltd.) Is used, pellets that are pressed at 20 MPa for 60 seconds and molded to a thickness of about 2 mm are used.

  The measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the concentration is calculated from the count rate (unit: cps) which is the number of X-ray photons per unit time.

As a method for quantifying the fine particles A in the toner, for example, when the fine particles A are silica, 100 parts by weight of the toner particles, silica (SiO ₂ ) fine powder is added to 0.10 parts by weight, and coffee Mix thoroughly using a mill. Similarly, silica fine powder is mixed with toner particles so as to be 0.20 parts by mass and 0.50 parts by mass, respectively, and these are used as samples for a calibration curve.

For each sample, a pellet for a calibration curve was prepared as described above using a tablet molding compressor, and the diffraction angle (2θ) was observed at 109.08 ° when PET was used as a spectroscopic crystal. The counting rate (unit: cps) of Si-Kα rays is measured. At this time, the acceleration voltage and current value of the X-ray generator are 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the X-ray count rate obtained on the vertical axis and the added amount of SiO ₂ in each calibration curve sample on the horizontal axis.

Next, the toner to be analyzed is pelletized as described above using a tablet molding compressor, and the counting rate of the Si-Kα rays is measured. Then, the SiO ₂ content in the toner is obtained from the above calibration curve.

  The ratio of the amount of fine particles A after washing with the amount of fine particles A in the initial toner calculated by the above method was determined and used as the adhesion rate of fine particles A.

  In the toner of the present invention, the second external additive B may be added. The second external additive B is preferably one obtained by subjecting silica fine particles or titania fine particles to a hydrophobic treatment. The number average particle diameter is preferably 5 nm or more and 40 nm or less. Examples of the hydrophobizing treatment include treatment with an organosilicon compound, silicone oil, long chain fatty acid and the like.

  Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylethoxysilane, isobutyltrimethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, and hexamethyl. Examples thereof include disiloxane. These may be used alone or as a mixture of two or more.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.

  The amount of the external additive B added is preferably 0.2% by mass or more and 2.0% by mass or less.

  In the toner of the present invention, it is preferable that both the external additive A and the external additive B are externally added using the toner processing apparatus of the present invention. This is because, first, the external additive A is fixed to the toner particle surface, and then the external additive B is treated while maintaining the fixed state.

  Examples of the sieving device used for sieving coarse particles after external addition include the following. Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokusu Kosakusha Co., Ltd.); Vibrasonic System (manufactured by Dalton Co.); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Turbo Screener (manufactured by Turboe Sangyo Co., Ltd.); Perform using a micro shifter (manufactured by Hadano Sangyo Co., Ltd.)

A method for measuring the wall friction angle θ of the toner of the present invention calculated from the following formula (1) will be described below.
θ = τ / 3.0 Formula (1)
(However, τ indicates that the disk-shaped disk is (π / 10) while allowing the disk-shaped disk to enter the toner powder layer formed by applying a vertical load of 9.0 kPa with a vertical load of 3.0 kPa. ) In rad / min, represents the shear stress obtained when (π / 36) rad rotation.

<Measurement method of wall friction angle θ>
In the present invention, the wall surface friction angle θ measured when the disk-shaped disk is pressed against the surface of the compacted toner powder layer is a powder fluidity provided with a rotary propeller blade and a rotary disk-shaped disk blade. Measurement is performed using an analyzer (FT-4 manufactured by Malvern).

  Specifically, the measurement is performed by the following operation. In the operation, the propeller type blade is a 48.0 mm diameter blade dedicated to FT-4 measurement (see FIG. 10; there is a rotation axis in the normal direction at the center of the 48 mm × 10 mm blade plate, The outer edge part (24 mm from the rotating shaft) is smoothly twisted counterclockwise, such as 70 ° and the part 12 mm from the rotating shaft is 35 °, and the material is made of SUS. Further, the wall friction angle θ is measured using a disk-shaped disk type blade (see FIG. 11; diameter 48.0 mm, thickness 1.5 mm, made of SUS, hereinafter abbreviated as disk). May be used). Note that a laminated sheet having a NANOS layer (a layer obtained by thinning a fluorine-based polymer in a nano-order) as the outermost surface is attached to the disk surface (the surface in contact with the toner). This laminated sheet is a sheet laminated in the order of (1) adhesive layer, (2) PET film, (3) antireflection layer, and (4) NANOS layer. The ten-point average roughness Rz of the surface of this laminated sheet is about 0.060 μm (Surface Corder SE3500, a surface roughness measuring machine manufactured by Kosaka Laboratory Ltd.). This laminated sheet can be obtained from Katsurayama Technology Co., Ltd. The purpose of sticking this sheet is to make it easy to measure the friction between the powder layer and the flat plate by making the disc-like disk slippery on the surface of the compacted powder layer.

  Dedicated to FT-4 measurement 50 mm diameter, 85 ml capacity cylindrical split container (height from the bottom of the container to the split part is 43 mm. Material is glass, hereinafter may be abbreviated as container), 23 ° C., 60% A powder layer (toner powder layer) is formed by adding 60 g of toner left in the environment for 3 days or more.

(1) Conditioning operation (a) The rotation speed of the blade in the clockwise direction with respect to the powder layer surface (the direction in which the powder layer is loosened by the rotation of the blade) is set to the peripheral speed 60 of the outermost edge of the blade. (Mm / sec), and the angle between the trajectory drawn by the outermost edge of the moving blade and the surface of the powder layer is a speed of 5 (deg) (hereinafter referred to as the vertical approach speed to the powder layer). In some cases, it may be omitted as an angle formed), and it is made to enter from the powder layer surface to a position of 10 mm from the bottom surface of the powder layer. Thereafter, in the clockwise rotation direction with respect to the powder layer surface, the rotation speed of the blade is 40 (mm / sec), and the angle forming the vertical entry speed to the powder layer is 2 (deg). After performing an operation to enter the position 1 mm from the bottom of the magnetic powder layer at a speed, the blade rotation speed is 60 (mm / sec) in the counterclockwise rotation direction with respect to the powder layer surface, and the powder The angle forming the extraction speed from the body layer is moved to a position of 80 mm from the bottom surface of the powder layer at a speed of 5 (deg), and extraction is performed. When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately in small clockwise and counterclockwise directions.

(2) Toner compaction operation Toner compression is performed by using a compression test piston (diameter 48.0 mm, height 20 mm, lower mesh tension) instead of the propeller blade, and a height of 80 mm from the bottom of the powder layer. To 0.5 mm / sec. After applying a load of 0.55 kPa to the surface of the powder layer at that speed, the blade approach speed was changed to 0.04 mm / sec, and after applying a load of 9.0 kPa, consolidation was performed for 60 seconds. Do.

(3) Split operation A toner powder layer having the same volume (43 ml) is formed by scraping off the toner powder layer at the split portion of the above-mentioned container dedicated for FT-4 measurement and removing the toner above the toner powder layer.

(4) Measurement operation (1) Subsequently, the compression test piston is replaced with a disk blade which is a blade for wall friction measurement, and consolidation is performed again at a load of 9.0 kPa at 0.08 (mm / sec).
(2) After that, the powder layer surface is pre-sheared by rotating (π / 3) rad clockwise (π / 10) rad / min with respect to the powder layer surface while being compacted. .
(3) Next, the shear load is removed, and only the vertical load σ3.0 kPa is applied to enter a standby state of 25 (sec).
(4) Calculated from the rotational torque when the disk blade is rotated (π / 36) rad at (π / 10) rad / min in the clockwise rotation direction with respect to the toner powder layer surface after standby. The shear stress τ is measured.
(5) Using the obtained values of the vertical load σ and shear stress τ, the wall friction angle θ was obtained from the following equation.
θ = τ / σ

  The wall friction angle θ indicates the friction resistance between the surface of the toner powder layer and the flat plate. When the wall friction angle θ is large, the friction resistance is high, and when the wall friction angle θ is small, the friction resistance is small.

  When the wall friction angle θ is 16 ° or less, the toner is smoothly transported from the toner group in the vicinity of the developer carrier to the surface of the developer carrier during long-term use. As a result, the toner is uniformly charged and good image formation without fogging can be achieved.

  A method for measuring the adhesion force Fp between two particles of the toner of the present invention will be described below.

(Adhesive force between two particles of toner: Fp)
The adhesion force Fp between the two particles of the toner is a value indicating the adhesion between particles obtained by measuring using a Agro robot (manufactured by Hosokawa Micron Co., Ltd.). Specifically, a fixed amount of powder was filled in a cylindrical cell that was divided into upper and lower parts under the following conditions, and after holding the powder with a load of 8 kg, the upper cell was lifted and the powder layer was broken. It can be calculated from the strength at the time, the height (distance) during compression, and the volume.

[Measurement condition]
Sample amount: 7.0 g,
Environmental temperature: 25 ° C
Humidity: 42%
Cell inner diameter: 25 mm,
Cell temperature: 25 ° C.
Spring wire diameter: 1.0 mm
Compression speed: 0.10 mm / sec,
Compression force: 8kgf,
Compression holding time: 300 seconds,
Tensile speed: 0.40 mm / sec,

  The two-particle adhesion force Fp of the toner indicates the adhesion force between the two toner particles at the time of compression, and the cohesiveness and fluidity between the two toner particles after compression can be evaluated.

  The production method for producing the toner particles of the present invention is not particularly limited. In addition to conventionally used pulverization methods, methods such as suspension polymerization method, interfacial polymerization method and dispersion polymerization method, which directly produce toner in a hydrophilic medium (hereinafter also referred to as polymerization method), emulsion association method, Examples thereof include an emulsion polymerization method, a suspension granulation method, and a method for producing a heat spheroidized pulverized toner.

  In the toner of the present invention, among them, a suspension polymerization method has high transferability because the individual particles are almost spherical, the contact area with the photosensitive drum is small, and the adhesion is low. The toner to be produced is preferred.

  In the suspension polymerization method, a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a wax and the like is dispersed in an aqueous medium to produce droplets of the polymerizable monomer composition. This is a polymerization method for producing toner particles through at least a granulation step and a polymerization step for polymerizing the polymerizable monomer in the droplets. And when manufacturing the toner of this invention, it is preferable to contain low molecular weight resin in a polymerizable monomer composition.

  The toner of the present invention is preferably a toner having toner particles having at least a core part and a shell part. The toner particles have a shell portion so as to cover the core portion. By adopting such a structure, it is possible to prevent poor charging and blocking due to leaching of the core part to the toner particle surface. Further, it is more preferable that a surface layer portion having a resin composition different from that of the shell portion is present on the surface of the shell portion. The presence of this surface layer portion can further improve environmental stability, durability, and blocking resistance.

  Preferred examples of the polymerizable monomer that can be used to produce the toner particles of the present invention include vinyl-based polymerizable monomers. For example, styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, styrene derivatives such as 2,4-dimethylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic polymerizable monomers such as iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, Methacrylic polymerizable monomers such as n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate And vinyl esters such as nyl, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate and vinyl formate.

  The shell portion is preferably formed of a resin such as polyester, styrene-acrylic copolymer, or styrene-methacrylic copolymer.

  The material constituting the core of the toner of the present invention is preferably wax.

  Examples of wax components that can be used in the toner according to the present invention include paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof according to the Fischer-Tropsch method, polyethylene, Polyolefin waxes such as polypropylene and derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof, and the like include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant-based waxes, animal waxes, and silicone resins can also be used. .

  As the black colorant, carbon black, a magnetic material, and a toned color of each color using a yellow / magenta / cyan colorant shown below are used. In particular, since dyes and carbon black have many polymerization-inhibiting properties, care must be taken when using them.

  Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 214.

  Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19.

  Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the polymerizable monomer or binder resin.

  Furthermore, the toner of the present invention may be a magnetic toner containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. Magnetic materials include iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, Examples include alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof. The magnetic material is more preferably a surface-modified magnetic material. When a magnetic toner is prepared by a polymerization method, it is preferable to apply a hydrophobic treatment with a surface modifier, which is a substance that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents. These magnetic materials preferably have a number average particle diameter (D1) of 2 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. The amount to be contained in the toner particles is 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin.

  In addition, as a manufacturing method for manufacturing toner mother particles by a pulverization method, a predetermined amount of a binder resin, a colorant, other additives, etc. are weighed and blended as materials constituting the toner particles in the raw material mixing step. And mix. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, an FM mixer, a nauter mixer, and a mechano-hybrid (manufactured by Nihon Coke Industries Co., Ltd.).

  Next, the mixed material is melt-kneaded to disperse the colorant and the like in the polyester resin. In the melt-kneading step, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Due to the advantage of continuous production, single-screw or twin-screw extruders are the mainstream. For example, KTK type twin screw extruder (manufactured by Kobe Steel), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai), twin screw extruder (manufactured by KC Corporation) , Co-kneader (manufactured by Buss), kneedex (manufactured by Nihon Coke Kogyo Co., Ltd.) and the like. Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

  Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill Fine pulverization with a fine pulverizer (Freund Turbo) or air jet type.

  Then, if necessary, classification such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) The toner particles are obtained by classification using a machine or a sieving machine.

  In addition, as a method of spheroidizing toner particles, after pulverization, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechano-fusion system (manufactured by Hosokawa Micron Corporation), a faculty (manufactured by Hosokawa Micron Corporation), Meteor Inbo MR Type (Nippon Pneumatic Co., Ltd.) Made).

  The average circularity of the toner of the present invention was measured by the following method.

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

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

  For the measurement, the flow type particle image analyzer equipped with “UPlanApro” (magnification 10 ×, numerical aperture 0.40) as an objective lens is used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. It was used. The dispersion liquid prepared according to the procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the total count mode in the HPF measurement mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

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

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

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

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

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

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

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

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

<Measurement method of true density>
The conditions are as follows. Cell: SM cell (10 ml), Sample amount: Depending on the specific gravity of the sample, an amount satisfying about 80% of the cell is added. This measuring apparatus measures the true density of a solid / liquid based on a gas phase substitution method. Similar to the liquid phase replacement method, it is based on Archimedes' principle, but has high accuracy because a gas (argon gas) is used as a replacement medium.

<Measurement of acid value>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the binder resin and the charge control agent (charge control resin) is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.

  7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 2.0 g of a sample is precisely weighed into a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S

  Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

  The toner of the present invention can be used as a one-component developer, but it can also be used as a two-component developer by mixing with a magnetic carrier.

  Examples of the magnetic carrier include iron powder with oxidized surface or non-oxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, rare earth, and alloy particles thereof. Commonly known materials such as magnetic particles such as oxide particles; ferrite; and a magnetic material-dispersed resin carrier (so-called resin carrier) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state are used. it can.

  When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carrier is preferably 2% by mass or more and 15% by mass or less as the toner concentration in the developer.

  Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on examples. However, this does not limit the embodiment of the present invention. The number of parts in the examples is part by mass.

<Production Example of Charge Control Agent 1 (for Fine Particle A Surface Treatment)>
A 3 L flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube is charged with 1000 parts of pure water and 4 parts of sodium dodecyl sulfate as an emulsifier, and nitrogen substitution is performed for 30 minutes. Charge 2 parts of potassium peroxodisulfate (KPS), stir and dissolve. The contents are heated to 80 ° C. while introducing nitrogen. When the temperature reaches 80 ° C., 300 parts of styrene, 60 parts of 2-ethylhexyl acrylate (2-EHA) and 40 parts of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) are added to 600 parts of pure water. The dissolved aqueous solution is dropped separately over 2 hours. Thereafter, polymerization was carried out at 80 ° C. for 8 hours to obtain an emulsion solution. The emulsion solution was dried with a vacuum dryer at 50 ° C. until the water content became 1% or less, whereby a charge control agent 1 was obtained. Table 1 shows the physical properties of the charge control agent 1.

<Production Example of Charge Control Agents 2 to 5 (for Fine Particle A Surface Treatment)>
In the production example of the charge control agent 1, the amount (parts) of monomers used was changed according to Table 2, and the charge control agents 2 to 5 were produced while controlling the molecular weight by adjusting the polymerization temperature and polymerization time. . Table 1 shows the physical properties of the charge control agents 2 to 5.

<Charge control agent 6>
T-77 (Hodogaya Chemical Co., Ltd.) was used.

<Production Example of Charge Control Agent 7 (For Fine Particle A Surface Treatment)>
18 parts of 2,4-dihydroxybenzoic acid was dissolved in 150 parts of methanol, 36.9 parts of potassium carbonate was added, and the mixture was heated to 65 ° C. To this reaction solution, a mixed solution of 18.7 parts of 4- (chloromethyl) styrene and 100 parts of methanol was added dropwise and reacted at 65 ° C. for 3 hours. The reaction solution was cooled and then filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dispersed in 1500 parts of water having a pH of 2, and extracted by adding ethyl acetate. Thereafter, it was washed with water and dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and purified by recrystallization from toluene and ethyl acetate to obtain a vinyl monomer represented by the following formula (6).

  Next, 13.1 parts of vinyl monomer represented by formula (6) and 81.9 parts of styrene were dissolved in 42.0 parts of toluene, stirred for 1 hour, and then heated to 110 ° C. To this reaction solution, a mixed solution of 3.0 parts of tert-butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) and 42 parts of toluene was added dropwise. Furthermore, it reacted at 110 degreeC for 4 hours. Then, it cooled and it was dripped at 1000 parts of methanol, and the deposit was obtained. The obtained precipitate is dissolved in 120 parts of THF, and then added dropwise to 1800 parts of methanol to precipitate a white precipitate, which is filtered and dried at 90 ° C. under reduced pressure, whereby styrene and the vinyl unit represented by the formula (6) are obtained. The charge control agent 6 which is a copolymer with a monomer was obtained. The physical properties of this charge control agent 6 are shown in Table 1.

  Production examples of the fine particle A raw material used for the external additive A will be shown.

<Production Example 1 of Fine Particle A Base>
Commercially available BET 50 m ² / g silica fine particles were passed through a burner at 1000 ° C. at a rate of 1 kg / hour, and silica particles were collected with a collection line and a filter by a blower. Thereafter, surface treatment was performed on 8 parts by mass of hexamethyldilalazan to 100 parts of silica particles, and the obtained fine particles were collected using an air classifier to obtain silica fine particles 1. This silica fine particle 1 was designated as fine particle A active ingredient 1 (BET 40.2 m ² / g). Table 3 shows the physical properties of the fine particle A active ingredient 1.

<Production Examples 2 and 3 of fine particle A active ingredient>
A commercially available BET ²⁰⁰ m ² / g silica fine particle was produced in the same manner as in Production Example 1 of the fine particle A raw material except that it was passed through an atmosphere of 900 ° C. and 800 ° C. made with a burner at a rate of 1 kg / hour. Silica fine particles were obtained. Table 3 shows the physical properties of these silica fine particle A active ingredients 2 and 3.

<Production Example 4 of Fine Particle A Base>
In a 3 liter glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 590.0 g of methanol, 42.0 g of water, and 48.0 g of 28% by mass ammonia water were added and mixed. The obtained solution was adjusted to 35 ° C., and 1100.0 g (7.23 mol) of tetramethoxysilane and 395.0 g of 5.5 mass% ammonia water were simultaneously added while stirring. Tetramethoxysilane was added dropwise over 6 hours and ammonia water was added over 5 hours. After the completion of the dropwise addition, the mixture was further stirred for 0.5 hours for hydrolysis to obtain a methanol-water dispersion of hydrophilic spherical sol-gel silica fine particles. Next, an ester adapter and a condenser tube were attached to a glass reactor, and the dispersion was sufficiently dried at 80 ° C. under reduced pressure. The obtained silica particles were heated at 400 ° C. for 10 minutes in a thermostatic bath.

  The above process was carried out several tens of times, and the resulting silica particles were crushed with a pulverizer (manufactured by Hosokawa Micron).

  Thereafter, 500 g of silica particles were charged into a polytetrafluoroethylene inner cylinder type stainless steel autoclave having an inner volume of 1000 ml. After the inside of the autoclave was replaced with nitrogen gas, 0.5 g of HMDS (hexamethyldisilazane) and 0.1 g of water were atomized with a two-fluid nozzle while rotating the stirring blade attached to the autoclave at 400 rpm. The silica powder was sprayed uniformly. After stirring for 30 minutes, the autoclave was sealed and heated at 220 ° C. for 2 hours. Subsequently, the system was depressurized while being heated to perform deammonia treatment, and a fine particle A raw material 4 that was silica fine particles was obtained using an air classifier. Table 3 shows the physical properties of the silica fine particle A precursor 4.

<Production example of titanium oxide fine particles>
Crude synthetic rutile ore, which is a raw material, and coke are mixed, placed in a fluidized bed chlorination furnace heated to a temperature of about 1000 ° C., and subjected to exothermic reaction with the supplied chlorine gas to obtain crude titanium tetrachloride. . Impurities were separated and purified from the resulting crude titanium tetrachloride to obtain an aqueous titanium tetrachloride solution. While maintaining this titanium tetrachloride aqueous solution at room temperature, a sodium hydroxide aqueous solution is added, the pH is adjusted to 7.0, colloidal titanium hydroxide is precipitated, and then aged at a temperature of 65 ° C. for 4 hours. Slurry titanium oxide mother particles having rutile nuclei were obtained. After adding sulfuric acid to this slurry to adjust the pH to 3, n-octyltrimethoxysilane was added, and the temperature was raised to 60 ° C. over 1 hour, whereby n-octyltrimethoxysilane was added to the surface of the titanium oxide mother particles. 18.0% by mass was coated on the base particles. Thereafter, filtration and washing were performed, and the obtained wet cake was heat-treated at a temperature of 120 ° C. for one day and pulverized to obtain rutile type titanium oxide fine particles. Titanium oxide fine particles 1 were obtained from the obtained fine particles using an air classifier. Table 3 shows the physical properties of the titanium oxide fine particle A base material 5.

<Example of production of alumina fine particles>
It was carried out by a manufacturing method by the buyer method using aluminum hydroxide as a starting material. The purity of the starting aluminum hydroxide was 99.0%, and alumina fine particles were synthesized by appropriately adjusting the sintering temperature conditions and atmosphere. The fine particles thus obtained were used to obtain alumina fine particles 1 using an air classifier. Table 3 shows the physical properties of the alumina fine particle A precursor 6.

<Example of production of external additive A>
<Example of production of external additive A-1>
Spray a liquid (10 mass% solution) in which 100 g of fine particle A active substance 1 and 10 g of charge control agent 1 are dissolved in toluene, dry-mix, heat-treat at 200 ° C. to volatilize toluene, and charge control agent on the surface A silica additive was obtained (external additive A-1). The physical properties are shown in Table 3.

<Production example of external additives A-2 to A-6>
External additives A-2 to A-6 were obtained in the same manner as in the production example of external additive A-1, except that the amounts of the external additive raw material and charge control agent 1 were changed as shown in Table 3. . The physical properties are shown in Table 3.

<Production Examples of External Additives A-7 and 8>
External additive A-7 and external additive A-8 are the additive described in Example 1 of Patent Document 1 (Japanese Patent Laid-Open No. 2007-65373) described above, and Patent Document 2 (Japanese Patent Laid-Open No. 2007-65237). 249088), Table 1 and Sample 1 were prepared.

<Example of production of external additive A-9>
When the external additive A-6 was produced, it was produced in the same manner as the external additive A-6 except that the surface treatment of the charge control agent 1 was not performed, and the external additive A-9 was obtained.

<Production example of external additive A-10-15>
External additives A-10 to 15 were obtained in the same manner as in the production example of external additive A-1, except that the amounts of the external additive raw material and charge control agent 1 added were changed as shown in Table 3. . The physical properties are shown in Table 3.

<Method for producing external additive B-1>
A commercially available BET 220 m ² / g silica fine particle was subjected to a surface treatment with 15% by mass of hexamethylsilazane to obtain an external additive B-1.

<Method for producing external additive B-2>
A commercially available BET 150 m ² / g titanium oxide fine particle was subjected to a surface treatment with 10% by mass of hexamethylsilazane to obtain an external additive B-2.

<Production Example 1 of Toner Particles>
In a four-necked vessel, 710 parts of ion-exchanged water and 850 parts of a 0.1 mol / L Na ₃ PO ₄ aqueous solution were added. K. The mixture was kept at 60 ° C. while stirring at 12,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 68 parts of 1.0 mol / L-CaCl ₂ aqueous solution was gradually added thereto to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene 122 parts n-butyl acrylate 36 parts Copper phthalocyanine pigment (Pigment Blue 15: 3) 13 parts Low molecular weight polystyrene (1) 40 parts (Glass transition point = 55 ° C., Mw = 3,000, Mn = 1 , 050)
Polyester resin (1) 10 parts (terephthalic acid-propylene oxide modified bisphenol A (2 mole adduct) (molar ratio = 51: 50), acid value = 10 mg KOH / g, glass transition point = 70 ° C., Mw = 10500 Mw / Mn = 3.20)
Negative charge control agent (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.8 parts wax (Fischer-Tropsch wax, endothermic main peak temperature = 78 ° C.)
15 parts The above materials were stirred for 3 hours using an attritor (manufactured by Nippon Coke Kogyo Co., Ltd.), and each component was dispersed in a polymerizable monomer to prepare a monomer mixture. To this monomer mixture, 20.0 parts of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (a 50% toluene solution) as a polymerization initiator was added to form a polymerizable monomer composition. A product was prepared.

  The polymerizable monomer composition was put into the aqueous dispersion medium and granulated for 5 minutes while maintaining the rotational speed of the stirrer at 10,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 6 hours with slow stirring.

Next, the temperature in the container was raised to 80 ° C. and maintained for 4 hours, and then gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain slurry 1. Dilute hydrochloric acid was added to the container containing the slurry 1 to remove the dispersion stabilizer. Further, filtration, washing and drying were performed to obtain polymer particles (toner particles 1) having a weight average particle diameter (D4) of 6.5 μm and an average circularity of 0.980. The true density of the toner particles 1 was 1.1 g / cm ³ .

<Toner Particle Production Example 2>
Toner particles were produced by an emulsion association method, which is an example of a toner production method according to the present invention.

Toner preparation by the emulsion association method can be produced according to the description in the examples of WO 2013/146234. Particles (toner particles 2) having a weight average particle diameter (D4) of 6.7 μm and an average circularity of 0.972 were obtained. The true density of the toner particles 2 was 1.1 g / cm ³ .

<Production Example 3 of Toner Particles>
Toner particles were prepared by an emulsion polymerization method, which is an example of a toner manufacturing method according to the present invention.

Toner preparation by the emulsion polymerization method can be produced according to the description of Examples in Japanese Patent Application Laid-Open No. 2007-4086. Particles (toner particles 3) having a weight average particle diameter (D4) of 6.0 μm and an average circularity of 0.975 were obtained. The true density of the toner particles 3 was 1.1 g / cm ³ .

<Toner Particle Production Example 4>
Toner particles were produced by a suspension granulation method, which is an example of a toner production method according to the present invention.

Toner production by the suspension granulation method can be produced according to the description of Examples in JP-A-2007-108630. Particles (toner particles 4) having a weight average particle diameter (D4) of 6.5 μm and an average circularity of 0.976 were obtained. The true density of the toner particles 4 was 1.1 g / cm ³ .

<Toner Particle Production Example 5>
A toner was prepared by a pulverization method according to the description in the examples of Patent Document 1 described above. Particles (toner particles 5) having a weight average particle diameter (D4) of 9.0 μm and an average circularity of 0.955 were obtained. The true density of the toner particles 5 was 1.05 g / cm ³ .

<Toner Particle Production Example 6>
A toner was prepared by a polymerization method in accordance with the description in the example of Patent Document 2 described above. Particles (toner particles 6) having a weight average particle diameter (D4) of 7.2 μm and an average circularity of 0.970 were obtained. The true density of the toner particles 6 was 1.06 g / cm ³ .

[Example 1]
To the obtained toner particles 1 (100 parts), 1.0 part of the external additive A-4 shown in Table 3 was added and treated for 10 minutes at 3800 rpm in the toner processing apparatus of the present invention. Thereafter, 0.5 part of the external additive B-2 was added, and the mixture was treated for 3 minutes at 3000 rpm, and then dust was removed using a # 200 mesh sieve to obtain toner 1. The formulation and various physical properties of Toner 1 are as described in Table 4.

  The following evaluation test was performed using the obtained toner. The evaluation results are shown in Table 5.

[Evaluation test]
In order to confirm the effect of the present invention, the toner was evaluated as follows.

  A laser beam printer LBP-9600 manufactured by Canon Inc. was used and a process speed modified to 0.36 m / sec was used for evaluation. As evaluation paper, CS-680 sold by Canon Marketing Japan was used. The evaluation environment was evaluated with a low-temperature and low-humidity ring (10 ° C., 14% RH) that easily affects the charging characteristics of toner. In order to evaluate the image output, halftone image density in-plane stability, fog density, and transfer efficiency were evaluated. The evaluation results are shown in Table 5.

<Image density in-plane stability>
In a low-temperature and low-humidity environment (10 ° C / 14% Rh), the image density of the initial halftone (30H) and the image density of the halftone (30H) after printing 20,000 sheets were measured. The image density in-plane stability was evaluated from the difference in image density at the center of the A4 paper and 4 cm × 4 cm from the edge. The image density was measured with a color reflection densitometer (manufactured by X-RITE 404 X-Rite).

A, B, and C ranks were accepted.
A: Image density difference is less than 0.1 B: Image density difference is 0.1 or more and less than 0.3 C: Image density difference is 0.3 or more and less than 0.5 D: Image density difference is 0.5 or more

<Evaluation of fog>
“Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.) in a low-temperature, low-humidity environment (10 ° C./14% Rh) with an initial 0% print ratio image and a 0% print ratio image after printing 100,000 sheets The fog density (%) was calculated from the difference between the whiteness of the white background portion of the printed image and the whiteness of the transfer paper measured in (1). The image fog was evaluated based on the result of the fog density based on the following criteria.

A, B, and C ranks were accepted.
A: Less than 1.0% B: 1.0% or more, less than 2.0% C: 2.0% or more, less than 4.0% D: 4.0% or more

<Transfer efficiency>
Using a chart capable of forming a plurality of 1 cm × 20 cm band images, D1 is the density of the remaining transfer portion on the photoreceptor and taped on the paper, D2 is the density of the tape transferred onto the paper, and the following formula It calculates as follows.
Transfer efficiency (%) = {D2 / (D1 + D2)} × 100

The difference in transfer efficiency between the initial stage and after 20,000 sheets was evaluated in a low temperature and low humidity environment (L / L; 10 ° C./14% RH). A, B, and C ranks were accepted.
A: Less than 2% B: 2% or more and less than 4% C: 4% or more and less than 6% D: 6% or more

[Examples 2 to 17]
Toners 2 to 17 were obtained in the same manner as in Example 1 except that the formulations shown in Table 4 were used. Various physical properties of the toner are as shown in Table 4. Table 5 shows the results of evaluation performed in the same manner as in Example 1.

[Comparative Examples 1 to 4]
Toners 18 to 21 were obtained in the same manner as in Example 1 except that the formulations shown in Table 4 were used. Various physical properties of the toner are as shown in Table 4. “TG-811” used as the external additive B of the toner 13 is hydrophobic silica manufactured by Cabot, and “NX-90” is hydrophobic silica manufactured by Nippon Aerosil. Table 5 shows the results of evaluation performed in the same manner as in Example 1.

  DESCRIPTION OF SYMBOLS 100 ... Toner processing apparatus, 110 ... Processing tank, 111 ... Drive shaft, 120 ... Stirring blade, 140 ... Processing blade, 141 ... Main body of processing blade, 142 ... Processing part, 150 ... Drive motor 160 Control unit

Claims (9)

A toner having toner particles containing a binder resin and a colorant, and fine particles A present on the surfaces of the toner particles,
The fine particles A are
(I) is attached or fixed to the toner particle surface;
(Ii) fine particles having a charge control agent on the surface;
(Iii) In the number-based particle size distribution of the fine particles A, the full width at half maximum of the maximum peak in the range of 1 μm or less is 200 nm or less,
The wall friction angle θ calculated from the following formula (1) of the toner is 16 ° or less,
Toner force between two particles Fp is 2.0 × 10 ⁻⁸ N or less,
A toner having a fixing ratio of the fine particles A on the surface of the toner of 50% by mass or more.
θ = τ / 3.0 Formula (1)
(However, τ indicates that the disk-shaped disk is (π / 10) while allowing the disk-shaped disk to enter the toner powder layer formed by applying a vertical load of 9.0 kPa with a vertical load of 3.0 kPa. ) In rad / min, represents the shear stress obtained when (π / 36) rad rotation.   The toner according to claim 1, wherein the fine particles A are one or more fine particles selected from silica, titanium oxide, and alumina. The toner according to claim 1, wherein the toner has a two-particle force Fp of 1.0 × 10 ⁻⁸ N or less.   The toner according to claim 1, wherein the number average particle size of the fine particles A is 100 nm or more and 300 nm or less.   The toner according to claim 1, wherein the coating amount of the charge control agent on the fine particles A is 1% by mass or more and 20% by mass or less based on the mass of the fine particles A.   The toner according to claim 1, wherein the toner has an average circularity of 0.970 or more.   The toner according to claim 1, wherein the charge control agent is a compound having a sulfonic acid structure in the molecule. The method for producing a toner according to claim 1, further comprising a step of processing an object to be processed including the toner particles and the fine particles A using a toner processing apparatus.
The toner processing apparatus includes a processing chamber that accommodates the object to be processed, and a rotating body that is provided inside the processing chamber so as to be rotatable around a drive shaft.
The rotating body is
(I) a rotating body body;
(Ii) A processing surface that collides with the object to be processed by the rotation of the rotating body and processes the object to be processed, extends radially outward from the outer peripheral surface of the main body of the rotating body, and the processing A processing unit having a processing surface formed such that a region of the surface that is away from the rotating body main body is positioned on the downstream side in the rotation direction of the rotating body from an area closer to the rotating body main body than the region. When,
A method for producing toner, comprising: A toner having toner particles containing a binder resin and a colorant, and fine particles A present on the surfaces of the toner particles,
The fine particles A are
(I) is attached or fixed to the toner particle surface;
(Ii) Aromatic carboxylic acid metal compound, azo dye or azo pigment metal compound, polymer having sulfonic acid group or carboxylic acid group, quaternary ammonium salt, polymer having quaternary ammonium salt, guanidine compound, nigrosine Fine particles having on the surface a compound selected from the group consisting of a compound and an imidazole compound,
(Iii) In the number-based particle size distribution of the fine particles A, the full width at half maximum of the maximum peak in the range of 1 μm or less is 200 nm or less,
The wall friction angle θ calculated from the following formula (1) of the toner is 16 ° or less,
Toner force between two particles Fp is 2.0 × 10 ⁻⁸ N or less,
A toner having a fixing ratio of the fine particles A on the surface of the toner of 50% by mass or more.
θ = τ / 3.0 Formula (1)
(However, τ indicates that the disk-shaped disk is (π / 10) while allowing the disk-shaped disk to enter the toner powder layer formed by applying a vertical load of 9.0 kPa with a vertical load of 3.0 kPa. ) In rad / min, represents the shear stress obtained when (π / 36) rad rotation.

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