JP6205760B2 - Toner, developer and image forming apparatus - Google Patents

Description

  One embodiment of the present invention relates to a toner, a developer, and an image forming apparatus.

  The image forming method includes a charging step for uniformly charging an image forming area on the surface of the photosensitive member, an exposure step for writing on the photosensitive member, and a developing step for forming an image with toner triboelectrically charged on the photosensitive member. A transfer process for transferring the image on the image carrier directly or via an intermediate transfer body to the printing paper, a fixing process for fixing the image on the printing paper, and a toner remaining without being transferred onto the photosensitive body. A cleaning step of scraping off;

  In recent years, the demand for higher image quality has increased, and in particular, color images have been required to form high-definition images. In order to form a high-definition image, filming resistance is required.

  Patent Document 1 discloses a toner for developing an electrostatic image containing at least a binder resin and a colorant, and a toner for developing an electrostatic image containing at least inorganic fine particles. At this time, the inorganic fine particles are composed of at least two kinds of inorganic fine particles, and contain at least silica and titanium oxide as the inorganic fine particles. Further, when ultrasonic vibration (output 20 W, frequency 20 KHz) is applied to the toner for 1 minute, the adhesion rate of titanium oxide adhering to the toner particles is 75% by weight or more before applying ultrasonic vibration, and silica The adhesion rate is 85% by weight or less before applying ultrasonic vibration, and the titanium oxide adhesion rate> silica adhesion rate.

  An object of one embodiment of the present invention is to provide a toner that is excellent in transfer stability and filming resistance in view of the problems of the related art.

One embodiment of the present invention is a toner in which inorganic particles are attached to the surface of base particles, wherein the base particles include a binder resin and a colorant, and the primary particles X are bonded to the inorganic particles. Particle size including the coalesced particles X and primary particles Y, the median diameter of the coalesced particles X being D ₅₀ [nm], and the cumulative particle size of the coalesced particles X from the smaller particle size side is 10% Is D ₁₀ [nm], the formula
D ₅₀ / D ₁₀ ≦ 1.2
The primary particles Y have a number average particle size of 30 nm or more and 60 nm or less, and the release rate of inorganic particles released by applying ultrasonic vibration with an output of 20 W and a frequency of 20 kHz to the toner for 1 minute is represented by A [ Mass%], an output of 60 W, and an ultrasonic vibration having a frequency of 20 kHz applied to the toner for 1 minute, where B [mass%] is the liberation rate of inorganic particles that are liberated, the formula 10 ≦ A ≦ 20
0 ≦ B−A ≦ 5
Meet.

  According to one embodiment of the present invention, a toner having excellent transfer stability and filming resistance can be provided.

3 is a SEM photograph showing an example of coalesced particles X. It is a SEM photograph which shows an example of the evaluation result of the number of the primary particles which have not joined among 1000 particles. 1 is a schematic diagram illustrating an example of an image forming apparatus. It is the schematic which shows the other example of an image forming apparatus. It is the schematic which shows the other example of an image forming apparatus. FIG. 6 is a partially enlarged view of the image forming apparatus in FIG. 5.

  Next, the form for implementing this invention is demonstrated with drawing.

  In the toner, inorganic particles are attached to the surface of the base particles, the base particles include a binder resin and a colorant, and the inorganic particles include coalesced particles X and primary particles Y in which the primary particles X are coalesced. including.

The toner is freed by applying ultrasonic vibration for 1 minute at an output of 20 W and a frequency of 20 kHz, and applying the ultrasonic vibration for 1 minute at an output of 60 W and a frequency of 20 kHz. When the release rate of inorganic particles to be used is B [mass%], the formula 10 ≦ A ≦ 20
0 ≦ B−A ≦ 5
And the formula 12 ≦ A ≦ 18
0 ≦ B−A ≦ 3
It is preferable to satisfy. At this time, A assumes the liberation rate of inorganic particles in the developing machine, for example, when subjected to weak stress when transporting the toner, and B indicates, for example, when the toner is stirred in the developing machine. Assuming the release rate of inorganic particles when subjected to a strong stress, if A is less than 10% by mass, if a weak stress is applied in the developing machine, the inorganic particles will be buried in the base particles and transfer of toner When the stability is lowered and the content exceeds 20% by mass, when subjected to a weak stress in the developing machine, the inorganic particles are released from the base particles and the filming resistance of the toner is lowered. Further, when B-A is less than 0% by mass, when subjected to a strong stress in the developing machine, inorganic particles are buried in the base particles, and the transfer stability of the toner is lowered, and when it exceeds 5% by mass, When a strong stress is applied in the developing machine, the inorganic particles are released from the base particles and the filming resistance of the toner is lowered.

  A and B can be controlled by the addition amount and particle size of coalesced particles X and primary particles Y.

  FIG. 1 shows an example of coalesced particles X.

  The coalesced particles 1 are non-spherical particles in which the primary particles 1A to 1D are coalesced, and are different from secondary particles in which the primary particles are simply aggregated while maintaining their shapes.

  The material constituting the primary particles X is not particularly limited, but silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica. , Wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. May be. Among these, silica is preferable in that it can be suppressed from being embedded in the base particles and released from the base particles.

  The number average particle size of the primary particles X is usually 20 to 150 nm, and preferably 35 to 150 nm. When the number average particle diameter of the primary particles X is less than 20 nm, the inorganic particles may be buried in the base particles due to external stress, and the transfer stability and heat-resistant storage stability of the toner may be reduced. The inorganic particles may be released from the base particles due to external stress, and the filming resistance of the toner may be reduced.

  In addition, the number average particle diameter of the primary particles X is the longest length of the whole image of the primary particles X estimated from 100 to 200 inorganic particles X measured using a scanning electron microscope (SEM). It is an average value of (the length of the arrow shown in FIG. 1A).

  The number average particle size of the coalesced particles X is usually 80 to 250 nm, preferably 100 to 180 nm, and more preferably 100 to 160 nm. When the number average particle size of the coalesced particles X is less than 80 nm, the inorganic particles may be buried in the base particles due to external stress, and the transfer stability and heat-resistant storage stability of the toner may be deteriorated. The inorganic particles may be separated from the base particles due to external stress, and the filming resistance of the toner may be reduced.

  The number average particle size of the coalesced particles X is measured using a scanning electron microscope (SEM), and is the longest length of 100 to 200 inorganic particles X (arrows shown in FIG. 1 (b)). Is the average value.

  The method for synthesizing the coalesced particles X is not particularly limited, and examples thereof include a method of coalescing by mixing or baking the primary particles and the treatment agent. Among these, a method of coalescing primary particles synthesized by a sol-gel method is preferable.

  In addition, when the primary particles synthesized by the sol-gel method are bonded together, the primary particles may be bonded together by a one-step reaction in the presence of a treatment agent.

  Although it does not specifically limit as a processing agent, A silane processing agent, an epoxy processing agent, etc. are mentioned, You may use 2 or more types together.

  When silica particles are used as the primary particles X, the siloxane bond formed by the silane-based treatment agent is more stable to heat than the Si—O—C bond formed by the epoxy-based treatment agent. For this reason, it is preferable to use a silane-based treating agent as the treating agent.

  In addition, you may use processing adjuvants, such as water and 1 mass% acetic acid aqueous solution, with a processing agent as needed.

  Although it does not specifically limit as a silane type | system | group processing agent, For example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, methyl Diethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane), silane coupling agent (for example, γ-aminopropyltolethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl) Methyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, methylvinyldimethoxysilane), vinyl tric Lorosilane, dimethyldichlorosilane, methylvinyldichlorosilane, methylphenyldichlorosilane, phenyltrichlorosilane, N, N′-bis (trimethylsilyl) urea, N, O-bis (trimethylsilyl) acetamide, dimethyltrimethylsilylamine, hexamethyldisilazane, Examples thereof include a mixture of cyclic silazane.

  When treating silica primary particles using alkoxysilanes or silane coupling agents as silane treatment agents, the reaction formula

(In the formula, R is an alkyl group.)
As shown, the siloxane bond is formed by the dealcoholization reaction between the alkoxy group of the silane-based treatment agent and the silanol group present on the surface of the silica primary particles, and the silica primary particles are bonded together.

  When treating silica primary particles using chlorosilanes as the silane treatment agent, the chloro group of chlorosilanes and the silanol groups present on the surface of the silica primary particles undergo a dehydrochlorination reaction, resulting in a siloxane bond. As a result, the silica primary particles coalesce with each other. In this case, when water is present in the system, a silanol group formed by hydrolysis of chlorosilanes and a silanol group present on the surface of the silica primary particles undergo a dehydration reaction, whereby a siloxane bond is formed, and the silica primary particles are Will wear.

  When silica primary particles are treated using silazanes as silane-based treatment agents, siloxane bonds are formed by deammonia reaction between the amino groups of silazanes and the silanol groups present on the surface of the silica primary particles. Then, the silica primary particles coalesce with each other.

  Although it does not specifically limit as an epoxy-type processing agent, A bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, a biphenol type epoxy resin, glycidylamine Type epoxy resin, alicyclic epoxy resin and the like.

  Epoxy treatment agent is reaction formula

As shown, the epoxy group possessed by the epoxy treatment agent and the silanol group present on the surface of the silica primary particles undergo an addition reaction to form Si—O—C bonds, and the silica primary particles combine. To wear.

The mass ratio of the treatment agent to the primary particles X is usually 1 × 10 ^{−4 to} 0.5.

  In addition, it exists in the tendency for the coalescence degree mentioned later to become large, so that the mass ratio of the processing agent with respect to the primary particle X is large.

  A method of mixing the treatment agent and the primary particles X is not particularly limited, and examples thereof include a method of mixing using a known mixer (for example, a spray dryer).

  Instead of mixing the treatment agent and the primary particles X, when the primary particles X are produced, the coalescent particles X may be produced by a one-step reaction in the presence of the treatment agent.

  The temperature for firing the treating agent and the primary particles X is usually 100 to 2500 ° C.

  In addition, it exists in the tendency for a coalescence degree to become large, so that the baking temperature which bakes a processing agent and the primary particle X is high.

  The time for firing the treating agent and the primary particles X is usually 0.5 to 30 hours.

When the median diameter of the coalesced particles X is D ₅₀ [nm] and the particle diameter of the coalesced particles X from the side where the particle size of the coalesced particles X is 10% is D ₁₀ [nm], the toner usually has the formula D ₅₀ / D ₁₀ ≦ 1.2
And the formula D ₅₀ / D ₁₀ ≦ 1.15
It is preferable to satisfy. When D ₅₀ / D ₁₀ exceeds 1.2, the particle size distribution of the coalesced particles X becomes wide, and the content of particles having a small particle size increases. At this time, the particles having a small particle size are particles in which primary particles not bonded or primary particles having a small particle size are bonded. If the content of primary particles that are not coalesced is large, inorganic particles may be released from the base particles due to external stress, and the filming resistance of the toner may be reduced. On the other hand, if the content of the primary particles having a small particle size is large, the inorganic particles are buried in the base particles due to external stress, and the transfer stability and heat-resistant storage stability of the toner may decrease. is there.

  A method for reducing the content of particles having a small particle size is not particularly limited, and examples thereof include a method of removing particles having a small particle size by classification.

D ₅₀ and D ₁₀ are the longest lengths of 100 to 200 coalesced particles X measured using a scanning electron microscope (SEM) (the length of the arrow shown in FIG. 1B). ).

  After putting 0.5 g of coalesced particles and 49.5 g of carrier into a 50 mL bottle, the number of primary particles that are not coalesed in 1000 particles stirred for 10 minutes at 67 Hz using a rocking mill is usually , 300 or less, and preferably 200 or less. After putting 0.5 g of coalesced particles and 49.5 g of carrier into a 50 mL bottle, the number of non-cohered primary particles occupying in 1000 particles stirred for 10 minutes at 67 Hz using a rocking mill is 300 If it exceeds, a large number of coalesced particles X collapse due to external stress. When the particle size of the coalesced coalesced particles X is large, the inorganic particles are separated from the base particles, and the filming resistance of the toner may be lowered. On the other hand, when the particle size of the coalesced coalesced particles X is small, the inorganic particles are buried in the base particles, and the transfer stability and heat resistant storage stability of the toner may be lowered.

  The primary particles that are not coalesced include primary particles that are produced when the coalesced particles X are cracked or collapsed by stirring using a rocking mill.

  The shape of the primary particles that are not bonded is generally substantially spherical (see the black frame in FIG. 2).

  In addition, after putting 0.5 g of coalesced particles X and 49.5 g of the carrier into a 50 mL bottle, the number of primary particles that are not coalesed in 1000 particles stirred for 10 minutes at 67 Hz using a rocking mill is It can be determined by observing using a scanning electron microscope (SEM).

  Note that the particles in the black frame in FIG. 2 are measured as one primary particle that is not coalesced, and the particles in the white frame in FIG. 2 are measured as one coalesced particle in which the primary particles are coalesced.

  As the carrier, a carrier in which a protective layer containing alumina particles, an acrylic resin, and a silicone resin is formed on the surface of a sintered ferrite powder having a median diameter of 35 μm is used.

  The 50 mL bottle is not particularly limited.

  The average coalescence degree of the coalesced particles X is usually 2.0 to 4.0, and preferably 2.5 to 3.0. If the average coalescence degree of the coalesced particles X is less than 2.0, the inorganic particles may be buried in the base particles due to external stress, and the toner transfer stability and heat-resistant storage stability may deteriorate. If it exceeds 0, the inorganic particles may be released from the base particles due to external stress, and the filming resistance of the toner may be reduced.

The degree of coalescence of the coalesced particles X is expressed by the formula (particle diameter of the coalesced particles X) / (number average particle diameter of primary particles X constituting the coalesced particles X).
It can be calculated from

  The average coalescence degree of the coalesced particles X is an average value of the cohesion degrees of 100 or more and 200 or less coalesced particles X.

  The content of particles having a coalescence degree of 1.3 or less in the coalesced particles X is usually 10% or less. When the content of the particles having a coalescence degree of 1.3 or less in the coalesced particles X exceeds 10%, the inorganic particles are buried in the base particles due to external stress, and the toner transfer stability and heat resistant storage stability May decrease.

  The content of the particles having a coalescence degree of 1.3 or less in the coalescence particles X is calculated by calculating the coalescence degree of 100 or more and 200 or less coalescence particles X. It can be calculated by dividing the number of particles below by the number of coalesced particles X.

  The mass ratio of the coalesced particles X to the base particles is usually 1.1 to 2.2 parts by weight, and preferably 1.2 to 1.8.

  The number average particle diameter of the primary particles Y is usually 30 to 60 nm and preferably 30 to 50 nm. Accordingly, it is possible to suppress the inorganic film from being separated from the base particles due to external stress and the toner filming resistance being lowered.

  Although it does not specifically limit as a material which comprises the primary particle Y, Fatty acid metal salt (for example, zinc stearate, aluminum stearate); Metal oxide (for example, silica, titania, alumina, tin oxide, antimony oxide) or these And the like. Of these, hydrophobized silica, titania and titania hydrophobized are preferable.

  Commercially available products of hydrophobized silica particles include HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303 (manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 ( As mentioned above, the Nippon Aerosil Co., Ltd.) etc. are mentioned.

  As commercial products of titania particles, P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (above, manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Titanium Industry Co., Ltd.); MT-150W , MT-500B, MT-600B, MT-150A (manufactured by TEIKA CORPORATION) and the like.

  As commercial products of hydrophobized titanium oxide particles, T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (above, manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T ( As mentioned above, Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (above, Teika Co., Ltd.); IT-S (Ishihara Sangyo Co., Ltd.), etc.

The mass ratio of the primary particles Y to the base particles is usually 3 × 10 ^{−3 to} 0.03, and preferably 5 × 10 ^{−3 to} 0.02.

  The coverage of the inorganic particles in the toner is usually 50 to 90%, preferably 60 to 80%. Accordingly, it is possible to suppress the inorganic film from being separated from the base particles due to external stress and the toner filming resistance being lowered.

  The base particles include a binder resin and a colorant, but may further include a release agent, a charge control agent, and the like as necessary.

  The binder resin is not particularly limited, but is polyester, silicone resin, styrene / acrylic resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol resin, terpene resin, coumarin resin, amideimide resin, butyral resin, urethane. Resin, ethylene vinyl acetate resin, etc. are mentioned, You may use together 2 or more types. Of these, polyesters and resins having a polyester segment are preferred because they are excellent in low-temperature fixability, can smooth the image surface, and have sufficient flexibility even when the molecular weight is lowered.

  The binder resin preferably contains an amorphous polyester and a crystalline polyester. Thereby, the low-temperature fixability of the toner can be improved.

Amorphous polyester has the general formula A- (OH) m (1)
(In the formula, A is an alkyl group having 1 to 20 carbon atoms, an alkylene group or an aromatic group or heterocyclic aromatic group which may have a substituent, and m is an integer of 2 to 4. is there.)
And a polyol represented by the general formula B- (COOH) n (2)
(In the formula, B is an alkyl group having 1 to 20 carbon atoms, an alkylene group or an aromatic group or heterocyclic aromatic group which may have a substituent, and n is an integer of 2 to 4). is there.)
It can synthesize | combine by polycondensing the polycarboxylic acid represented by these.

  The polyol represented by the general formula (1) is not particularly limited, but ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl. Glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1, 2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycero 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, etc. may be mentioned, and two or more may be used in combination.

  The polycarboxylic acid represented by the general formula (2) is not particularly limited, but maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, Sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid Acid, isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2 , 5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarbo Cypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid , Butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, ethylene glycol bis (trimellitic acid), and the like, and two or more of them may be used in combination.

  Although it does not specifically limit as an alcohol component used when synthesize | combining crystalline polyester, It is C2-C12 saturated aliphatic diol compound (For example, 1, 4- butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1,10-decanediol, 1,12-dodecanediol) and derivatives thereof. Among them, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecane can be used because the difference between the endothermic peak temperature and the endothermic shoulder temperature can be reduced. Diols are preferred.

  Although it does not specifically limit as an acidic component used when synthesize | combining crystalline polyester, C2-C12 dicarboxylic acid (for example, fumaric acid) which has a carbon-carbon double bond, C2-C12 Saturated dicarboxylic acids (eg, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid) and derivatives thereof Etc. Among them, fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid can be used because the difference between the endothermic peak temperature and the endothermic shoulder temperature can be reduced. Acid, 1,12-dodecanedioic acid is preferred.

  As a method for controlling the crystallinity and softening point of the crystalline polyester, a trihydric or higher polyhydric alcohol such as glycerin is added as an alcohol component, or a trivalent or higher polyvalent such as trimellitic anhydride is used as an acid component. And a method of polycondensation by adding a polyvalent carboxylic acid.

  The molecular structure of the crystalline polyester can be confirmed by NMR measurement, X-ray diffraction, GC / MS, LC / MS, IR measurement or the like in a solution or solid.

  The content of the crystalline polyester in the toner is usually 3 to 15% by mass, and preferably 5 to 10% by mass. When the content of the crystalline polyester in the toner is less than 3% by mass, the low-temperature fixability of the toner may be lowered, and when it exceeds 15% by mass, the heat-resistant storage stability of the toner may be lowered.

  The binder resin preferably contains a modified polyester.

  The modified polyester resin can be synthesized by reacting a compound having an active hydrogen group with a polyester prepolymer capable of reacting with the active hydrogen group.

  When reacting a compound having an active hydrogen group with a polyester prepolymer having a group capable of reacting with the active hydrogen group, a reaction terminator (for example, diethylamine, dibutylamine, butylamine, laurylamine) is optionally used. The reaction may be stopped using a compound in which the amino group of a monoamine such as ketimine is blocked).

  Although it does not specifically limit as an active hydrogen group, A hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned, You may use together 2 or more types.

  Although it does not specifically limit as a compound which has an active hydrogen group, When using the polyester prepolymer which has an isocyanate group, amines are preferable at the point from which high molecular weight is attained.

  Although it does not specifically limit as amines, A diamine, a trivalent or more polyamine, amino alcohol, an amino mercaptan, an amino acid, etc. are mentioned, You may use 2 or more types together.

  Examples of the diamine include aromatic diamines (for example, phenylene diamine, diethyl toluene diamine, 4,4′-diaminodiphenylmethane), alicyclic diamines (for example, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diamine). Cyclohexane, isophorone diamine), aliphatic diamines (for example, ethylene diamine, tetramethylene diamine, hexamethylene diamine) and the like.

  Examples of trivalent or higher polyamines include diethylenetriamine and triethylenetetramine.

  Examples of amino alcohols include ethanolamine and hydroxyethylaniline.

  Examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan.

  Examples of amino acids include aminopropionic acid and aminocaproic acid.

  A compound in which the amino group of the amine is blocked may be used instead of the amine.

  Examples of the compound in which the amino group of the amine is blocked include ketimines and oxazolidones in which the amino group of the amine is blocked with a ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone).

  Among them, diamine or a mixture of a diamine and a small amount of a trivalent or higher polyamine is preferable.

  The polyester prepolymer having a group capable of reacting with an active hydrogen group is not particularly limited, but is excellent in transparency, easy to adjust the molecular weight of the polymer component, high fluidity at the time of melting, oil in dry toner A polyester prepolymer having an isocyanate group is preferred because of its excellent low-temperature fixing property and releasability.

  Although it does not specifically limit as a synthesis method of the polyester prepolymer which has an isocyanate group, The method etc. with which the polyester which has an active hydrogen group reacts with polyisocyanate are mentioned.

  Although it does not specifically limit as a synthesis method of polyester which has an active hydrogen group, The method etc. which polycondensate a polyol and polycarboxylic acid are mentioned.

  Although it does not specifically limit as a polyol, For example, alkylene glycol (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol), alkylene ether glycol ( For example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol), alicyclic diol (eg, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A), bisphenols (eg, , Bisphenol A, bisphenol F, bisphenol S), alkylene oxides of alicyclic diols (eg, ethylene oxide, propylene oxide, butylene) Diols such as alkylene oxides (eg, ethylene oxide, propylene oxide, butylene oxide) adducts; polyhydric aliphatic alcohols (eg, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol) ) Trivalent or higher phenols (for example, phenol novolac, cresol novolak), trivalent or higher polyols such as alkylene oxide adducts of trivalent or higher polyphenols, and the like may be used in combination. Among these, a diol or a mixture of a diol and a small amount of a trivalent or higher polyol is preferable.

  Diols include alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols (for example, ethylene oxide 2 mol adduct of bisphenol A, propylene oxide 2 mol adduct of bisphenol A, propylene oxide 3 mol of bisphenol A) An adduct).

  Content of the structural unit derived from the polyol in the polyester prepolymer which has an isocyanate group is 0.5-40 mass% normally, it is preferable that it is 1-30 mass%, and it is 2-20 mass%. Is more preferable. When the content of the structural unit derived from the polyol in the polyester prepolymer having an isocyanate group is less than 0.5% by mass, the heat-resistant storage stability of the toner may be deteriorated. Fixability may be reduced.

  Although it does not specifically limit as polycarboxylic acid, Alkylene dicarboxylic acid (For example, succinic acid, adipic acid, sebacic acid); Alkenylene dicarboxylic acid (For example, maleic acid, fumaric acid); Aromatic dicarboxylic acid (For example, terephthalic acid, Isophthalic acid, naphthalenedicarboxylic acid); trivalent or higher polycarboxylic acids (for example, aromatic polycarboxylic acids having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid) and the like. May be. Among these, alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.

  In place of polycarboxylic acid, polycarboxylic acid anhydride, lower alkyl ester (for example, methyl ester, ethyl ester, isopropyl ester) or the like may be used.

  The molar ratio [OH] / [COOH] of the hydroxyl group [OH] of the polyol and the carboxyl group [COOH] of the polycarboxylic acid when synthesizing the polyester having a hydroxyl group is usually 1 to 2, It is preferable that it is 1.02-1.3.

  The polyisocyanate is not particularly limited, but aliphatic polyisocyanate (for example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradeca Methylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate), alicyclic polyisocyanates (eg, isophorone diisocyanate, cyclohexylmethane diisocyanate), aromatic diisocyanates (eg, tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, Diphenylene-4,4′-diisocyanate, 4 , 4′-diisocyanato-3,3′-dimethyldiphenyl, 3-methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate); araliphatic diisocyanates (eg, α, α, α ′, α'-tetramethylxylylene diisocyanate); isocyanurates (for example, tris (isocyanatoalkyl) isocyanurate, triisocyanatocycloalkyl isocyanurate), and the like may be used in combination.

  In place of polyisocyanate, a phenol derivative of polyisocyanate or a compound in which the isocyanate group of polyisocyanate is blocked by oxime, caprolactam or the like may be used.

  The molar ratio [NCO] / [OH] of the isocyanate group [NCO] of the polyisocyanate and the hydroxyl group [OH] of the polyester having a hydroxyl group when synthesizing the polyester prepolymer having an isocyanate group is usually 1 to 5, It is preferably 1.2 to 4, and more preferably 1.5 to 3. When [NCO] / [OH] is less than 1, the heat-resistant storage stability of the toner may be lowered, and when it exceeds 5, the low-temperature fixability of the toner may be lowered.

  Content of the structural unit derived from polyisocyanate in the polyester prepolymer having an isocyanate group is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, and 2 to 20% by mass. More preferably. When the content of the structural unit derived from polyisocyanate in the polyester prepolymer having an isocyanate group is less than 0.5% by mass, the heat-resistant storage stability of the toner may be reduced. When the content exceeds 40% by mass, Low temperature fixability may be reduced.

  The average number of isocyanate groups per molecule of the polyester prepolymer having an isocyanate group is usually 1 or more, preferably 1.2 to 5, and more preferably 1.5 to 4. If the average number of isocyanate groups per molecule of the polyester prepolymer having an isocyanate group is less than 1, the molecular weight of the urea-modified polyester may be lowered, and the heat resistant storage stability of the toner may be lowered.

  The molar ratio [NCO] / [NHx] of the isocyanate group [NCO] of the polyester prepolymer having an isocyanate group and the amino group [NHx] of amines when synthesizing the urea-modified polyester is usually 1/3 to 3 Yes, it is preferably 1/2 to 2, and more preferably 2/3 to 3/2. When [NCO] / [NHx] is less than 1/3, the low-temperature fixability of the toner may be lowered. When [NCO] / [NHx] is more than 3, the molecular weight of the urea-modified polyester is lowered, and the heat resistant storage stability of the toner is reduced. May decrease.

  The polyester prepolymer having an isocyanate group is prepared by heating a polyol and a polycarboxylic acid to 150 to 280 ° C. in the presence of a known esterification catalyst (for example, titanium tetrabutoxide, dibutyltin oxide). It can synthesize | combine by making the polyester which has a hydroxyl group and polyisocyanate react at 40-140 degreeC, after distilling the water to produce | generate, decompressing, and obtaining the polyester which has a hydroxyl group.

  The weight average molecular weight of the polyester prepolymer having a group capable of reacting with an active hydrogen group is usually 3000 to 40000, and preferably 4000 to 30000. When the weight average molecular weight of the polyester prepolymer having a group capable of reacting with an active hydrogen group is less than 3000, the heat-resistant storage stability of the toner may be reduced. May decrease.

  The weight average molecular weight of the polyester prepolymer having a group capable of reacting with an active hydrogen group is a molecular weight in terms of polystyrene of a component soluble in tetrahydrofuran, measured using GPC.

  It does not specifically limit as a coloring agent, A well-known dye or pigment can be used.

  The color of the colorant is not particularly limited, and examples thereof include black, cyan, magenta, and yellow.

  The toner of each color can be obtained by appropriately selecting the type of the colorant, but is preferably a color toner.

  Examples of black pigments include furnace black, lamp black, acetylene black, channel black, and other carbon blacks (CI pigment black 7), copper, iron (CI pigment black 11), titanium oxide, and the like. Examples thereof include organic pigments such as metals and aniline black (CI Pigment Black 1).

  Examples of the magenta pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of cyan pigments include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is usually 1 to 15% by mass, and preferably 3 to 10% by mass. When the content of the colorant in the toner is less than 1% by mass, the coloring power of the toner may be reduced. When the content exceeds 15% by mass, poor pigment dispersion occurs and the coloring power of the toner decreases. Or the electrical characteristics of the toner may deteriorate.

  The pigment may be combined with a resin and used as a master batch.

  The resin is not particularly limited, but it is preferable to use a binder resin or a resin having a structure similar to the binder resin from the viewpoint of compatibility with the binder resin.

  The master batch can be manufactured by applying shearing force and mixing or kneading the resin and the pigment. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the pigment and the resin. Also, the so-called flushing method is preferable in that the wet cake of the pigment can be used as it is and does not need to be dried. The flushing method is a method of mixing or kneading an aqueous pigment paste together with a resin and an organic solvent, and transferring the pigment to the resin side to remove water and the organic solvent.

  When applying the shearing force, a high shearing dispersion device such as a three-roll mill can be used.

  Although it does not specifically limit as a mold release agent, For example, plant wax (for example, carnauba wax, cotton wax, wood wax, rice wax), animal wax (for example, beeswax, lanolin), mineral wax (for example, ozokerite, cercin) ), Waxes and waxes such as petroleum wax (eg, paraffin, microcrystallin, petrolatum); synthetic hydrocarbon wax (eg, Fischer-Tropsch wax, polyethylene wax), synthetic wax (eg, ester, ketone, ether), etc. Non-natural waxes; fatty acid amides such as 1,2-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide; polyacrylate homopolymers (for example, poly (n-stearyl methacrylate), poly (n-methacrylic acid n-) Lauryl), Copolymers of Li acrylates (e.g., acrylic acid n- stearyl - ethyl methacrylate copolymer) and the crystalline polymer or the like having a long chain alkyl group in the side chain, such as.

  The melting point of the release agent is usually 50 to 120 ° C, preferably 60 to 90 ° C. When the melting point of the release agent is less than 50 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 120 ° C., the low-temperature fixability of the toner may be lowered.

  In addition, melting | fusing point of a mold release agent is calculated | required by measuring the maximum endothermic peak using differential scanning calorimeter TG-DSC system TAS-100 (made by Rigaku Corporation).

  The melt viscosity at a temperature 20 ° C. higher than the melting point of the release agent is usually 5 to 1000 cps, and preferably 10 to 100 cps. If the melt viscosity at a temperature 20 ° C. higher than the melting point of the release agent is less than 5 cps, the release property of the toner may be lowered, and if it exceeds 1000 cps, the hot offset resistance and the low-temperature fixability of the toner are lowered. Sometimes.

  The release agent is preferably present in a state of being dispersed in the base particles. For this reason, it is preferable that the release agent and the binder resin are not compatible.

  The method of finely dispersing the release agent in the base particles is not particularly limited, and examples thereof include a method of dispersing by applying a shearing force during kneading.

  The dispersion state of the release agent can be confirmed by observing a thin film slice of the toner with a transmission electron microscope (TEM).

  The dispersion diameter of the release agent is preferably small, but if it is too small, the bleeding at the time of fixing may be insufficient. For this reason, it is preferable that the mold release agent can be confirmed at a magnification of 10,000 times. If the release agent cannot be confirmed at a magnification of 10,000 times, the bleeding at the time of fixing may be insufficient.

  The content of the release agent in the toner is usually 1 to 20% by mass, and preferably 3 to 10% by mass. When the content of the release agent in the toner is less than 1% by mass, the hot offset resistance of the toner may be reduced. When the content exceeds 20% by mass, the heat resistant storage stability, chargeability, transferability, Stress resistance may be reduced.

  The charge control agent is not particularly limited, but triphenylmethane dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide, phosphorus A single substance or a compound thereof, a single substance of tungsten or a compound thereof, a fluorine-based surfactant, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like may be used, and two or more of them may be used in combination. Among these, a colorless or nearly white material is preferable.

The mass ratio of the charge control agent to the binder resin is usually 1 × 10 ^{−4 to} 0.05, and preferably 2 × 10 ^{−4 to} 0.02. When the mass ratio of the charge control agent to the binder resin is less than 1 × 10 ⁻⁴ , the charge rise property and the charge amount may be insufficient, which may affect the toner image. The chargeability of the toner is too high, the effect of the charge control agent is diminished, the electrostatic attraction with the developing roller is increased, the toner fluidity is lowered, and the image density is lowered. is there.

  The method for producing the base particles is not particularly limited, and examples thereof include a kneading and pulverizing method, a so-called chemical method of granulating the base particles in an aqueous medium, and the like.

  Chemical methods include suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization, in which a monomer is used as a starting material; a composition containing a binder resin and / or a binder resin precursor in an organic solvent. Dissolving or suspending after dissolving or dispersing in an aqueous medium; water in a liquid in which a binder resin and / or a composition containing a binder resin precursor and an emulsifier is dissolved or dispersed in an organic solvent For example, a phase inversion emulsification method in which phase inversion emulsification is performed; agglomeration method in which the resin particles obtained by these methods are aggregated in a state of being dispersed in an aqueous medium, and heated and melted. Among these, the dissolution suspension method and the aggregation method are preferable from the viewpoint of granulation properties (for example, control of particle size distribution, control of particle shape) of the base particles containing the crystalline resin.

  The kneading and pulverizing method is a method in which a composition containing a colorant, a binder resin, and a release agent is mixed, melted and kneaded, the kneaded product is pulverized, and the pulverized product is classified.

  The melt kneader used for melt kneading the composition is not particularly limited, and examples thereof include a uniaxial or biaxial continuous kneader and a batch kneader using a roll mill.

  Commercially available melt kneaders include KTK type twin screw extruder (Kobe Steel Co., Ltd.), TEM type extruder (Toshiba Machine Co., Ltd.), twin screw extruder (casey Kay company), PCM type twin screw extrusion. Machine (Ikegai Iron Works Co., Ltd.), Conyder (Bus Co., Ltd.), etc.

  When the kneaded product is pulverized, it is preferable that the kneaded product is coarsely pulverized and then finely pulverized.

  The method of pulverizing the kneaded material is not particularly limited, but is a method of pulverizing by colliding with a collision plate in a jet stream, a method of pulverizing particles by colliding with each other in a jet stream, a mechanically rotating rotor and stator And a method of pulverizing with a narrow gap.

  A method of classifying the pulverized product is not particularly limited, and examples thereof include a method of removing fine particles using a cyclone, a decanter, a centrifuge, or the like.

  The classified pulverized product may be classified in an air stream by centrifugal force or the like.

  The dissolution suspension method is a method in which a solution obtained by dissolving or dispersing a binder resin and / or a binder resin precursor, a colorant and a release agent in an organic solvent is dispersed in an aqueous medium. is there.

  The organic solvent is not particularly limited, but ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc. Ether solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, ketone solvents such as cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl Examples include alcohol solvents such as alcohol and benzyl alcohol, and two or more of them may be used in combination.

  The organic solvent is preferably volatile with a boiling point of less than 100 ° C. Thereby, the organic solvent can be easily removed.

  When the liquid obtained by dissolving or dispersing the composition in an organic solvent is dispersed in an aqueous medium, an emulsifier or a dispersant may be used as necessary.

  As the emulsifier or dispersant, known surfactants, water-soluble polymers and the like can be used.

  Although it does not specifically limit as surfactant, Anionic surfactant (for example, alkylbenzenesulfonic acid, phosphate ester), cationic surfactant (for example, quaternary ammonium salt type, amine salt type), amphoteric surfactant Agents (for example, carboxylate type, sulfate ester type, sulfonate type, phosphate ester type), nonionic surfactants (for example, alkylene oxide (AO) addition type, polyhydric alcohol type) and the like. Two or more kinds may be used in combination.

  The water-soluble polymer is not particularly limited, but cellulosic compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, Polymers having structural units derived from chitin, chitosan, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) (for example, sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, poly Sodium hydroxide partially neutralized product of acrylic acid, sodium acrylate-acrylic acid ester copolymer), styrene-none Sodium hydroxide maleic acid copolymer (partially) neutralized product, water-soluble polyurethane (e.g., polyethylene glycol, reaction products of polycaprolactone diol and a polyisocyanate), and the like, may be used in combination.

  Moreover, you may use together an organic solvent, a plasticizer, etc. as an adjuvant of an emulsifier or a dispersing agent.

  In the dissolution suspension method, a liquid in which a composition containing a binder resin, a polyester prepolymer having a group capable of reacting with active hydrogen groups, a colorant and a release agent is dissolved or dispersed in an organic solvent, It is preferable that a compound having active hydrogen groups dispersed in an aqueous medium containing resin particles and a polyester prepolymer having groups capable of reacting with active hydrogen groups are reacted in an aqueous medium.

The method for preparing the resin particles is not particularly limited, and examples thereof include a method for preparing an aqueous dispersion of resin particles (a) to (h).
(A) A method in which an aqueous dispersion of resin particles is directly prepared using a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, and a dispersion polymerization method.
(B) A precursor of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin (for example, monomer, oligomer) or a solution thereof is dispersed in water in the presence of a dispersant, and then heated or hardened. A method of preparing an aqueous dispersion of resin particles by adding and curing.
(C) Polyaddition or condensation resin precursors (eg, monomers, oligomers) such as polyesters, polyurethanes, epoxy resins or the like, or an emulsifier is dissolved in the solution, and then water is added to effect phase inversion emulsification. A method of preparing an aqueous dispersion of particles.
(D) A resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. A method of preparing an aqueous dispersion of resin particles by obtaining resin particles by the method described above and then dispersing the resin particles in water in the presence of a dispersant.
(E) The presence of a dispersant after obtaining resin particles by spraying a solution of a resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization) in the form of a mist. A method of preparing an aqueous dispersion of resin particles by dispersing resin particles in water.
(F) A poor solvent is added to a resin solution synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization), or a resin solution previously dissolved in a solvent by heating. A method of preparing an aqueous dispersion of resin particles by precipitating resin particles by cooling, removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a dispersant.
(G) A resin solution synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization) is dispersed in water in the presence of a dispersant, and then heated, decompressed, etc. A method of preparing an aqueous dispersion of resin particles by removing the solvent by the method.
(H) After dissolving an emulsifier in a resin solution synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization), water is added to effect phase inversion emulsification, A method for preparing an aqueous dispersion of resin particles.

  The volume average particle diameter of the resin particles is usually 10 to 300 nm, preferably 30 to 120 nm. When the volume average particle diameter of the resin particles is less than 10 nm or exceeds 300 nm, the particle size distribution of the base particles may be wide.

  The solid content concentration of a solution obtained by dissolving or dispersing the composition in an organic solvent is usually 40 to 80% by mass. If the solid content concentration of the liquid in which the composition is dissolved or dispersed in an organic solvent is too high, it may be difficult to dissolve or disperse the composition, and the viscosity may increase. The production efficiency may be reduced.

  In addition, components other than the binder resin, such as a colorant and a release agent, or a masterbatch thereof may be individually dissolved or dispersed in an organic solvent and then mixed into the binder resin solution or dispersion. .

  The aqueous medium is usually water, but a solvent miscible with water may be used in combination.

  The solvent miscible with water is not particularly limited, but alcohol (eg, methanol, isopropanol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolve (eg, methylcellosolve), lower ketone (eg, acetone, Methyl ethyl ketone) and the like.

  The disperser used when the liquid obtained by dissolving or dispersing the composition in an organic solvent is dispersed in the aqueous medium is not particularly limited, but a low-speed shear disperser, a high-speed shear disperser, a friction disperser, Examples thereof include a high-pressure jet disperser and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable because the base particle size can be reduced.

  The rotation speed when using a high-speed shearing disperser is usually 1000 to 30000 rpm, and preferably 5000 to 20000 rpm.

  The temperature when using a high-speed shearing disperser is usually 0 to 150 ° C. (under pressure), and preferably 20 to 80 ° C.

  The method for removing the organic solvent from the liquid in which the liquid obtained by dissolving or dispersing the composition in the organic solvent is dispersed in the aqueous medium is not particularly limited, but while stirring the whole system under normal pressure or reduced pressure Examples include a method of gradually raising the temperature and evaporating and removing the organic solvent.

  The base particles dispersed in the aqueous medium from which the organic solvent has been removed are subjected to solid-liquid separation using a centrifuge, a filter press, etc., and redispersed in ion exchange water at room temperature to 40 ° C. Washing can be performed by adjusting the pH with an acid or alkali and repeating the operation of solid-liquid separation again several times. As a result, impurities, surfactants and the like can be removed. At this time, the fine particles may be removed by centrifugation or the like.

  The washed base particles can be dried using an air dryer, a circulation dryer, a vacuum dryer, a vibration fluidized dryer or the like. At this time, a desired particle size distribution can be obtained using a known classifier.

  The agglomeration method is a method in which a binder resin dispersion, a colorant dispersion, and if necessary, a release agent dispersion are mixed and then aggregated.

  The dispersion of the binder resin is obtained by an emulsion polymerization method, a seed polymerization method, a phase inversion emulsification method, or the like.

  The dispersion of the colorant or the release agent is obtained by dispersing the colorant or the release agent in the aqueous medium by a wet dispersion method or the like.

  The method for controlling the aggregation state is not particularly limited, and examples thereof include a heating method, a method of adding a metal salt, and a method of adjusting pH.

  Although it does not specifically limit as metal ion which comprises metal salt, Monovalent metal ions, such as sodium ion and potassium ion; Divalent metal ions, such as calcium ion and magnesium ion; Trivalent metal ion, such as aluminum ion Etc.

  Although it does not specifically limit as an anion which comprises a metal salt, A chloride ion, a bromide ion, an iodide ion, a carbonate ion, a sulfate ion, etc. are mentioned.

  The metal salt is preferably magnesium chloride, aluminum chloride and a complex or multimer thereof.

  Further, from the viewpoint of the uniformity of the base particles, it is preferable to heat during the aggregation or after the aggregation is completed. Thereby, fusion | melting of binder resin can be accelerated | stimulated. Furthermore, the shape of the base particles can be controlled by heating. At this time, the base particles become nearly spherical by heating.

  The base particles dispersed in the aqueous medium can be washed and dried in the same manner as described above.

  Further, in order to improve the fluidity, heat resistant storage stability, developability, and transfer stability of the toner, the base particles and inorganic particles produced as described above are mixed. When mixing the base particles and the inorganic particles, a known powder mixer can be used. Among these, a mixer equipped with a jacket or the like and capable of adjusting the internal temperature is preferable.

  In order to change the load history applied to the inorganic particles, the inorganic particles may be added in the middle or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Moreover, after giving a strong load at the beginning, you may give a comparatively weak load and vice versa.

  Although it does not specifically limit as a mixer, A V-type mixer, a rocking mixer, a Laedige mixer, a Nauter mixer, a Henschel mixer, etc. are mentioned.

  After the base particles and the inorganic particles are mixed, the coarse particles and the agglomerated particles are removed by passing through a sieve of 250 mesh or more to obtain a toner.

  The average circularity of the toner is usually from 0.95 to 0.98, and preferably from 0.96 to 0.975. At this time, the content of particles having an average circularity of 0.95 or less of the toner is usually 15% or less. If the average circularity of the toner is less than 0.95, the transfer stability of the toner may be lowered. If it exceeds 0.980, in an image forming system employing blade cleaning or the like, In some cases, a cleaning failure on the transfer belt may occur, or the charging roller that contacts and charges the photosensitive member may be contaminated.

  Here, the circularity of the toner is a value obtained by dividing the circumference of an equivalent circle having the same area as the projected area of the toner by the circumference of the toner.

  The average circularity of the toner is measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation), and then analyzed using analysis software FPIA-2100 Data Processing Program for FPIA version 00-10. it can.

  The volume average particle diameter of the toner is usually 3 to 10 μm, and preferably 4 to 7 μm. When the volume average particle diameter of the toner is less than 3 μm, the two-component developer may cause the toner to be fused to the surface of the carrier during long-term agitation in the developing device, which may reduce the charging ability of the carrier. In addition, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle size may increase.

  The ratio of the volume average particle diameter to the number average particle diameter of the toner is usually 1.00 to 1.25, preferably 1.00 to 1.15.

  The volume average particle size and number average particle size of the toner are measured using a particle size measuring device Multisizer III (manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm and then analyzed using analysis software Beckman Coulter Multisizer 3 Version 3.51. Can do.

  The developer has the above-described toner and carrier.

  The carrier usually has a protective layer formed on the surface of the core particles.

  The material constituting the core particle is not particularly limited as long as it has magnetism, but there are ferromagnetic metals such as iron and cobalt; iron oxides such as magnetite, hematite and ferrite; and magnetic materials such as various alloys and compounds. Examples thereof include resin particles dispersed in the resin. Among these, Mn-based ferrite, Mn-Mg-based ferrite, and Mn-Mg-Sr-based ferrite are preferable from the viewpoint of environmental considerations.

  The median diameter of the core particles is usually 10 to 80 μm, and preferably 20 to 65 μm.

The median diameter of the core particle is a microtrack particle size distribution analyzer HRA9320-X100.
(Manufactured by Honeywell) can be used for measurement.

  The protective layer contains a resin, and may further contain other components such as a filler, if necessary.

  Although it does not specifically limit as resin, Crosslinkability containing polyolefin (for example, polyethylene, polypropylene) or its modified material, polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, etc. Polyesters; Polyurethanes; Polycarbonates; Urea resins; Melamine resins; Benzoguanamine resins; Epoxy resins; Ionomer resins; Polyimides and derivatives thereof may be used in combination of two or more. Of these, silicone resins are preferred.

  Although it does not specifically limit as a silicone resin, Straight silicone resin which consists only of organosiloxane bonds, alkyd modified silicone resin, polyester modified silicone resin, epoxy modified silicone resin, acrylic modified silicone resin, urethane modified silicone resin etc. are mentioned.

  Examples of commercially available straight silicone resins include KR271, KR272, KR282, KR252, KR255, KR152 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2405, SR2406 (above, manufactured by Toray Dow Corning Silicone).

  Commercially available modified silicone resins include epoxy-modified silicone resin (ES-1001N), acrylic-modified silicone resin (KR-5208), polyester-modified silicone resin (KR-5203), alkyd-modified silicone resin (KR-206), and urethane. Examples thereof include modified silicone resin (KR-305) (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified silicone resin (SR2115), alkyd-modified silicone resin (SR2110) (manufactured by Toray Dow Corning Silicone).

  The silicone resin may be used in combination with a crosslinking reactive component, a charge amount adjusting component and the like.

  Although it does not specifically limit as a crosslinking reaction component, For example, a silane coupling agent (For example, methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, an aminosilane coupling agent) etc. are mentioned.

  Although it does not specifically limit as a filler, A conductive filler, a nonelectroconductive filler, etc. are mentioned, You may use 2 or more types together. Especially, combined use of a conductive filler and a nonconductive filler is preferable.

  The conductive filler means a filler having a powder specific resistance value of 100 Ω · cm or less. On the other hand, the non-conductive filler means a filler having a powder specific resistance value exceeding 100 Ω · cm.

  The powder specific resistance value of the filler was measured using a powder resistance measurement system MCP-PD51 (manufactured by Dia Instruments) and a 4-terminal 4-probe resistivity meter Loresta GP (manufactured by Mitsubishi Chemical Analytech). The measurement can be performed under the conditions of 1.0 g of the distance between the electrodes, 3 mm between the electrodes, a radius of the sample of 10.0 mm, and a load of 20 kN.

  Although it does not specifically limit as a conductive filler, The conductive filler by which the layer containing a tin dioxide, an indium oxide, etc. is formed in base | substrates, such as aluminum oxide, a titanium oxide, a zinc oxide, barium sulfate, a silicon oxide, a zirconium oxide, is formed. A conductive filler formed using carbon black, and the like. Among these, a conductive filler containing aluminum oxide, titanium oxide, and barium sulfate is preferable.

  Although it does not specifically limit as a nonelectroconductive filler, The nonelectroconductive filler etc. which are formed using aluminum oxide, titanium oxide, barium sulfate, zinc oxide, silicon dioxide, zirconium oxide, etc. are mentioned. Among these, nonconductive fillers containing aluminum oxide, titanium oxide, and barium sulfate are preferable.

  Although it does not specifically limit as a manufacturing method of a carrier, The method etc. which apply | coat the coating liquid for protective layers on the surface of a core particle using a fluid bed type coating device, etc. are mentioned.

  When applying the protective layer coating solution, the resin contained in the protective layer coating solution may be condensed, or after the protective layer coating solution is applied, the resin contained in the protective layer coating solution is added. It may be condensed.

The method of condensing the resin is not particularly limited, and examples thereof include a method of condensing the resin by applying heat, light, etc. to the protective layer coating solution.
The median diameter of the carrier is usually 10 to 80 μm, and preferably 20 to 65 μm.

  The median diameter of the core particles can be measured using a Microtrac particle size distribution analyzer HRA9320-X100 (manufactured by Honeywell).

  The mass ratio of the toner to the carrier is usually 0.02 to 0.12, and preferably 0.025 to 0.1.

  The image forming apparatus includes a photoconductor, a charger that uniformly charges the surface of the photoconductor, an exposure device that forms an electrostatic latent image by exposing the surface of the charged photoconductor imagewise, A developing device that develops the electrostatic latent image formed on the surface using the toner described above to form a toner image, a transfer device that transfers the toner image formed on the surface of the photoreceptor to a recording medium, and a recording medium A fixing device for fixing the transferred toner image, and may further include a static eliminator, a cleaner, a recycler, a control unit, and the like, if necessary.

  The shape of the photoreceptor is preferably a drum shape.

  The photoreceptor is not particularly limited, and examples thereof include inorganic photoreceptors such as amorphous silicon photoreceptors and selenium photoreceptors, and organic photoreceptors such as polysilane photoreceptors and phthalopolymethine photoreceptors. Among these, an amorphous silicon photoreceptor is preferable in terms of long life.

  Examples of the charger include, but are not limited to, contact chargers including conductive or semiconductive rolls, brushes, films, rubber blades, non-contact chargers using corona discharge such as corotron and scorotron. .

  The charger is preferably disposed in contact or non-contact with the photoreceptor, and the surface of the photoreceptor is charged by applying a direct current and an alternating voltage in a superimposed manner.

  Further, it is preferable that the charging device is a charging roller that is disposed in close proximity to the photosensitive member via a gap tape, and the surface of the photosensitive member is charged by applying a direct current and an alternating voltage to the charging roller in a superimposed manner.

  The exposure device is not particularly limited as long as it can image-wise expose the surface of the photoreceptor uniformly charged by the charger, but is not limited to a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal. Various exposure devices such as a shutter optical system may be mentioned.

  In addition, you may employ | adopt the optical back surface system exposed imagewise from the back surface side of a photoconductor.

  The developing device accommodates the developer and preferably applies the developer to the electrostatic latent image in a contact or non-contact manner, more preferably a developing device including a developer-containing container.

  The developing device may be a single-color developing device or a multi-color developing device.

  The developing device preferably has a stirrer for charging the developer by frictional stirring and a rotatable magnet roller.

  In the developing device, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. Since the magnet roller is disposed in the vicinity of the photoconductor, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the photoconductor by electrical attraction. As a result, the electrostatic latent image is developed with toner, and a toner image is formed on the surface of the photoreceptor.

  The transfer device preferably includes a primary transfer device that transfers a toner image of two or more colors onto an intermediate transfer member to form a composite toner image, and a secondary transfer device that transfers the composite toner image onto a recording medium.

  Although it does not specifically limit as an intermediate transfer body, A transfer belt etc. are mentioned.

  The transfer device (primary transfer device, secondary transfer device) preferably peels and charges the toner image formed on the photoreceptor toward the recording medium.

  Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

  Although it does not specifically limit as a recording medium, A well-known recording medium (recording paper) can be used.

  Although it does not specifically limit as a fixing device, The combination of a heating roller and a pressure roller, the combination of a heating roller, a pressure roller, and an endless belt etc. are mentioned.

  The fixing device includes a heating body provided with a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and a toner image is formed between the film and the pressure member. It is preferable to fix the recording medium by passing it through.

  The temperature of a heating body is 80-200 degreeC normally.

  A known optical fixing device may be used together with the fixing device or instead of the fixing device.

  The static eliminator is not particularly limited as long as it can apply a static elimination bias to the photoreceptor, and examples thereof include a static elimination lamp.

  The cleaner is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and examples thereof include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner. It is done.

  The recycler is not particularly limited as long as the toner removed by the cleaner can be recycled by the developing device, but a known conveying unit or the like can be used.

  The controller is not particularly limited as long as it can control the operation of the image forming apparatus, and examples thereof include a sequencer and a computer.

  FIG. 3 shows an example of the image forming apparatus.

  The image forming apparatus 100A includes a photosensitive drum 10, a charging roller 20, an exposure device (not shown), a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a static elimination lamp 70. .

  The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged on the inner side, and can move in the direction of the arrow in the figure. A part of the three rollers 51 also functions as a transfer bias roller that can apply a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer belt 50. Further, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring the toner image to the transfer paper 95 is disposed to face the intermediate transfer belt 50. Further, around the intermediate transfer belt 50, a corona charging device 58 for applying a charge to the toner image transferred to the intermediate transfer belt 50 is connected to the photosensitive drum 10 with respect to the rotation direction of the intermediate transfer belt 50. It is disposed between the contact portion of the intermediate transfer belt 50 and the contact portion of the intermediate transfer belt 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Each color developing unit 45 includes a developer container 42, a developer supply roller 43, and a developing roller (developer carrier) 44. The developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can move in the direction of the arrow in the figure. Further, a part of the developing belt 41 is in contact with the photosensitive drum 10.

  Next, a method for forming an image using the image forming apparatus 100A will be described. First, the charging roller 20 is used to uniformly charge the surface of the photosensitive drum 10, and then the exposure light L is exposed to the photosensitive drum 10 using an exposure device (not shown) to form an electrostatic latent image. Form. Next, the electrostatic latent image formed on the photosensitive drum 10 is developed with the toner supplied from the developing device 40 to form a toner image. Further, after the toner image formed on the photosensitive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, the transfer bias applied from the transfer roller 80 is used. Then, it is transferred (secondary transfer) onto the transfer paper 95. On the other hand, the photosensitive drum 10 on which the toner image is transferred to the intermediate transfer belt 50 is discharged by the discharging lamp 70 after the toner remaining on the surface is removed by the cleaning device 60.

  FIG. 4 shows another example of the image forming apparatus.

  In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are arranged directly facing each other around the photosensitive drum 10 without providing the developing belt 41. Other than that, the configuration is the same as that of the image forming apparatus 100A.

  FIG. 5 shows another example of the image forming apparatus.

  The image forming apparatus 100 </ b> C is a tandem type color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The intermediate transfer belt 50 provided at the center of the copying apparatus main body 150 is an endless belt stretched around three rollers 14, 15 and 16, and can move in the direction of the arrow in the figure. In the vicinity of the roller 15, a cleaning device 17 having a cleaning blade for removing toner remaining on the intermediate transfer belt 50 on which the toner image has been transferred onto the recording paper is disposed. The image forming units 120Y, 120C, 120M, and 120K for yellow, cyan, magenta, and black are juxtaposed along the conveyance direction while facing the intermediate transfer belt 50 stretched by the rollers 14 and 15. An exposure device 21 is disposed in the vicinity of the image forming unit 120. Further, the secondary transfer belt 24 is disposed on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is disposed. The secondary transfer belt 24 is an endless belt stretched around a pair of rollers 23, and the recording paper and the intermediate transfer belt 50 conveyed on the secondary transfer belt 24 are between the rollers 16 and 23. Can touch. Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 is provided with a fixing belt 26 that is an endless belt stretched between a pair of rollers, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26. Is arranged. A sheet reversing device 28 for reversing the recording paper when an image is formed on both sides of the recording paper is disposed in the vicinity of the secondary transfer belt 24 and the fixing device 25.

  Next, a method for forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a color document is set on the contact glass 32 of the scanner 300 to automatically convey the document. The device 400 is closed. When a start switch (not shown) is pressed, when an original is set on the automatic document feeder 400, the original is conveyed and moved onto the contact glass 32, and then the original is set on the contact glass 32. In this case, the scanner 300 is immediately driven, and the first traveling body 33 including the light source and the second traveling body 34 including the mirror travel. At this time, the reflected light from the original surface of the light irradiated from the first traveling body 33 is reflected by the second traveling body 34 and then received by the reading sensor 36 via the imaging lens 35, whereby the original is received. It is read and image information of black, yellow, magenta and cyan is obtained.

  The image information for each color is transmitted to the image forming unit 120 for each color, and a toner image for each color is formed. As shown in FIG. 6, each color image forming unit 120 includes a photosensitive drum 10, a charging roller 160 that uniformly charges the photosensitive drum 10, and image information of each color, respectively. An exposure device that exposes the exposure light L to form an electrostatic latent image of each color; a developing device 61 that develops the electrostatic latent image with a developer of each color to form a toner image of each color; A transfer roller 62 for transferring onto the transfer belt 50, a cleaning device 63 having a cleaning blade, and a static elimination lamp 64 are provided.

  The toner images of the respective colors formed by the image forming units 120 of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is stretched and moved by the rollers 14, 15, and 16, and superimposed to form a composite toner image. It is formed.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, guided to the manual paper feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied in order to remove paper dust from the recording paper. Next, by rotating the registration roller 49 in synchronization with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is sent. The toner image is transferred onto the recording paper (secondary transfer). The toner remaining on the intermediate transfer belt 50 to which the composite toner image has been transferred is removed by the cleaning device 17.

  The recording paper on which the composite toner image has been transferred is conveyed by the secondary transfer belt 24 and then the composite toner image is fixed by the fixing device 25. Next, the conveyance path of the recording paper is switched by the switching claw 55, and the recording paper is discharged onto the paper discharge tray 57 by the discharge roller 56. Alternatively, the recording path of the recording paper is switched by the switching claw 55, reversed by the sheet reversing device 28, an image is similarly formed on the back side, and then discharged onto the discharge tray 57 by the discharge roller 56. .

  Examples of the present invention will be described below, but the present invention is not limited to the examples. In addition, a part means a mass part and% means the mass%.

<Preparation of fused silica particles 1>
100 parts of silica primary particles having a number average particle diameter of 59 nm, 10 parts of methyltrimethoxysilane, and 1 part of 1% acetic acid aqueous solution were mixed using a spray dryer and then calcined at 800 ° C. for 16 hours. Next, classification was performed using a classifier to obtain non-spherical fused silica particles 1.

<Preparation of fused silica particles 2>
Nonspherical fused silica particles 2 are obtained in the same manner as the fused silica particles 1 except that silica primary particles having a number average particle size of 29 nm are used instead of the silica primary particles having a number average particle size of 59 nm. It was.

<Preparation of fused silica particles 3>
Nonspherical fused silica particles 3 are obtained in the same manner as the fused silica particles 1 except that silica primary particles having a number average particle size of 109 nm are used instead of the silica primary particles having a number average particle size of 59 nm. It was.

<Preparation of fused silica particles 4>
Non-spherical fused silica particles 4 are obtained in the same manner as the fused silica particles 1 except that silica primary particles having a number average particle diameter of 19 nm are used instead of the silica primary particles having a number average particle diameter of 59 nm. It was.

<Preparation of fused silica particles 5>
Nonspherical fused silica particles 5 are obtained in the same manner as the fused silica particles 1 except that silica primary particles having a number average particle size of 120 nm are used instead of the silica primary particles having a number average particle size of 59 nm. It was.

<Preparation of fused silica particles 6>
Nonspherical fused silica particles 6 are obtained in the same manner as the fused silica particles 1 except that silica primary particles having a number average particle diameter of 65 nm are used instead of the silica primary particles having a number average particle diameter of 59 nm. It was.

<Preparation of fused silica particles 7>
Nonspherical fused silica particles 7 are obtained in the same manner as the fused silica particles 1 except that silica primary particles having a number average particle size of 60 nm are used instead of the silica primary particles having a number average particle size of 59 nm. It was.

<Preparation of fused silica particles 8>
100 parts of silica primary particles having a number average particle diameter of 70 nm, 10 parts of methyltrimethoxysilane and 1 part of 1% aqueous acetic acid solution were mixed using a spray dryer and then calcined at 800 ° C. for 8 hours. Next, classification was performed using a classifier to obtain non-spherical fused silica particles 8.

<Preparation of fused silica particles 9>
100 parts of silica primary particles having a number average particle diameter of 58 nm, 10 parts of methyltrimethoxysilane and 1 part of 1% acetic acid aqueous solution were mixed using a spray dryer and then calcined at 400 ° C. for 8 hours. Next, classification was performed using a classifier to obtain non-spherical fused silica particles 9.

<Preparation of fused silica particles 10>
100 parts of silica primary particles having a number average particle diameter of 72 nm, 10 parts of methyltrimethoxysilane and 1 part of 1% acetic acid aqueous solution were mixed using a spray dryer and then calcined at 400 ° C. for 8 hours. Next, classification was performed using a classifier to obtain non-spherical fused silica particles 10.

<Preparation of hydrophobized silica primary particles 1>
100 parts of silica primary particles having a number average particle diameter of 160 nm, 10 parts of methyltrimethoxysilane and 1 part of 1% acetic acid aqueous solution were mixed using a spray dryer to obtain hydrophobized silica primary particles 1.

  Table 1 shows the characteristics of the fused silica particles and the hydrophobized silica primary particles.

<Particle size>
After dispersing the particles in tetrahydrofuran, the tetrahydrofuran was removed on the substrate and dried to obtain a sample. Using the field emission scanning electron microscope (FE-SEM) ULTRA55 (manufactured by Zeiss), the obtained sample was measured for particle size in the field of view with an acceleration voltage of 5 to 8 kV and an observation magnification of 8000 to 10,000 times. . At this time, the number average particle diameter, D ₅₀ and D ₁₀ were determined from the particle diameters of 150 particles.

<Preparation of carrier A>
65 parts of a silicone resin solution SR2410 (made by Toray Dow Corning) with a solid content of 23%, 21 parts of an acrylic resin solution with a solid content of 50%, 6.4 parts of a guanamine resin solution with a solid content of 70%, average primary particles 7.6 parts of alumina particles having a diameter of 0.3 μm and a volume resistivity of 1 × 10 ¹⁴ Ω · cm, 1.0 part of silane coupling agent SH6020 (manufactured by Toray Dow Corning), 60 parts of toluene and 60 parts of butyl cellosolve Was dispersed for 10 minutes using a homomixer to obtain a coating solution for a protective layer.

Spiral coater (MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 1000 parts with a median diameter of 35 μm, so that the thickness of the protective layer is 0.15 μm ( The coating liquid for protective layer was applied using Okada Seiko Co., Ltd. and then dried. Next, it was baked at 180 ° C. for 2 hours using an electric furnace and then cooled. Further, the carrier A having a median diameter of 35 μm was obtained by crushing using a sieve having an opening of 106 μm.

<Median diameter>
The median diameter was measured under the following conditions using a Microtrac particle size distribution analyzer HRA9320-X100 (manufactured by Honeywell).

[1] Particle size range: 100 μm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42
<Number Nx of unattached primary particles in 1000 particles>
Into a 50 mL bottle (manufactured by Nidec Rika Glass Co., Ltd.) 0.5 g of fused silica particles and 49.5 g of carrier A were added, and then stirred at 67 Hz for 10 minutes using a rocking mill (manufactured by Seiwa Giken Co., Ltd.). Next, the stirred particles were dispersed in tetrahydrofuran and then centrifuged. Further, tetrahydrofuran was removed from the supernatant on the substrate to dry the sample, thereby obtaining a sample. The obtained sample was observed using a field emission scanning electron microscope (FE-SEM) ULTRA55 (manufactured by Zeiss) at an acceleration voltage of 5 to 8 kV and an observation magnification of 8000 to 10,000 times. Further, the number Nx of unattached primary particles in 1000 particles was determined.

<Synthesis of crystalline polyester 1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 202 parts of sebacic acid, 154 parts of 1,6-hexanediol and 0.5 part of condensation catalyst tetrabutoxy titanate were added, and then generated under a nitrogen stream. The reaction was carried out at 180 ° C. for 8 hours while distilling off the water. Next, after gradually raising the temperature to 220 ° C. and reacting for 4 hours while distilling off generated water and 1,6-hexanediol in a nitrogen stream, the weight average molecular weight is 5 to 20 mmHg under reduced pressure. The reaction was continued until it reached 15000 to obtain crystalline polyester 1. Crystalline polyester 1 had a weight average molecular weight of 14,000 and a melting point of 66 ° C.

<Synthesis of Amorphous Polyester 1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 222 parts of an ethylene oxide 2 mol adduct of bisphenol A, 129 parts of a propylene oxide 2 mol adduct of bisphenol A, 150 parts of terephthalic acid, 15 parts of adipic acid and a condensation catalyst After adding 0.5 part of tetrabutoxy titanate, the reaction was carried out at 230 ° C. for 8 hours while distilling off the generated water under a nitrogen stream. Next, the reaction is carried out under reduced pressure of 5 to 20 mmHg, and after cooling to 180 ° C. when the acid value becomes 2 mg KOH / g, 35 parts of trimellitic anhydride is added and reacted for 3 hours. 1 was obtained. Amorphous polyester 1 had a weight average molecular weight of 6000 and a glass transition point of 54 ° C.

<Synthesis of Amorphous Polyester 2>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 212 parts of an ethylene oxide 2 mol adduct of bisphenol A, 116 parts of a propylene oxide 2 mol adduct of bisphenol A, 166 parts of terephthalic acid, and a condensation catalyst tetrabutoxy titanate. After putting 5 parts, it was made to react at 230 degreeC for 8 hours, distilling off the water to produce | generate under nitrogen stream. Next, it was made to react under reduced pressure of 5-20 mmHg, and it was made to react until a weight average molecular weight reached 15000, and the amorphous polyester 2 was obtained. Amorphous polyester 2 had a weight average molecular weight of 14,000 and a glass transition point of 60 ° C.

<Synthesis of Amorphous Polyester 3>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 204 parts of an ethylene oxide 2 mol adduct of bisphenol A, 106 parts of a 2 mol propylene oxide adduct of bisphenol A, 166 parts of terephthalic acid, and a condensation catalyst tetrabutoxy titanate. After putting 5 parts, it was made to react at 230 degreeC for 8 hours, distilling off the water to produce | generate under nitrogen stream. Next, it was made to react under reduced pressure of 5-20 mmHg, and it was made to react until a weight average molecular weight reached 40000, and the amorphous polyester 3 was obtained. Amorphous polyester 3 had a weight average molecular weight of 38000 and a glass transition point of 62 ° C.

<Synthesis of polyester prepolymer 1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 720 parts of an ethylene oxide 2 mol adduct of bisphenol A, 90 parts of a propylene oxide 2 mol adduct of bisphenol A, 290 parts of terephthalic acid and 1 part of a condensation catalyst tetrabutoxy titanate Then, the reaction was carried out at 230 ° C. for 8 hours while distilling off the water produced under a nitrogen stream. Next, it was made to react under reduced pressure of 10-15 mmHg for 7 hours, and the polyester which has a hydroxyl group was obtained. The polyester having a hydroxyl group had a number average molecular weight of 3,200 and a weight average molecular weight of 9,300.

  In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 400 parts of polyester having a hydroxyl group, 95 parts of isophorone diisocyanate and 500 parts of ethyl acetate were added and reacted at 80 ° C. for 8 hours in a nitrogen stream. A 50% by mass ethyl acetate solution of polyester prepolymer 1 having an isocyanate group at the end was obtained. The free isocyanate of the polyester prepolymer 1 was 1.47%.

<Synthesis of graft copolymer>
Into a reaction vessel equipped with a stir bar and a thermometer, 480 parts of xylene and 100 parts of low molecular weight polyethylene sun wax LEL-400 (manufactured by Sanyo Chemical Industries) having a softening point of 128 ° C. were substituted with nitrogen. The temperature was raised to 170 ° C. Next, a mixture of 740 parts of styrene, 100 parts of acrylonitrile, 60 parts of butyl acrylate, 36 parts of di-t-butylperoxyhexahydroterephthalate and 100 parts of xylene is dropped in 3 hours, and then kept at 170 ° C. for 30 minutes. did. Further, the solvent was removed to obtain a graft copolymer. The graft copolymer had a weight average molecular weight of 24,000 and a glass transition point of 67 ° C.

<Preparation of base particle 1 (ester elongation method)>
-Preparation of release agent dispersion 1-
In a container equipped with a stir bar and a thermometer, 50 parts of paraffin wax HNP-9 (manufactured by Nippon Seiki Co., Ltd.) having a melting point of 75 ° C., 30 parts of graft copolymer and 420 parts of ethyl acetate were added, and then 80 ° C. The temperature was raised to and maintained for 5 hours. Next, after cooling to 30 ° C. in 1 hour, using a bead mill Ultra Visco Mill (manufactured by IMEX), the liquid feeding speed is 1 kg / h, the peripheral speed of the disk is 6 m / s, and the particle size is 0.00. Filled with 80% by volume of 5 mm zirconia beads and dispersed under conditions of 3 passes, release agent dispersion 1 was obtained.

-Preparation of crystalline polyester dispersion 1-
In a container equipped with a stir bar and a thermometer, 100 parts of crystalline polyester 1 and 400 parts of ethyl acetate were added, and the temperature was raised to 75 ° C. Next, after cooling to 10 ° C. or less in 1 hour, using a bead mill Ultra Visco Mill (manufactured by IMEX), the liquid feeding speed is 1 kg / h, the peripheral speed of the disk is 6 m / s, and the particle size is 0 Filled with 80% by volume of 5 mm zirconia beads and dispersed for 5 hours, a crystalline polyester dispersion 1 was obtained.

-Production of master batch 1-
100 parts of amorphous polyester 1, DBP oil absorption 42 mL / 100 g, pH 9.5 carbon black Printex 35 (Degussa) 100 parts and ion-exchanged water 50 parts, Henschel mixer (Mitsui Mining Co., Ltd.) After mixing using, it knead | mixed using two rolls. At this time, kneading was started from 90 ° C. and then gradually cooled to 50 ° C. Next, it grind | pulverized using the pulperizer (made by Hosokawa Micron Corporation), and the masterbatch 1 was obtained.

-Preparation of oil phase 1-
In a container equipped with a thermometer and a stirrer, 93 parts of amorphous polyester 1, 68 parts of crystalline polyester dispersion 1, 75 parts of release agent dispersion 1, 18 parts of masterbatch 1 and ethyl acetate 19 parts were added and dispersed using a stirrer, and then dispersed at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to obtain oil phase 1.

-Preparation of aqueous dispersion 1 of resin particles-
In a reaction vessel equipped with a stirrer and a thermometer, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, and an alkylallylsulfosuccinate sodium salt, Eleminol JS-2 (manufactured by Sanyo Chemical Industries) After adding 10 parts and 1 part of ammonium persulfate, the mixture was stirred at 400 rpm for 20 minutes. Next, after heating up to 75 degreeC and making it react for 6 hours, 30 parts of 1% ammonium persulfate aqueous solution was added, and it age | cure | ripened for 6 hours, and obtained the aqueous dispersion 1 of the resin particle. The aqueous dispersion 1 of resin particles had a volume average particle diameter of 60 nm, and the resin particles had a weight average molecular weight of 140000 and a glass transition point of 73 ° C.

-Preparation of aqueous phase 1-
990 parts of water, 83 parts of an aqueous dispersion of resin particles 1, 37 parts of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed, Aqueous phase 1 was obtained.

―Emulsification or dispersion―
To 273 parts by mass of oil phase 1, after adding 45 parts of 50% by weight ethyl acetate solution of polyester prepolymer 1 and 3 parts of 50% by weight ethyl acetate solution of isophoronediamine, TK type homomixer (manufactured by Tokushu Kika Co., Ltd.) Was used and dispersed at 5000 rpm to obtain an oil phase 1 ′.

  Into a container equipped with a stirrer and a thermometer, 400 parts of the aqueous phase 1 was put, and then the oil phase 1 ′ was stirred while stirring at 13000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.). In addition, the mixture was emulsified for 1 minute to obtain an emulsified slurry 1.

-Solvent removal-Cleaning-Drying-
After the emulsified slurry 1 was put in a container equipped with a stirrer and a thermometer, the solvent was removed at 30 ° C. for 8 hours to obtain a slurry 1.

  Slurry 1 was filtered under reduced pressure. 100 parts of ion-exchanged water was added to the filter cake, and the mixture was dispersed at 6000 rpm for 5 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), followed by filtration. 100 parts of 10% aqueous sodium hydroxide solution was added to the filter cake, and the mixture was dispersed at 6000 rpm for 10 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), followed by filtration under reduced pressure. 100 parts of 10% hydrochloric acid was added to the filter cake, and the mixture was dispersed at 6000 rpm for 5 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), followed by filtration. After adding 300 parts of ion-exchanged water to the filter cake and dispersing the mixture at 6000 rpm for 5 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), the operation of filtering was repeated twice to obtain filter cake 1.

  The filter cake 1 was dried for 48 hours at 45 ° C. using a circulating dryer, and then sieved with a mesh having an opening of 75 μm to obtain base particles 1.

<Preparation of parent particles 2 (dissolution suspension method)>
-Preparation of oil phase 2-
In a container equipped with a thermometer and a stirrer, 93 parts of amorphous polyester 1, 23 parts of amorphous polyester 3, 68 parts of crystalline polyester dispersion 1, 75 parts of release agent dispersion 1, 18 parts of masterbatch 1 and 43 parts of ethyl acetate were added and dispersed using a stirrer, and then dispersed at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to obtain oil phase 2. It was.

―Emulsification or dispersion―
After putting 400 parts of the aqueous phase 1 in a container equipped with a stirrer and a thermometer, the oil phase 2 was added while stirring at 13,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). And emulsified for 1 minute to obtain an emulsified slurry 2.

-Solvent removal-Cleaning-Drying-
A base particle 2 was obtained in the same manner as the base particle 1 except that the emulsified slurry 2 was used instead of the emulsified slurry 1.

<Preparation of base particle 3 (emulsion aggregation method)>
-Preparation of amorphous polyester dispersion 2-
60 parts of amorphous polyester 2 and 60 parts of ethyl acetate were mixed to obtain an oil phase.

  120 parts of water, 2 parts of anionic surfactant Neogen R (Daiichi Kogyo Seiyaku Co., Ltd.) and 2.4 parts of 2% aqueous sodium hydroxide were mixed to obtain an aqueous phase.

  120 parts of an oil phase was added to the water phase, and after emulsification using a homogenizer Ultra Turrax T50 (manufactured by IKA), emulsification was performed using a Manton Gorin high-pressure homogenizer (manufactured by Gorin) to obtain an emulsified slurry.

  The emulsified slurry was placed in a container equipped with a stirrer and a thermometer, and then the solvent was removed at 30 ° C. for 4 hours to obtain an amorphous polyester dispersion 2. The amorphous polyester dispersion 2 had a volume average particle size of 0.15 μm.

-Preparation of amorphous polyester dispersion 3-
Amorphous polyester dispersion 3 was obtained in the same manner as amorphous polyester dispersion 2, except that amorphous polyester 3 was used instead of amorphous polyester dispersion 2 and amorphous polyester 2. . The amorphous polyester dispersion 3 had a volume average particle size of 0.16 μm.

-Preparation of crystalline polyester dispersion 2-
60 parts of crystalline polyester 1 and 60 parts of ethyl acetate were mixed at 60 ° C. to obtain an oil phase.

  120 parts of water, 2 parts of anionic surfactant Neogen R (Daiichi Kogyo Seiyaku Co., Ltd.) and 2.4 parts of 2% aqueous sodium hydroxide were mixed to obtain an aqueous phase.

  120 parts of an oil phase was added to the aqueous phase and emulsified using a homogenizer Ultra Turrax T50 (manufactured by IKA), followed by emulsification using a Manton Gorin high-pressure homogenizer (manufactured by Gorin) to obtain an emulsified slurry. .

  The emulsified slurry was put into a container equipped with a stirrer and a thermometer, and then the solvent was removed at 60 ° C. for 4 hours to obtain a crystalline polyester dispersion 2. The crystalline polyester dispersion 2 had a volume average particle size of 0.17 μm.

-Preparation of release agent dispersion 2-
After mixing 25 parts of paraffin wax HNP-9 (manufactured by Nippon Seiki Co., Ltd.) with a melting point of 75 ° C., 1 part of anionic surfactant Neogen R (made by Daiichi Kogyo Seiyaku Co., Ltd.) and 200 parts of water, the mixture was melted at 90 ° C. It was. Next, emulsification was performed using a homogenizer Ultra Turrax T50 (manufactured by IKA), followed by emulsification using a Menton Gorin high-pressure homogenizer (manufactured by Gorin) to obtain a release agent dispersion 2.

-Preparation of Colorant Dispersion 1-
20 parts of carbon black Printex 35 (manufactured by Degussa) having DBP oil absorption of 42 mL / 100 g and pH of 9.5, 0.5 part of anionic surfactant Neogen R (manufactured by Daiichi Kogyo Seiyaku) and 80 parts of water were mixed. Then, it was made to disperse | distribute using TK type | system | group homomixer (made by a special machine company), and the colorant dispersion liquid 1 was obtained.

―Agglomeration―
In a container equipped with a thermometer and a stirrer, 207 parts of amorphous polyester dispersion 2, 57 parts of amorphous polyester dispersion 3, 28 parts of crystalline polyester dispersion 2, 45 parts of release agent After 2 parts of dispersion 2, 26 parts of colorant dispersion 1 and 600 parts of water were added, the mixture was stirred at 30 ° C. for 30 minutes, and the pH was adjusted to 10 using a 2% aqueous sodium hydroxide solution. Next, the temperature of the aggregated particles was increased to 45 ° C. while gradually stirring 50 parts of a 5% magnesium chloride aqueous solution while stirring at 5000 rpm using an ultra turrax T50 (manufactured by IKA), a homogenizer. The emulsion slurry 3 was obtained by maintaining the temperature at 45 ° C. until the average particle size became 5.3 μm and cooling to 20 ° C.

-Solvent removal-Cleaning-Drying-
Base particle 3 was obtained in the same manner as base particle 1 except that emulsified slurry 3 was used instead of emulsified slurry 1.

<Preparation of base particles 4 (grinding method)>
-Production of master batch 2-
100 parts of amorphous polyester 2, DBP oil absorption 42 mL / 100 g, pH 9.5 carbon black Printex 35 (Degussa) 100 parts, ion-exchanged water 50 parts, Henschel mixer (Mitsui Mining Co., Ltd.) After mixing using, it knead | mixed using two rolls. At this time, kneading was started from 90 ° C. and then gradually cooled to 50 ° C. Next, it grind | pulverized using the pulperizer (made by Hosokawa Micron Corporation), and the masterbatch 2 was obtained.

-Melt kneading, grinding, classification-
54 parts of amorphous polyester 2, 27 parts of amorphous polyester 3, 8 parts of crystalline polyester 1, 6 parts of paraffin HNP-9 (manufactured by Nippon Seiki Co., Ltd.) with a melting point of 75 ° C. and 12 parts of master batch 2 was mixed at 1500 rpm for 3 minutes using a Henschel mixer Henschel 20B (Mitsui Mining Co., Ltd.), and then melt kneaded using a small-sized bus co-kneader (Buss Co., Ltd.). At this time, the preset temperature at the inlet of the uniaxial kneader was 90 ° C., the preset temperature at the outlet was 60 ° C., and the feed rate was 10 kg / h. Next, after rolling and cooling, coarsely pulverizing using a pulverizer (manufactured by Hosokawa Micron), fine pulverizing using an I-type mill IDS-2 type (manufactured by Nippon Pneumatic Co., Ltd.). At this time, the air pressure of the I-type mill was 6.0 atm / cm ² , the feed amount was 0.5 kg / h, and a planar collision plate was used. Furthermore, classification was performed using a classifier 132MP (manufactured by Alpine Co., Ltd.) to obtain base particles 4.

<Preparation of base particle 5 (ester elongation method)>
Base particles 5 were obtained in the same manner as the base particles 1 except that the crystalline polyester dispersion 1 was not used.

<Example 1>
100 parts of base particles 1, 2 parts of fused silica particles 1, hydrophobized silica primary particles NX90G (manufactured by Nippon Aerosil Co., Ltd.) NX90G having a number average particle diameter of 30 nm, hydrophobized having a number average particle diameter of 20 nm After 0.6 parts of treated titanium oxide primary particles JMT-150IB (manufactured by Teika) were mixed using a Henschel mixer (manufactured by Mitsui Mining), the mesh was passed through 500 mesh to obtain a toner.

<Example 2>
A toner was obtained in the same manner as in Example 1 except that the fused silica particles 10 were used instead of the fused silica particles 1.

< Reference Example 3>
Hydrophobized silica primary particles HDK H1303VP having a number average particle size of 20 nm (manufactured by WACKER) instead of 1.5 parts of hydrophobic treated silica primary particles NX90G (manufactured by Nippon Aerosil Co., Ltd.) having a number average particle size of 30 nm A toner was obtained in the same manner as in Example 1 except that 7 parts were used.

<Example 4>
A toner was obtained in the same manner as in Example 1 except that the addition amount of hydrophobized silica primary particles NX90G (manufactured by Nippon Aerosil Co., Ltd.) having a number average particle size of 30 nm was changed to 1.7 parts.

< Reference Example 5>
Hydrophobicized silica primary particles HDK H2000 (manufactured by WACKER) having a number average particle diameter of 12 nm instead of 1.5 parts of hydrophobized silica primary particles NX90G (manufactured by Nippon Aerosil Co., Ltd.) having a number average particle diameter of 30 nm A toner was obtained in the same manner as in Example 1 except that 7 parts were used.

<Example 6>
A hydrophobized silica primary particle NX90G (manufactured by Nippon Aerosil Co., Ltd.) having a number average particle diameter of 30 nm was used instead of hydrophobized silica primary particle NAX50 (manufactured by Nippon Aerosil Co., Ltd.) having a number average particle size of 50 nm. In the same manner as in Example 1, a toner was obtained.

<Example 7>
A toner was obtained in the same manner as in Example 1 except that the fused silica particles 2 were used instead of the fused silica particles 1.

<Example 8>
A toner was obtained in the same manner as in Example 1 except that the fused silica particles 3 were used instead of the fused silica particles 1.

<Example 9>
A toner was obtained in the same manner as in Example 1 except that the fused silica particles 4 were used instead of the fused silica particles 1.

<Example 10>
A toner was obtained in the same manner as in Example 1 except that the fused silica particles 5 were used instead of the fused silica particles 1.

<Example 11>
A toner was obtained in the same manner as in Example 1 except that the fused silica particles 6 were used instead of the fused silica particles 1.

<Example 12>
A toner was obtained in the same manner as in Example 1 except that the fused silica particles 7 were used instead of the fused silica particles 1.

<Example 13>
A toner was obtained in the same manner as in Example 1 except that the fused silica particles 8 were used instead of the fused silica particles 1.

< Reference Example 14>
A toner was obtained in the same manner as in Example 1 except that the fused silica particles 9 were used instead of the fused silica particles 1.

<Example 15>
A toner was obtained in the same manner as in Example 1 except that the base particle 2 was used instead of the base particle 1.

<Example 16>
A toner was obtained in the same manner as in Example 1 except that the base particle 3 was used instead of the base particle 1.

<Example 17>
A toner was obtained in the same manner as in Example 1 except that the base particles 4 were used instead of the base particles 1.

<Example 18>
A toner was obtained in the same manner as in Example 1 except that the base particles 5 were used instead of the base particles 1.

<Comparative Example 1>
A toner was obtained in the same manner as in Example 1 except that the hydrophobic treated silica primary particles 1 were used in place of the fused silica particles 1.

<Comparative example 2>
A toner was obtained in the same manner as in Example 1 except that the addition amount of the fused silica particles 1 was changed to 1 part.

<Comparative Example 3>
A toner was obtained in the same manner as in Example 1 except that the addition amount of the fused silica particles 1 was changed to 2.3 parts.

<Comparative Example 4>
A toner was obtained in the same manner as in Example 1 except that the addition amount of the fused silica particles 1 was changed to 0.9 part.

Table 2 shows the toner characteristics of Examples 1, 2, 4, 6 to 13 , 15 to 18, Reference Examples 3 , 5 , and 14 and Comparative Examples 1 to 4.

<Inorganic particle liberation rate>
In a 500 mL beaker, 10 g of polyoxyalkylene alkyl ether Neugen ET-165 (Daiichi Kogyo Seiyaku Co., Ltd.) and 300 mL of pure water were added and then ultrasonically dispersed for 1 hour to obtain dispersion A. Next, the dispersion A was transferred to a 2 L volumetric flask to make a volume up, and then ultrasonically dispersed for 1 hour to obtain 0.5% dispersion B.

  After adding 50 mL of dispersion B and 3.75 g of toner to a 110 mL screw tube, the mixture was stirred for 30 to 90 minutes until the screw tube became compatible with the dispersion, whereby dispersion C was obtained.

A vibration part of a 750 W ultrasonic homogenizer VCX750 (manufactured by SONICS) (750 watts) was allowed to enter the dispersion C by 2.5 cm, and the output energy was 20 W. The mixture was vibrated for 1 minute to obtain a dispersion D.

After the dispersion D was put into a 50 mL centrifuge tube, the mixture was centrifuged at 2000 rpm for 2 minutes, and then the precipitate was poured into a separator while being washed with 60 mL of pure water, and suction filtered. Next, after putting filtered material and 60 mL of pure water into a minicup, the mixture was stirred 5 times with a spatula handle and suction filtered.
Furthermore, after collecting the filtrate, it was dried in a constant temperature bath at 40 ° C. for 8 hours. 3g of dried filter cake is pellets whose diameter is 3mm and thickness is 2mm using automatic pressure molding machine T-BRB-32 (manufactured by Maekawa) with a load of 6.0t and pressurization time of 60 seconds. And processed sample A was obtained.

Sample B after treatment was obtained in the same manner except that the output energy was changed to 60 W.

  3 g of toner was molded into pellets having a diameter of 3 mm and a thickness of 2 mm using an automatic pressure molding machine T-BRB-32 (manufactured by Maekawa) with a load of 6.0 t and a pressing time of 60 seconds. A sample before processing was obtained.

Using a fluorescent X-ray apparatus ZSX-100e (manufactured by Rigaku Corporation), the content [parts] of metal (silicon and titanium) in the sample was measured. At this time, a calibration curve was prepared in advance using toners having a metal content of 0.1 part, 1 part, and 1.8 parts, and the formula Xs = {(metal content in the toner before the treatment [parts] ])-(Metal content in toner after treatment [parts])} / (Metal content in toner before treatment [parts]) × 100
From these, the liberation rates A and B [mass%] of the inorganic particles were calculated.

<Preparation of carrier 1>
26 parts of a silicone resin solution SR2410 having a solid content of 23% (manufactured by Dow Corning Toray), 2.5 parts of acrylic resin Hitaloid 3001 (manufactured by Hitachi Chemical Co., Ltd.) having a solid content of 50%, and having a solid content of 77% 5 parts of benzoguanamine resin Mycoat 106 (Mitsui Cytec), 18 parts of alumina particles having an average primary particle size of 0.3 μm and a volume resistivity of 1 × 10 ¹⁴ Ω · cm, catalyst titanium diisopropoxybis (ethyl) Acetoacetate) 2 parts of TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) and 0.2 part of silane coupling agent SH6020 (manufactured by Toray Dow Corning Co., Ltd.) were diluted with toluene, then dispersed for 10 minutes using a homomixer and solid A coating solution for a protective layer having a content of 10% was obtained.

Spiral coater (MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 1000 parts with a median diameter of 35 μm, so that the thickness of the protective layer is 0.15 μm ( The coating liquid for protective layer was applied using Okada Seiko Co., Ltd. and then dried. Next, it was baked at 180 ° C. for 2 hours using an electric furnace and then cooled. Furthermore, the carrier 1 having a median diameter of 35 μm was obtained by crushing using a sieve having an opening of 106 μm.

Next, developers were prepared using the toners of Examples 1, 2, 4 , 6 to 13 , 15 to 18, Reference Examples 3 , 5 , and 14 and Comparative Examples 1 to 4, and Carrier 1.

<Production of developer>
After putting 70 parts of toner and 930 parts of carrier 1 in a commercially available ointment bottle, the mixture was mixed at 81 rpm for 5 minutes using a tumbler mixer to obtain a developer.

Next, transfer stability, filming resistance, and low-temperature fixability were evaluated using the obtained developer. Further, the heat-resistant storage stability of the toners of Examples 1, 2, 4 , 6 to 13 , 15 to 18, Reference Examples 3 , 5 , and 14 and Comparative Examples 1 to 4 were evaluated.
<Transfer stability>
Using a digital full-color printer imagio MPC7501 (manufactured by Ricoh Co., Ltd.), after transferring a chart with an image area ratio of 20% from the photoconductor to paper, the toner remaining on the photoconductor immediately before cleaning is removed from Scotch tape (Sumitomo 3M). And a reflection density was measured using a Macbeth reflection densitometer RD514 type. In addition, the case where the difference between the blank and the reflection density is less than 0.005 is ◎, the case where it is 0.005 or more and less than 0.010 is ○, the case where it is 0.011 or more and less than 0.02 is Δ, 0.02 The case where it was above was determined as x.

<Film resistance>
Using a digital full-color printer imagio MPC7501 (manufactured by Ricoh), the filming on the developing roller and the photoconductor after the output of 1000 band charts with an image area ratio of 100%, 75% and 50% was observed, Filming property was evaluated. In addition, when filming does not occur at all, ◎, when filming occurs slightly, ◯, when filming occurs in a streak pattern, filming occurs on the entire surface The case was determined as x.

<Low temperature fixability>
A copying test was performed on recording paper type 6200 (manufactured by Ricoh) using a device in which the fixing unit of the digital full-color printer imagio MPC6000 (manufactured by Ricoh) was modified, and low-temperature fixability was evaluated. Specifically, the fixing lower limit temperature was determined by changing the fixing temperature under the conditions of a linear speed of paper feed of 260 to 280 mm / s, a surface pressure of 1.2 kgf / cm ² , and a nip width of 11 mm. The case where the fixing lower limit temperature is less than 120 ° C. is judged as ◎, the case where it is 120 ° C. or more and less than 130 ° C., the case where it is 130 ° C. or more and less than 140 ° C. did.

<Heat resistant storage stability>
After storing the toner in an environment of 40 ° C. and 70% RH for 14 days, the toner was sieved with a 200 mesh sieve for 1 minute to determine the residual ratio of the toner on the wire mesh, and the heat resistant storage stability was evaluated. In addition, when the residual ratio of the toner is less than 0.1%, ◎, when it is 0.1% or more and less than 0.5%, ◯, when it is 0.5% or more and less than 1%, △, 1% The case where it was above was determined as x.

  Table 3 shows the evaluation results of the transfer stability, filming resistance and low-temperature fixability of the developer, and the evaluation results of the heat resistant storage stability of the toner.

From Table 3, the toners of Examples 1, 2, 4, 6 to 13, 15 to 18 and Reference Examples 3 , 5 , and 14 are excellent in transfer stability, filming resistance, low-temperature fixability, and heat-resistant storage stability. I understand.

  On the other hand, since the toner of Comparative Example 1 does not contain fused silica particles, the transfer stability, filming resistance, low-temperature fixability, and heat-resistant storage stability are reduced.

  In the toner of Comparative Example 2, since A is 7% by mass, the toner transfer stability and heat-resistant storage stability are lowered.

  In the toner of Comparative Example 3, since A is 22% by mass, the filming resistance and heat resistant storage stability of the toner are lowered.

  In the toner of Comparative Example 4, since A is 7% by mass and B-A is 8% by mass, the toner transfer stability and heat-resistant storage stability are deteriorated.

DESCRIPTION OF SYMBOLS 10 Photosensitive drum 18 Image forming means 20 Charging roller 21 Exposure apparatus 22 Secondary transfer apparatus 23 Roller 24 Secondary transfer belt 25 Fixing apparatus 26 Fixing belt 27 Pressure belt 40 Developing apparatus 41 Developing belt 42 Developer accommodating part 43 Developer Supply roller 44 Developing roller 45 Developing unit 50 Intermediate transfer belt 51 Roller 58 Corona charging device 60 Cleaning device 61 Developing device 62 Transfer roller 63 Cleaning device 64 Static elimination lamp 70 Static elimination lamp 80 Transfer roller 95 Transfer paper 100A, 100B, 100C Image forming apparatus 120 Image forming unit 160 Charging roller

JP 2006-58502 A

Claims (8)

A toner in which inorganic particles are attached to the surface of base particles,
The base particles include a binder resin and a colorant,
The inorganic particles include coalescence particles X and primary particles Y to which the primary particles X are coalesced,
When the median diameter of the coalesced particles X is D ₅₀ [nm], and the particle diameter of the coalesced particles X from the side where the particle diameter is small is 10% , the formula is D ₁₀ [nm].
D ₅₀ / D ₁₀ ≦ 1.2
The filling,
The primary particles Y have a number average particle size of 30 nm to 60 nm.
By applying ultrasonic vibration with an output of 20 W and a frequency of 20 kHz to the toner for 1 minute, the liberation rate of inorganic particles released is A [mass%], and ultrasonic vibration with an output of 60 W and a frequency of 20 kHz is applied to the toner for 1 minute. When the liberation rate of the inorganic particles liberated is B [mass%], the formula 10 ≦ A ≦ 20
0 ≦ B−A ≦ 5
A toner characterized by satisfying Formula 0 ≦ B−A ≦ 3
The toner according to claim 1, wherein: After putting 0.5 g of the coalesced particles X and 49.5 g of the carrier into a 50 mL bottle, the number of non-cohered primary particles occupying in 300 particles stirred for 10 minutes at 67 Hz using a rocking mill is 300. the toner according to claim 1 or 2, characterized in that a number less. The binder resin, the toner according to any one of claims 1 to 3, characterized in that it comprises a non-crystalline and crystalline polyesters. The binder resin, the toner according to any one of claims 1 to 4, characterized in that it comprises a urea-modified polyester. The coalesced particles X, the toner according to any one of claims 1 to 5 number average particle diameter is equal to or is 80nm or more 250nm or less. A developer comprising the toner according to any one of claims 1 to 6 and a carrier. A photoreceptor,
Charging means for charging the photoreceptor;
Exposure means for exposing the charged photoreceptor to form an electrostatic latent image;
An electrostatic latent image formed on the photosensitive member, using a toner according to any one of claims 1 to 6, a developing means for forming a toner image by developing,
Transfer means for transferring a toner image formed on the photoreceptor to a recording medium;
An image forming apparatus comprising fixing means for fixing a toner image transferred to the recording medium.