JP2022050140A - Toner and organic-inorganic complex particle - Google Patents

Abstract

To provide a toner excellent in low temperature fixability and storage stability.SOLUTION: A toner has toner particles having a binder resin and a colorant, and an external additive. The external additive is organic-inorganic complex particles including inorganic fine particles, a crystalline resin, and an amorphous thermoplastic resin. The organic-inorganic complex particles each have a core that contains the crystalline resin and a shell that contains the amorphous thermoplastic resin. The degree of hydrophobization of the inorganic fine particles is 50% or more. At least part of the inorganic fine particles are exposed on the surface of the organic-inorganic complex particle to form convex parts. The median diameter of the organic-inorganic complex particles is 80 nm-500 nm.SELECTED DRAWING: None

Description

The present invention relates to toner, organic-inorganic composite particles, and a method for producing organic-inorganic composite particles used in an image forming method such as an electrophotographic method.

The electrophotographic image forming apparatus is required to have high speed, long life, energy saving, and the like, and in order to meet these demands, further improvement of various performances of toner is also required. In particular, in order to extend the service life, it is important that the developability of the toner is maintained even after long-term use. Further, from the viewpoint of high speed and energy saving, the toner is required to be further improved in low temperature fixability.

Furthermore, as the market expands, the frequency of use of electrophotographic image forming devices in hot and humid areas such as Southeast Asia and the Middle East is increasing, so they are left in high temperature and high humidity assuming such areas. The storage stability of toner is also becoming important.

Therefore, various toners have been proposed in order to satisfy stable developability over a long period of time, further improvement in low temperature fixability, and storage stability under high temperature and high humidity.

For example, Patent Document 1 proposes to reduce the environmental dependence of toner by externally adding composite particles in which inorganic fine particles are embedded in the surface of resin fine particles to toner particles. Further, Patent Document 2 proposes that the low temperature fixability of the toner can be improved by using an external additive for the toner, which is composed of composite particles in which inorganic fine particles are embedded in crystalline resin particles.

Japanese Unexamined Patent Publication No. 2017-15868 JP-A-2015-45859

The present inventors have repeatedly studied the toners described in Patent Documents 1 and 2 described above.
As a result, in the external additive according to Patent Document 1 and the toner using the external additive, since the coating layer of the external additive is formed by using a thermosetting resin, the toner using this external additive is used. There was still room for improvement in the low temperature fixability of the. Further, the toner according to Patent Document 2 still has room for improvement in storage stability under high temperature and high humidity.

Therefore, an object of the present invention is to provide a toner which is excellent in low temperature fixing property and also excellent in storage stability under high temperature and high humidity.

The present invention is a toner particle having a binder resin and a colorant and a toner having an external additive, wherein the external additive is an organic inorganic substance containing inorganic fine particles, a crystalline resin and an amorphous thermoplastic resin. The organic-inorganic composite particles have a core containing the crystalline resin and a shell containing the amorphous thermoplastic resin, and the degree of hydrophobicity of the inorganic fine particles is 50%. As described above, at least a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles to form convex portions, and the medium diameter of the organic-inorganic composite particles is 80 nm to 500 nm. Regarding the toner.

By using the toner of the present invention, good low temperature fixability can be obtained, and excellent storage stability can be obtained even under high temperature and high humidity.

Hereinafter, the present invention will be described in detail.
As described above, toner is required to satisfy excellent developability, low temperature fixability, and storage stability under high temperature and high humidity at a higher level.

If the viscosity of the toner particles (meaning the toner base) is lowered in order to improve the low temperature fixability, the developability and the storage stability under high temperature and high humidity may be lowered. In addition, a large amount of inorganic fine particles may be externally added in order to maintain the developability of the toner due to the speeding up of the process of forming an electrophotographic image. Such toner has good developability and storage stability under high temperature and high humidity, but may be inferior in low temperature fixability. As described above, it has not been easy to obtain a toner that satisfies the developability, low temperature fixability, and storage stability under high temperature and high humidity at a high level.

In order to improve the low temperature fixability, it is effective to externally add a low melting point material to the toner particles. If a material that melts at a low temperature is present on the surface of the toner particles by external addition or the like, the surface of the toner is melted even for a short heating time, and the toners or the toner and the paper are bonded to each other. This is because it can be done. However, by itself, the presence of the low melting point material on the surface of the toner may lead to a decrease in chargeability and adhesion of the low melting point material to the developer carrier of the developing device, which in turn may lead to a decrease in developability. be. Adhesion of the low melting point material to the developer carrier reduces the ability of the developer carrier to impart charge to the toner, resulting in a decrease in developability. Further, the toner externally added with a low melting point material may have a reduced storage stability under high temperature and high humidity.

Therefore, the present inventors have devised an external additive having a low melting point material to suppress its exposure and make it less susceptible to the influence of humidity and temperature. As a result, it was found that the storage stability under high temperature and high humidity can be maintained while maintaining the low temperature fixing property.

Specifically, the present inventors have a core containing inorganic fine particles, a crystalline resin and an amorphous thermoplastic resin, and a core containing the crystalline resin, and a shell containing the amorphous thermoplastic resin. The degree of hydrophobicity of the inorganic fine particles is 50% or more, at least a part of the inorganic fine particles is exposed on the surface to form a convex portion, and the median diameter is 80 nm to 500 nm. It has been found that by allowing the organic-inorganic composite particles to be present on the surface of the toner particles, a toner that can simultaneously satisfy low temperature fixability and storage stability at a high level can be obtained.

When such organic-inorganic composite particles are used as an external additive, the external additive melts in an extremely short time due to the heat received from the fuser. Then, since the external additive existing on the toner surface melts in a short time, the toners or the toner and the paper can be quickly connected to each other, so that the low temperature fixability is improved.

Further, according to such an organic-inorganic composite particle, fusion of the organic-inorganic composite particle on the toner particle and the organic-inorganic composite particle on another toner particle or the toner particle can be prevented, so that the development of the developer can be performed. It is possible to prevent the resin from adhering to the surface of the agent carrier, and it is possible to further improve the storage stability under high temperature and high humidity.
Further, by exposing at least a part of the inorganic fine particles to the surface of the organic-inorganic composite particles to form convex portions, the external additive (organic-inorganic composite particles) comes into contact with the toner particles and the paper in the fixing step. The area can be increased. By doing so, it is possible to increase the adhesive force of the unfixed toner to the paper and prevent the unfixed toner from being detached from the paper.

<Organic-inorganic composite particles>
The organic-inorganic composite particles according to the present invention will be described.
In the organic-inorganic composite particles according to the present invention, inorganic fine particles having a hydrophobicity of 50% or more are dispersed in a resin portion composed of a core containing a crystalline resin and a shell containing an amorphous thermoplastic resin. The inorganic fine particles have a structure in which at least a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles to form convex portions, and the median diameter of the organic-inorganic composite particles is 80 nm to 500 nm. When the resin particles and the inorganic fine particles are externally added to the toner particles at the same time, or when the resin particles and the inorganic fine particles are externally added to the toner particles in order, the resin particles and the inorganic fine particles agglomerate on the toner particles. In some cases, it is apparently an integral organic-inorganic composite particle. However, in this method, the uniformity of the resin particles and the inorganic fine particles is often insufficient, or the composite of the inorganic fine particles with the resin particles is insufficient, so that it is difficult to obtain the effect of the present invention.

The median diameter of the organic-inorganic composite particles according to the present invention is 80 nm to 500 nm. When the median diameter of the organic-inorganic composite particles is in this range, the organic-inorganic composite particles tend to melt when the organic-inorganic composite particles receive heat from the fuser, so that the toners and the toner and the paper are firmly adhered to each other. Can be made to. It is also effective in maintaining developability.

The content of the inorganic fine particles in the organic-inorganic composite particles according to the present invention is preferably 50% by mass or more and 80% by mass or less, preferably 60% by mass or more and 80% by mass or less, based on the mass of the organic-inorganic composite particles. It is more preferable to have. When the organic-inorganic composite particles having the content of inorganic fine particles in this range are used as an external additive for toner, the external additive is easily melted instantly by the heat received from the fuser, and the low-temperature fixability of the toner is low. Can be further improved.

In the organic-inorganic composite particles according to the present invention, the exposed area of the shell containing the amorphous thermoplastic resin is preferably 30% or more and 70% or less with respect to the surface area of the organic-inorganic composite particles. When the organic-inorganic composite particles having an exposed area of 30% or more of the shell are used as an external additive for the toner, the external additive has a high thermal conductivity of heat received from the fuser, and the low temperature fixability of the toner is improved. Further improvement can be achieved. Further, when the organic-inorganic composite particles having an exposed area of 70% or less of the shell are used as an external additive for toner, they are not easily affected by humidity and temperature, and storage stability under higher temperature and high humidity is further improved. Improvements can be made.

<Inorganic fine particles>
The organic-inorganic composite particles according to the present invention contain inorganic fine particles. The inorganic fine particles used in the organic-inorganic composite particles according to the present invention have a degree of hydrophobicity of 50% or more. When the degree of hydrophobicity of the inorganic fine particles is lower than 50%, the adhesiveness with the resin forming the organic-inorganic composite particles, particularly the crystalline resin forming the core of the organic-inorganic composite particles, is lowered. When such organic-inorganic composite particles are used as a toner external additive, the organic-inorganic composite particles are deformed during toner storage, and the storage stability is lowered.

As the inorganic fine particles used in the organic-inorganic composite particles according to the present invention, known inorganic fine particles can be used as long as the degree of hydrophobicity is 50% or more. Examples of such inorganic fine particles include silica fine particles, alumina fine particles, titania fine particles, zinc oxide fine particles, strontium titanate fine particles, cerium oxide fine particles, calcium carbonate fine particles and the like. It is also possible to use two or more kinds selected by any combination from these fine particle groups.

In particular, the toner according to the present invention, which is obtained by externally adding organic-inorganic composite particles using silica fine particles as inorganic fine particles having a degree of hydrophobicity of 50% or more, is preferable because it has particularly excellent chargeability. As the silica fine particles, those obtained by a dry method such as fumed silica or those obtained by a wet method such as a sol-gel method can be used. Examples of such silica fine particles include AEROSIL NX90G (manufactured by Nippon Aerosil Co., Ltd.) and organosilica sol TOR-ST (manufactured by Nissan Chemical Industries, Ltd.).

The inorganic fine particles used for the organic-inorganic composite particles can be made hydrophobic by chemically treating the inorganic fine particles with an organic silicon compound that reacts or physically adsorbs.

As a preferred hydrophobization method, there is a method of treating silica fine particles produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound. Examples of organosilicon compounds include the following.

Hexamethyldisilazane, methyltrimethoxysilane, octyltrimethoxysilane, isobutyltrimethoxysilane, trimethylsilane, trimethylchlorsilane, trimethylethoxysilane, dimethyldichlorosilane, methyltricrolsilane, allyldimethylchlorsilane, allylphenyldichlorosilane , Benzyldimethylchlorsilane, brommethyldimethylchlorsilane, α-chlorethyltrichlorosilane, β-chlorethyltrichlorsilane, chlormethyldimethylchlorsilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, Dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1-hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, dimethylpolysiloxane and the like. These are used in one or a mixture of two or more.

The inorganic fine particles used for the organic-inorganic composite particles may be treated with silicone oil, or may be treated in combination with the above-mentioned hydrophobizing treatment.

As a preferable silicone oil, one having a viscosity at 25 ° C. of 30 mm ² / s or more and 1000 mm ² / s or less is used. Specific examples of such silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, α-methyl styrene modified silicone oil, chlorphenyl silicone oil, fluorine-modified silicone oil and the like.

Examples of the method for treating silicone oil include the following methods. A method of directly mixing silica fine particles treated with a silane coupling agent and silicone oil using a mixer such as a Henschel mixer. A method of spraying silicone oil on the base silica fine particles. Alternatively, a method in which the silicone oil is dissolved or dispersed in an appropriate organic solvent, and then silica fine particles are added and mixed to remove the organic solvent is more preferable.

The inorganic fine particles preferably have a median diameter of 5 nm or more and 100 nm or less, and more preferably 10 nm or more and 30 nm or less. When the median diameter of the inorganic fine particles is 5 nm or more and 100 nm or less, it is easy to cover the surface of the organic-inorganic composite particles, which is effective in suppressing contamination of the developer carrier and storage stability at high temperatures.

<Crystalline resin>
The organic-inorganic composite particles according to the present invention have a core containing a crystalline resin. Known crystalline resins can be used. The crystalline resin is not limited to the following, and examples thereof include polyester, polyethylene, polypropylene, ethylene-ethyl (meth) acrylate copolymer, and ethylene-vinyl acetate copolymer. Among these, crystalline polyester is preferable.

When a crystalline polyester is used as the crystalline resin, the acid value of the crystalline polyester is preferably 5 mgKOH / g or less. Although the reason for this is not clear, when the acid value of the crystalline polyester is larger than 5 mgKOH / g, the crystalline polyester bleeds on the surface of the organic-inorganic composite particles over time, and the elastic modulus of the surface of the organic-inorganic composite particles decreases. It is considered that the storage stability under high temperature and high humidity is reduced.

When polyester is used as the crystalline resin, examples of the aliphatic diol that can be used for synthesizing the crystalline polyester include the following. 1,4-Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1, , 11-Undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like. These can be used alone or in combination. The aliphatic diol according to the present invention is not limited to these.

Further, as the aliphatic diol, an aliphatic diol having a double bond can also be used. Examples of the aliphatic diol having a double bond include the following. 2-Butene-1,4-diol, 3-hexene-1,6-diol, 4-octene-1,8-diol, etc.

Next, the acid component that can be used for the synthesis of the crystalline polyester will be described.
As the acid component that can be used for the synthesis of the crystalline polyester, a polyvalent carboxylic acid is preferable.

Examples of the aliphatic dicarboxylic acid include the following. Glyric acid, malonic acid, amber acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonandicarboxylic acid, 1,10-decandicarboxylic acid, 1,11-undecandicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanediocarboxylic acid. Or its lower alkyl ester or acid anhydride. Among these, sebacic acid, adipic acid, 1,10-decandicarboxylic acid or its lower alkyl ester, acid anhydride and the like. These can be used alone or in combination. Moreover, it is not limited to these.

Examples of the aromatic dicarboxylic acid include the following. Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid and the like. Of these, terephthalic acid is preferable because it is easily available and easily forms a polymer having a low melting point.

Further, as the acid component, a dicarboxylic acid having a double bond can also be used. Examples of such dicarboxylic acids include fumaric acid, maleic acid, 3-hexendioic acid, 3-octendioic acid and the like. Further, these lower alkyl esters and acid anhydrides can also be used. Of these, fumaric acid and maleic acid are preferable in terms of cost.

The method for producing the crystalline polyester is not particularly limited, and the crystalline polyester can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. For example, depending on the type of monomer, direct polycondensation or transesterification method can be appropriately used for production.

The crystalline polyester is preferably produced at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower, and if necessary, the pressure inside the reaction system is reduced, and the reaction is carried out while removing water and alcohol generated during condensation. preferable.

If the monomer dissolves or does not dissolve at the reaction temperature, it is preferable to add a high boiling point organic solvent as a dissolution aid to dissolve the monomer. The polycondensation reaction is carried out while distilling off the dissolution auxiliary solvent. When a monomer having poor compatibility is present in the copolymerization reaction, it is preferable to condense the monomer having poor compatibility with the monomer and an acid or alcohol to be polycondensed in advance, and then polycondensate with the main component.

Examples of the catalyst that can be used in the production of the crystalline polyester include a titanium catalyst and a tin catalyst.
Examples of the titanium catalyst include, for example, titanium tetraethoxydo, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide and the like. Examples of tin catalysts include dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide and the like.

The melting point of the crystalline resin according to the present invention is preferably 70 ° C. or higher and 150 ° C. or lower.
In the organic-inorganic composite particles according to the present invention, the core containing the crystalline resin preferably contains the above-mentioned inorganic fine particles having a specific degree of hydrophobicity and a specific median diameter. When the core of the organic-inorganic composite particles contains the above-mentioned inorganic fine particles having a specific degree of hydrophobicity and a specific median diameter, the mechanical strength of the particles increases, so that the high temperature of the toner when externally added to the toner particles is high. Improves storage stability under wet conditions.

<Amorphous thermoplastic resin>
The organic-inorganic composite particles according to the present invention have a shell containing an amorphous thermoplastic resin. As the amorphous thermoplastic resin, known ones can be used. Examples of the amorphous thermoplastic resin include vinyl resin, polyester resin, epoxy resin and the like, and among them, vinyl resin is preferable.

As the amorphous vinyl resin, known ones can be used. For example, polystyrene, polymethylmethacrylate, polybutylmethacrylate, poly (meth) acrylic acid, and copolymers thereof can be mentioned. In particular, a styrene- (meth) acrylic acid copolymer is preferable.

When a styrene- (meth) acrylic acid copolymer is used as the amorphous thermoplastic resin, its acid value is preferably 10 mgKOH / g or more and 25 mgKOH / g or less. When the acid value of the styrene- (meth) acrylic acid copolymer is less than 10 mgKOH / g, the crystallinity is highly compatible with the crystalline resin forming the core, so that the crystalline resin bleeds over time and is subjected to high temperature and high humidity. Storage stability is reduced. When the acid value of the styrene- (meth) acrylic acid copolymer exceeds 25 mgKOH / g, the hydrophobicity of the surface of the organic-inorganic composite particle according to the present invention is lowered, so that the amount of water adsorbed in the air is increased and the organic-inorganic is organic-inorganic. Liquid cross-linking adhesion between composite particles increases and fusion occurs.

<Manufacturing method of organic-inorganic composite particles>
As a method for obtaining the organic-inorganic composite particles according to the present invention, a known method can be used.
For example, thermoplastic resin particles can be produced by emulsion polymerization in the presence of inorganic fine particles and emulsified crystalline polyester to produce organic-inorganic composite particles. In addition, the inorganic fine particles are also embedded in the resin particles by a method in which crystalline polyester and a thermoplastic resin are dissolved in an organic solvent, inorganic fine particles are added to the solution, and phase inversion emulsification or forced emulsification is performed in this state. It is possible to produce organic-inorganic composite particles having the same structure.

In the method for producing organic-inorganic composite particles of the present invention, a dispersion liquid containing inorganic fine particles, a crystalline resin, an amorphous thermoplastic resin and an organic solvent is prepared, and a neutralizing agent and water are mixed with the dispersion liquid. It is characterized by having a step of preparing an emulsion by stirring the mixture and forming organic-inorganic composite particles by distilling off an organic solvent from the emulsion. The median diameter of the organic-inorganic composite particles produced by this method tends to be 100 nm to 150 nm, which is suitable as an external additive.

The organic solvent used when the organic-inorganic composite particles according to the present invention are produced by phase inversion emulsification or forced emulsification is not particularly limited as long as it dissolves a resin, and is, for example, tetrahydrofuran, toluene, methyl ethyl ketone, hexane, acetic acid. Ethyl, acetone, etc. can be used.

The surface of the organic-inorganic composite particles according to the present invention is preferably treated with an organosilicon compound or silico oil. By treating with an organosilicon compound or silico oil, the hydrophobicity of the external additive can be enhanced, so that the toner has stable developability even in a high temperature and high humidity environment.

As a method for producing an external additive surface-treated with an organosilicon compound or silicone oil, a method of surface-treating organic-inorganic composite particles and inorganic fine particles previously surface-treated with an organosilicon compound or silicone oil are used as a resin. There is a method of compounding.

Similar to the inorganic fine particles used for the organic-inorganic composite particles, the organic-inorganic composite particles can be made hydrophobic by chemically treating the organic-inorganic composite particles with an organic silicon compound that reacts or physically adsorbs.

The organic-inorganic composite particles may be treated with silicone oil in the same manner as the inorganic fine particles used for the organic-inorganic composite particles, or may be treated in combination with the above-mentioned hydrophobization treatment.

<Toner>
The toner according to the present invention has toner particles having a binder resin and a colorant, and an external additive. The content of the external additive (organic-inorganic composite particles) according to the present invention in the toner according to the present invention is preferably 0.1 part by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles. The toner according to the present invention may contain an external additive other than the organic-inorganic composite particles. In particular, in order to improve the fluidity and chargeability of the toner, it is preferable to add a fluidity improver as another external additive.

<Liquidity improver>
The following can be used as the fluidity improver.
For example, vinylidene fluoride fine powder, fluororesin powder such as polytetrafluoroethylene fine powder; wet manufacturing silica, fine powder silica such as dry silica, fine powder titanium oxide, fine powder alumina, silane compounds, titanium cups. Treated silica surface-treated with ringing agent, silicone oil; oxides such as zinc oxide and tin oxide; compound oxides such as strontium titanate, barium titanate, calcium titanate, strontium titanate and calcium zirconate; carbonic acid Calcium and carbonate compounds such as magnesium carbonate.

A preferable fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is so-called dry silica or fumed silica. For example, it utilizes the pyrolysis oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this manufacturing process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound, and these are also included as silica. do.

It is preferable that the average primary particle size in the particle size distribution based on the number is 5 nm or more and 30 nm or less because high chargeability and fluidity can be obtained.

Further, as the fluidity improver used in the present invention, treated silica fine powder obtained by hydrophobizing the silica fine powder produced by the vapor phase oxidation of the silicon halogen compound is more preferable. As the hydrophobization treatment, the same method as the surface treatment on the organic-inorganic composite particles or the inorganic fine particles used for the organic-inorganic composite particles can be used.

The fluidity improver preferably has a specific surface area of 30 m ² / g or more and 300 m ² / g or less due to nitrogen adsorption measured by the BET method. Further, it is preferable to use a total amount of 0.01 parts by mass or more and 3 parts by mass or less of the fluidity improver with respect to 100 parts by mass of the toner.

The toner according to the present invention can be used as a one-component developer by mixing with the fluidity improver and, if necessary, with another external additive (for example, a charge control agent). It can also be used as a two-component developer in combination with a carrier.

As the carrier used in the two-component developing method, all conventionally known carriers can be used. Specifically, metals such as surface-oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, and rare earths, and alloys or oxides thereof are preferably used.

Further, those in which a substance of a styrene resin, an acrylic resin, a silicone resin, a fluororesin, or a polyester resin is adhered or coated on the surface of the carrier particles are preferably used.

<Toner particles>
Next, the toner particles according to the present invention will be described.
First, the binder resin used for the toner particles according to the present invention will be described.
Examples of the binder resin include polyester-based resin, vinyl-based resin, epoxy resin, and polyurethane resin.
From the viewpoint of storage stability, the binder resin preferably has a glass transition point (Tg) of 45 ° C. or higher and 70 ° C. or lower.

The toner according to the present invention may further contain magnetic iron oxide particles and be used as a magnetic toner. In this case, the magnetic iron oxide particles can also serve as a colorant.
In the present invention, the magnetic iron oxide particles contained in the magnetic toner include iron oxide particles such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, and lead. Examples include alloys of metals such as magnesium, tin, zinc, antimony, bismuth, calcium, manganese, titanium, tungsten, vanadium and mixtures thereof.

The average particle size of these magnetic iron oxide particles is preferably 2 μm or less. More preferably, it is 0.05 μm or more and 0.5 μm or less. The amount of magnetic iron oxide particles contained in the toner is preferably 20 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the resin component, and more preferably 40 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the resin component. It is less than a part.

Examples of colorants used in the present invention are given below.
As the black colorant, for example, carbon black, grafted carbon, or a black colorant using the following iro / magenta / cyan colorants can be used. Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds and the like. Examples of the cyan colorant include a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound. These colorants can be used alone or in a mixed state or in a solid solution state.

The colorant according to the present invention is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in toner. The amount of the colorant added is 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner according to the present invention may further contain a known wax. Specific examples of the wax include, for example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, aliphatic hydrocarbon wax such as Fishertropsh wax, and fat such as polyethylene oxide wax. Examples thereof include oxides of group hydrocarbon waxes, block copolymers of aliphatic hydrocarbon waxes, and oxides thereof.

Specific examples of wax include Viscol 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries, Ltd.), High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals, Inc.), Sazole H1, H2, C80, C105, C77 (Schumann Sazole, Inc.), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Sei) Wax), Unilin 350, 425, 550, 700, Unisid, Unisid 350, 425, 550, 700 (Toyo Petrolite), Wood wax, Beeswax, Rice wax, Candelilla wax, Carnauba wax (Cerarica NODA) Can be mentioned.

It is preferable to use a charge control agent for the toner according to the present invention in order to stabilize its chargeability. As such a charge control agent, an organic metal complex or a chelate compound in which an acid group or a hydroxyl group existing at the terminal of the binder resin used in the present invention easily interacts with a central metal is effective. Examples thereof include monoazo metal complexes; acetylacetone metal complexes; aromatic hydroxycarboxylic acids or aromatic dicarboxylic acid metal complexes or metal salts.
Specific examples of charge control agents that can be used include Spiron Black TRH, T-77, T-95 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E-. 84, E-88, E-89 (Orient Chemical Co., Ltd.) can be mentioned. Further, the charge control resin can also be used in combination with the above-mentioned charge control agent.

<Manufacturing method of toner particles>
The method for producing the toner particles according to the present invention is not particularly limited, and for example, a so-called polymerization method such as a pulverization method, an emulsion polymerization method, a suspension polymerization method and a dissolution suspension method can be used.
In the pulverization method, first, the binder resin, the colorant, the wax, the charge control agent and the like constituting the toner particles are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Next, the obtained mixture is melt-kneaded using a heat kneader such as a twin-screw kneading extruder, a heating roll, a kneader, and an extruder, cooled and solidified, and then pulverized and classified. As a result, the toner particles according to the present invention can be obtained.
Further, if necessary, the desired external additive can be sufficiently mixed with a mixer such as a Henschel mixer to obtain the toner according to the present invention.

Examples of the mixer include the following. Henschel Mixer (Mitsui Mining Co., Ltd.); Super Mixer (Kawata Co., Ltd.); Ribocorn (Okawara Seisakusho Co., Ltd.); Nowter Mixer, Turbulizer, Cyclomix (Hosokawa Micron Co., Ltd.); Spiral Pin Mixer (Pacific Kiko Co., Ltd.) Ladyge mixer (manufactured by Matsubo).

Examples of the kneading machine include the following. KRC kneader (manufactured by Kurimoto Iron Works); Busco kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Japan Steel Works); PCM kneader (manufactured by Ikegai) Iron Works); Three roll mill, mixing roll mill, kneader (Inoue Mfg. Co., Ltd.); Kneedex (Mitsui Mine Co., Ltd.); MS type pressurized kneader, Nidar Luder (Moriyama Mfg. Co., Ltd.); Banbury mixer (Kobe Steel) Made by Tokorosha).

Examples of the crusher include the following. Counter jet mill, micron jet, innomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industries); cross jet mill (manufactured by Kurimoto Iron Works); Ulmax (manufactured by Nippon Soda Engineering Co., Ltd.) ); SK Jet O Mill (manufactured by Seishin Enterprise Co., Ltd.); Cryptron (manufactured by Kawasaki Heavy Industries); Turbo Mill (manufactured by Turbo E Co., Ltd.); Super Rotor (manufactured by Nisshin Engineering Co., Ltd.).

Examples of the classifier include the following. Classil, Micron Classifier, Spedic Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nisshin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron); Elbow Jet (Japan) Iron Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Co., Ltd.); YM Microcut (manufactured by Yasukawa Shoji Co., Ltd.).

In the polymerization method, first, a polymerizable monomer capable of producing a binder resin and various additives as needed are mixed, and the material is dissolved or dispersed using a disperser. Prepare the composition. Examples of various additives include colorants, waxes, charge control agents, polymerization initiators, chain transfer agents and the like. Dispersers include homogenizers, ball mills, colloid mills, or ultrasonic dispersers. Next, the polymerizable monomer composition is put into an aqueous medium containing poorly water-soluble inorganic fine particles, and the polymerizable monomer composition is composed using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser. Prepare droplets of material (granulation process). Then, the polymerizable monomer in the droplet is polymerized to obtain toner mother particles (polymerization step). The polymerization initiator may be mixed when preparing the polymerizable monomer composition, or may be mixed in the polymerizable monomer composition immediately before forming droplets in the aqueous medium. Further, it can be added in a state of being dissolved in a polymerizable monomer or another solvent, if necessary, during the granulation of the droplets or after the completion of the granulation, that is, immediately before the start of the polymerization reaction. After polymerizing the polymerizable monomer to obtain a binder resin, it is advisable to perform a solvent removal treatment as necessary to obtain a dispersion liquid of toner mother particles.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

<Measurement method of various physical properties>
The measurement method used in the examples is shown below.

<Measuring method of toner cohesion>
The degree of toner aggregation was measured as follows.
As a measuring device, a digital display type vibrometer "DigiVibro MODEL 1332A" (trade name; manufactured by Showa Sokki Co., Ltd.) is connected to the side surface of the shaking table of "Powder Tester" (trade name; manufactured by Hosokawa Micron). board. Then, a sieve with a mesh opening of 38 μm (400 mesh), a sieve with a mesh opening of 75 μm (200 mesh), and a sieve with a mesh opening of 150 μm (100 mesh) were stacked and set on the shaking table of the powder tester in this order from the bottom. The measurement was carried out in the environment of 23 ° C. and 60% RH as follows.
(1) The vibration width of the shaking table was adjusted in advance so that the displacement value of the digital display type vibration meter was 0.60 mm (peak-to-peak).
(2) 5 g of toner left in advance at 23 ° C. and 60% RH environment for 24 hours was precisely weighed and gently placed on a sieve having an opening of 150 μm on the uppermost stage.
(3) After vibrating the sieve for 15 seconds, the mass of the toner remaining on each sieve was measured, and the degree of cohesion was calculated based on the following formula.
Cohesion (%)
= {(Sample mass (g) on a sieve with an opening of 150 μm) / 5 (g)} × 100
+ {(Sample mass (g) on a sieve with an opening of 75 μm) / 5 (g)} × 100 × 0.6
+ {(Sample mass (g) on a sieve with an opening of 38 μm) / 5 (g)} × 100 × 0.2

<Measurement method of hydrophobicity of inorganic fine particles>
The degree of hydrophobicity of the inorganic fine particles was measured by the methanol titration method. The degree of hydrophobicity by the methanol titration method was measured by the following procedure. That is, in a mixed solution in which 0.2 g of inorganic fine particles was added to 50 ml of water, methanol was added dropwise from the burette while stirring the mixed solution until the entire amount of the inorganic fine particles was wetted. Whether or not the entire amount was wet was determined by whether or not all the inorganic fine particles suspended on the water surface were submerged in the liquid and suspended in the liquid. At this time, the value of the percentage of methanol with respect to the total amount of the mixed solution and the dropped methanol at the end of the dropping is defined as the degree of hydrophobicity. The higher the value of the degree of hydrophobicity, the higher the hydrophobicity.

<Evaluation method for exposure of inorganic fine particles>
The presence or absence of exposure of the inorganic fine particles in the organic-inorganic composite particles can be evaluated by X-ray photoelectron spectroscopy (XPS). Specifically, in XPS, the total of the carbon atom concentration dC, the oxygen atom concentration dO, and the metal and silicon atom concentration dM derived from the inorganic fine particles is 100.0 atomic% on the surface of the organic-inorganic composite particle. At this time, the content of the metal and silicon atoms derived from the inorganic fine particles obtained by the following formula (i) is expressed as Za [mass%].
Za [mass%] = {dM × (atomic weight of metal and silicon atom)} / [{dC × (atomic weight of carbon)} + {dO × (atomic weight of oxygen)} + {dM × (atomic weight of metal and silicon atom) )}] × 100 ... (i)

When Za is less than 1% by mass, it means that the inorganic fine particles are not exposed on the surface layer of the organic-inorganic composite particles. When Za is 1% by mass or more, it means that the inorganic fine particles are exposed on the surface layer of the organic-inorganic composite particles. Za can be controlled by the degree of hydrophobicity of the inorganic fine particles, the content of the inorganic fine particles with respect to the organic-inorganic composite particles, the temperature at the time of preparing the organic-inorganic composite particles, the pH, and the like.
The XPS device and measurement conditions are as follows.
-Device used: Quantum 2000 manufactured by ULVAC-PHI
・ Analysis method: Narrow analysis ・ X-ray source: Al-Kα
・ X-ray conditions: 100 μm, 25 W, 15 kV
・ Optoelectronic capture angle: 45 °
-PassEnergy: 58.70eV
・ Measurement range: φ100 μm

<Measuring method of shell surface exposure>
The amount of surface exposure of the shell on the surface of the organic-inorganic composite particles was measured as follows. The cross section of the organic-inorganic composite particles was observed using a scanning electron microscope (SEM) (S-4800, manufactured by Hitachi High-Technologies Corporation) to obtain an SEM photographed image. From the obtained SEM image, the circle obtained by connecting the shell surface with a line is used as the contour, and the ratio of the shell excluding the inorganic fine particle portion to the contour is measured for the cross section of 10 external particle particles. It was performed on the SEM photographed image. Subsequently, the average value of these was calculated.

<Method for measuring acid value of resin>
The acid value of the resin was determined by the following method.
The basic operation is based on JIS K-0070.
1) Weigh 0.5 to 2.0 g of the sample. The mass at this time is M1 (g).
2) Place the sample in a 50 ml beaker and add 25 ml of a mixed solution of tetrahydrofuran / ethanol (2/1) to dissolve.
3) Using a 0.1 mol / l potassium hydroxide ethanol solution, titration is performed using a potentiometric titration measuring device [for example, an automatic titration measuring device "COM-2500" manufactured by Hiranuma Sangyo Co., Ltd. can be used. ].
4) The amount of the potassium hydroxide solution used at this time is A (ml). At the same time, the blank is measured, and the amount of potassium hydroxide used at this time is defined as B (ml).
5) Calculate the acid value by the following formula (ii). f is a factor of the potassium hydroxide solution.
Equation (ii)
Acid value [mgKOH / g] = [(AB) x f x 5.61] / M1 ... (ii)

<Measurement method of median diameter of organic-inorganic composite particles>
After diluting the organic-inorganic composite particles with purified water, measurement is performed using Nanotrack 150 (manufactured by Nikkiso Co., Ltd.) in a range setting of 0.001 μm to 10 μm, and the measurement is performed as the number average particle diameter. Was evaluated.

<Measuring method of the content of inorganic fine particles in organic-inorganic composite particles>
The content of the inorganic fine particles in the organic-inorganic composite particles was evaluated by measuring the weight change with a STA7200RV (differential thermal thermogravimetric simultaneous measuring device, manufactured by Hitachi High-Tech Science Co., Ltd.).

<Manufacturing method of crystalline resin>
[Manufacturing method of crystalline polyester 1]
In a reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube, 159 g of decandicarboxylic acid as an acid component and 90 g of 1,6-hexanediol as an alcohol component were placed. Subsequently, 0.1% by mass of tetraisobutyl titanate was added to the total amount of the raw material, and the mixture was reacted at 180 ° C. for 4 hours, then heated to 210 ° C. at a rate of 10 ° C./1 hour, and then heated to 210 ° C. at 210 ° C. for 8 hours. Retained. Then, the reaction was carried out at 8.3 kPa for 1 hour to obtain crystalline polyester 1. The melting point of the crystalline polyester 1 was 72 ° C.

[Manufacturing method of crystalline polyester 2]
A crystalline polyester 2 was obtained in the same manner as in the method for producing the crystalline polyester 1 except that the raw material was 159 g of sebacic acid as an acid component and 90 g of 1,9-nonanediol as an alcohol component.

[Manufacturing method of crystalline polyester 3]
A crystalline polyester 3 was obtained in the same manner as in the method for producing the crystalline polyester 1 except that the raw material was 159 g of sebacic acid as an acid component and 90 g of 1,6-hexanediol as an alcohol component.

<Manufacturing method of amorphous thermoplastic resin>
[Manufacturing method of amorphous polyester 1]
100 parts by mass of terephthalic acid, 125 parts by mass of isophthalic acid, 285 parts by mass of ethylene oxide 2 mol adduct of bisphenol A, 60 parts by mass of ethylene glycol, 20 parts by mass of neopentyl glycol in a reaction kettle equipped with a stirrer, a thermometer, and a cooler for reflux. Add 0.1 parts by mass of n-tetrabutyl titanate as a catalyst, 2 parts by mass of Irganox 1330 as an antioxidant, and 0.3 parts by mass of sodium acetate as a polymerization stabilizer, and transesterify at 220 ° C. for 2 hours. The reaction was carried out. Then, the pressure inside the reaction system was reduced while raising the temperature from 220 ° C. to 270 ° C., and then a polycondensation reaction was carried out at 1 Torr or less for 5 hours. After completion of the reaction, the system was returned from vacuum to normal pressure using nitrogen. Further, 2.88 parts by mass of trimellitic anhydride was added as an acid value-imparting polycarboxylic acid, and the mixture was reacted at 220 ° C. for 30 minutes to obtain a polyester.
100 parts by mass of the obtained polyester was dissolved in 200 parts by mass of chloroform, placed in a separating funnel together with 300 parts by mass of ion-exchanged water, stirred and allowed to stand, and the upper layer was discarded. Further, the lower layer was washed twice with water, and then chloroform was distilled off by an evaporator to obtain an amorphous polyester 1.

<Production example of organic-inorganic composite particles 1>
In a glass container, 5 g of crystalline polyester 1 (acid value: 2 mgKOH / g) and styrene-acrylic copolymer 1 (copolymerization ratio: styrene / acrylic acid = 24/1, acid value: 22.3 mgKOH / g) are placed. 5 g and 65 g of methyl ethyl ketone were charged and heated to 65 ° C. to dissolve them.
Next, while stirring at 60 ° C., 58. 3 g was added. Subsequently, 200 g of a 0.01 mol / l sodium hydroxide aqueous solution at 60 ° C. was added, and forced emulsification was performed by high-speed stirring (rotation speed 15000 rpm) using a homogenizer (manufactured by IKA: Ultratalax T50). .. Subsequently, methyl ethyl ketone and toluene were volatilized with a rotary evaporator at a temperature of 50 ° C. to obtain a dispersion liquid of the organic-inorganic composite particles 1. Then, it was filtered and dried to obtain organic-inorganic composite particles 1.
The organic-inorganic composite particles 1 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 57%, and the median diameter was 115 nm.

<Production example of organic-inorganic composite particles 2>
Organic-inorganic composite particles 2 were obtained in the same manner as in the production example of the organic-inorganic composite particles 1 except that the crystalline polyester 2 (acid value: 5 mgKOH / g) was used instead of the crystalline polyester 1.
The organic-inorganic composite particles 2 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 42%, and the median diameter was 123 nm.

<Production example of organic-inorganic composite particles 3>
Organic-inorganic composite except that styrene-acrylic copolymer 2 (copolymer ratio: styrene / acrylic acid = 24/1, acid value: 21.5 mgKOH / g) was used instead of styrene-acrylic copolymer 1. The organic-inorganic composite particles 3 were obtained in the same manner as in the production example of the particles 1.
The organic-inorganic composite particles 3 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 64%, and the median diameter was 119 nm.

<Production example of organic-inorganic composite particles 4>
Organic-inorganic composite particles 4 were obtained in the same manner as in the production example of the organic-inorganic composite particles 3 except that the crystalline polyester 2 was used instead of the crystalline polyester 1.
The organic-inorganic composite particles 4 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 32%, and the median diameter was 122 nm.

<Production example of organic-inorganic composite particles 5>
Organic-inorganic composite particles 1 except that 23.3 g of vapor-phase silica (trade name: AEROSIL NX90G, manufactured by Nippon Aerosil Co., Ltd., average particle diameter 20 nm, hydrophobicity 70 wt%) was used instead of the organosilica SOL TOR-ST. Organic-inorganic composite particles 5 were obtained in the same manner as in the production example of.
The organic-inorganic composite particles 5 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 43%, and the median diameter was 134 nm.

<Production example of organic-inorganic composite particles 6>
Organic-inorganic composite particles 6 were obtained in the same manner as in the production example of the organic-inorganic composite particles 5, except that the crystalline polyester 2 was used instead of the crystalline polyester 1.
The organic-inorganic composite particles 6 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 47%, and the median diameter was 131 nm.

<Production example of organic-inorganic composite particles 7>
Organic-inorganic composite particles 7 were obtained in the same manner as in the production example of the organic-inorganic composite particles 5, except that the styrene-acrylic copolymer 2 was used instead of the styrene-acrylic copolymer 1.
The organic-inorganic composite particles 7 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 58%, and the median diameter was 128 nm.

<Production example of organic-inorganic composite particles 8>
Organic-inorganic composite particles 8 were obtained in the same manner as in the production example of the organic-inorganic composite particles 7 except that the crystalline polyester 2 was used instead of the crystalline polyester 1.
The organic-inorganic composite particles 8 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 54%, and the median diameter was 135 nm.

<Production example of organic-inorganic composite particles 9>
Organosilica sol MEK-ST-40 (trade name: Organosilica sol MEK-ST-40, manufactured by Nissan Chemical Industries, Ltd., average particle size 15 nm, solid weight ratio 40%, hydrophobicity 60 wt%) instead of organosilica sol TOR-ST Organic-inorganic composite particles 9 were obtained in the same manner as in the production example of the organic-inorganic composite particles 1 except that they were used.
The organic-inorganic composite particles 9 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 50%, and the median diameter was 105 nm.

<Production example of organic-inorganic composite particles 10>
For 77.7 g of organosilica sol EAC-ST (trade name: organosilica sol EAC-ST, manufactured by Nissan Chemical Industries, Ltd., average particle size 15 nm, solid weight ratio 30%, hydrophobicity 50 wt%) instead of organosilica sol TOR-ST. The organic-inorganic composite particles 10 were obtained in the same manner as in the production example of the organic-inorganic composite particles 1 except for the above.
The organic-inorganic composite particles 10 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 38%, and the median diameter was 116 nm.

<Production example of organic-inorganic composite particles 11>
Organic-inorganic composite particles 11 in the same manner as in the production example of the organic-inorganic composite particles 1 except that 200 g of 0.02 mol / l sodium hydroxide aqueous solution was used instead of 200 g of 0.01 mol / l sodium hydroxide aqueous solution. Got
The organic-inorganic composite particles 11 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 62%, and the median diameter was 85 nm.

<Production example of organic-inorganic composite particles 12>
In a glass container, 5 g of crystalline polyester 1 and 35 g of methyl ethyl ketone were charged and heated to 65 ° C. to dissolve them.
Next, 200 g of a 0.01 mol / l sodium hydroxide aqueous solution at 60 ° C. was added, and forced emulsification was performed by high-speed stirring (rotation speed 15000 rpm) using a homogenizer.
Subsequently, in a separable flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 240 g of an emulsified solution prepared by forced emulsification, 46 g of water, 23.1 g of organosilica sol TOR-ST as inorganic fine particles, and acrylic. 0.14 g of acid and 4.86 g of styrene were added and heated to 60 ° C. with stirring to prepare an emulsified particle dispersion.
Subsequently, 0.27 g of a 2,2'-azobis (2,4-dimethylvaleronitrile) 50% by mass toluene solution as a polymerization initiator was added to the emulsified particle dispersion and kept at 60 ° C. for 4 hours under a nitrogen atmosphere. The polymerization reaction was carried out in.
Subsequently, methyl ethyl ketone and toluene were volatilized with a rotary evaporator at a temperature of 50 ° C. to obtain a dispersion liquid of the organic-inorganic composite particles 12. Then, it was filtered and dried to obtain an organic-inorganic composite particle 12.
The organic-inorganic composite particles 12 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 57%, and the median diameter was 450 nm.

<Production example of organic-inorganic composite particles 13>
Organic-inorganic composite particles 13 were obtained in the same manner as in the production example of the organic-inorganic composite particles 1 except that the crystalline polyester 3 (acid value: 6 mgKOH / g) was used instead of the crystalline polyester 1.
The organic-inorganic composite particles 13 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 65%, and the median diameter was 125 nm.

<Production example of organic-inorganic composite particles 14>
Organic-inorganic composite particles 14 in the same manner as in the production example of the organic-inorganic composite particles 1 except that EV150 (ethylene-vinyl acetate copolymer manufactured by Mitsui Dow Polychemical Co., Ltd.) was used instead of the crystalline polyester 1. Got
The organic-inorganic composite particles 14 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 45%, and the median diameter was 132 nm.

<Production example of organic-inorganic composite particles 15>
The organic-inorganic composite particles 15 were obtained in the same manner as in the production example of the organic-inorganic composite particles 14 except that the amount of the organosilica sol TOR-ST added was 30.56 g.
The organic-inorganic composite particles 15 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 43%, and the median diameter was 129 nm.

<Production example of organic-inorganic composite particles 16>
The organic-inorganic composite particles 16 were obtained in the same manner as in the production example of the organic-inorganic composite particles 14 except that the amount of the organosilica sol TOR-ST added was 141.67 g.
The organic-inorganic composite particles 16 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 56%, and the median diameter was 128 nm.

<Production example of organic-inorganic composite particles 17>
Organic-inorganic composite particles 17 were obtained in the same manner as in the production example of the organic-inorganic composite particles 14 except that the amount of the organosilica sol TOR-ST added was 23.1 g.
The organic-inorganic composite particles 18 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 51%, and the median diameter was 133 nm.

<Production example of organic-inorganic composite particles 18>
In a glass container, 5 g of EV150 and 35 g of methyl ethyl ketone were charged and heated to 65 ° C. to dissolve them.
Next, 200 g of a 0.01 mol / l sodium hydroxide aqueous solution at 60 ° C. was added, and forced emulsification was performed by high-speed stirring (rotation speed 15000 rpm) using a homogenizer.
Subsequently, 5 g of the styrene-acrylic copolymer 1 was dissolved in 30 g of methyl ethyl ketone by heating at 65 ° C., and a mixed solution containing 23.1 g of the organosilica sol TOR-ST was added to the emulsified solution prepared by forced emulsification. High-speed stirring (rotation speed 15000 rpm) was performed using a homogenizer. Subsequently, methyl ethyl ketone and toluene were volatilized with a rotary evaporator at a temperature of 50 ° C. to obtain a dispersion liquid of the organic-inorganic composite particles 18. Then, it was filtered and dried to obtain organic-inorganic composite particles 18.
The organic-inorganic composite particles 18 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. Was absent, the surface exposure of the shell was 60%, and the median diameter was 111 nm.

<Production example of organic-inorganic composite particles 19>
The organic-inorganic composite particles 19 were obtained in the same manner as in the production example of the organic-inorganic composite particles 18 except that the volatilization operation of methyl ethyl ketone and toluene in the rotary evaporator was performed at a temperature of 60 ° C.
The organic-inorganic composite particles 19 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. Was absent, the exposure of the shell was 24%, and the median diameter was 125 nm.

<Production example of organic-inorganic composite particles 20>
The organic-inorganic composite particles 20 were obtained in the same manner as in the production example of the organic-inorganic composite particles 18 except that the volatilization operation of methyl ethyl ketone and toluene in the rotary evaporator was performed at a temperature of 40 ° C.
The organic-inorganic composite particles 20 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. Was absent, the exposure of the shell was 72%, and the median diameter was 132 nm.

<Production example of organic-inorganic composite particles 21>
Organic-inorganic composite except that styrene-acrylic copolymer 3 (copolymer ratio: styrene / acrylic acid = 15/1, acid value: 27.1 mgKOH / g) was used instead of the styrene-acrylic copolymer 1. The organic-inorganic composite particles 21 were obtained in the same manner as in the production example of the particles 19.
The organic-inorganic composite particles 21 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. Was absent, the surface exposure of the shell was 21%, and the median diameter was 117 nm.

<Production example of organic-inorganic composite particles 22>
Organic-inorganic composite except that styrene-acrylic copolymer 4 (copolymer ratio: styrene / acrylic acid = 50/1, acid value: 9.2 mgKOH / g) was used instead of the styrene-acrylic copolymer 1. The organic-inorganic composite particles 22 were obtained in the same manner as in the production example of the particles 19.
The organic-inorganic composite particles 22 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. Was absent, the surface exposure of the shell was 27%, and the median diameter was 134 nm.

<Production example of organic-inorganic composite particles 23>
Organic-inorganic composite particles 23 were obtained in the same manner as in the production example of the organic-inorganic composite particles 19 except that HF77 (polystyrene manufactured by PS Japan Corporation) was used instead of the styrene-acrylic copolymer 1.
The organic-inorganic composite particles 23 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. Was absent, the surface exposure of the shell was 24%, and the median diameter was 106 nm.

<Production example of organic-inorganic composite particles 24>
The organic-inorganic composite particles 24 are similar to the production examples of the organic-inorganic composite particles 19 except that the amorphous polyester 1 (acid value: 12.6 mgKOH / g) is used instead of the styrene-acrylic copolymer 1. Got
The organic-inorganic composite particles 24 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. Was absent, the surface exposure of the shell was 25%, and the median diameter was 117 nm.

<Production example of organic-inorganic composite particles 25>
Organic-inorganic composite particles 25 were obtained in the same manner as in the production example of the organic-inorganic composite particles 1 except that the styrene-acrylic copolymer 2 was used instead of the crystalline polyester 1.
The organic-inorganic composite particles 25 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 52%, and the median diameter was 121 nm.

<Production example of organic-inorganic composite particles 26>
In a glass container, 5 g of crystalline polyester 1, 58.3 g of organosilica sol TOR-ST, and 35 g of methyl ethyl ketone were charged and heated to 65 ° C. to dissolve them.
Next, 200 g of a 0.01 mol / l sodium hydroxide aqueous solution at 60 ° C. was added, and forced emulsification was performed by high-speed stirring (rotation speed 15000 rpm) using a homogenizer.
Subsequently, methyl ethyl ketone and toluene were volatilized at a temperature of 50 ° C. using a rotary evaporator to obtain a dispersion liquid. The solid content concentration of the dispersion was adjusted to 60%.
The glass container was set in a water bath set to a water temperature of 30 ° C., and 313 g of water was added. Hydrochloric acid was added to the water in the container to adjust the pH of the aqueous solution to 4. To the aqueous solution, 6.25 g of an aqueous solution of a hexamethylol melamine initial polymer (Milben Resin SM-607, manufactured by Showa Denko KK, solid content concentration 80% by mass) was added and dissolved. After adding 47.2 g of the dispersion liquid to the solution and stirring, 625 g of water was added to prepare a mixed liquid.
While stirring the mixture, the temperature of the mixture was raised to 70 ° C. at a rate of 1 ° C./min, and the mixture was further stirred for 2 hours. Subsequently, the pH of the mixed solution was adjusted to 7. The contents of the container were filtered, and the obtained solid was washed and dried to obtain organic-inorganic composite particles 26.
The organic-inorganic composite particles 26 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 47%, and the median diameter was 123 nm.

<Production example of organic-inorganic composite particles 27>
Organic-inorganic composite particles 27 were obtained in the same manner as in the production example of the organic-inorganic composite particles 1 except that the crystalline polyester 1 was not used and the weight of the styrene-acrylic copolymer 1 used was 10 g.
The organic-inorganic composite particles 27 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 59%, and the median diameter was 114 nm.

<Production example of organic-inorganic composite particles 28>
10 g of crystalline polyester 1 and 58.3 g of organosilica sol TOR-ST were put into a separable flask, and the temperature was raised to 130 ° C. over 1 hour in an oil bath while stirring at 200 rpm with a three-one motor. After holding at 130 ° C. for 1 hour, the mixture was slowly cooled at a rate of −15 ° C. per hour to prepare an organic-inorganic composite particle precursor. The obtained organic-inorganic composite particle precursor was in the form of a paste.
The organic-inorganic composite particle precursor was filled in a classic line P-6 (planetary bead mill, manufactured by Fritsch) together with a zirconia crushed ball (manufactured by Tosoh) having a diameter of 0.5 mm, and crushed at room temperature at 200 rpm for 4 hours. Then, an organic-inorganic composite particle dispersion (solid content: 50% by mass) was obtained. Then, it was filtered and dried to obtain organic-inorganic composite particles 28.
The organic-inorganic composite particles 28 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 40%, and the median diameter was 135 nm.

<Production example of organic-inorganic composite particles 29>
Organosilica sol IPA-ST (trade name: Organosilica sol IPA-ST, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm, solid weight ratio 30%, hydrophobicity 48 wt%) is used for 77.7 g instead of organosilica sol TOR-ST. Organic-inorganic composite particles 29 were obtained in the same manner as in the production example of the organic-inorganic composite particles 1 except for the above.
The organic-inorganic composite particles 29 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 47%, and the median diameter was 122 nm.

<Production example of organic-inorganic composite particles 30>
In a glass container, 5 g of crystalline polyester 1, 58.3 g of organosilica sol TOR-ST, and 30 g of methyl ethyl ketone were charged and heated to 65 ° C. to dissolve them.
Next, 200 g of a 0.01 mol / l sodium hydroxide aqueous solution at 60 ° C. was added, and forced emulsification was performed by high-speed stirring (rotation speed 15000 rpm) using a homogenizer.
Subsequently, a solution prepared by heating and dissolving 5 g of the styrene-acrylic copolymer 1 in 35 g of methyl ethyl ketone at 65 ° C. was added to the emulsified solution prepared by forced emulsification, and the mixture was stirred at high speed (rotation speed 15000 rpm) using a homogenizer. Subsequently, methyl ethyl ketone and toluene were volatilized with a rotary evaporator at a temperature of 50 ° C. to obtain a dispersion liquid of the organic-inorganic composite particles 30.
Subsequently, methyl ethyl ketone and toluene were volatilized with a rotary evaporator at a temperature of 50 ° C. to obtain a dispersion liquid of the organic-inorganic composite particles 30. Then, it was filtered and dried to obtain organic-inorganic composite particles 30.
The organic-inorganic composite particles 30 have a structure in which the inorganic fine particles are embedded in the resin particles, and the inorganic fine particles are not exposed on the surface of the organic-inorganic composite particles and are completely covered with the resin, and are included in the core. It had inorganic fine particles, the surface exposure of the shell was 100%, and the median diameter was 137 nm.

<Production example of organic-inorganic composite particles 31>
Organic-inorganic composite particles 31 in the same manner as in the production example of the organic-inorganic composite particles 1 except that 200 g of 0.05 mol / l sodium hydroxide aqueous solution was used instead of 200 g of 0.01 mol / l sodium hydroxide aqueous solution. Got
The organic-inorganic composite particles 31 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 63%, and the median diameter was 75 nm.

<Production example of organic-inorganic composite particles 32>
Organic-inorganic composite particles 32 in the same manner as in the production example of the organic-inorganic composite particles 1 except that 200 g of 0.001 mol / l sodium hydroxide aqueous solution was used instead of 200 g of 0.01 mol / l sodium hydroxide aqueous solution. Got
The organic-inorganic composite particles 32 have a structure in which inorganic fine particles are embedded in resin particles, and a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles, and the inorganic fine particles included in the core. The surface exposure rate of the shell was 58%, and the median diameter was 550 nm.
Table 1-1 shows the configurations and characteristics of the above-mentioned organic-inorganic composite particles 1 to 32.

<Manufacturing example of toner particles 1>
Amorphous polyester resin 1 by 100 parts by mass, magnetic iron oxide particles by 75 parts by mass, Fisher Tropush wax (C105 manufactured by Sazole Co., melting point: 105 ° C.) by 2 parts by mass, charge control agent (manufactured by Hodoya Chemical Co., Ltd., After premixing 2 parts by mass of T-77) with a Henshell mixer, the melt temperature at the discharge port is set to 150 ° C. using a twin-screw extruder (trade name: PCM-30, manufactured by Ikekai Iron Works Co., Ltd.). The temperature was set so as to be, and the mixture was melt-kneaded.
The obtained kneaded product was cooled, roughly pulverized with a hammer mill, and then finely pulverized using a crusher (trade name: Turbo Mill T250, manufactured by Turbo Industries, Ltd.). The obtained finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 1 having a weight average particle size of 7.2 μm.

<Manufacturing example of toner 1>
The external addition of the organic-inorganic composite fine particles to the toner particles 1 was performed by a dry method. To a Henschel mixer, 100 parts by mass of toner particles 1, 3 parts by mass of organic-inorganic composite particles 1 and fumed silica (BET specific surface area: 200 m2 / g) were added by 1.5 parts by mass and mixed externally. Then, it was sieved with a mesh having an opening of 150 μm to obtain a toner 1 in which the organic-inorganic composite particles 1 were externally added to the toner particles 1.

<Manufacturing example of toners 2 to 24>
Toners 2 to 24 were obtained in the same manner as in the production example of the toner 1 except that the organic-inorganic composite particles 2 to 24 were used instead of the organic-inorganic composite particles 1.

<Manufacturing example of comparative toner 1>
Comparative toner 1 was obtained in the same manner as in the production example of toner 1 except that the organic-inorganic composite particles 25 were used instead of the organic-inorganic composite particles 1.

<Manufacturing examples of comparative toners 2 to 8>
Comparative toners 2 to 8 were obtained in the same manner as in the production example of the comparative toner 1 except that the organic-inorganic composite particles 26 to 32 were used instead of the organic-inorganic composite particles 25.

<Example 1>
The following evaluation was carried out using toner 1.
<Evaluation of low temperature fixability of toner>
A commercially available magnetic one-component printer HP LaserJet Enterprise600 M603dn (manufactured by Hewlett-Packard Company: process speed 350 mm / s) was used. This evaluation machine was modified so that the fixing temperature of the fixing device could be set arbitrarily.
Using this device, the temperature of the fuser is adjusted every 5 ° C in the range of 180 ° C or higher and 220 ° C or lower so that the image density on the bonded paper (75 g / m ² ) becomes 0.60 to 0.65. Outputs a halftone image to. The obtained image is rubbed 5 times with Sylbon paper loaded with 4.9 kPa, and the lowest temperature at which the density reduction rate of the image density before and after rubbing is 10% or less is measured, and the rank is as follows. Divided into. The lower this temperature, the better the low temperature fixing property.
Rank 10: Less than 180 ° C Rank 9: 180 ° C or more and less than 185 ° C Rank 8: 185 ° C or more and less than 190 ° C Rank 7: 190 ° C or more and less than 195 ° C Rank 6: 195 ° C or more and less than 200 ° C Rank 5: 200 ° C or more and 205 ° C Less than Rank 4: 205 ° C or more and less than 210 ° C Rank 3: 210 ° C or more and less than 215 ° C Rank 2: 215 ° C or more and less than 220 ° C Rank 1: 220 ° C or more In the above rank, if Rank 6 or more, organic-inorganic composite particles It was judged that the low temperature fixability of the toner externally added was good. The evaluation results are shown in Table 1-2.

<Evaluation of toner storage stability>
10 g of toner 1 was placed in a 100 ml poly cup, and the degree of cohesion after being left at 50 ° C. for 3 days was measured and divided into the following ranks. The smaller this value is, the better the fluidity is.
Rank 10: 10% or less Rank 9: 10% or more and less than 15% Rank 8: 15% or more and less than 20% Rank 7: 20% or more and less than 25% Rank 6: 25% or more and less than 30% Rank 5: 30% or more and 35% Less than Rank 4: 35% or more and less than 40% Rank 3: 40% or more and less than 45% Rank 2: 45% or more and less than 50% Rank 1: 50% or more In the above rank, if Rank 5 or more, organic-inorganic composite particles are used. It was judged that the storage stability of the externally added toner was good. The evaluation results are shown in Table 1-2.

<Evaluation of storage stability of organic-inorganic composite particles>
10 g of the organic-inorganic composite particles 1 were placed in a 100 ml poly cup, and the degree of cohesion after being left at 50 ° C. for 3 days was measured and divided into the following ranks. The smaller this value is, the better the fluidity is.
Rank 10: 10% or less Rank 9: 10% or more and less than 15% Rank 8: 15% or more and less than 20% Rank 7: 20% or more and less than 25% Rank 6: 25% or more and less than 30% Rank 5: 30% or more and 35% Less than Rank 4: 35% or more and less than 40% Rank 3: 40% or more and less than 45% Rank 2: 45% or more and less than 50% Rank 1: 50% or more In the above rank, if it is rank 5 or more, it is an organic-inorganic composite particle. It was judged that the storage stability was good. The evaluation results are shown in Table 1-2.
Good results were obtained for Example 1.

<Examples 2 to 24, Comparative Examples 1 to 8>
Using toners 2 to 24 and comparative toners 1 to 8, the low temperature fixability of the toner, the storage stability of the toner, and the storage stability of the organic-inorganic composite particles were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1-2.

From the results in Table 1, in Comparative Example 2 which is the prior art, the low temperature fixability of the toner externally added with the organic-inorganic composite particles is poor, and in Comparative Example 4 which is the prior art, the organic-inorganic composite particles and the externally added organic-inorganic composite particles are added. It can be seen that the storage stability of the used toner is poor. On the other hand, in Examples 1 to 12 of the present invention, good low-temperature fixing property of the toner externally added with the organic-inorganic composite particles and good storage stability of the organic-inorganic composite particles and the toner externally added thereto are obtained. It turns out that it can be done.

Further, from the comparison between Examples 1 and 12, by producing the organic-inorganic composite particles by the forced emulsification method instead of the polymerization method, better low-temperature fixing property of the toner externally added with the organic-inorganic composite particles can be obtained. It turns out that it can be done.

Furthermore, from the comparison between Example 1 and Example 13, it can be seen that even better storage stability can be obtained by using a crystalline polyester having an acid value of 5 mgKOH / g or less.

Further, from the comparison between Example 13 and Example 14, it can be seen that even better low temperature fixability can be obtained by using the crystalline polyester as the crystalline resin contained in the organic-inorganic composite particles.

Further, from the comparison between Examples 14 and 15 to 17, the content of the inorganic fine particles in the organic-inorganic composite particles is 50% by mass or more and 80% by mass or less, so that good storage stability and low-temperature fixing property can be obtained. It can be seen that even better storage stability and low temperature fixability can be obtained by obtaining 60% by mass or more and 80% by mass or less.

Furthermore, from the comparison between Examples 17 and 18, it can be seen that better storage stability can be obtained by including the inorganic fine particles contained in the core of the organic-inorganic composite particles.

Further, from the comparison between Examples 18 and 19 and 20, the exposed area of the shell is 30% or more and 70% or less with respect to the surface area of the organic-inorganic composite particles, so that good storage stability and low-temperature fixing property are obtained. It turns out that is obtained.

Further, from the comparison between Examples 19 and 21 and 22, the acid value of the styrene- (meth) acrylic acid copolymer contained in the shell is set to 10 mgKOH / g or more and 25 mgKOH / g or less to achieve good storage stability. It can be seen that the property and low temperature fixability can be obtained.

Furthermore, from the comparison between Examples 19, 21, 22 and Example 23, good storage stability and low temperature fixability can be obtained by using a styrene- (meth) acrylic acid copolymer as the vinyl resin contained in the shell. It turns out that it can be done.

Further, from the comparison between Examples 19, 21, 22, 23 and Example 24, it can be seen that good storage stability and low temperature fixability can be obtained by using a vinyl resin as the thermoplastic resin contained in the shell.

According to the present invention, it is possible to provide a toner having excellent low temperature fixability and storage stability.

Claims (21)

Toner particles having a binder resin and a colorant and toner having an external additive.
The external additive is an organic-inorganic composite particle containing inorganic fine particles, a crystalline resin and an amorphous thermoplastic resin.
The organic-inorganic composite particles have a core containing the crystalline resin and a shell containing the amorphous thermoplastic resin.
The degree of hydrophobicity of the inorganic fine particles is 50% or more, and at least a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles to form convex portions.
A toner characterized in that the median diameter of the organic-inorganic composite particles is 80 nm to 500 nm. The toner according to claim 1, wherein the thermoplastic resin is a vinyl resin. The toner according to claim 2, wherein the vinyl resin is a styrene- (meth) acrylic acid copolymer. The toner according to claim 3, wherein the acid value of the styrene- (meth) acrylic acid copolymer is 10 mgKOH / g or more and 25 mgKOH / g or less. The toner according to any one of claims 1 to 4, wherein the exposed area of the shell containing the thermoplastic resin is 30% or more and 70% or less with respect to the surface area of the organic-inorganic composite particles. The toner according to any one of claims 1 to 5, wherein the organic-inorganic composite particles contain inorganic fine particles contained in the core. The toner according to any one of claims 1 to 6, wherein the content of the inorganic fine particles in the organic-inorganic composite particles is 50% by mass or more and 80% by mass or less based on the mass of the organic-inorganic composite particles. The toner according to claim 7, wherein the content of the inorganic fine particles in the organic-inorganic composite particles is 60% by mass or more and 80% by mass or less based on the mass of the organic-inorganic composite particles. The toner according to any one of claims 1 to 8, wherein the crystalline resin is crystalline polyester. The toner according to claim 9, wherein the crystalline polyester has an acid value of 5 mgKOH / g or less. Organic-inorganic composite particles containing inorganic fine particles, crystalline resin, and amorphous thermoplastic resin.
The organic-inorganic composite particles have a core containing the crystalline resin and a shell containing the amorphous thermoplastic resin.
The degree of hydrophobicity of the inorganic fine particles is 50% or more, and at least a part of the inorganic fine particles is exposed on the surface of the organic-inorganic composite particles to form convex portions.
An organic-inorganic composite particle having an organic-inorganic composite particle having a median diameter of 80 nm to 500 nm. The organic-inorganic composite particle according to claim 11, wherein the thermoplastic resin is a vinyl resin. The organic-inorganic composite particle according to claim 12, wherein the vinyl resin is a styrene- (meth) acrylic acid copolymer. The organic-inorganic composite particle according to claim 13, wherein the acid value of the styrene- (meth) acrylic acid copolymer is 10 mgKOH / g or more and 25 mgKOH / g or less. The organic-inorganic composite particle according to any one of claims 11 to 14, wherein the exposed area of the shell containing the thermoplastic resin is 30% or more and 70% or less with respect to the surface area of the organic-inorganic composite particle. The organic-inorganic composite particle according to any one of claims 11 to 15, wherein the organic-inorganic composite particle contains inorganic fine particles included in the core. The organic-inorganic according to any one of claims 11 to 16, wherein the content of the inorganic fine particles in the organic-inorganic composite particles is 50% by mass or more and 80% by mass or less based on the mass of the organic-inorganic composite particles. Composite particles. The organic-inorganic composite particle according to claim 17, wherein the content of the inorganic fine particles in the organic-inorganic composite particles is 60% by mass or more and 80% by mass or less based on the mass of the organic-inorganic composite particles. The organic-inorganic composite particle according to any one of claims 11 to 18, wherein the crystalline resin is a crystalline polyester. The organic-inorganic composite particle according to claim 19, wherein the crystalline polyester has an acid value of 5 mgKOH / g or less. A method for producing an organic-inorganic composite particle for producing the organic-inorganic composite particle according to any one of claims 11 to 20.
The production method prepares a dispersion liquid containing inorganic fine particles, a crystalline resin, an amorphous thermoplastic resin and an organic solvent, mixes the dispersion liquid, a neutralizing agent and water, and stirs the emulsion liquid. A method for producing organic-inorganic composite particles, which comprises a step of forming the organic-inorganic composite particles by distilling off the organic solvent from the emulsion.