JP2009037206A - Toner, its manufacturing method, two-component developer, developing apparatus, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner suppressing environmental contamination, free from degradation of toner durability, securing a sufficiently wide color reproduction range even if applied to color toner and reducing characteristic variation among toner particles, and also to provide its manufacturing method, a two-component developer, a developing apparatus and an image forming apparatus. <P>SOLUTION: The toner containing at least binding resin has the biomass resin-containing domain 2 formed in the toner particle 1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a toner and a manufacturing method thereof, a two-component developer, a developing device, and an image forming apparatus.

  In an image forming apparatus using an electrophotographic system, a toner image is formed by supplying toner to an electrostatic latent image formed on the surface of a photoreceptor and developing the electrostatic latent image, and the toner image is formed on a recording medium. An image is formed by fixing. The toner used in such an image forming apparatus is manufactured by blending raw materials such as a colorant, a release agent, and a charge control agent in a binder resin, and granulating the mixture so as to obtain a predetermined particle size. Is done.

  Spent toner is buried or incinerated in the soil and discarded, but when incinerated, it is discharged by increasing the carbon dioxide, a greenhouse gas, in the atmosphere. There is also a possibility that metals contained in can become a source of environmental pollution. Therefore, many toners that can be disposed of while suppressing environmental pollution have been proposed.

  For example, Patent Document 1 discloses a toner including at least a binder resin, a colorant, a charge control agent, and a biodegradable resin, and a toner including a photodecomposition agent. Since the toner disclosed in Patent Document 1 contains a biodegradable resin, when the toner is buried in the soil and discarded, the toner is decomposed and environmental pollution can be suppressed. However, biodegradable resins have poor grindability and are difficult to make into fine particles. Therefore, it is difficult to produce a small particle size toner for forming a high quality and high resolution image.

  In order to solve such problems, Patent Document 2 discloses that a biodegradable resin and a colorant are dissolved or dispersed in an organic solvent to prepare a color liquid, and the color liquid and an aqueous medium are mixed. Thus, a toner manufacturing method for producing colored resin fine particles is disclosed. By producing the toner by the method disclosed in Patent Document 2, even a biodegradable resin having poor pulverization properties can be easily made into fine particles, and a toner having a small particle diameter can be produced.

JP-A-4-218063 JP 2004-177554 A

  FIG. 8 is a cross-sectional view of toner particles 51 in the prior art. In the toner disclosed in Patent Document 1, since the binder resin and the biodegradable resin are once melted or softened and then mixed and cooled, the biodegradable resin is crystallized and dispersed in the toner particles in a sea island state. The That is, in the toner disclosed in Patent Document 1, as shown in FIG. 8, island components composed of biodegradable resins 52 of various sizes are individually identified in the toner particles 51 that are sea components. It is scattered in an irregular state that cannot be done.

  In such a toner, the toner is easily cracked from the interface between the binder resin and the biodegradable resin, and the biodegradable resin cannot be contained in the toner particles in a high ratio. Further, since the crystallized portion of the biodegradable resin is various in size and is very complicated, the transparency of the toner is reduced. As a result, when applied to color toner, the color reproduction width is narrowed. Further, since the biodegradable resin is not uniformly dispersed and the toner composition is non-uniform, the characteristics of the toner particles vary, and the toner physical properties such as charging characteristics cannot be controlled.

  In the toner production method disclosed in Patent Document 2, a biodegradable resin is melted or softened in an organic solvent, and phase-inverted and emulsified in an aqueous medium to obtain a toner. In such a toner, since a biodegradable resin is contained as a binder resin, it is crystallized by heat at the time of fixing to a recording medium, resulting in a decrease in transparency, and color reproduction when applied to a color toner. The width becomes narrower. Moreover, durability is also low.

  In order to solve the above-described problems, an object of the present invention is to provide a toner capable of suppressing environmental pollution. Another object of the present invention is to sufficiently prevent toner contamination while at the same time suppressing environmental contamination. Furthermore, an object of the present invention is to provide a toner that ensures a sufficient color reproduction width as a color toner.

  Another object of the present invention is to provide a toner for achieving the above-described object, a manufacturing method for obtaining the toner, a developer using the toner, a developing device for developing using the developer, and the developing device. An image forming apparatus is provided.

The present invention is a toner containing at least a binder resin,
A toner characterized in that a domain containing a biomass resin is formed in toner particles.

  Further, the present invention is characterized in that the domain containing the biomass resin is substantially spherical or a conjugate thereof.

The present invention is also characterized in that the biomass resin is a crystalline resin.
The present invention is also characterized in that the biomass resin content is 20 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the toner.

  Moreover, the present invention is characterized in that a colorant is not contained in the domain containing the biomass resin.

  The present invention is also characterized in that the domain diameter of the domain containing the biomass resin is 1 μm or less.

  In the present invention, the domain diameter of the domain containing the biomass resin is 0.5 μm or more and 1 μm or less.

In the invention, the binder resin is a polyester resin.
The present invention is also characterized in that the surface of the toner is covered with a resin film.

  The present invention is also characterized in that the resin film is formed of a styrene acrylic resin produced by an emulsion polymerization method.

The present invention also includes a binder resin particle dispersion step in which at least a binder resin is dispersed in a liquid medium to obtain a binder resin particle slurry.
A biomass resin particle dispersion step of dispersing at least a biomass resin in a liquid medium to obtain a biomass resin particle slurry; and
A toner manufacturing method comprising: a binder resin particle slurry and a biomass resin particle slurry mixed, and a coagulation step of aggregating the binder resin particles and the biomass resin particles.

The present invention is also characterized in that the binder resin particles contain a colorant.
Further, the present invention further includes a colorant particle dispersion step of obtaining a colorant particle slurry by dispersing at least a colorant in a liquid medium,
In the aggregation step, the binder resin particle slurry, the biomass resin particle slurry, and the colorant particle slurry are mixed, and the binder resin particles, the biomass resin particles, and the colorant particles are aggregated.

  The present invention is also characterized in that the particle diameter of the binder resin particles is ¼ or more and ½ or less of the particle diameter of the biomass resin particles.

In the present invention, the biomass resin particle dispersing step
A fine granulation step for producing a biomass resin particle slurry under heat and pressure;
A depressurization step of depressurizing the biomass resin particle slurry in a heated and pressurized state;
A cooling step of cooling the decompressed biomass resin particle slurry.

  In addition, the present invention is characterized in that the biomass resin particle dispersion step is performed by a high-pressure homogenizer method.

  The present invention also provides a toner manufactured by the toner manufacturing method.

  According to another aspect of the present invention, there is provided a two-component developer comprising the toner and a carrier.

In addition, the present invention is a developing device that performs development using a developer containing the toner or the two-component developer.
The present invention also provides an image forming apparatus comprising the developing device.

  According to the present invention, since the domain containing the biomass resin is formed and dispersed in the toner particles, the biomass resin can be prevented from being dispersed in the toner particles in the sea island state. Therefore, the biomass resin can be contained in the toner particles at a high ratio without reducing the durability of the toner, and environmental pollution can be suppressed. Further, since it can prevent white turbidity due to crystallization of biomass resin, it does not reduce the transparency of the toner, and even when applied to a color toner, a sufficient color reproduction width can be secured, and toner particles It is possible to suppress variations in characteristics between the two.

  According to the present invention, the domain containing the biomass resin is substantially spherical or a combination thereof. By making the shape of the domain containing the biomass resin substantially constant, it is possible to reduce the characteristic difference between the toner particles.

  According to the invention, the biomass resin is a crystalline resin. Since the crystalline resin generally has a sharp melt property as compared with the amorphous resin, the toner containing the crystalline resin can improve the storage stability while maintaining the fixing temperature.

  According to the invention, the biomass resin content is 20 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the toner. Thereby, the effect of suppressing environmental pollution by biomass resin is sufficiently exhibited. Further, by setting the biomass resin content to 60 parts by weight or less, sufficient toner durability can be obtained.

  Moreover, according to this invention, the coloring agent is not contained in the domain containing biomass resin. When the biomass resin contains a colorant, the biomass resin is reinforced by the filling effect of the colorant to increase the hardness and the softening point. By not containing a colorant in the domain containing the biomass resin, it is possible to prevent an increase in the softening point of the biomass resin. Decrease can be prevented.

  Moreover, according to this invention, the domain diameter of the domain containing biomass resin is 1 micrometer or less. By setting the domain diameter to 1 μm or less, it is possible to prevent the domain diameter from becoming too large and increasing the particle diameter of the toner particles. Therefore, a toner having a small particle diameter can be produced. Further, by setting the domain diameter to 1 μm or less, a toner having excellent transparency can be obtained. Furthermore, since the rate at which the biomass resin is exposed to the toner surface can be kept low, the storage stability of the toner can be maintained at a high level, and the rate at which the biomass resin contacts the recording medium during fixing is increased. It is possible to prevent the toner fixability from deteriorating.

  Moreover, according to this invention, the domain diameter of the domain containing biomass resin is 0.5 micrometer or more and 1 micrometer or less. By making the domain diameter 0.5 μm or more, the domain diameter becomes too small to prevent the binder resin and the biomass resin from being compatibilized by heating when forming a domain containing the biomass resin. Can do. Therefore, the glass transition temperature (Tg) of the binder resin can be prevented from being lowered, and the storage stability of the toner can be prevented from being lowered.

  According to the invention, the binder resin is a polyester resin. As a result, a toner having excellent transparency and durability can be obtained.

  According to the invention, the surface of the toner is covered with the resin film. Thereby, the durability of the toner can be further improved.

  Moreover, according to this invention, a resin film is formed with the styrene acrylic resin produced by the emulsion polymerization method. Since the styrene acrylic resin produced by emulsion polymerization has a small resin particle size and is uniform, a uniform and thin resin film can be formed when it is coated on the toner surface. In addition, since the styrene acrylic resin has a low content of polar groups such as ester bonds, the hygroscopic property is small, and the stability of charging of the toner can be improved even in a high humidity environment.

  According to the invention, the binder resin particle slurry and the biomass resin particle slurry are mixed, and the binder resin particles and the biomass resin particles are aggregated. Therefore, the biomass resin can be dispersed in the toner particles in a state where the binder resin and the biomass resin are not compatible. As a result, the biomass resin can be contained in the toner particles at a high ratio without reducing the durability of the toner, and environmental pollution can be suppressed. Moreover, biomass resin may become cloudy once it is melted and cooled. Since the domain including the biomass resin is formed by aggregating the binder resin particles and the biomass resin particles, the melting of the biomass resin can be suppressed. Therefore, the cloudiness of the biomass resin can be suppressed, and the toner transparency can be prevented from being lowered. As a result, the toner can be effectively used as a raw material for color toners that particularly require toner transparency.

  According to the invention, the binder resin particles contain a colorant. Therefore, the dispersion of the colorant in the toner particles can be improved, and the color development and the saturation can be improved.

  In addition, according to the present invention, it further includes a colorant particle dispersion step in which at least a colorant is dispersed in a liquid medium to obtain a colorant particle slurry. In the aggregation step, the binder resin particle slurry, the biomass resin particle slurry, The colorant particle slurry is mixed to agglomerate the binder resin particles, the biomass resin particles, and the colorant particles. Therefore, it becomes easy to control the shape of the toner particles. In addition, since there is no step of previously kneading the colorant into the binder resin, the manufacturing process can be simplified.

  Moreover, according to this invention, the particle diameter of binder resin particle is 1/4 or more and 1/2 or less with respect to the particle diameter of biomass resin particle. Thereby, it is possible to prevent the particle diameter of the binder resin particles having an effect of maintaining the durability of the toner from becoming too small. Therefore, it is possible to prevent the toner from being deteriorated. Further, it is possible to prevent the biomass resin domains dispersed in the toner particles from being brought into contact with each other due to the domain diameter becoming too large. Therefore, it is possible to prevent the toner from being deteriorated.

  Moreover, it can prevent that binder resin and biomass resin compatibilize because the particle diameter of binder resin particle shall be 1/4 or more with respect to the particle diameter of biomass resin particle. Therefore, the glass transition temperature (Tg) of the binder resin can be prevented from being lowered, and the storage stability of the toner can be prevented from being lowered. Furthermore, since the particle diameter of the binder resin particles is ½ or less than the particle diameter of the biomass resin particles, the ratio of the biomass resin exposed to the toner surface during long-term running can be kept low. The durability of the toner can be maintained in a high state, and the ratio of the biomass resin to contact with the recording medium at the time of fixing can be prevented from increasing, thereby preventing the toner fixing property from being lowered.

  According to the present invention, when producing a biomass resin particle slurry, first, the biomass resin is pulverized under heat and pressure conditions and dispersed in a liquid medium to obtain a dispersion. Next, the dispersion under heating and pressurizing conditions is decompressed and cooled to produce a biomass resin particle slurry. Since the biomass resin is pulverized under heating and pressing conditions, the biomass resin can be pulverized efficiently. In addition, when the biomass resin is cooled over a long time after being heated, it may become cloudy. The dispersion containing the biomass resin under heating and pressing conditions is forcibly reduced in pressure and cooled, so that the biomass resin can be prevented from becoming clouded and the transparency of the toner is prevented from being lowered. be able to.

  According to the invention, the biomass resin particle slurry is produced by a high pressure homogenizer method. Thereby, the biomass resin can be pulverized in a state where the particle diameter is small and the width of the particle size distribution is small.

  According to the present invention, since the toner is obtained by the toner manufacturing method, the domain containing the biomass resin has a particle diameter within a certain range and is dispersed almost uniformly in the toner particles. Therefore, the biomass resin can be contained in the toner particles at a high ratio without reducing the durability of the toner, and environmental pollution can be suppressed. Further, since it can prevent white turbidity due to crystallization of biomass resin, it does not reduce the transparency of the toner, and even when applied to a color toner, a sufficient color reproduction width can be secured, and toner particles It is possible to suppress variations in characteristics between the two.

  According to the invention, the two-component developer includes the toner and a carrier. Therefore, it is possible to obtain a two-component developer that suppresses environmental contamination without deteriorating the durability of the toner. Furthermore, since the two-component developer includes the toner, which is a highly transparent toner that can be applied to a color toner, a two-component developer capable of forming a high-quality image with high transparency is obtained. be able to.

  According to the invention, the developing device performs development using the developer containing the toner or the two-component developer. Therefore, it is possible to form a high-quality toner image on the photoconductor, and to suppress environmental contamination.

  According to the invention, an image forming apparatus includes the developing device. Therefore, a high-quality image with high transparency can be formed. In addition, toner that is no longer needed during image formation is collected and discarded, but environmental contamination due to the waste toner can be suppressed.

  FIG. 1 is a diagram showing a cross section of toner particles 1 according to an embodiment of the present invention. Moreover, FIG. 2 is a figure which shows the cross-sectional shape of the domain 2 containing biomass resin. The toner of the present invention is a toner containing at least a biomass resin and a binder resin, and is a toner in which a domain 2 containing a biomass resin is formed in toner particles 1.

  In the present invention, the domain 2 containing the biomass resin is preferably approximately spherical or a combination thereof. Such a shape cannot be obtained by a method of manufacturing toner particles containing a biodegradable resin by once melting or softening a binder resin and a biodegradable resin as in the prior art. It can be obtained by the production method of the invention.

  Here, the substantially spherical shape or a combination thereof is a sphere whose cross-sectional shape is a circle as shown in FIG. 2 (a), an ellipsoid whose cross-sectional shape is an ellipse as shown in FIG. 2 (b), or a cross-sectional shape. Is an oval body having an oval shape as shown in FIG. 2 (c), a combined body in which two spheres having a cross-sectional shape as shown in FIG. 2 (d) are joined, and a cross-sectional shape is shown in FIG. 2 (e). And a combination of three spheres having a shape as shown in FIG. Moreover, although the example which the some spherical body couple | bonded as a coupling body was shown, the form which the ellipsoid couple | bonded may be sufficient, for example, and the form which the sphere and the ellipsoid couple | bonded may be sufficient. In addition, the shape of the domain 2 containing the biomass resin described above is conceptual, and includes shapes close to these shapes, for example, shapes close to a sphere or ellipsoid whose center is biased. By making the shape of the domain 2 containing the biomass resin substantially constant, the characteristic difference between the toner particles 1 can be reduced. In addition, the domain diameter of the domain 2 containing the biomass resin which is a substantially spherical shape or a combination thereof is calculated in terms of the diameter of a circle having the same area as the cross-sectional area of the domain.

  In the present invention, the biomass resin is a resin containing, as a raw material, a compound having a skeleton of carbon atoms fixed by plants by photosynthesis from carbon dioxide in the atmosphere. Therefore, even if the biomass resin is burned and carbon dioxide is generated, it is possible to substantially suppress the increase of carbon dioxide in the atmosphere. Therefore, it can be said that the toner containing biomass resin is a toner that can be discarded while suppressing environmental pollution.

  Biomass resins are broadly divided into natural product resins that can be used as polymers, chemically synthesized resins that chemically polymerize biomass-derived polymers and monomers, and microbial-produced resins that are polymerized in the body of microorganisms. Is done. Examples of the natural product resin include cellulose acetate, esterified starch, chitosan, fibroin, collagen, gelatin, and natural rubber. Examples of the chemically synthesized resin include polylactic acid, polyglycol, polymethylene terephthalate, and polybutylene succinate. Examples of the microorganism-producing resin include polyhydroxybutyrate, polyhydroxyalkanoate, bacterial cellulose, and polyglutamic acid. The biomass resin is not particularly limited, and is synthesized using, for example, polylactic acid, polymethylene terephthalate, polybutylene succinate, polyhydroxybutyrate, polyhydroxyalkanoate, succinic acid, 1,3-propanediol or itaconic acid as a monomer. The polyester etc. which can be used can be used, and 1 type may be used independently or 2 or more types may be used together.

  Biomass resins can be either crystalline or not, and both can be used, but crystalline resins are preferred. Since the crystalline resin generally has a sharp melt property as compared with the amorphous resin, the toner containing the crystalline resin can improve the storage stability while maintaining the fixing temperature. Examples of the crystalline material include polylactic acid, polymethylene terephthalate, polybutylene succinate, polyhydroxybutyrate, polyhydroxyalkanoate, and the like, and polyesters synthesized from monomers include crystalline materials.

  There are two types of biomass resins, one that is hardly degradable and one that is biodegradable, but both can be used. Examples of the biomass resin exhibiting hardly decomposability include soybean polyol which is a polyol derived from soybean oil, polyester using 1,3 propanediol obtained by fermentation method and terephthalic acid derived from fossil resources as raw materials. Biodegradable biomass resins include polybutyric acids, aliphatic polyesters, copolymers of aromatic polyesters and aliphatic polyesters, copolymers of aliphatic polyesters and polyamides, polylactic acid, polylactic acid and aliphatic polyesters. A copolymer etc. are mentioned. Specific examples of the biodegradable resin include the following. Poly (3-hydroxybutyric acid), 3-hydroxybutyric acid and 3-hydroxyvaleric acid copolymer, polybutyric acid such as 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, lactide, glycolide, β-propio Aliphatic polyester compounds which are ring-opening polymers such as lactone, γ-valerolactone, ε-caprolactone, polyesters composed of adipic acid and 1,4-butanediol, polyesters composed of oxalic acid and 1,4-butanediol, Examples thereof include polyesters composed of an aliphatic dibasic acid and an aliphatic diol, such as a polyester composed of an acid and 1,6-hexanediol.

  As the copolymer of the aliphatic polyester and the aromatic polyester, the above-described aliphatic polyester compound, or an aromatic such as 1 to 50% by mass of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid when synthesizing these compounds. Examples thereof include resins obtained by reacting an aromatic oxycarboxylic acid such as dicarboxylic acid, P-hydroxybenzoic acid, P-hydroxyethylbenzoic acid, and P-hydroxyphenylacetic acid. The copolymer of polylactic acid and aliphatic polyester includes polylactic acid and ethylene glycol, 1,2-butylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, triethylene glycol, dipropylene glycol. , Dibutanediol, polytetramethylene glycol and other polyhydric alcohols and oxalic acid, methylglutaric acid, adipic acid, azelaic acid, sebacic acid, brassic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, maleic anhydride, fumaric acid, etc. And an aliphatic polyester copolymer obtained from the polyvalent carboxylic acid. As the biodegradable resin, it is preferable to use polybutyric acid, polylactic acid, and a copolymer of polylactic acid and aliphatic polyester among the resins described above.

  The binder resin is not particularly limited as long as it can be granulated in a molten state. For example, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyamide, styrene polymer, (meth) acrylic resin, polyvinyl butyral, Examples thereof include silicone resins, polyurethanes, epoxy resins, phenol resins, xylene resins, rosin-modified resins, terpene resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, and aromatic petroleum resins. A synthetic resin can be used individually by 1 type, or can use 2 or more types together. Among these, polyesters, styrene polymers, (meth) acrylic acid polymers, polyurethanes, epoxy resins, and the like that can easily obtain particles having high surface smoothness by wet granulation in water are preferable.

  Known polyesters can be used, and examples thereof include polycondensates of polybasic acids and polyhydric alcohols. As the polybasic acid, those known as polyester monomers can be used, for example, terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid and other aromatic carboxylic acids, maleic anhydride Examples thereof include aliphatic carboxylic acids such as acid, fumaric acid, succinic acid, alkenyl succinic anhydride, and adipic acid, and methyl esterified products of these polybasic acids. A polybasic acid can be used individually by 1 type, or can use 2 or more types together. As the polyhydric alcohol, those known as polyester monomers can be used. For example, aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, hexanediol, neopentylglycol, glycerin, cyclohexanediol, cyclohexanedimethanol And aromatic diols such as alicyclic polyhydric alcohols such as hydrogenated bisphenol A, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, and the like. A polyhydric alcohol can be used individually by 1 type, or can use 2 or more types together. The polycondensation reaction between the polybasic acid and the polyhydric alcohol can be carried out according to a conventional method. For example, the polybasic acid and the polyhydric alcohol are contacted in the presence or absence of an organic solvent and in the presence of a polycondensation catalyst. The process is terminated when the acid value, softening point, etc. of the polyester to be produced reach a predetermined value. Thereby, polyester is obtained. When a methyl esterified product of a polybasic acid is used as a part of the polybasic acid, a demethanol polycondensation reaction is performed. In this polycondensation reaction, for example, the carboxyl group content at the end of the polyester can be adjusted by appropriately changing the mixing ratio of polybasic acid and polyhydric alcohol, the reaction rate, etc., and thus the properties of the resulting polyester are modified. it can. When trimellitic anhydride is used as the polybasic acid, a modified polyester can also be obtained by easily introducing a carboxyl group into the main chain of the polyester. A self-dispersible polyester in water in which a hydrophilic group such as a carboxyl group or a sulfonic acid group is bonded to the main chain and / or side chain of the polyester can also be used.

  Examples of the styrenic polymer include homopolymers of styrenic monomers and copolymers of styrene monomers and monomers copolymerizable with styrenic monomers. Examples of the styrene monomer include styrene, o-methyl styrene, ethyl styrene, p-methoxy styrene, p-phenyl styrene, 2,4-dimethyl styrene, pn-octyl styrene, pn-decyl styrene, p. -N-dodecyl styrene etc. are mentioned. Examples of monomers copolymerizable with the styrenic monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, ( (Meth) acrylates such as n-octyl acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc. ) (Meth) acrylic monomers such as acrylic esters, acrylonitrile, methacrylamide, glycidyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 2-hydroxyethyl acrylate, vinyl methyl ether, vinyl ethyl ether Vinyl ethers such as vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone, vinyl ketones such as methyl isopropenyl ketone, N- vinylpyrrolidone, N- vinyl carbazole, etc. N- vinyl compounds such as N- vinyl indole, and the like. The styrene monomer and the monomer copolymerizable with the styrene monomer can be used alone or in combination of two or more.

  Examples of the (meth) acrylic resin include homopolymers of (meth) acrylic acid esters, copolymers of (meth) acrylic acid esters and monomers copolymerizable with (meth) acrylic acid esters, and the like. As the (meth) acrylic acid esters, the same ones as described above can be used. Examples of the monomer copolymerizable with (meth) acrylic acid esters include (meth) acrylic monomers, vinyl ethers, vinyl ketones, and N-vinyl compounds. These can be the same as those described above. As the (meth) acrylic resin, an acidic group-containing acrylic resin can also be used. The acidic group-containing acrylic resin is, for example, an acrylic resin monomer or an acrylic resin monomer containing an acidic group or a hydrophilic group and / or a vinyl having an acidic group or a hydrophilic group when an acrylic resin monomer or an acrylic resin monomer and a vinyl monomer are polymerized. It can manufacture by using together a system monomer. Known acrylic resin monomers can be used, for example, acrylic acid that may have a substituent, methacrylic acid that may have a substituent, acrylic ester that may have a substituent, and a substituent. Methacrylic acid ester and the like. Acrylic resin monomers can be used alone or in combination of two or more. As the vinyl monomer, known monomers can be used, and examples thereof include styrene, α-methylstyrene, vinyl bromide, vinyl chloride, vinyl acetate, acrylonitrile and methacrylonitrile. A vinyl monomer can be used individually by 1 type, or can use 2 or more types together. Polymerization of the styrene-based polymer and the (meth) acrylic resin is performed by solution polymerization, suspension polymerization, emulsion polymerization or the like using a general radical initiator.

  Although it does not restrict | limit especially as a polyurethane, For example, an acidic group or a basic group containing polyurethane can be used preferably. The acidic group or basic group-containing polyurethane can be produced according to a known method. For example, an acid group or basic group-containing diol, polyol and polyisocyanate may be subjected to addition polymerization. Examples of the acidic group or basic group-containing diol include dimethylolpropionic acid and N-methyldiethanolamine. Examples of the polyol include polyether polyols such as polyethylene glycol, polyester polyols, acrylic polyols, and polybutadiene polyols. Examples of the polyisocyanate include tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Each of these components can be used alone or in combination of two or more. Although it does not restrict | limit especially as an epoxy resin, An acidic group or a basic group containing epoxy resin can be used preferably. An acidic group or basic group-containing epoxy resin is produced, for example, by adding or addition polymerizing a base epoxy resin with a polycarboxylic acid such as adipic acid and trimellitic anhydride or an amine such as dibutylamine or ethylenediamine. be able to.

  Among these binder resins, polyester is preferable. Polyester is excellent in transparency and can provide a toner excellent in durability. Further, polyester and acrylic resin may be grafted. Binder resins can be used alone or in combination of two or more different types. Furthermore, even if it is the same resin, multiple types which are different in any or all of molecular weight, monomer composition, etc. can be used.

In the present invention, a self-dispersing resin may be used as the binder resin. The self-dispersing resin is a resin having a hydrophilic group in the molecule and dispersibility with respect to a liquid such as water. Examples of the hydrophilic group include a —COO— group, —SO ₃ — group, —CO group, —OH group, —OSO ₃ — group, —PO ₃ H ₂ group, —PO ₄ — group, and salts thereof. Is mentioned. Among these, an anionic hydrophilic group such as —COO— group and —SO ₃ — group is particularly preferable. Such a self-dispersing resin having one or more hydrophilic groups is dispersed in water without using a dispersing agent or using only a very small amount of a dispersing agent. Although the amount of the hydrophilic group contained in the self-dispersing resin is not particularly limited, it is preferably 0.001 to 0.050 mol, more preferably 0.005 to 0.030 mol with respect to 100 g of the self-dispersing resin. It is. The self-dispersing resin can be produced, for example, by bonding a compound having a hydrophilic group and an unsaturated double bond (hereinafter referred to as “hydrophilic group-containing compound”) to the resin. Bonding of the hydrophilic group-containing compound to the resin can be performed according to a technique such as graft polymerization or block polymerization. The self-dispersing resin can also be produced by polymerizing a hydrophilic group-containing compound or a hydrophilic group-containing compound and a compound copolymerizable therewith.

  Examples of the resin that binds the hydrophilic group-containing compound include polystyrene, poly-α-methylstyrene, chloropolystyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, and styrene- Vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylic acid ester-methacrylic acid ester copolymer Polymer, styrene-α-chloromethyl acrylate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, styrene resin such as styrene-vinyl methyl ether copolymer, (meth) acrylic resin, polycarbonate, polyester, Polyethylene, polyethylene Polypropylene, polyvinyl chloride, epoxy resin, urethane modified epoxy resin, silicone modified epoxy resin, rosin modified maleic acid resin, ionomer resin, polyurethane, silicone resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyral Terpene resin, phenol resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, and the like.

  Examples of the hydrophilic group-containing compound include an unsaturated carboxylic acid compound and an unsaturated sulfonic acid compound. Examples of the unsaturated carboxylic acid compound include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid and isocrotonic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid and citraconic acid, Acid anhydrides such as maleic anhydride and citraconic anhydride, their alkyl esters, dialkyl esters, alkali metal salts, alkaline earth metal salts, ammonium salts and the like can be mentioned. As the unsaturated sulfonic acid compound, for example, styrene sulfonic acids, sulfoalkyl (meth) acrylates, metal salts thereof, ammonium salts, and the like can be used. A hydrophilic group containing compound can be used individually by 1 type, or can use 2 or more types together. Moreover, as a monomer compound other than the hydrophilic group-containing compound, for example, a sulfonic acid compound can be used. Examples of the sulfonic acid compound include sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid, sulfosuccinic acid, sulfobenzoic acid, sulfosalicylic acid, their metal salts, and ammonium salts.

  The binder resin used in the present invention may contain one or more general synthetic resin additives. Specific examples of the additive for synthetic resin include, for example, inorganic fillers in various shapes (particulate, fibrous, scale-like), colorants, antioxidants, release agents, antistatic agents, charge control agents, Lubricants, heat stabilizers, flame retardants, anti-drip agents, UV absorbers, light stabilizers, light-shielding agents, metal deactivators, anti-aging agents, lubricants, plasticizers, impact strength improvers, compatibilizers, etc. It is done.

  The toner of the present invention may contain a colorant in addition to the biomass resin and the binder resin. The colorant is not particularly limited, and for example, organic dyes, organic pigments, inorganic dyes, inorganic pigments, and the like can be used. Examples of the black colorant include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, magnetic ferrite, and magnetite. Examples of yellow colorants include chrome yellow, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, and Benzidine Yellow. GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 180, C.I. I. And CI Pigment Yellow 185.

  Examples of the orange colorant include red chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indanthrene brilliant orange RK, benzidine orange G, indanthrene brilliant orange GK, C.I. I. Pigment orange 31, C.I. I. And CI Pigment Orange 43. Examples of red colorants include bengara, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, risor red, pyrazolone red, watching red, calcium salt, lake red C, lake red D, brilliant carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.

  Examples of purple colorants include manganese purple, fast violet B, and methyl violet lake. Examples of the blue colorant include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated product, first sky blue, indanthrene blue BC, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. And CI Pigment Blue 60. Examples of the green colorant include chrome green, chromium oxide, pigment green B, micalite green lake, final yellow green G, and C.I. I. And CI Pigment Green 7. Examples of the white colorant include compounds such as zinc white, titanium oxide, antimony white, and zinc sulfide. One colorant can be used alone, or two or more different colorants can be used in combination. Moreover, even if it is the same color, 2 or more types can be used together.

  As will be described in detail later, the toner particles 1 in which the domains 2 including the biomass resin are formed are prepared by, for example, binding resin particle slurry prepared by dispersing at least a binder resin and biomass resin being dispersed. It can be obtained by agglomerating the biomass resin particle slurry.

FIG. 3 is a flowchart showing a first example of a method for producing toner particles 1.
[Binder resin particle dispersion process]
The binder resin particle dispersion step of step a1 is a step of producing a binder resin particle slurry by dispersing at least the binder resin in a liquid medium. The binder resin particle slurry may contain other toner components such as a release agent and a charge control agent. The release agent is added to impart releasability to the toner when fixing the toner to the recording medium. Therefore, compared with the case where a mold release agent is not used, the high temperature offset start temperature can be increased and the high temperature offset resistance can be improved. Further, the release agent is melted by heating at the time of fixing the toner, the fixing start temperature is lowered, and the low-temperature fixing property can be improved. The release agent is not particularly limited, and examples thereof include petroleum waxes such as paraffin wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, polyolefin wax and derivatives thereof, low molecular weight polypropylin wax and derivatives thereof. Derivatives, polyolefin polymer wax (low molecular weight polyethylene wax, etc.) and hydrocarbon synthetic waxes such as derivatives thereof, carnauba wax and derivatives thereof, rice wax and derivatives thereof, candelilla wax and derivatives thereof, plant waxes such as wood wax Animal waxes such as beeswax and spermaceti, oils and fats synthetic waxes such as fatty acid amides and phenol fatty acid esters, long chain carboxylic acids and derivatives thereof, long chain alcohols and derivatives thereof, silicone polymers, higher fatty acids, etc. And the like. Derivatives include oxides, block copolymers of vinyl monomers and waxes, graft modified products of vinyl monomers and waxes, and the like. A mold release agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The charge control agent is added in order to impart preferable chargeability to the toner. The charge control agent is not particularly limited, and those for positive charge control and negative charge control can be used. Examples of charge control agents for positive charge control include nigrosine dyes, basic dyes, quaternary ammonium salts, quaternary phosphonium salts, aminopyrines, pyrimidine compounds, polynuclear polyamino compounds, aminosilanes, nigrosine dyes and derivatives thereof, and triphenylmethane. Derivatives, guanidine salts, amidine salts and the like can be mentioned. As charge control agents for controlling negative charges, oil-soluble dyes such as oil black and spiron black, metal-containing azo compounds, azo complex dyes, metal salts of naphthenic acid, salicylic acid and its derivatives, metal complexes and metal salts (metal is Chromium, zinc, zirconium, etc.), fatty acid soaps, long-chain alkyl carboxylates, resin acid soaps, and the like. The charge control agent can be used alone or in combination of two or more as required.

  Dispersion of the binder resin particles in the liquid medium can be carried out by a known method without any particular limitation, but the step a1- (a) granulation step and the step a1- (b) decompression step And the cooling step of step a1- (c) is preferably performed by a high-pressure homogenizer method. Thereby, the binder resin can be pulverized in a state where the particle diameter is small and the width of the particle size distribution is small. In the present embodiment, the binder resin particle dispersion step is performed by a high-pressure homogenizer.

  The high-pressure homogenizer includes a tank, a pressurizing unit, a heater, a pulverizing nozzle, a decompression module, and a cooler. The tank is a container-like member having an internal space, and stores a dispersion liquid in which a binder resin is dispersed in a liquid medium. The pressure unit pressurizes the dispersion liquid of the binder resin. The heater heats the binder resin dispersion that is pressurized by the pressure unit. The crushing nozzle pulverizes the binder resin into binder resin particles by flowing a dispersion of the binder resin in a heated and pressurized state through a flow path formed therein, and the binder resin particles Make a slurry. The decompression module decompresses the binder resin particle slurry in a heated and pressurized state so that bubbles are not generated due to bumping. The cooler cools the binder resin particle slurry in a heated state. High pressure homogenizers are commercially available. Specific examples thereof include NANO3000 (trade name, manufactured by Migrain Co., Ltd.).

(Granulation process)
In the step a1- (a), the finely pulverizing step is a step in which the binder resin is pulverized and dispersed in a liquid medium to obtain a binder resin particle slurry. First, the dispersion liquid containing the binder resin is stored in a tank included in the high-pressure homogenizer. The liquid medium to be mixed with the binder resin is preferably a hydrophilic medium such as water or alcohol, and a dispersion stabilizer, a thickener, a surfactant and the like can be appropriately added. The dispersion liquid containing the binder resin stored in the tank is pressurized by the pressure unit, heated by the heater, and passed through the flow path formed in the pulverizing nozzle, so that the binder resin is coarsely crushed. Is done. The pressure and heating conditions of the binder resin dispersion at this time are not particularly limited, but are preferably 15 to 120 MPa and preferably 10 ° C. or higher and lower than the glass transition temperature (Tg) of the binder resin. The dispersion obtained by roughly pulverizing the binder resin further flows through a flow path formed in the pulverizing nozzle, whereby the binder resin is finely divided to obtain a binder resin particle slurry. Although the pressure heating conditions at this time are not particularly limited, it is preferable that the pressure is increased to 50 MPa to 250 MPa and heated to 50 ° C. or higher. Thus, since the binder resin is pulverized under pressure and heating conditions, the binder resin can be efficiently pulverized.

(Decompression step)
The depressurization step of step a1- (b) is a step of depressurizing the binder resin particle slurry in a pressurized and heated state. The binder resin particle slurry in a heated and pressurized state is depressurized to atmospheric pressure or a pressure close thereto by a depressurizing module so that bubbles are not generated due to bumping.

(Cooling process)
The cooling process of step a1- (c) is a process of cooling the binder resin particle slurry in a heated state. The binder resin particle slurry in a heated state is cooled in a relatively short time to about 20 to 40 ° C. by a cooler.

  In this way, a binder resin particle slurry is obtained. In this production method, the binder resin obtained by appropriately adjusting the pressure and / or temperature applied when the pulverizing nozzle is passed through, the solid content concentration in the binder resin particle slurry, the number of times of pulverization, etc. The particle size of the particles can be controlled. The volume average particle diameter of the binder resin particles is preferably 1 μm or less, and more preferably each condition is adjusted to be 0.01 to 1 μm. When the volume average particle diameter exceeds 1 μm, the particle size distribution of the finally obtained toner particles becomes wide, free particles are generated, and the toner performance and reliability are easily lowered.

[Biomass resin particle dispersion process]
The biomass resin particle dispersion step of step a2 is a step of producing a biomass resin particle slurry that is a slurry of biomass resin particles by dispersing the biomass resin in a liquid medium. Although dispersion | distribution of the biomass resin particle | grains to a liquid medium can be performed by a well-known method without being specifically limited, Step a2- (a) The granulation process and Step a2- (b) The decompression process It is preferable to carry out by a high-pressure homogenizer method including the cooling step of Step a2- (c). Thereby, the biomass resin can be pulverized in a state where the particle diameter is small and the width of the particle size distribution is small. In the present embodiment, the biomass resin particle dispersion step is performed by the high-pressure homogenizer used in the binder resin particle dispersion step described above.

(Granulation process)
In the step a2- (a), the fine granulation step is a step in which the biomass resin is pulverized and dispersed in a liquid medium to obtain a biomass resin particle slurry. The liquid medium to be mixed with the biomass resin is preferably a hydrophilic medium such as water or alcohol, like the liquid medium used in the binder resin particle dispersion step, and a dispersion stabilizer, a thickener, a surfactant, and the like are appropriately added. Can do. At this time, it is preferable not to add a colorant. When the biomass resin contains a colorant, the biomass resin is reinforced by the filling effect of the colorant to increase the hardness and the softening point. By not containing a colorant in the biomass resin particle slurry, the softening point of the biomass resin can be prevented from increasing, and when the toner is fixed by heating and pressurizing the recording medium, the fixability of the toner is reduced. Can be prevented. Similarly to the binder resin particle dispersion step, the dispersion containing the biomass resin flows through a crushing nozzle under pressure and heating conditions, and the biomass resin is pulverized and finely divided. obtain. Thus, since biomass resin is grind | pulverized on pressurization heating conditions, biomass resin can be grind | pulverized efficiently.

(Decompression step)
The depressurization step of Step a2- (b) is a step of depressurizing the biomass resin particle slurry in a pressurized and heated state. The biomass resin particle slurry in a heated and pressurized state is depressurized to atmospheric pressure or a pressure close thereto by a depressurization module so that bubbles are not generated due to bumping.

(Cooling process)
The cooling process of step a2- (c) is a process of cooling the biomass resin particle slurry in a heated state. The biomass resin particle slurry in a heated state is cooled in a relatively short time to about 20 to 40 ° C. by a cooler. As described above, the biomass resin particle slurry is forcibly cooled in a relatively short time, so that the crystallization of the biomass resin particles can be suppressed and the transparency of the toner can be prevented from being lowered. be able to.

  In this way, a biomass resin particle slurry is obtained. In this production method, by appropriately adjusting the pressure and / or temperature applied when the pulverizing nozzle is passed through, the solid content concentration in the biomass resin particle slurry, the number of times of pulverization, The particle size can be controlled. In the present invention, it is preferable to adjust each condition so that the volume average particle diameter of the biomass resin particles is preferably 0.5 μm or more and 1 μm or less. As will be described in detail later, the domain diameter of the domain 2 containing the biomass resin contained in the toner particles 1 can be controlled preferably to 1 μm or less, more preferably from 0.5 μm to 1 μm.

[Aggregation process]
In the aggregating step of step a3, a flocculant is added to the mixed slurry obtained by mixing the binder resin particle slurry and the biomass resin particle slurry, and the binder resin particles and the biomass resin particles are aggregated to form a slurry of toner particles 1. (Hereinafter referred to as “toner particle slurry”). In the agglomeration step, the mixed slurry is agitated using a granulating apparatus having a stirring vessel for storing the mixed slurry of the binder resin particle slurry and the biomass resin particle slurry, and a stirring means provided in the stirring vessel for stirring the slurry. To do.

  As a flocculant for aggregating the binder resin particles and the biomass resin particles, a monovalent salt, a divalent salt, a trivalent salt, or the like can be used. Examples of monovalent salts include cationic dispersants such as alkyltrimethylammonium chloride and inorganic salts such as sodium chloride, potassium chloride, and ammonium chloride. Examples of the divalent salt include magnesium chloride, calcium chloride, zinc chloride, copper (II) chloride, magnesium sulfate, and manganese sulfate. Examples of the trivalent salt include aluminum chloride and iron (III) chloride. Among the flocculants exemplified above, alkyltrimethylammonium chloride is preferable. Specific examples of alkyltrimethylammonium chloride include stearyltrimethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride, lauryltrimethylammonium chloride, and the like. A flocculant can be used individually by 1 type, or can use 2 or more types together. The addition amount of the flocculant is not particularly limited and can be appropriately selected from a wide range.

  In the present embodiment, after the flocculant is added to the mixed slurry, the mixed slurry is stirred by a granulator while heating. The heating temperature of the mixed slurry is not particularly limited, and is appropriately determined according to the particle diameter of the toner particles 1 to be obtained, the solid content concentration in the mixed slurry, the coagulant used, and the like. The heating temperature of the mixed slurry is preferably 65 ° C. or higher and lower than 90 ° C. When the temperature is lower than 65 ° C., the formed domain 2 containing the biomass resin may not be fused with the binder resin particles, and the durability of the toner may be lowered. When the temperature is 90 ° C. or higher, the formed domain 2 including the biomass resin may be compatible with the binder resin particles, and the durability of the toner may be reduced. The heating temperature of the mixed slurry may be appropriately changed according to the progress of aggregation.

  Further, the stirring time and the stirring speed by the granulator are not particularly limited, and are appropriately determined according to the particle diameter of the toner particles 1 to be obtained, the solid content concentration in the mixed slurry, the coagulant used, and the like. It is done. The stirring time and stirring speed of the mixed slurry may be appropriately changed according to the progress of aggregation.

  In this way, a slurry of toner particles 1 in which the domain 2 containing biomass resin is formed is obtained. Since the domain 2 containing the biomass resin has a particle diameter within a certain range and is dispersed almost uniformly in the toner particles 1, the biomass resin is prevented from being dispersed in the toner particles 1 in a sea island state. be able to. Therefore, the biomass resin can be contained in the toner particles 1 at a high ratio without deteriorating the durability of the toner, and environmental pollution can be suppressed. Further, since it can prevent white turbidity due to crystallization of biomass resin, it does not reduce the transparency of the toner, and even when applied to a color toner, a sufficient color reproduction width can be secured, and toner particles It is possible to suppress variations in characteristics between the two.

  In this production method, the particle diameter of the toner particles 1 obtained can be controlled by appropriately adjusting the heating temperature, stirring time, stirring speed, etc. of the mixed slurry, and the domain containing the biomass resin formed in the toner particles 1 2 domain diameter can be controlled. In the present invention, the toner particles 1 are preferably produced by controlling the particle size so that the volume average particle size is 4 μm or more and 8 μm or less. When used as a toner, toner particles 1 having a volume average particle size of 4 μm or more and 8 μm or less have excellent charging stability, high density and high definition, good image reproducibility, and stable high-quality images without image defects. Can be manufactured.

  In addition, the domain 2 containing the biomass resin is preferably manufactured by controlling the domain diameter to be 1 μm or less, more preferably 0.5 μm to 1 μm. By controlling the domain diameter in this way, it is possible to prevent the binder resin and the biomass resin from being compatibilized by heating in the aggregation process due to the domain diameter becoming too small. Therefore, the glass transition temperature (Tg) of the binder resin can be prevented from being lowered, and the storage stability of the toner can be prevented from being lowered. Further, it can be prevented that the domain diameter becomes too large and the particle diameter of the toner particles 1 becomes large. Therefore, a toner with a small particle diameter of the toner particles 1 can be produced. Further, when the domain diameter is 1 μm or less, a toner having excellent transparency can be obtained. Furthermore, since the rate at which the biomass resin is exposed to the toner surface can be kept low, the storage stability of the toner can be maintained at a high level, and the rate at which the biomass resin contacts the recording medium during fixing is increased. It is possible to prevent the toner fixability from deteriorating.

[Washing process]
The cleaning process of step a4 is a process of cleaning the toner particles 1 contained in the toner particle slurry after cooling the toner particle slurry. The toner particles 1 are washed in order to remove surfactants, dispersants, thickeners, and the like, and impurities derived therefrom, contained in the toner particle slurry. In the washing method, for example, water is added to the toner particle slurry and stirred, and the supernatant liquid separated by centrifugation or the like is removed. The toner particles 1 are preferably washed repeatedly until the conductivity of the supernatant measured with a conductivity meter or the like becomes 10 μS / cm or less, preferably 5 μS / cm or less.

[Separation process]
The separation step of step a5 is a step of separating and collecting the toner particles 1 from the liquid mixture of the liquid medium containing the toner particles 1 after washing. Separation of the toner particles 1 from the liquid medium is not particularly limited, and can be performed, for example, by filtration, suction filtration, centrifugation, or the like.

[Drying process]
In the drying step of step a6, the toner particles 1 after washing and separation are dried. The drying of the toner particles 1 is not particularly limited, but can be performed by a freeze drying method, an airflow drying method, or the like. When the toner particles 1 are dried, the production of the toner particles 1 is finished.

FIG. 4 is a flowchart showing a second example of the method for producing toner particles 1.
[Colored resin melt-kneading process]
The colored resin melt-kneading step of step s1 is a step of preparing a melt-kneaded product containing a binder resin and a colorant as essential components and further containing a release agent, a charge control agent and the like. The release agent is added to impart releasability to the toner when fixing the toner to the recording medium. Therefore, compared with the case where a mold release agent is not used, the high temperature offset start temperature can be increased and the high temperature offset resistance can be improved. Further, the release agent is melted by heating at the time of fixing the toner, the fixing start temperature is lowered, and the low-temperature fixing property can be improved. The release agent is not particularly limited, and examples thereof include petroleum waxes such as paraffin wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, polyolefin wax and derivatives thereof, low molecular weight polypropylin wax and derivatives thereof. Derivatives, polyolefin polymer wax (low molecular weight polyethylene wax, etc.) and hydrocarbon synthetic waxes such as derivatives thereof, carnauba wax and derivatives thereof, rice wax and derivatives thereof, candelilla wax and derivatives thereof, plant waxes such as wood wax Animal waxes such as beeswax and spermaceti, oils and fats synthetic waxes such as fatty acid amides and phenol fatty acid esters, long chain carboxylic acids and derivatives thereof, long chain alcohols and derivatives thereof, silicone polymers, higher fatty acids, etc. And the like. Derivatives include oxides, block copolymers of vinyl monomers and waxes, graft modified products of vinyl monomers and waxes, and the like. A mold release agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The charge control agent is added in order to impart preferable chargeability to the toner. The charge control agent is not particularly limited, and those for positive charge control and negative charge control can be used. Examples of charge control agents for positive charge control include nigrosine dyes, basic dyes, quaternary ammonium salts, quaternary phosphonium salts, aminopyrines, pyrimidine compounds, polynuclear polyamino compounds, aminosilanes, nigrosine dyes and derivatives thereof, and triphenylmethane. Derivatives, guanidine salts, amidine salts and the like can be mentioned. As charge control agents for controlling negative charges, oil-soluble dyes such as oil black and spiron black, metal-containing azo compounds, azo complex dyes, metal salts of naphthenic acid, salicylic acid and its derivatives, metal complexes and metal salts (metal is Chromium, zinc, zirconium, etc.), fatty acid soaps, long-chain alkyl carboxylates, resin acid soaps, and the like. The charge control agent can be used alone or in combination of two or more as required.

  The melt-kneaded product can be produced, for example, by dry-mixing a binder resin and a colorant and, if necessary, a release agent, a charge control agent, etc. with a mixer, and kneading the resulting powder mixture with a kneader. . The kneading temperature is a temperature equal to or higher than the melting temperature of the binder resin (usually about 80 to 200 ° C., preferably about 100 to 150 ° C.). Known mixers can be used, such as Henschel mixer (trade name, manufactured by Mitsui Mining Co., Ltd.), super mixer (trade name, manufactured by Kawata Co., Ltd.), Mechano Mill (trade name, manufactured by Okada Seiko Co., Ltd.), etc. Henschel type mixing apparatus, ongmill (trade name, manufactured by Hosokawa Micron Corporation), hybridization system (trade name, manufactured by Nara Machinery Co., Ltd.), Cosmo system (trade name, manufactured by Kawasaki Heavy Industries, Ltd.), and the like.

  Known kneaders can be used, and general kneaders such as a kneader, a twin-screw extruder, a two-roll mill, a three-roll mill, and a lab blast mill can be used. More specifically, for example, TEM-100B (trade name, manufactured by Toshiba Machine Co., Ltd.), PCM-65 / 87, PCM-30 (all of which are trade names, manufactured by Ikegai Co., Ltd.), etc. Extruder, Needex (trade name, manufactured by Mitsui Mining Co., Ltd.) and other open roll type kneaders. Melt kneading may be performed using a plurality of kneaders.

[Colored resin particle dispersion step]
The colored resin particle dispersion step of step s2 is a step of producing a colored resin particle slurry that is a slurry of colored resin particles by dispersing the melt-kneaded material produced in the colored resin melt-kneading step in a liquid medium. The dispersion of the colored resin particles in the liquid medium is not particularly limited and can be performed by a known method. However, the fine-graining step in step s2- (a) and the decompression step in step s2- (b) It is preferable to carry out by a high-pressure homogenizer method including the cooling step of step s2- (c). Thereby, the melt-kneaded product can be pulverized in a state where the particle size is small and the width of the particle size distribution is small. In the present embodiment, the colored resin particle dispersion step is performed by the high-pressure homogenizer used in the binder resin particle dispersion step described above.

(Granulation process)
The fine graining step of step s2- (a) is a step of obtaining a colored resin particle slurry by pulverizing and dispersing the melt-kneaded product in a liquid medium. First, the dispersion liquid containing the melt-kneaded material is stored in a tank of the high-pressure homogenizer. The liquid medium to be mixed with the melt-kneaded product is not particularly limited as long as it is a liquid material that does not dissolve and uniformly disperse the melt-kneaded product, but the ease of process management, waste liquid treatment after all steps, and ease of handling. In view of the above, a hydrophilic medium such as water or alcohol is preferable, and a hydrophilic medium containing a dispersion stabilizer is more preferable. The dispersion stabilizer is preferably added to the hydrophilic medium before the melt-kneaded product is added to the hydrophilic medium.

  As the dispersion stabilizer, those commonly used in this field can be used. Of these, hydrophilic polymer dispersion stabilizers are preferred. Examples of hydrophilic polymer dispersion stabilizers include acrylic monomers such as (meth) acrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and maleic anhydride. Mer, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloroacrylate 2-hydroxypropyl, hydroxyl group-containing acrylic monomers such as 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Ester monomers such as acid esters, vinyl alcohol monomers such as N-methylol acrylamide and N-methylol methacrylamide, ethers with vinyl alcohol, vinyl such as vinyl methyl ether, vinyl ethyl ether and vinyl propyl ether Alkyl ether monomers, vinyl alkyl ester monomers such as vinyl acetate, vinyl propionate and vinyl butyrate, aromatic vinyl monomers such as styrene, α-methylstyrene and vinyl toluene, acrylamide, methacrylamide, Diacetone acrylamide, amide monomers such as these methylol compounds, nitrile monomers such as acrylonitrile and methacrylonitrile, acid chloride monomers such as acrylic acid chloride and methacrylic acid chloride, vinylpyridine One or two selected from vinyl nitrogen-containing heterocyclic monomers such as vinylpyrrolidone, vinylimidazole, and ethyleneimine, and crosslinkable monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, allyl methacrylate, and divinylbenzene (Meth) acrylic polymers containing various hydrophilic monomers, polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxy Polyoxyethylene such as ethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Cellulose polymers such as tylene polymer, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyoxyethylene lauryl phenyl ether sodium sulfate, polyoxyethylene lauryl phenyl ether potassium sulfate, polyoxyethylene nonylphenyl ether sodium sulfate, polyoxyethylene oleyl phenyl Polyoxyalkylene alkyl aryl ether sulfate such as sodium ether sulfate, polyoxyethylene cetyl phenyl ether sodium sulfate, polyoxyethylene lauryl phenyl ether ammonium sulfate, polyoxyethylene nonylphenyl ether ammonium sulfate, polyoxyethylene oleyl phenyl ether ammonium sulfate, polyoxyethylene Laurierue Polyoxyalkylene alkyl ether sulfates such as sodium tersulfate, polyoxyethylene lauryl ether potassium sulfate, polyoxyethylene oleyl ether sodium sulfate, polyoxyethylene cetyl ether sodium sulfate, polyoxyethylene lauryl ether ammonium sulfate, polyoxyethylene oleyl ether ammonium sulfate Etc. A dispersion stabilizer can be used individually by 1 type, or can use 2 or more types together. The addition amount of the dispersion stabilizer is not particularly limited, but is preferably 0.05% by weight to 10% by weight, more preferably 0.1% by weight to 3% by weight of the colored resin particle slurry.

  A thickener, a surfactant and the like may be added to the dispersion of the melt-kneaded product together with the dispersion stabilizer. The thickener is effective, for example, for further atomization of the colored resin particles. The surfactant further improves the dispersibility of the colored resin particles in the hydrophilic medium, for example. The thickener is preferably a polysaccharide thickener selected from synthetic polymer polysaccharides and natural polymer polysaccharides. As the synthetic polymer polysaccharide, known ones can be used, and examples thereof include cationized cellulose, hydroxyethyl cellulose, starch, ionized starch derivatives, and a block polymer of starch and synthetic polymer. Examples of the natural polymer polysaccharide include hyaluronic acid, carrageenan, locust bean gum, xanthan gum, guar gum, gellan gum and the like. A thickener can be used individually by 1 type, or can use 2 or more types together. The addition amount of the thickener is not particularly limited, but is preferably 0.01% by weight or more and 2% by weight or less of the total amount of the colored resin particle slurry.

  Examples of the surfactant include lauryl sulfosuccinate disodium, polyoxyethylene sulfosuccinate lauryl disodium, polyoxyethylene alkyl (C12 to C14) sulfosuccinic acid disodium, sulfosuccinic acid polyoxyethylene lauroyl ethanolamide 2 Examples include sodium and sulfosuccinic acid ester salts such as dioctyl sodium sulfosuccinate. Surfactant can be used individually by 1 type, or can use 2 or more types together. The addition amount of the surfactant is not particularly limited, but is preferably 0.05% by weight or more and 0.2% by weight or less based on the total amount of the colored resin particle slurry.

  The dispersion of the melt-kneaded product stored in the tank of the high-pressure homogenizer is pressurized by the pressurizing unit, heated by the heater, and passed through the flow path formed in the pulverizing nozzle, so that the melt-kneaded product is Is coarsely crushed. The conditions for pressurizing and heating the dispersion of the melt-kneaded product at this time are not particularly limited, but are preferably 15 to 120 MPa and preferably 10 ° C. or more and less than the glass transition temperature (Tg) of the binder resin. The dispersion obtained by roughly pulverizing the melt-kneaded product is further passed through a flow path formed in the pulverizing nozzle, and the melt-kneaded product is finely divided to obtain a colored resin particle slurry. Although the pressure heating conditions at this time are not particularly limited, it is preferable that the pressure is increased to 50 MPa to 250 MPa and heated to 50 ° C. or higher. Thus, since the melt-kneaded material is pulverized under pressure and heating conditions, it can be efficiently pulverized.

(Decompression step)
The depressurization step of step s2- (b) is a step of depressurizing the colored resin particle slurry in a pressurized and heated state. The colored resin particle slurry in a heated and pressurized state is depressurized to atmospheric pressure or a pressure close thereto by a depressurizing module so that bubbles are not generated due to bumping.

(Cooling process)
The cooling step of step s2- (c) is a step of cooling the colored resin particle slurry in a heated state. The colored resin particle slurry in a heated state is cooled in a relatively short time to about 20 to 40 ° C. by a cooler.

  In this way, a colored resin particle slurry containing the binder resin and the colorant as essential components is obtained. In this production method, the pressure and / or temperature applied when the pulverizing nozzle is allowed to flow through, the solid content concentration in the colored resin particle slurry, the number of times of pulverization, etc. are adjusted as appropriate to obtain the colored resin particles obtained. The particle size can be controlled. In the present invention, the volume average particle diameter of the colored resin particles is preferably adjusted so that the volume average particle diameter is 0.2 μm or more and 0.5 μm or less, and the volume average of the biomass resin particles forming the domain 2 containing the biomass resin described later. It is preferable to control so as to be ¼ or more and ½ or less with respect to the particle diameter. This can prevent the particle diameter of the colored resin particles having an effect of maintaining the durability of the toner from becoming too small. Therefore, it is possible to prevent the toner from being deteriorated. In addition, it is possible to prevent the domains 2 including the biomass resin dispersed in the toner particles 1 from being brought into contact with each other due to an excessively large domain diameter. Therefore, it is possible to prevent the toner from being deteriorated.

  Moreover, it can prevent that colored resin and biomass resin are compatibilized because the volume average particle diameter of colored resin particle shall be 1/4 or more with respect to the volume average particle diameter of biomass resin particle. Therefore, the glass transition temperature (Tg) of the binder resin contained in the colored resin can be prevented from being lowered, and the storage stability of the toner can be prevented from being lowered. Furthermore, by setting the volume average particle diameter of the colored resin particles to ½ or less of the volume average particle diameter of the biomass resin particles, the ratio of the biomass resin exposed to the toner surface during long-term running use can be kept low. Therefore, the durability of the toner can be maintained in a high state, and the ratio of the biomass resin contacting the recording medium at the time of fixing can be prevented from increasing, thereby preventing the toner fixing property from being lowered. .

[Biomass resin particle dispersion process]
Since the biomass resin particle dispersion step of step s3 in the second example of the production method can be performed in the same manner as the biomass resin particle dispersion step of step a2 in the first example of the production method described above, description thereof is omitted.

[Aggregation process]
In the aggregation step of step s4, a flocculant is added to the mixed slurry obtained by mixing the colored resin particle slurry and the biomass resin particle slurry to agglomerate the colored resin particles and the biomass resin particles. (Referred to as “toner particle slurry”). In the agglomeration step, the mixed slurry is stirred using a granulating apparatus including a stirring vessel for storing the mixed slurry of the colored resin particle slurry and the biomass resin particle slurry, and a stirring unit provided in the stirring vessel for stirring the slurry. .

  As the aggregating agent for aggregating the colored resin particles and the biomass resin particles, monovalent salts, divalent salts, trivalent salts and the like can be used. Examples of monovalent salts include cationic dispersants such as alkyltrimethylammonium chloride and inorganic salts such as sodium chloride, potassium chloride, and ammonium chloride. Examples of the divalent salt include magnesium chloride, calcium chloride, zinc chloride, copper (II) chloride, magnesium sulfate, and manganese sulfate. Examples of the trivalent salt include aluminum chloride and iron (III) chloride. Among the flocculants exemplified above, alkyltrimethylammonium chloride is preferable. Specific examples of alkyltrimethylammonium chloride include stearyltrimethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride, lauryltrimethylammonium chloride, and the like. A flocculant can be used individually by 1 type, or can use 2 or more types together. The addition amount of the flocculant is not particularly limited and can be appropriately selected from a wide range.

  In the present embodiment, after the flocculant is added to the mixed slurry, the mixed slurry is stirred by a granulator while heating. The heating temperature of the mixed slurry is not particularly limited, and is appropriately determined according to the particle diameter of the toner particles 1 to be obtained, the solid content concentration in the mixed slurry, the coagulant used, and the like. The heating temperature of the mixed slurry is preferably 65 ° C. or higher and lower than 90 ° C. If it is less than 65 degreeC, the domain 2 containing the biomass resin to be formed may not be fused with the colored resin particles, and the durability of the toner may be lowered. When the temperature is 90 ° C. or higher, the formed domain 2 containing the biomass resin may be compatible with the colored resin particles, and the durability of the toner may be reduced. The heating temperature of the mixed slurry may be appropriately changed according to the progress of aggregation.

  Further, the stirring time and the stirring speed by the granulator are not particularly limited, and are appropriately determined according to the particle diameter of the toner particles 1 to be obtained, the solid content concentration in the mixed slurry, the coagulant used, and the like. It is done. The stirring time and stirring speed of the mixed slurry may be appropriately changed according to the progress of aggregation.

  In this way, a slurry of toner particles 1 in which the domain 2 containing biomass resin is formed is obtained. Since the domain 2 containing the biomass resin has a particle diameter within a certain range and is dispersed almost uniformly in the toner particles 1, the biomass resin is prevented from being dispersed in the toner particles 1 in a sea island state. be able to. Therefore, the biomass resin can be contained in the toner particles 1 at a high ratio without deteriorating the durability of the toner, and environmental pollution can be suppressed. In addition, it is possible to prevent white turbidity caused by crystallization of biomass resin, so that the transparency of the toner is not deteriorated, and even when a color toner is used, a sufficient color reproduction width can be secured, and between toner particles Variation in characteristics can be suppressed.

  In this production method, the particle diameter of the toner particles 1 obtained can be controlled by appropriately adjusting the heating temperature, stirring time, stirring speed, etc. of the mixed slurry, and the domain containing the biomass resin formed in the toner particles 1 2 domain diameter can be controlled. In the present invention, the toner particles 1 are preferably produced by controlling the particle size so that the volume average particle size is 4 μm or more and 8 μm or less. Toner particles 1 having a volume average particle size of 4 μm or more and 8 μm or less are excellent in storage stability under heating in a developing tank or the like, have high density and high definition, good image reproducibility, and poor image quality. High-quality images can be stably produced.

  In addition, the domain 2 containing the biomass resin is preferably manufactured by controlling the domain diameter to be 1 μm or less, more preferably 0.5 μm to 1 μm. By controlling the domain diameter in this way, it is possible to prevent the binder resin and the biomass resin from being compatibilized by heating in the aggregation process due to the domain diameter becoming too small. Therefore, it is possible to prevent the toner from being deteriorated. Further, it can be prevented that the domain diameter becomes too large and the particle diameter of the toner particles 1 becomes large. Therefore, a toner with a small particle diameter of the toner particles 1 can be produced.

  Further, when the domain diameter is 1 μm or less, a toner having excellent transparency can be obtained. Furthermore, since the rate at which the biomass resin is exposed to the toner surface can be kept low, the storage stability of the toner can be maintained at a high level, and the rate at which the biomass resin contacts the recording medium during fixing is increased. It is possible to prevent the toner fixability from deteriorating.

[Washing process]
The cleaning step of step s5 is a step of cleaning the toner particles 1 contained in the toner particle slurry after cooling the toner particle slurry. The toner particles 1 are washed in order to remove surfactants, dispersants, thickeners, and the like, and impurities derived therefrom, contained in the toner particle slurry. In the washing method, for example, water is added to the toner particle slurry and stirred, and the supernatant liquid separated by centrifugation or the like is removed. The toner particles 1 are preferably washed repeatedly until the conductivity of the supernatant measured with a conductivity meter or the like becomes 10 μS / cm or less, preferably 5 μS / cm or less.

[Separation process]
The separation step of step s6 is a step of separating and collecting the toner particles 1 from the liquid mixture of the liquid medium containing the toner particles 1 after washing. Separation of the toner particles 1 from the liquid medium is not particularly limited, and can be performed, for example, by filtration, suction filtration, centrifugation, or the like.

[Drying process]
In the drying step of step s7, the toner particles 1 after washing and separation are dried. The drying of the toner particles 1 is not particularly limited, but can be performed by a freeze drying method, an airflow drying method, or the like. When the toner particles 1 are dried, the production of the toner particles 1 is finished.

FIG. 5 is a flowchart showing a third example of the method for producing toner particles 1.
[Binder resin particle dispersion process]
Since the binder resin particle dispersing step of step b1 in the third example of the manufacturing method can be performed in the same manner as the binder resin particle dispersing step of step a1 in the first example of the manufacturing method described above, the description thereof is omitted. .

[Biomass resin particle dispersion process]
The biomass resin particle dispersion step of step b2 in the third example of the production method may be performed in the same manner as the biomass resin particle dispersion step of step a2 in the first example of the production method and step s3 in the second example of the production method. Since it can, the description is omitted.

[Colorant particle dispersion step]
The colorant particle dispersion step of step b3 is a step of producing a colorant particle slurry that is a slurry of colorant particles by dispersing the colorant in a liquid medium. As the liquid medium, like the liquid medium used in the binder resin particle dispersion step, a hydrophilic medium such as water or alcohol is preferable, and a dispersion stabilizer, a thickener, a surfactant, and the like can be appropriately added. The colorant is preferably used in a proportion of 5 to 50 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of the liquid medium. If the use ratio of the colorant is less than 5 parts by weight, the dispersion uniformity is lowered because the amount of the colorant relative to the liquid medium is too small. If the proportion of the colorant used exceeds 50 parts by weight, the amount of the colorant relative to the liquid medium is too large, so that the viscosity of the colorant particle slurry becomes too high, and this also reduces the dispersibility.

  As the dispersion stabilizer, an inorganic or organic dispersant can be used, and the inorganic dispersant is preferably a hydrophilic inorganic dispersant. By using a hydrophilic inorganic dispersant, the particle size of the fine powder of the colorant in the liquid medium can be made more uniform. Examples of the hydrophilic inorganic dispersant include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, clay, diatomaceous earth, and bentonite. Among these, calcium carbonate is preferable.

  The inorganic dispersant preferably has a number average particle size of primary particles of 1 nm to 1000 nm, more preferably 5 nm to 500 nm, and still more preferably 10 nm to 300 nm. When the number average particle size of the primary particles of the inorganic dispersant is less than 1 nm, it is difficult to disperse the inorganic dispersant in the liquid medium. When the number average particle size of the primary particles of the inorganic dispersant exceeds 1000 nm, the difference between the particle size of the colorant coarse powder and the particle size of the inorganic dispersant is reduced, and the colorant coarse powder is placed in the liquid medium. It becomes difficult to maintain stable dispersion.

  The inorganic dispersant is preferably used in the range of 1 part by weight to 300 parts by weight and more preferably in the range of 4 parts by weight to 100 parts by weight with respect to 100 parts by weight of the colorant. When the amount of the inorganic dispersant used is less than 1 part by weight, it is difficult to disperse the inorganic dispersant in the liquid medium. When the usage-amount of an inorganic dispersing agent exceeds 300 weight part, there exists a possibility that the viscosity of a coloring agent particle slurry may become high too much, and a dispersibility may fall.

  In addition, a polymer dispersant may be added to the liquid medium together with the inorganic dispersant. As the polymer dispersant, for example, a hydrophilic one is preferably used, one having a carboxyl group is more preferable, and one having no lipophilic group such as a hydroxypropoxyl group or a methoxyl group is particularly preferable. Examples of such a polymer dispersant include water-soluble cellulose ethers such as carboxymethyl cellulose and carboxyethyl cellulose. Among these, carboxymethyl cellulose is particularly preferable. The polymer dispersant is preferably used in a proportion of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the colorant.

  The organic dispersant is preferably an anionic dispersant. Anionic dispersants are excellent in the ability to improve the dispersibility of colorant particles in water. Examples of the anionic dispersant include a sulfonic acid type anionic dispersant, a sulfate ester type anionic dispersant, a polyoxyethylene ether type anionic dispersant, a phosphate ester type anionic dispersant, and a polyacrylate. Can be mentioned. As specific examples of the anionic dispersant, for example, sodium dodecylbenzenesulfonate, sodium polyacrylate, polyoxyethylene phenyl ether and the like can be preferably used. An anionic dispersing agent can be used individually by 1 type, or can use 2 or more types together.

  Moreover, as an organic dispersing agent, it is not limited to an anionic dispersing agent, A cationic dispersing agent may be sufficient. Examples of the cationic dispersant include alkyltrimethylammonium type cationic dispersants, alkylamidoamine type cationic dispersants, alkyldimethylbenzylammonium type cationic dispersants, cationized polysaccharide type cationic dispersants, and alkylbetaine type cationic dispersants. Dispersants, alkylamide betaine type cationic dispersants, sulfobetaine type cationic dispersants, amine oxide type cationic dispersants, metal salts and the like are preferable. Examples of the metal salt include chlorides such as sodium, potassium, calcium, and magnesium, and sulfates.

  Among these, alkyltrimethylammonium cationic dispersants are more preferable. Specific examples of the alkyl trimethyl ammonium type cationic dispersant include stearyl trimethyl ammonium chloride, tri (polyoxyethylene) stearyl ammonium chloride, lauryl trimethyl ammonium chloride and the like. A cationic dispersing agent can be used individually by 1 type, or can use 2 or more types together.

  The addition amount of the organic dispersant is not particularly limited and can be appropriately selected from a wide range, but is preferably 0.1 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the colorant. When the addition amount is less than 0.1 parts by weight, the effect of dispersing the colorant by the dispersant becomes insufficient and aggregation may occur. Even if the organic dispersant is added in an amount exceeding 5 parts by weight, the dispersion effect is not further improved, and the dispersibility of the colorant is lowered by increasing the viscosity of the colorant slurry. As a result, aggregation may occur.

  A commercially available thing can also be used as a dispersion stabilizer. Examples of commercially available dispersants include BYK-182, BYK-161, BYK-116, BYK-111, BYK-2000 (manufactured by Big Chemie Japan Co., Ltd.), Solsperse-2000, Solsperse-38500 (above Avicia Co., Ltd.). Product), EFKA-4046, EFKA-4047 (manufactured by Efcar Chemicals), Surfynol GA (manufactured by Air Products), and the like. One of these commercially available dispersants may be used alone, or two or more thereof may be mixed and used.

  Such a commercially available dispersant is preferably used in a ratio of 10 parts by weight or more and 100 parts by weight or less, and in a ratio of 20 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the colorant. Is more preferable. If the ratio of the commercially available dispersant used is less than 10 parts by weight, the effect of dispersing the colorant by the dispersant becomes insufficient, and aggregation may occur. When the use ratio of the commercially available dispersant exceeds 100 parts by weight, the dispersibility of the colorant decreases due to an increase in the viscosity of the colorant particle slurry. As a result, aggregation may occur.

  Mixing of the liquid medium and the dispersion stabilizer can be performed by a known method without any particular limitation. When mixing an inorganic dispersant and a liquid medium, the inorganic dispersant can be dispersed in water in a liquid medium using a disperser containing a medium such as a ball mill or a sand mill, a high-pressure disperser, an ultrasonic disperser, or the like. . When the organic dispersant and the liquid medium are mixed, the addition and dispersion may be performed by any method as long as the dispersant can be uniformly dissolved in the liquid medium. The colorant particle dispersion step is preferably performed by a high-pressure homogenizer including a fine graining step, a decompression step, and a cooling step. Thereby, the colorant can be pulverized in a state where the particle diameter is small and the width of the particle size distribution is small. In the present embodiment, the colorant particle dispersion step is performed by the high-pressure homogenizer used in the binder resin particle dispersion step described above.

(Granulation process)
The step b3- (a) fine graining step is a step of obtaining a colorant particle slurry by pulverizing and dispersing the colorant in a liquid medium. The liquid medium to be mixed with the colorant is preferably a hydrophilic medium such as water or alcohol like the liquid medium used in the binder resin particle dispersion step, and a dispersion stabilizer, a thickener, a surfactant and the like are appropriately added. Can do. Also, the dispersion containing the colorant is passed through a nozzle for crushing under pressure and heating conditions in the same manner as in the binder resin particle dispersion step, and the colorant is pulverized and finely divided. obtain. Thus, since the colorant is pulverized under pressure and heating conditions, the colorant can be efficiently pulverized.

(Decompression step)
The depressurization step of Step b3- (b) is a step of depressurizing the colorant particle slurry that is in a pressurized and heated state. The colorant particle slurry in the heated and pressurized state is depressurized to atmospheric pressure or a pressure close thereto by a depressurization module so that bubbles are not generated due to bumping.

(Cooling process)
The cooling process of step b3- (c) is a process of cooling the colorant particle slurry in a heated state. The colorant particle slurry in a heated state is cooled in a relatively short time to about 20 to 40 ° C. by a cooler.

  In this way, a colorant particle slurry is obtained. In this production method, the pressure and / or temperature applied when the pulverizing nozzle is allowed to flow through, the solid content concentration in the colorant particle slurry, the number of times of pulverization, and the like are appropriately adjusted, whereby the colorant particles obtained The particle size can be controlled. In the present invention, it is preferable to adjust each condition so that the average particle diameter of the colorant particles is preferably 50 nm or more and 200 nm or less. If the average particle diameter of the colorant particles is less than 50 nm, it takes a long time to make fine particles by the high-pressure homogenizer, and re-aggregation of the finely divided colorant particles may occur. If the average particle diameter of the colorant particles exceeds 200 nm, the dispersibility of the colorant in the toner particles may be reduced. The average particle diameter of the colorant particles can be measured using, for example, a laser light scattering microscope (trade name: DLS-700, manufactured by Otsuka Electronics Co., Ltd.).

[Aggregation process]
In the aggregation step of step b4, the flocculant is added to the mixed slurry obtained by mixing the binder resin particle slurry, the biomass resin particle slurry, and the colorant particle slurry, and the binder resin particles, the biomass resin particles, and the colorant particles are added. Is a step of agglomerating toner particles 1 to produce a slurry of toner particles 1 (hereinafter referred to as “toner particle slurry”). In the agglomeration step, a granulation apparatus comprising a stirring container for storing a mixed slurry of a binder resin particle slurry, a biomass resin particle slurry, and a colorant particle slurry, and a stirring means provided in the stirring container and stirring the slurry is used. And stir the mixed slurry.

  As a flocculant for aggregating the binder resin particles, the biomass resin particles, and the colorant particles, a monovalent salt, a divalent salt, a trivalent salt, or the like can be used. Examples of monovalent salts include cationic dispersants such as alkyltrimethylammonium chloride and inorganic salts such as sodium chloride, potassium chloride, and ammonium chloride. Examples of the divalent salt include magnesium chloride, calcium chloride, zinc chloride, copper (II) chloride, magnesium sulfate, and manganese sulfate. Examples of the trivalent salt include aluminum chloride and iron (III) chloride. Among the flocculants exemplified above, alkyltrimethylammonium chloride is preferable. Specific examples of alkyltrimethylammonium chloride include stearyltrimethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride, lauryltrimethylammonium chloride, and the like. A flocculant can be used individually by 1 type, or can use 2 or more types together. The addition amount of the flocculant is not particularly limited and can be appropriately selected from a wide range.

  In the present embodiment, after the flocculant is added to the mixed slurry, the mixed slurry is stirred by a granulator while heating. The heating temperature of the mixed slurry is not particularly limited, and is appropriately determined according to the particle diameter of the toner particles 1 to be obtained, the solid content concentration in the mixed slurry, the coagulant used, and the like. The heating temperature of the mixed slurry is preferably 65 ° C. or higher and lower than 90 ° C. When the temperature is lower than 65 ° C., the formed domain 2 containing the biomass resin may not be fused with the binder resin particles, and the durability of the toner may be lowered. When the temperature is 90 ° C. or higher, the formed domain 2 including the biomass resin may be compatible with the binder resin particles, and the durability of the toner may be reduced. The heating temperature of the mixed slurry may be appropriately changed according to the progress of aggregation.

  Further, the stirring time and the stirring speed by the granulator are not particularly limited, and are appropriately determined according to the particle diameter of the toner particles 1 to be obtained, the solid content concentration in the mixed slurry, the coagulant used, and the like. It is done. The stirring time and stirring speed of the mixed slurry may be appropriately changed according to the progress of aggregation.

  In this way, a slurry of toner particles 1 in which a plurality of domains 2 containing biomass resin are formed is obtained. Since the domain 2 containing the biomass resin has a particle diameter within a certain range and is dispersed almost uniformly in the toner particles 1, the biomass resin is prevented from being dispersed in the toner particles 1 in a sea island state. be able to. Therefore, the biomass resin can be contained in the toner particles 1 at a high ratio without deteriorating the durability of the toner, and environmental pollution can be suppressed. In addition, it is possible to prevent white turbidity caused by crystallization of biomass resin, so that the transparency of the toner is not deteriorated, and even when a color toner is used, a sufficient color reproduction width can be secured, and between toner particles Variation in characteristics can be suppressed.

  In this production method, the particle diameter of the toner particles 1 obtained can be controlled by appropriately adjusting the heating temperature, stirring time, stirring speed, etc. of the mixed slurry, and the domain containing the biomass resin formed in the toner particles 1 2 domain diameter can be controlled. In the present invention, the toner particles 1 are preferably produced by controlling the particle size so that the volume average particle size is 4 μm or more and 8 μm or less. Toner particles 1 having a volume average particle size of 4 μm or more and 8 μm or less are excellent in storage stability under heating in a developing tank or the like, have high density and high definition, good image reproducibility, and poor image quality. High-quality images can be stably produced.

  In addition, the domain 2 containing the biomass resin is preferably manufactured by controlling the domain diameter to be 1 μm or less, more preferably 0.5 μm to 1 μm. By controlling the domain diameter in this way, it is possible to prevent the binder resin and the biomass resin from being compatibilized by heating in the aggregation process due to the domain diameter becoming too small. Therefore, it is possible to prevent the toner from being deteriorated. Further, it can be prevented that the domain diameter becomes too large and the particle diameter of the toner particles 1 becomes large and the particle diameter distribution and shape distribution become wide. Therefore, a toner with a small particle diameter of the toner particles 1 can be produced.

  Further, when the domain diameter is 1 μm or less, a toner having excellent transparency can be obtained. Furthermore, since the rate at which the biomass resin is exposed to the toner surface can be kept low, the storage stability of the toner can be maintained at a high level, and the rate at which the biomass resin contacts the recording medium during fixing is increased. It is possible to prevent the toner fixability from deteriorating.

[Washing process]
The cleaning process of step b5 is a process of cleaning the toner particles 1 contained in the toner particle slurry after cooling the toner particle slurry. The toner particles 1 are washed in order to remove surfactants, dispersants, thickeners, and the like, and impurities derived therefrom, contained in the toner particle slurry. In the washing method, for example, water is added to the toner particle slurry and stirred, and the supernatant liquid separated by centrifugation or the like is removed. The toner particles 1 are preferably washed repeatedly until the conductivity of the supernatant measured with a conductivity meter or the like becomes 10 μS / cm or less, preferably 5 μS / cm or less.

[Separation process]
The separation step of step b6 is a step of separating and collecting the toner particles 1 from the liquid mixture of the liquid medium containing the toner particles 1 after washing. Separation of the toner particles 1 from the liquid medium is not particularly limited, and can be performed, for example, by filtration, suction filtration, centrifugation, or the like.

[Drying process]
In the drying step of step b7, the toner particles 1 after washing and separation are dried. The drying of the toner particles 1 is not particularly limited, but can be performed by a freeze drying method, an airflow drying method, or the like. When the toner particles 1 are dried, the production of the toner particles 1 is finished.

  In this way, the toner particles 1 in which the domains 2 containing the biomass resin are formed in the toner particles 1 can be produced. At this time, it is preferable to set the biomass resin content to 20 parts by weight and 60 parts by weight with respect to 100 parts by weight of the toner. As a result, the effect of suppressing environmental pollution by the biomass resin is sufficiently exhibited, and the durability of the toner can be sufficiently obtained.

  Further, it is preferable to coat the surface of the toner with a resin film. Thereby, the durability of the toner can be further improved. Examples of the resin constituting the resin film include polyacrylate, polymethacrylate, polystyrene and derivatives thereof, and styrene acrylic resin. As a method for coating the surface of the toner with a resin film, for example, a spray method in which a solution in which the resin is dissolved or dispersed is jetted onto the toner to form a resin film, or in a solution in which the resin is dissolved or dispersed is used. A dipping method in which a resin film is formed by dipping, a coacervation method in which fine particles obtained by emulsion polymerization are precipitated on the toner surface by salting out, and a resin obtained by, for example, emulsion polymerization of the monomers constituting the resin on the toner surface. Examples include an in-situ method for forming a film. Among these, it is preferable to form emulsion resin fine particles made of styrene acrylic resin on the toner surface to form a resin film.

  Since the styrene acrylic resin produced by emulsion polymerization has a small resin particle size and is uniform, a uniform and thin resin film can be formed when it is coated on the toner surface. In addition, since the styrene acrylic resin has a low content of polar groups such as ester bonds, the hygroscopic property is small, and the stability of charging of the toner can be improved even in a high humidity environment. When the emulsion polymerized fine particles are deposited on the toner surface to form a resin film made of a styrene acrylic resin, first, the fine particles obtained by the emulsion polymerization method are added to the toner dispersion. Next, an aggregating agent such as calcium chloride is added while stirring under heating to precipitate emulsion-polymerized fine particles on the toner surface. In this way, the styrene acrylic resin can be coated on the toner surface.

  The toner particles produced as described above are responsible for functions such as powder flowability improvement, triboelectric chargeability improvement, heat resistance, long-term storage stability improvement, cleaning property improvement and photoreceptor surface wear property control. Additives may be mixed. Examples of the external additive include silica fine powder, titanium oxide fine powder, and alumina fine powder. One type of external additive can be used alone, or two or more types can be used in combination. The external additive is added in an amount of 0.1 to 100 parts by weight of the toner particles in consideration of the charge amount necessary for the toner, the effect of adding the external additive on the wear of the photoreceptor and the environmental characteristics of the toner. 1 to 10 parts by weight is preferred.

  The toner of the present invention thus produced is used for developing an electrostatic image when forming an image by electrophotography or electrostatic recording, or for developing a magnetic latent image when forming an image by magnetic recording. Can be used. Further, it can be used as a one-component developer or a two-component developer.

  When used as a one-component developer, a blade is used, frictionally charged by a developing sleeve, and toner is transported by adhering the toner onto the sleeve for image formation. Includes a highly durable toner in which the degree of crystallinity of the domain 2 containing the biomass resin is suppressed to be low, so that it is difficult to cause fusion to a blade or the like and photoconductor filming.

  The two-component developer of the present invention includes the toner and the carrier described above. Therefore, it is possible to obtain a two-component developer that suppresses environmental contamination without deteriorating the durability of the toner. Furthermore, since the two-component developer includes the toner, which is a highly transparent toner that can be applied to a color toner, a two-component developer capable of forming a high-quality image with high transparency is obtained. be able to.

  As the carrier, magnetic particles can be used. Specific examples of the particles having magnetism include metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum or lead. Among these, ferrite is preferable. Alternatively, a resin-coated carrier in which magnetic particles are coated with a resin, or a resin-dispersed carrier in which magnetic particles are dispersed in a resin may be used as the carrier. The resin that coats the magnetic particles is not particularly limited, and examples thereof include olefin resins, styrene resins, styrene / acrylic resins, silicone resins, ester resins, and fluorine-containing polymer resins. . Moreover, although it does not restrict | limit especially as resin used for a resin dispersion type carrier, For example, a styrene acrylic resin, a polyester resin, a fluorine resin, a phenol resin, etc. are mentioned.

The shape of the carrier is preferably a spherical shape or a flat shape. The volume average particle diameter of the carrier is not particularly limited, but is preferably 10 μm or more and 100 μm or less, and more preferably 20 μm or more and 50 μm or less, considering high image quality. Furthermore, the resistivity of the carrier is preferably 10 ⁸ Ω · cm or more, more preferably 10 ¹² Ω · cm or more. The carrier resistivity is determined by placing the carrier in a container having a cross-sectional area of 0.50 cm ² and tapping it, then applying a load of 1 kg / cm ² to the particles packed in the container and placing the load between the load and the bottom electrode. This is a value obtained by reading a current value when a voltage generating an electric field of 1000 V / cm is applied. When the resistivity is low, when a bias voltage is applied to the developing sleeve, charges are injected into the carrier, and carrier particles easily adhere to the photoreceptor. Further, breakdown of the bias voltage is likely to occur.

  The magnetization strength (maximum magnetization) of the carrier is preferably 10 emu / g or more and 60 emu / g or less, more preferably 15 emu / g or more and 40 emu / g or less. The magnetization strength depends on the magnetic flux density of the developing roller, but under the general magnetic flux density conditions of the developing roller, if it is less than 10 emu / g, the magnetic binding force does not work and causes carrier scattering. There is a fear. On the other hand, if the magnetization strength exceeds 60 emu / g, it is difficult to maintain a non-contact state with the image carrier in the non-contact development in which the carrier spikes are too high. Further, in the contact development, there is a risk that a sweep is likely to appear in the toner image.

  The usage ratio of the toner and the carrier in the two-component developer is not particularly limited and can be appropriately selected according to the type of the toner and the carrier. However, if the ferrite carrier is taken as an example, the toner is contained in the developer in the total amount. The toner may be used so that it is contained in an amount of 2 wt% to 30 wt%, preferably 2 wt% to 20 wt%. In the two-component developer, the coverage of the carrier with the toner is preferably 40% by weight or more and 80% by weight or less.

  FIG. 6 is a cross-sectional view illustrating a configuration of an image forming apparatus 100 according to an embodiment of the present invention. The image forming apparatus 100 includes a developing unit 14 that is a developing device that performs development using the two-component developer described above. Therefore, it is possible to form a high-quality toner image on the photosensitive drum 11 by the developing unit 14 while suppressing environmental pollution, and it is possible to form a high-quality image with high transparency.

  The image forming apparatus 100 is a multifunction device having both a copying function, a printer function, and a facsimile function, and forms a full-color or monochrome image on a recording medium in accordance with transmitted image information. That is, the image forming apparatus 100 has three types of printing modes, ie, a copier mode (copying mode), a printer mode, and a FAX mode. A print mode is selected by a control unit (not shown) in response to reception of a print job from an external device using a recording storage medium or a memory device. The image forming apparatus 100 includes a toner image forming unit 7, a transfer unit 3, a fixing unit 4, a recording medium supply unit 5, and a discharge unit 6. Each member constituting the toner image forming unit 7 and some members included in the transfer unit 3 are black (b), cyan (c), magenta (m), and yellow (y) colors included in the color image information. In order to correspond to the image information, four each are provided. Here, each member provided by four according to each color is distinguished by attaching an alphabet representing each color to the end of the reference symbol, and when referring collectively, only the reference symbol is used.

  The toner image forming unit 7 includes a photosensitive drum 11, a charging unit 12, an exposure unit 13, a developing unit 14, and a cleaning unit 15. The charging unit 12, the developing unit 14, and the cleaning unit 15 are arranged in this order around the rotation direction of the photosensitive drum 11. The charging unit 12 is disposed below the developing unit 14 and the cleaning unit 15 in the vertical direction.

  The photosensitive drum 11 is supported by a driving unit (not shown) so as to be rotatable around an axis, and includes a conductive substrate (not shown) and a photosensitive layer formed on the surface of the conductive substrate. The conductive substrate can take various shapes, and examples thereof include a cylindrical shape, a columnar shape, and a thin film sheet shape. Among these, a cylindrical shape is preferable. The conductive substrate is formed of a conductive material. As the conductive material, those commonly used in this field can be used. For example, metals such as aluminum, copper, brass, zinc, nickel, stainless steel, chromium, molybdenum, vanadium, indium, titanium, gold, platinum, etc. A conductive layer made of one or more of aluminum, aluminum alloy, tin oxide, gold, indium oxide and the like is formed on a film-like substrate such as two or more alloys, synthetic resin film, metal film, paper, etc. And a resin composition containing a conductive film, conductive particles and / or a conductive polymer. In addition, as a film-form base | substrate used for an electroconductive film, a synthetic resin film is preferable and a polyester film is especially preferable. Moreover, as a formation method of the electroconductive layer in an electroconductive film, vapor deposition, application | coating, etc. are preferable.

  The photosensitive layer is formed, for example, by laminating a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material. In that case, it is preferable to provide an undercoat layer between the conductive substrate and the charge generation layer or the charge transport layer. By providing an undercoat layer, the scratches and irregularities present on the surface of the conductive substrate are coated to smooth the surface of the photosensitive layer, to prevent deterioration of the chargeability of the photosensitive layer during repeated use. Alternatively, an advantage of improving the charging characteristics of the photosensitive layer in a low humidity environment can be obtained. Further, a laminated photoreceptor having a three-layer structure having a high durability and having a photoreceptor surface protective layer as the uppermost layer may be used.

  The charge generation layer is mainly composed of a charge generation material that generates a charge when irradiated with light, and contains a known binder resin, plasticizer, sensitizer and the like as necessary. As the charge generation material, those commonly used in this field can be used. Phthalocyanine pigments such as metal-free phthalocyanine, squalium dye, azulenium dye, thiapyrylium dye, carbazole skeleton, styryl stilbene skeleton, triphenylamine skeleton, dibenzothiophene skeleton, oxadiazole skeleton, fluorenone skeleton, bis stilbene skeleton, distyryl oxa And azo pigments having a diazole skeleton or a distyrylcarbazole skeleton.

  Among these, metal-free phthalocyanine pigments, oxotitanyl phthalocyanine pigments, bisazo pigments containing a fluorene ring and / or a fluorenone ring, bisazo pigments composed of aromatic amines, trisazo pigments, etc. have high charge generation ability and high sensitivity. Suitable for obtaining a photosensitive layer. One type of charge generating material can be used alone, or two or more types can be used in combination. Although the content of the charge generation material is not particularly limited, it is preferably 5 parts by weight or more and 500 parts by weight or less, more preferably 10 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the binder resin in the charge generation layer. is there. As the binder resin for the charge generation layer, those commonly used in this field can be used. For example, melamine resin, epoxy resin, silicone resin, polyurethane, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, polycarbonate, phenoxy resin , Polyvinyl butyral, polyarylate, polyamide, polyester and the like. Binder resin can be used individually by 1 type, or can use 2 or more types together as needed.

  The charge generation layer generates charge by dissolving or dispersing appropriate amounts of charge generation materials, binder resins and, if necessary, plasticizers and sensitizers in an appropriate organic solvent capable of dissolving or dispersing these components. It can be formed by preparing a layer coating solution, applying this charge generation layer coating solution to the surface of the conductive substrate and drying. The film thickness of the charge generation layer thus obtained is not particularly limited, but is preferably 0.05 μm or more and 5 μm or less, more preferably 0.1 μm or more and 2.5 μm or less.

  The charge transport layer laminated on the charge generation layer has a charge transport material having the ability to accept and transport the charge generated from the charge generation material and a binder resin for the charge transport layer as essential components. Contains known antioxidants, plasticizers, sensitizers, lubricants and the like. As the charge transport material, those commonly used in this field can be used, for example, poly-N-vinylcarbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensation product and derivatives thereof, Polyvinylpyrene, polyvinylphenanthrene, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, 9- (p-diethylaminostyryl) anthracene, 1,1-bis (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, pyrazoline Derivatives, phenylhydrazones, hydrazone derivatives, triphenylamine compounds, tetraphenyldiamine compounds, triphenylmethane compounds, stilbene compounds, 3-methyl-2-benzothiazoline -Donating substances such as azine compounds, fluorenone derivatives, dibenzothiophene derivatives, indenothiophene derivatives, phenanthrenequinone derivatives, indenopyridine derivatives, thioxanthone derivatives, benzo [c] cinnoline derivatives, phenazine oxide derivatives, tetracyano Examples include electron-accepting substances such as ethylene, tetracyanoquinodimethane, promanyl, chloranil, and benzoquinone.

  The charge transport materials can be used alone or in combination of two or more. Although the content of the charge transport material is not particularly limited, it is preferably 10 parts by weight or more and 300 parts by weight or less, more preferably 30 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the binder resin in the charge transport material. . As the binder resin for the charge transport layer, those commonly used in this field and capable of uniformly dispersing the charge transport material can be used. For example, polycarbonate, polyarylate, polyvinyl butyral, polyamide, polyester, polyketone, epoxy resin, polyurethane , Polyvinyl ketone, polystyrene, polyacrylamide, phenol resin, phenoxy resin, polysulfone resin, and copolymer resins thereof. Among these, in consideration of film formability, wear resistance of the resulting charge transport layer, electrical characteristics, etc., polycarbonate containing bisphenol Z as a monomer component (hereinafter referred to as “bisphenol Z type polycarbonate”), bisphenol Z type polycarbonate And a mixture of polycarbonate with other polycarbonates are preferred. Binder resin can be used individually by 1 type, or can use 2 or more types together.

  The charge transport layer preferably contains an antioxidant together with the charge transport material and the binder resin for the charge transport layer. As the antioxidant, those commonly used in this field can be used, and examples thereof include vitamin E, hydroquinone, hindered amine, hindered phenol, paraphenylenediamine, arylalkane and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds. It is done. One antioxidant can be used alone, or two or more antioxidants can be used in combination. The content of the antioxidant is not particularly limited, but is 0.01% by weight or more and 10% by weight or less, preferably 0.05% by weight or more and 5% by weight or less of the total amount of components constituting the charge transport layer. The charge transport layer is dissolved or dispersed in a suitable organic solvent that can dissolve or disperse these components in an appropriate amount such as a charge transport material and a binder resin, and if necessary, an antioxidant, a plasticizer, and a sensitizer. The charge transport layer coating liquid is prepared, and the charge transport layer coating liquid is applied to the surface of the charge generation layer and dried.

  The film thickness of the charge generation layer thus obtained is not particularly limited, but is preferably 10 μm or more and 50 μm or less, more preferably 15 μm or more and 40 μm or less. Note that a photosensitive layer in which a charge generation material and a charge transport material are present can be formed in one layer. In that case, the type, content, binder resin, and other additives of the charge generation material and the charge transport material may be the same as in the case of separately forming the charge generation layer and the charge transport layer.

  In this embodiment, the photosensitive drum formed by forming the organic photosensitive layer using the charge generation material and the charge transport material as described above is used. Instead, an inorganic photosensitive layer using silicon or the like is formed. Can be used.

  The charging unit 12 faces the photosensitive drum 11 and is arranged so as to be separated from the surface of the photosensitive drum 11 along the longitudinal direction of the photosensitive drum 11 with a gap, and the surface of the photosensitive drum 11 has a predetermined polarity and Charge to potential. As the charging unit 12, a charging brush type charger, a charger type charger, a sawtooth type charger, an ion generator, or the like can be used. In the present embodiment, the charging unit 12 is provided so as to be separated from the surface of the photosensitive drum 11, but is not limited thereto. For example, a charging roller may be used as the charging unit 12 and the charging roller may be disposed so that the charging roller and the photosensitive drum are in pressure contact with each other, or a contact charging type charger such as a charging brush or a magnetic brush may be used. .

  The exposure unit 13 is arranged such that light of each color information emitted from the exposure unit 13 passes between the charging unit 12 and the developing unit 14 and is irradiated on the surface of the photosensitive drum 11. The exposure unit 13 branches the image information into light of each color information of b, c, m, and y in the unit, and the surface of the photosensitive drum 11 charged to a uniform potential by the charging unit 12 is light of each color information. To form an electrostatic latent image on the surface. As the exposure unit 13, for example, a laser scanning unit including a laser irradiation unit and a plurality of reflecting mirrors can be used. In addition, a unit in which an LED (Light Emitting Diode) array, a liquid crystal shutter, and a light source are appropriately combined may be used.

  FIG. 7 is a diagram showing the configuration of the developing means 14 which is the developing device of the present invention. The developing unit 14 includes a developing tank 20 and a toner hopper 21. The developing tank 20 is disposed so as to face the surface of the photosensitive drum 11, and is a container that supplies toner to the electrostatic latent image formed on the surface of the photosensitive drum 11 and develops it to form a visible toner image. It is a shaped member. The developing tank 20 accommodates toner in its internal space and accommodates a roller member such as the developing roller 22, the supply roller 23, and the stirring roller 24 or a screw member, and rotatably supports the developing tank 20. An opening is formed on a side surface of the developing tank 20 facing the photosensitive drum 11, and a developing roller 22 is rotatably provided at a position facing the photosensitive drum 11 through the opening.

  The developing roller 22 is a roller-like member that supplies toner to the electrostatic latent image on the surface of the photoconductor 11 at the pressure contact portion or the closest portion with the photoconductor drum 11. When supplying the toner, a potential having a polarity opposite to the charging potential of the toner is applied to the surface of the developing roller 22 as a developing bias voltage (hereinafter simply referred to as “developing bias”). As a result, the toner on the surface of the developing roller 22 is smoothly supplied to the electrostatic latent image. Further, by changing the developing bias value, the amount of toner (toner adhesion amount) supplied to the electrostatic latent image can be controlled.

  The supply roller 23 is a roller-like member that faces the developing roller 22 and can be driven to rotate, and supplies toner to the periphery of the developing roller 22. The agitating roller 24 is a roller-like member provided so as to be able to rotate and face the supply roller 23, and supplies the toner newly supplied from the toner hopper 21 into the developing tank 20 to the periphery of the supply roller 23. The toner hopper 21 is provided so that a toner replenishing port (not shown) provided at the lower part in the vertical direction communicates with a toner receiving port (not shown) provided at the upper part in the vertical direction of the developing tank 20. The toner is replenished according to the toner consumption status of 20. Further, the toner hopper 21 may not be used, and the toner may be directly supplied from each color toner cartridge.

  The cleaning unit 15 removes the toner remaining on the surface of the photosensitive drum 11 after transferring the toner image to the recording medium, and cleans the surface of the photosensitive drum 11. For the cleaning unit 15, for example, a plate-like member such as a cleaning blade is used. In the image forming apparatus 100 of the present invention, an organic photosensitive drum is mainly used as the photosensitive drum 11, and the surface of the organic photosensitive drum is mainly composed of a resin component. Surface degradation is likely to proceed due to the chemical action of ozone generated by the discharge. However, the deteriorated surface portion is worn by receiving a rubbing action by the cleaning unit 15 and is gradually but surely removed. Therefore, the problem of surface deterioration due to ozone or the like is practically solved, and the charging potential by the charging operation can be stably maintained over a long period of time. Although the cleaning unit 15 is provided in this embodiment, the present invention is not limited to this, and the cleaning unit 15 may not be provided.

  According to the toner image forming unit 7, an electrostatic latent image is formed by irradiating the surface of the photosensitive drum 11 that is uniformly charged by the charging unit 12 with signal light corresponding to the image information from the exposure unit 13. Toner is supplied from the developing means 14 to form a toner image, and after the toner image is transferred to the intermediate transfer belt 25, the toner remaining on the surface of the photosensitive drum 11 is removed by the cleaning unit 15. This series of toner image forming operations is repeatedly executed.

  The transfer unit 3 is disposed above the photosensitive drum 11, and includes an intermediate transfer belt 25, a driving roller 26, a driven roller 27, an intermediate transfer roller 28 (b, c, m, y), and a transfer belt cleaning unit. 29 and the transfer roller 30. The intermediate transfer belt 25 is an endless belt-like member that is stretched by a driving roller 26 and a driven roller 27 to form a loop-shaped movement path, and is driven to rotate in the direction of an arrow B. When the intermediate transfer belt 25 passes through the photosensitive drum 11 while being in contact with the photosensitive drum 11, an intermediate transfer roller 28 disposed on the surface of the photosensitive drum 11 is opposed to the photosensitive drum 11 via the intermediate transfer belt 25. A transfer bias having a polarity opposite to the charging polarity of the toner is applied, and the toner image formed on the surface of the photosensitive drum 11 is transferred onto the intermediate transfer belt 25.

  In the case of a full-color image, each color toner image formed on each photoconductor drum 11 is sequentially transferred onto the intermediate transfer belt 25 to form a full-color toner image. The driving roller 26 is provided so as to be rotatable around its axis by driving means (not shown), and the intermediate transfer belt 25 is driven to rotate in the direction of arrow B by the rotational driving. The driven roller 27 is provided so as to be able to be driven and rotated by the rotational drive of the driving roller 26, and applies a certain tension to the intermediate transfer belt 25 so that the intermediate transfer belt 25 does not loosen. The intermediate transfer roller 28 is provided in pressure contact with the photosensitive drum 11 via the intermediate transfer belt 25 and capable of being driven to rotate about its axis by a driving unit (not shown). The intermediate transfer roller 28 is connected to a power source (not shown) for applying a transfer bias as described above, and has a function of transferring the toner image on the surface of the photosensitive drum 11 to the intermediate transfer belt 25.

  The transfer belt cleaning unit 29 is provided so as to face the driven roller 27 through the intermediate transfer belt 25 and to contact the outer peripheral surface of the intermediate transfer belt 25. Since the toner adhering to the intermediate transfer belt 25 due to contact with the photosensitive drum 11 causes the back surface of the recording medium to be contaminated, the transfer belt cleaning unit 29 removes and collects the toner on the surface of the intermediate transfer belt 25. The transfer roller 30 is provided in pressure contact with the drive roller 26 via the intermediate transfer belt 25, and can be driven to rotate about an axis by a drive unit (not shown). At the pressure contact portion (transfer nip portion) between the transfer roller 30 and the drive roller 26, the toner image carried and conveyed by the intermediate transfer belt 25 is transferred to the recording medium fed from the recording medium supply means 5 described later. Is done. The recording medium carrying the toner image is fed to the fixing unit 4. According to the transfer unit 3, the toner image transferred from the photosensitive drum 11 to the intermediate transfer belt 25 at the pressure contact portion between the photosensitive drum 11 and the intermediate transfer roller 28 rotates the intermediate transfer belt 25 in the arrow B direction. It is conveyed to a transfer nip portion by driving, and transferred to a recording medium there.

  The fixing unit 4 is provided downstream of the transfer unit 3 in the conveyance direction of the recording medium, and includes a fixing roller 31 and a pressure roller 32. The fixing roller 31 is rotatably provided by a driving unit (not shown), and heats and melts the toner constituting the unfixed toner image carried on the recording medium to fix it on the recording medium. A heating unit (not shown) is provided inside the fixing roller 31. The heating unit heats the fixing roller 31 so that the surface of the fixing roller 31 reaches a predetermined temperature (heating temperature). For example, a heater or a halogen lamp can be used as the heating means. The heating means is controlled by fixing condition control means described later. The control of the heating temperature by the fixing condition control means will be described in detail later.

  A temperature detection sensor is provided near the surface of the fixing roller 31 to detect the surface temperature of the fixing roller 31. The detection result by the temperature detection sensor is written in the storage unit of the control means described later. The pressure roller 32 is provided so as to be in pressure contact with the fixing roller 31 and is supported so as to be driven to rotate by the rotation drive of the pressure roller 32. The pressure roller 32 assists fixing of the toner image on the recording medium by pressing the toner and the recording medium when the toner is melted and fixed on the recording medium by the fixing roller 31. A pressure contact portion between the fixing roller 31 and the pressure roller 32 is a fixing nip portion. According to the fixing unit 4, the recording medium onto which the toner image is transferred by the transfer unit 3 is sandwiched between the fixing roller 31 and the pressure roller 32, and the toner image is recorded under heating when passing through the fixing nip portion. By being pressed against the medium, the toner image is fixed on the recording medium and an image is formed.

  The recording medium supply unit 5 includes an automatic paper feed tray 35, a pickup roller 36, a transport roller 37, a registration roller 38, and a manual paper feed tray 39. The automatic paper feed tray 35 is a container-like member that is provided in the lower part of the image forming apparatus 100 in the vertical direction and stores a recording medium. Recording media include plain paper, color copy paper, overhead projector sheets, postcards, and the like. The pick-up roller 36 takes out the recording medium stored in the automatic paper feed tray 35 one by one and feeds it to the paper transport path S1. The conveyance rollers 37 are a pair of roller members provided so as to be in pressure contact with each other, and convey the recording medium toward the registration rollers 38.

  The registration rollers 38 are a pair of roller members provided so as to be in pressure contact with each other, and the recording medium fed from the conveyance roller 37 is used to convey the toner image carried on the intermediate transfer belt 25 to the transfer nip portion. Synchronously, it is fed to the transfer nip. The manual paper feed tray 39 is a device for taking a recording medium into the image forming apparatus 100 by a manual operation. The recording medium taken from the manual paper feed tray 39 passes through the paper conveyance path S2 by the conveyance roller 37. Then, it is fed to the registration roller 38. According to the recording medium supply means 5, the toner image carried on the intermediate transfer belt 25 is conveyed to the transfer nip portion of the recording medium supplied one by one from the automatic paper feed tray 35 or the manual paper feed tray 39. In synchronism with this, the sheet is fed to the transfer nip portion.

  The discharge unit 6 includes a conveyance roller 37, a discharge roller 40, and a discharge tray 41. The conveyance roller 37 is provided downstream of the fixing nip portion in the sheet conveyance direction, and conveys the recording medium on which the image is fixed by the fixing unit 4 toward the discharge roller 40. The discharge roller 40 discharges the recording medium on which the image is fixed to a discharge tray 41 provided on the upper surface in the vertical direction of the image forming apparatus 100. The discharge tray 41 stores a recording medium on which an image is fixed.

  The image forming apparatus 100 includes a control unit (not shown). For example, the control unit is provided in an upper part of the internal space of the image forming apparatus 100 and includes a storage unit, a calculation unit, and a control unit. In the storage unit of the control means, various setting values via an operation panel (not shown) arranged on the upper surface of the image forming apparatus 100, detection results from sensors (not shown) arranged at various locations inside the image forming apparatus 100, external devices The image information from is input. In addition, programs for executing various means are written. Examples of the various means include a recording medium determination unit, an adhesion amount control unit, and a fixing condition control unit. As the storage unit, those commonly used in this field can be used, and examples thereof include a read only memory (ROM), a random access memory (RAM), and a hard disk drive (HDD).

As the external device, an electric / electronic device capable of forming or obtaining image information and electrically connected to the image forming apparatus 100 can be used. For example, a computer, a digital camera, a television receiver, a video recorder DVD (Digital Versatile Disc) recorder, HDDVD (High-Definition Digital Versatile Disc), Blu-ray disc recorder, facsimile apparatus, portable terminal apparatus, and the like. The arithmetic unit takes out various data (image formation command, detection result, image information, etc.) written in the storage unit and programs of various means, and performs various determinations. The control unit sends a control signal to the corresponding device according to the determination result of the calculation unit, and performs operation control. The control unit and the calculation unit are a central processing unit (CPU, Central
A processing circuit realized by a microcomputer, a microprocessor, or the like including a processing unit is included. The control means includes a main power supply together with the processing circuit described above, and the power supply supplies power not only to the control means but also to each device in the image forming apparatus 100.

  By forming an image using the toner, the two-component developer, the developing device, and the image forming apparatus of the present invention, it is possible to form a high-quality image with high transparency while suppressing environmental contamination.

(Example)
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The glass transition point (Tg) and softening point (Tm) of the binder resin that is the toner raw material and the melting point of the release agent were measured as follows.

<Glass transition point of binder resin>
Using a differential scanning calorimeter (trade name: DSC220, manufactured by Seiko Denshi Kogyo Co., Ltd.), according to Japanese Industrial Standard (JIS) K7121-1987, 1 g of a sample was heated at a heating rate of 10 ° C. per minute and a DSC curve was measured. did. Draw the endothermic peak corresponding to the glass transition of the obtained DSC curve at a point where the slope is maximum with respect to the straight line that extends the base line on the high temperature side to the low temperature side and the curve from the rising part of the peak to the vertex. The temperature at the intersection with the tangent was determined as the glass transition point (Tg).

<Softening point of binder resin>
In a flow characteristic evaluation apparatus (trade name: Flow Tester CFT-100C, manufactured by Shimadzu Corporation), a load of 10 kgf / cm ² (9.8 × 10 ⁵ Pa) was applied and a sample 1 g was a die (nozzle diameter 1 mm, length). 1 mm), and heated at a heating rate of 6 ° C. per minute. The temperature at which half of the sample flowed out of the die was determined and used as the softening point.

<Melting point of release agent>
Using a differential scanning calorimeter (trade name: DSC220, manufactured by Seiko Denshi Kogyo Co., Ltd.), 1 g of the sample is heated from a temperature of 20 ° C. to 200 ° C. at a heating rate of 10 ° C. per minute, and then rapidly cooled from 200 ° C. to 20 ° C. The operation was repeated twice and the DSC curve was measured. The temperature at the top of the endothermic peak corresponding to the melting of the DSC curve measured in the second operation was determined as the melting point of the release agent.

Example 1
[Production of colored resin particle slurry]
82 parts by weight of a polyester resin (glass transition temperature (Tg): 58 ° C., softening point (Tm): 110 ° C.), 8 parts by weight of phthalocyanine blue (trade name: copper phthalocyanine 15: 3, manufactured by Clariant), paraffin wax ( 8 parts by weight of a melting point of 85 ° C. and 2 parts by weight of a charge control agent (trade name: TRH, manufactured by Hodogaya Chemical Co., Ltd.) were mixed for 10 minutes by a Henschel mixer, and then a twin-screw extrusion kneader (trade name: PCM65, stock) Melt-kneaded at Ikegai Corporation. 100 g (10 parts by weight) of this melt-kneaded product, 3 g (0.3 parts by weight) of sodium polyacrylate (trade name: D-H14-N L-7403KN, manufactured by Nippon Emulsifier Co., Ltd.) as an anionic surfactant , 897 g (89.7 wt%) of water (temperature 20 ° C., conductivity 0.5 μS / cm), and the resulting mixture is placed in a tank of a high-pressure homogenizer (trade name: NANO3000, manufactured by Mie Co., Ltd.). Then, coarse pulverization was performed under conditions of 25 ° C. and 100 MPa. Subsequently, atomization was performed by circulating three passes under conditions of 150 ° C. and 160 MPa, and a colored resin particle slurry was produced. The obtained colored resin particles had a volume average particle size of 0.35 μm (coefficient of variation (CV value): 30).

[Manufacture of biomass resin particle slurry]
3 kg of L-lactide, 2 kg of DL-lactide, and 1.2 g of tin octylate were charged into a polymerization reaction vessel and subjected to ring-opening polymerization by heating at 195 ° C. for 1 hour in a nitrogen atmosphere, and then 100 g of 1,3-propanediol and 50 g of terephthalic acid. And further polymerized at 190 ° C. for 2 hours to obtain a polylactic acid copolymer having a molecular weight of Mw: 10500, a number average molecular weight Mn: 3900, and a softening point of 135 ° C. and having an acid value of 8.8 (CE- 1) was obtained. 100 g (10 parts by weight) of this polylactic acid copolymer (CE-1) and 5 g of sodium polyacrylate (trade name: D-H14-N L-7403KN, manufactured by Nippon Emulsifier Co., Ltd.) as an anionic surfactant 0.5 parts by weight) and water (temperature 20 ° C., conductivity 0.5 μS / cm) 895 g (89.5 wt%) were mixed, and the resulting mixture was mixed with a high-pressure homogenizer (trade name: NANO3000, Inc. The product was put into a tank (made of beautiful grains) and coarsely pulverized under conditions of 25 ° C. and 100 MPa. Next, atomization was performed under the conditions of 160 ° C. and 180 MPa to prepare a biomass resin particle slurry. The obtained biomass resin particles had a volume average particle size of 0.85 μm (coefficient of variation (CV value): 32).

[Manufacture of toner particles]
To the obtained colored resin particle slurry 50 parts by weight and biomass resin particle slurry 50 parts by weight, 3.0 parts by weight of sodium chloride (trade name: special grade sodium chloride, manufactured by Kishida Chemical Co., Ltd.) is added as a flocculant. In an emulsifier (trade name: CLEARMIX, manufactured by M Technique Co., Ltd.), the mixture was stirred for 10 minutes at a coagulation temperature of 80 ° C. and a rotor rotation speed of 8000 rpm, and then further stirred at 85 ° C. for 5 minutes to give resin. An agglomerated particle slurry was produced by agglomerating fine particles. The obtained aggregated particle slurry was washed, separated, and dried to obtain toner particles (aggregated particles) having a volume average particle diameter of 5.8 μm (coefficient of variation (CV value): 22). The toner powder of Example 1 was obtained by mixing 200 parts by weight of the toner powder and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 2)
[Production of colored resin particle slurry]
86 parts by weight of a polyester resin (glass transition temperature (Tg): 58 ° C., softening point (Tm): 110 ° C.), 4 parts by weight of phthalocyanine blue (trade name: copper phthalocyanine 15: 3, manufactured by Clariant), paraffin wax ( 8 parts by weight of a melting point of 85 ° C. and 2 parts by weight of a charge control agent (trade name: TRH, manufactured by Hodogaya Chemical Co., Ltd.) were mixed for 10 minutes by a Henschel mixer, and then a twin-screw extrusion kneader (trade name: PCM65, stock) Melt-kneaded at Ikegai Corporation. 100 g (10 parts by weight) of this melt-kneaded product, 3 g (0.3 parts by weight) of sodium polyacrylate (trade name: D-H14-N L-7403KN, manufactured by Nippon Emulsifier Co., Ltd.) as an anionic surfactant , 897 g (89.7 wt%) of water (temperature 20 ° C., conductivity 0.5 μS / cm), and the resulting mixture is placed in a tank of a high-pressure homogenizer (trade name: NANO3000, manufactured by Mie Co., Ltd.). Then, coarse pulverization was performed under conditions of 25 ° C. and 100 MPa. Subsequently, atomization was performed by circulating three passes under conditions of 160 ° C. and 160 MPa, and a colored resin particle slurry was produced. The obtained colored resin particles had a volume average particle size of 0.52 μm (coefficient of variation (CV value): 29).

[Manufacture of biomass resin particle slurry]
After 96 parts by weight of polylactic acid (CE-1) and 4 parts by weight of phthalocyanine blue (trade name: copper phthalocyanine 15: 3, manufactured by Clariant) were mixed for 10 minutes by a Henschel mixer, a twin-screw extrusion kneader (trade name: PCM65) , Manufactured by Ikegai Co., Ltd.). 100 g (10 parts by weight) of this kneaded product, 5 g (0.5 parts by weight) of sodium polyacrylate (trade name: DH14-N L-7403KN, manufactured by Nippon Emulsifier Co., Ltd.) as an anionic surfactant, 895 g (89.5 wt%) of water (temperature 20 ° C., conductivity 0.5 μS / cm) is mixed, and the resulting mixture is put into a tank of a high-pressure homogenizer (trade name: NANO3000, manufactured by Mie Co., Ltd.). Then, coarse pulverization was performed under the conditions of 25 ° C. and 100 MPa. Subsequently, atomization was performed under the conditions of 170 ° C. and 200 MPa to prepare a biomass resin particle slurry. The obtained biomass resin particles had a volume average particle size of 0.75 μm (coefficient of variation (CV value): 35).

[Manufacture of toner particles]
Using the resulting colored resin particle slurry and biomass resin particle slurry, toner particles having a volume average particle size of 5.6 μm (coefficient of variation (CV value): 23) were obtained in the same manner as in Example 1. The toner of Example 2 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 3)
In the production of biomass resin particle slurry, the temperature condition and pressure condition of the micronization process are 180 ° C. and 250 MPa, respectively, and a biomass resin particle slurry having a volume average particle diameter of 0.60 μm (coefficient of variation (CV value): 40) is produced. Except for the above, toner particles having a volume average particle size of 5.4 μm (coefficient of variation (CV value): 22) were obtained in the same manner as in Example 1. The toner of Example 3 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

Example 4
In the production of biomass resin particle slurry, the temperature condition and pressure condition of the micronization process are 160 ° C. and 160 MPa, respectively, and a biomass resin particle slurry having a volume average particle diameter of 1.15 μm (coefficient of variation (CV value): 40) is prepared. Except for the above, toner particles having a volume average particle size of 6.4 μm (coefficient of variation (CV value): 25) were obtained in the same manner as in Example 1. The toner of Example 4 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 5)
Fine particles comprising 0.1 μm styrene acrylic resin (glass transition temperature (Tg): 64 ° C., softening point (Tm): 122 ° C.) obtained by the emulsion polymerization method were formed on the surface of the toner of Example 1. A toner film having a volume average particle size of 5.8 μm (coefficient of variation (CV value): 22) was obtained by depositing a resin film having a thickness of 0.15 μm. The toner of Example 5 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 6)
In the production of colored resin particle slurry, the temperature and pressure conditions of the micronization step are 150 ° C. and 200 MPa, respectively, and a colored resin particle slurry having a volume average particle size of 0.24 μm (coefficient of variation (CV value): 28) is prepared. Except for the above, toner particles having a volume average particle size of 5.7 μm (coefficient of variation (CV value): 20) were obtained in the same manner as in Example 1. The toner of Example 6 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 7)
Toner particles having a volume average particle diameter of 6.1 μm (coefficient of variation (CV value): 21) were obtained in the same manner as in Example 3 except that the colored resin particle slurry produced in Example 6 was used. The toner of Example 7 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 8)
In the production of colored resin particle slurry, the temperature and pressure conditions of the micronization step are 150 ° C. and 140 MPa, respectively, and a colored resin particle slurry having a volume average particle size of 0.40 μm (coefficient of variation (CV value): 32) is prepared. Except that, toner particles having a volume average particle size of 6.5 μm (coefficient of variation (CV value): 26) were obtained in the same manner as in Example 1. The toner of Example 8 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

Example 9
A volume average particle diameter of 5.5 μm (coefficient of variation (CV value) was obtained in the same manner as in Example 3 except that the colored resin particle slurry produced in Example 8 and the biomass resin particle slurry produced in Example 2 were used. ): 22) toner particles were obtained. The toner of Example 9 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 10)
In the production of colored resin particle slurry, the temperature condition and pressure condition of the micronization step are 150 ° C. and 230 MPa, respectively, and a colored resin particle slurry having a volume average particle diameter of 0.12 μm (coefficient of variation (CV value): 28) is prepared. Except for the above, toner particles having a volume average particle size of 5.5 μm (coefficient of variation (CV value): 22) were obtained in the same manner as in Example 3. The toner of Example 10 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 11)
In the production of the biomass resin particle slurry, the temperature condition and pressure condition of the micronization process are set to 185 ° C. and 260 MPa, respectively, and a biomass resin particle slurry having a volume average particle diameter of 0.50 μm (coefficient of variation (CV value): 35) is prepared. Except for the above, toner particles having a volume average particle size of 5.5 μm (coefficient of variation (CV value): 22) were obtained in the same manner as in Example 6. The toner of Example 11 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

Example 12
In the production of the toner particles, the volume average particle diameter is 5.6 μm in the same manner as in Example 1 except that the blending amounts of the colored resin particle slurry and the biomass resin particle slurry are changed to 35 parts by weight and 65 parts by weight, respectively. Toner particles having a coefficient of variation (CV value) of 22) were obtained. The toner of Example 12 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 13)
In the production of biomass resin particle slurry, biomass resin particles having a volume average particle diameter of 0.75 μm (coefficient of variation (CV value): 38) obtained by setting the temperature condition and pressure condition of the micronization step to 175 ° C. and 190 MPa, respectively. 40 parts by weight of slurry, 47 parts by weight of resin particle slurry consisting of 0.25 μm styrene acrylic resin (glass transition temperature (Tg): 58 ° C., softening point (Tm): 112 ° C.) obtained by emulsion polymerization method, 0 0.08 μm dispersed phthalocyanine blue slurry (trade name: copper phthalocyanine 15: 3, manufactured by Clariant), 5 parts by weight, paraffinic wax (melting point 85 ° C.) dispersed in 0.4 μm, sodium chloride as a flocculant (Product name: Special grade sodium chloride, manufactured by Kishida Chemical Co., Ltd.) In an emulsifying machine (trade name: CLEARMIX, manufactured by M Technique Co., Ltd.), the mixture is stirred for 10 minutes at a coagulation temperature of 80 ° C. and a rotor rotation speed of 8000 rpm, and then further stirred at 85 ° C. for 5 minutes. Then, an aggregated particle slurry in which resin fine particles were aggregated was produced. The obtained aggregated particle slurry was washed, separated, and dried to obtain toner particles (aggregated particles) having a volume average particle size of 5.3 μm (coefficient of variation (CV value): 20). The toner powder of Example 13 was obtained by mixing 200 parts by weight of the toner powder and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 14)
Dispersed in 87 parts by weight of resin particle slurry consisting of 0.25 μm styrene acrylic resin (glass transition temperature (Tg): 58 ° C., softening point (Tm): 112 ° C.) obtained by emulsion polymerization method, 0.08 μm. 5 parts by weight of phthalocyanine blue slurry (trade name: copper phthalocyanine 15: 3, manufactured by Clariant), 8 parts by weight of paraffinic wax (melting point 85 ° C.) dispersed in 0.4 μm, sodium chloride as a flocculant (trade name: special grade) (Sodium chloride, manufactured by Kishida Chemical Co., Ltd.) 2.5 parts by weight, and using a single motion emulsifier (trade name: Claremix, manufactured by M Technique Co., Ltd.) at a coagulation temperature of 80 ° C. and a rotor rotational speed of 8000 rpm The mixture was agitated for 10 minutes, and further stirred at 85 ° C. for 5 minutes to agglomerate the resin fine particles. A particle collection slurry was prepared. The obtained aggregated particle slurry was washed, separated and dried to obtain toner particles (aggregated particles) having a volume average particle diameter of 5.5 μm (variation coefficient (CV value): 18). The toner powder of Example 14 was obtained by mixing 200 parts by weight of this toner powder and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 15)
Toner particles having a volume average particle size of 5.4 μm (coefficient of variation (CV value): 18) were obtained in the same manner as in Example 14 except that the phthalocyanine blue slurry was not used. The toner of Example 15 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Example 16)
Fine particles comprising 0.1 μm styrene acrylic resin (glass transition temperature (Tg): 64 ° C., softening point (Tm): 122 ° C.) obtained by the emulsion polymerization method were formed on the surface of the toner of Example 14. A toner film having a volume average particle size of 5.6 μm (coefficient of variation (CV value): 20) was obtained by depositing a resin film having a thickness of 0.15 μm. The toner of Example 16 was obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

(Comparative Example 1)
In the production method in Comparative Example 1, toner particles are obtained from a mixture prepared by melt-kneading polylactic acid as a biomass resin and polyester resin as a binder resin. For this reason, the biomass resin is dispersed in the toner particles in a state of being compatible with the binder resin. A method for producing toner particles in Comparative Example 1 will be described below.

  40.5 parts by weight of polylactic acid (CE-1), polyester resin (glass transition temperature (Tg): 60 ° C., softening point (Tm): 110 ° C.) 40.5 parts by weight, phthalocyanine blue (trade name: copper phthalocyanine 15 : 3, Clariant Co., Ltd.) 4 parts by weight, paraffin wax (melting point 85 ° C) 4 parts by weight, charge control agent (trade name: TRH, Hodogaya Chemical Co., Ltd.) 1 part by weight is mixed with a Henschel mixer for 10 minutes. Then, the mixture was melt-kneaded in a twin-screw extrusion kneader (trade name: PCM65, manufactured by Ikekai Co., Ltd.) 100 g (10 parts by weight) of this melt-kneaded product and 5 g (0.5 parts by weight) of sodium polyacrylate (trade name: D-H14-N L-7403KN, manufactured by Nippon Emulsifier Co., Ltd.) as an anionic surfactant , 895 g (89.5 wt%) of water (temperature 20 ° C., conductivity 0.5 μS / cm), and the resulting mixture is placed in a tank of a high-pressure homogenizer (trade name: NANO3000, manufactured by Mie Co., Ltd.). Then, coarse pulverization was performed under conditions of 25 ° C. and 100 MPa. Next, atomization was performed under the conditions of 160 ° C. and 185 MPa to prepare a resin particle slurry. The volume average particle diameter of the obtained resin particles was 0.82 μm (coefficient of variation (CV value): 29).

  Next, 3.2 parts by weight of sodium chloride (trade name: special grade sodium chloride, manufactured by Kishida Chemical Co., Ltd.) as a flocculant is added to 100 parts by weight of the obtained resin particle slurry, and a single motion type emulsifier (trade name: Agglomerated resin in which resin particles are agglomerated by agitation treatment at a coagulation temperature of 80 ° C. and a rotor rotation speed of 8000 rpm for 10 minutes, and further agitation at 85 ° C. for 5 minutes. A particle slurry was prepared. The obtained aggregated resin particle slurry was washed, separated, and dried to obtain toner particles having a volume average particle size of 5.8 μm (coefficient of variation (CV value): 22). The toner particles of Comparative Example 1 were obtained by mixing 200 parts by weight of the toner particles and 2.5 parts by weight of hydrophobic silica fine powder (trade name: RX-200, manufactured by Nippon Aerosil Co., Ltd.).

  The toners of Examples and Comparative Examples were evaluated for domain diameter, volume average particle diameter, coefficient of variation, fixability, durability, and transparency. The evaluation method is as follows.

<Domain diameter>
The domain diameter of the domain containing the biomass resin in the toner particles is the diameter when the domain cross section is converted into a circle. The dispersion state of the domain containing the biomass resin in the toner particles is obtained by using a microtome having diamond teeth and solidifying the solid particles obtained by embedding the toner particles in a room temperature curable epoxy resin to an extremely thin thickness of about 100 μm. This can be confirmed by sectioning and observing the cross section of the toner particles at 20000 times with a transmission electron microscope (TEM, trade name: H-8100, manufactured by Hitachi, Ltd.). The domain diameter of the domain containing the biomass resin confirmed in this manner was the diameter when the domain cross section was converted to a circle.

<Volume average particle size and coefficient of variation>
20 ml of a sample and 1 ml of sodium alkyl ether sulfate are added to 50 ml of an electrolytic solution (trade name: ISOTON-II, manufactured by Beckman Coulter, Inc.), and ultrasonic waves are applied using an ultrasonic disperser (trade name: UH-50, manufactured by STM). A sample for measurement was prepared by dispersion treatment at a frequency of 20 kHz for 3 minutes. This sample for measurement was measured using a particle size distribution measuring device (trade name: Multisizer 3, manufactured by Beckman Coulter, Inc.) under the conditions of aperture diameter: 20 μm, number of measured particles: 50000 count, and volume particle size distribution of sample particles. From this, the volume average particle size was determined. Further, the coefficient of variation of the toner was calculated from the following formula based on the volume average particle diameter and its standard deviation. In addition, it measured by this method also about the volume average particle diameter and variation coefficient of the colored resin particle and biomass resin particle which were mentioned above.
Coefficient of variation CV (%) = (standard deviation in volume particle size distribution / volume average particle size) × 100

<Fixability>
Developers containing toners of Examples and Comparative Examples were filled into ARC-150 manufactured by Sharp Corporation as an image forming apparatus. In such a state, the image forming apparatus is operated so that the process speed is 88 mm / sec, and an unfixed image is formed on a recording sheet (basis weight 52 g / m ² ) with a predetermined chart. I let you. The unfixed image formed on the recording paper is fixed to the recording paper while changing the temperature using an oilless type external fixing machine, and the fixing roller rotates to the recording paper after the second rotation. The presence or absence of offset was visually evaluated. The evaluation criteria are as follows.
A: Very good. No offset occurs when the fixing temperature is in the range of 120 to 200 ° C.
○: Good. No offset occurs when the temperature during fixing is in the range of 130 to 190 ° C.
Δ: No problem in actual use.
×: Unbearable for actual use.

<Durability>
Developers containing toners of Examples and Comparative Examples were filled into ARC-150 manufactured by Sharp Corporation as an image forming apparatus. The image forming apparatus is operated so that the process speed is 88 mm / sec in an environment with an air temperature of 20 ° C. and a relative humidity of 50%, and an image is displayed on an A4 size recording paper (basis weight 75 g / m ² ) on a predetermined chart. An image having been removed was formed. At this time, an image was formed on 10,000 sheets of recording paper, and the blank paper portion after 10,000 sheets was visually evaluated. The evaluation criteria are as follows.
A: Very good.
○: Good.
Δ: No problem in actual use.
×: Unbearable for actual use.

  For the toner of Example 14, the particle size distribution of the toner after processing 10,000 sheets was measured with a Coulter counter, and it was confirmed that the particle size distribution was almost unchanged before and after the processing.

<Transparency>
Developers containing toners of Examples and Comparative Examples were filled into ARC-150 manufactured by Sharp Corporation as an image forming apparatus. In this state, the image forming apparatus was operated so that the process speed was 88 mm / sec. With development and fixing conditions that optimize chromaticity and saturation,
On the OHP sheet (manufactured by Sharp Document System: IJ188OHP), an image obtained by imaging with a predetermined chart was formed, and the actual usability was evaluated by visual observation. The evaluation criteria are as follows.
A: Very good.
○: Good.
Δ: No problem in actual use.
×: Unbearable for actual use.

<Preservability>
300 g of the toners of Examples and Comparative Examples were put into a dedicated toner bottle and left in a thermostatic bath at 50 ° C. for 2 days, and then the presence of aggregates was visually checked with a 400 mesh sieve. The evaluation criteria are as follows.
A: Very good.
○: Good.
Δ: No problem in actual use.
×: Unbearable for actual use.

The overall evaluation was based on the following criteria.
A: When all items are ○ or more.
○: When there is one or more Δ.
X: When there is one or more x.

  Table 1 shows the evaluation results for the domain diameter, volume average particle diameter, coefficient of variation, fixability, durability, transparency, storage stability, and comprehensive evaluation of the toners of Examples and Comparative Examples.

  From Table 1, it is clear that the toner of the present invention has good fixability and is excellent in durability, transparency and storage stability. In particular, the domain diameter of the domain containing the biomass resin is 0.5 μm or more and 1 μm or less, and the ratio (a / c) of the particle diameter of the binder resin particles to the particle diameter of the biomass resin particles is ¼ or more and ½ or less. In addition, the toners of Examples 1, 5 to 7, and 13 to 16 in which the content of the biomass resin with respect to 100 parts by weight of the toner is 60 parts by weight or less have high overall toner quality, and the overall evaluation is “ ◎ ”.

1 is a view showing a cross section of toner particles 1 according to an embodiment of the present invention. It is a figure which shows the cross-sectional shape of the domain 2 containing biomass resin. 4 is a flowchart showing a first example of a method for producing toner particles 1. 4 is a flowchart showing a second example of a method for producing toner particles 1. 6 is a flowchart showing a third example of a method for producing toner particles 1. 1 is a cross-sectional view illustrating a configuration of an image forming apparatus 100 according to an embodiment of the present invention. It is a figure which shows the structure of the developing means 14 which is a developing device of this invention. It is a figure which shows the cross section of the toner particle 51 in a prior art.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Toner particle 2 Domain containing biomass resin 3 Transfer means 4 Fixing means 5 Recording medium supply means 6 Discharge means 7 Toner image forming means 11 Photosensitive drum 12 Charging means 13 Exposure unit 14 Developing means 15 Cleaning unit 100 Image forming apparatus

Claims (20)

A toner containing at least a binder resin,
A toner, wherein a domain containing a biomass resin is formed in toner particles.   The toner according to claim 1, wherein the domain containing the biomass resin is substantially spherical or a combination thereof.   The toner according to claim 1, wherein the biomass resin is a crystalline resin.   The toner according to claim 1, wherein the biomass resin content is 20 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the toner.   The toner according to claim 1, wherein a colorant is not contained in the domain containing the biomass resin.   The toner according to claim 1, wherein the domain diameter of the domain containing the biomass resin is 1 μm or less.   The toner according to claim 6, wherein the domain diameter of the domain containing the biomass resin is 0.5 μm or more and 1 μm or less.   The toner according to claim 1, wherein the binder resin is a polyester resin.   The toner according to claim 1, wherein the surface of the toner is coated with a resin film.   The toner according to claim 9, wherein the resin film is formed of a styrene acrylic resin produced by an emulsion polymerization method. At least a binder resin dispersed in a liquid medium to obtain a binder resin particle slurry;
A biomass resin particle dispersion step of dispersing at least a biomass resin in a liquid medium to obtain a biomass resin particle slurry; and
A method for producing a toner, comprising: an aggregating step of mixing a binder resin particle slurry and a biomass resin particle slurry and aggregating the binder resin particles and the biomass resin particles.   The method for producing a toner according to claim 11, wherein the binder resin particles contain a colorant. A colorant particle dispersion step of dispersing a colorant in a liquid medium to obtain a colorant particle slurry;
The aggregating step mixes the binder resin particle slurry, the biomass resin particle slurry, and the colorant particle slurry to aggregate the binder resin particles, the biomass resin particles, and the colorant particles. 2. A method for producing the toner according to 1.   The method for producing a toner according to claim 11, wherein the particle diameter of the binder resin particles is ¼ or more and ½ or less of the particle diameter of the biomass resin particles. The biomass resin particle dispersion process
A fine granulation step for producing a biomass resin particle slurry under heat and pressure;
A depressurization step of depressurizing the biomass resin particle slurry in a heated and pressurized state;
The method for producing a toner according to claim 11, further comprising a cooling step of cooling the depressurized biomass resin particle slurry.   The method for producing a toner according to any one of claims 11 to 15, wherein the biomass resin particle dispersion step is performed by a high-pressure homogenizer method.   A toner manufactured by the toner manufacturing method according to claim 11.   A two-component developer comprising the toner according to any one of claims 1 to 10 and 17, and a carrier.   A developing device that performs development using the developer containing the toner according to any one of claims 1 to 10, or the two-component developer according to claim 18.   An image forming apparatus comprising the developing device according to claim 19.

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