JP2022018292A - Toner and method for manufacturing toner - Google Patents

Abstract

To provide a toner that can be fixed at a low temperature, can improve the heat-resistant storage property of the toner, and can efficiently diffuse a perfume from the toner on a print, and provide a method for manufacturing the toner.SOLUTION: A toner includes a toner core particles and perfume microcapsules in each of which a perfume is included in thermosetting resin and formed into a microcapsule. The perfume microcapsules are adhered to the toner core particle by a shell layer that covers the surface of the toner core particle. A method for manufacturing the toner includes a first step of attaching shell particles to the surfaces of the perfume microcapsules, and a second step of attaching, to the surface of the toner core particle, the perfume microcapsules the surfaces of which the shell particles are attached to.SELECTED DRAWING: Figure 1

Description

The present invention relates to a toner used in an electrophotographic image forming apparatus and a method for manufacturing the toner.

In recent years, the demand for printed matter with a taste has increased, and one example is printed matter that emits a scent. Also in the field of electrophotographic, as a toner used in an electrophotographic image forming apparatus, an aromatic toner and a method for producing the same are conventionally known (see, for example, Patent Documents 1 and 2).

Specifically, Patent Document 1 proposes a toner in which aromatic particles are immobilized on colored particles, and resin particles for forming an outer shell are further immobilized to form an outer shell. Further, Patent Document 2 proposes a toner in which microcapsules containing a fragrance are located in a region from the surface of the toner particles to a depth of 1 μm or inside the region.

Japanese Unexamined Patent Publication No. 3-48861 Japanese Unexamined Patent Publication No. 2016-212264

However, in the toner described in Patent Document 1, the fragrance in the aromatic particles is a solid substance at room temperature, and although it is liquefied by the heat of fixing, it does not vaporize, so that the fragrance is effectively released from the toner in the printed matter. It cannot be made to, and therefore the printed matter does not have sufficient aroma. Further, in the toner described in Patent Document 2, the fragrance in the microcapsules is instantly vaporized by the heat of fixing, and the printed matter does not have a sufficient scent, or the scent does not last, and therefore the toner in the printed matter. It is not possible to effectively dissipate the fragrance. Therefore, in order to fix the toner at a low temperature, it is necessary to lower the glass transition point (Tg), but there is a problem in heat-resistant storage due to the low glass transition point (Tg).

Therefore, the present invention provides a toner and a method for producing a toner, which is a toner that can be fixed at a low temperature, yet can improve the heat-resistant storage stability of the toner and can effectively dissipate a fragrance from the toner in a printed matter. The purpose is to do.

The present invention provides the following toner and a method for producing the toner in order to solve the above-mentioned problems.

(1) Toner The toner according to the present invention is a toner containing toner core particles and fragrance microcapsules in which fragrance is encapsulated in a thermosetting resin and is microencapsulated. The fragrance microcapsules are the toner core. It is characterized in that it is fixed to the toner core particles by a shell layer that covers the surface of the particles.

(2) Method for Producing Toner The method for producing a toner according to the present invention is a method for producing a toner for producing the toner according to the present invention, and is a first step of adhering the shell particles to the surface of the fragrance microcapsules. It is characterized by including a second step of adhering the perfume microcapsules to which the shell particles have adhered to the surface to the surface of the toner core particles.

According to the present invention, although the toner can be fixed at a low temperature, the heat-resistant storage stability of the toner can be improved, and the fragrance can be effectively emitted from the toner in the printed matter.

It is a schematic diagram which shows the cross-sectional structure of the toner which concerns on embodiment of this invention. It is a process drawing which shows a part of the manufacturing method of the toner which concerns on this embodiment. It is a schematic diagram which shows how the shell particles adhering to the surface of a fragrance microcapsule are deformed in the toner manufacturing method which concerns on this embodiment. It is a schematic diagram which shows the appearance that the shell particle adhering to the surface of a fragrance microcapsule is deformed and covers the shell layer formed from the shell particle on the surface of a toner core particle in the method of manufacturing a toner which concerns on this embodiment. .. It is a process drawing which shows the whole manufacturing method of the toner which concerns on this embodiment. It is a schematic diagram of the stirrer used in the process of forming a fragrance microcapsule-shell particle complex. It is a schematic diagram of the Henschel mixer type dryer used in the composite particle forming process. It is a front view which shows the schematic structure of the hybridization system used in the capsule particle formation step. FIG. 7 is a schematic cross-sectional view of the hybridization system shown in FIG. 7A as viewed from the cut plane lines A200-A200. It is sectional drawing which shows the size of the particle size of a fragrance microcapsule. It is sectional drawing which shows the magnitude of the particle size of the perfume microcapsule in the toner. It is explanatory drawing for demonstrating the influence with respect to the image quality. It is explanatory drawing for demonstrating the influence on performance and quality. It is sectional drawing for demonstrating how to take the thickness of the shell layer in a toner particle.

1. 1. Toner FIG. 1 is a schematic view showing a cross-sectional configuration of the toner 100 according to the embodiment of the present invention. The toner 100 (toner particles) according to the present embodiment includes toner core particles 101, perfume microcapsules 102, and a shell layer 103. The shell layer 103 is sometimes referred to as a coating layer. The fragrance microcapsule 102 is a thermosetting resin 102a in which the fragrance 102b is encapsulated and microencapsulated.

The fragrance microcapsules 102 are fixed to the toner core particles 101 by the shell layer 103 that covers the surface 101a of the toner core particles 101. Specifically, the perfume microcapsules 102 are fixed to the outside of the toner core particles 101 by the shell layer 103. That is, the perfume microcapsules 102 are not present in the toner core particles 101.

In the present embodiment, when the toner 100 is fixed at a low temperature, the heat resistant temperature of the thermosetting resin 102a is higher than the fixing temperature (for example, about 160 ° C. to 190 ° C.) even if the glass transition point (Tg) is lowered. Since the temperature is high (for example, about 200 ° C.), the heat-resistant temperature of the fragrance microcapsule 102 can be increased, and the heat-resistant storage stability of the toner 100 can be improved. Moreover, since the perfume microcapsules 102 contain the perfume 102b in the thermosetting resin 102a, the heat resistant temperature of the thermosetting resin 102a as the perfume microcapsules 102 is higher than the fixing temperature (for example, about 160 ° C. to 190 ° C.). By using a high-priced material, the fragrance 102b is not emitted from the printed matter due to the heat of fixing, and the fragrance 102b is emitted from the printed matter by breaking the fragrance microcapsules 102 by an external pressure such as the user touching the toner with his / her hand. (Generates fragrance) can be generated. Therefore, the fragrance 102b can be effectively dissipated from the toner 100 in the printed matter.

As described above, according to the present embodiment, the toner 100 can be fixed at a low temperature, but the heat-resistant storage stability of the toner 100 can be improved, and the fragrance 102b can be effectively dissipated from the toner 100 in the printed matter. Can be done.

Further, the thermosetting resin 102a in the fragrance microcapsules 102 has no or almost no thermoplasticity, and the fragrance microcapsules 102 are not easily deformed (hard). Therefore, when the shell layer 103 is not used, the fragrance microcapsules 102 Where it is difficult to adhere to the toner core particles 101, in the present embodiment, the perfume microcapsules 102 can be effectively adhered to the toner core particles 101 by using the shell layer 103.

In the toner 100 according to the present embodiment, all or part of the perfume microcapsules 102 is covered with a shell layer.

By the way, when the shell layer 103 and the thermosetting resin 102a in the fragrance microcapsules 102 have different charging polarities (for example, when the shell layer 103 has a negative charging polarity and the thermosetting resin 102a has a positive charging polarity). If a part of the fragrance microcapsules 102 (thermosetting resin 102a) having the opposite polarity to the shell layer 103 is exposed too much from the shell layer 103, the chargeability of the toner 100 tends to deteriorate. Then, for example, fog occurs in the formed image.

Therefore, in the toner 100 according to the present embodiment, the ratio of the entire fragrance microcapsule 102 covered with the shell layer 103 (the surface area of the portion where the entire fragrance microcapsule 102 is covered with the shell layer 103 is the surface area of the fragrance microcapsule 102). It is preferable that the area ratio divided by the whole is a predetermined value (for example, 10%) or more. For example, when the shell layer 103 and the thermosetting resin 102a in the fragrance microcapsules 102 have different charging polarities, the ratio of the entire fragrance microcapsules 102 being covered with the shell layer 103 is set to a predetermined value (for example, 20%) or more. By doing so, the chargeability of the toner 100 can be improved. For example, it is possible to effectively prevent the charging abnormality of the toner 100, and it is possible to effectively prevent the generation of fog in the formed image. Here, the coverage of the shell particles with respect to the fragrance microcapsules 102 is a value calculated in a state before the shell particles are deformed. As shown in FIG. 3A, which will be described later, the shell particles can be deformed, and the deformation of the shell particles reduces the actual exposed portion of the perfume microcapsules 102, so that the amount is preferably 10% or more, more preferably 20%. The above can be done.

By the way, if the coating thickness of the shell layer 103 covering the fragrance microcapsules 102 becomes too small, the coating state of the fragrance microcapsules 102 by the shell layer 103 tends to deteriorate. On the other hand, if the coating thickness of the shell layer 103 covering the fragrance microcapsules 102 becomes too large, it becomes difficult to maintain the low temperature fixability.

In this respect, in the present embodiment, the coating thickness of the shell layer 103 is preferably about 0.8 μm to 2.2 μm, more preferably about 1.0 μm to 2.2. By doing so, it is possible to suppress the detachment of the fragrance microcapsules 102 from the shell layer 103.

In the present embodiment, the heat distortion temperature of the perfume microcapsule 102 can be exemplified at about 70 ° C. to 180 ° C. By doing so, the heat resistance of the fragrance microcapsules 102 can be enhanced. As a result, the perfume 102b can be reliably held in the thermosetting resin 102a without breaking the perfume microcapsules 102 when the toner 100 is manufactured. Moreover, the heat-resistant storage stability of the toner 100 can be improved.

In the present embodiment, the perfume microcapsule 102 is preferably microencapsulated with a thermosetting resin 102a selected from a urea resin, a melamine resin, and a polyurethane resin. By doing so, the thermosetting resin 102a containing various positive charges can be used.

Next, the details of the toner 100 will be described below.

[Toner core particles]
The toner core particles 101 include a binder resin, a colorant, and a mold release agent. The binding resin is the main resin of the toner core particles 101. As the binder resin, a styrene acrylic copolymer resin can be used. Examples of the monomer that can be used as a resin raw material include styrene derivatives such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, and 2,4-dimethylstyrene. Acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, octyl acrylate, 2-chlorethyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylic acid, methacrylic acid Acrylic acid derivatives such as ethyl acid acid, propyl methacrylic acid, n-butyl methacrylic acid, isobutyl methacrylic acid, n-octyl methacrylic acid, 2-ethylhexyl methacrylic acid, phenyl methacrylic acid, dimethylamino ester methacrylic acid. And methacrylic acid derivatives can be exemplified.

Further, as the resin raw material, vinyl monomers such as maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monophenyl ester, maleic acid monoallyl ester, and divinylbenzene may be used.

The glass transition point of the binder resin is preferably 40 ° C. or higher and 60 ° C. or lower. If the glass transition point of the binder resin is less than 40 ° C., blocking in which the toner particles are thermally aggregated inside the image forming apparatus is likely to occur, and the storage stability may be deteriorated. If the glass transition point of the binder resin exceeds 60 ° C., the low temperature fixability may be impaired.

[Colorant]
As the colorant, carbon black, an organic pigment, or the like commonly used in the electrophotographic field can be used.

As the black colorant, for example, carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, non-magnetic ferrite, magnetic ferrite, magnetite and the like can be used.

Examples of the yellow colorant include 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. Pigment Yellow 185 and the like can be used.

Examples of the magenta colorant include 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. Pigment Red 222 and the like can be used.

Examples of the cyan colorant include 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. Pigment Blue 60 and the like can be mentioned.

The amount of the colorant used is not particularly limited, but is preferably 5 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the binder resin. The colorant may be used as a masterbatch in order to be uniformly dispersed in the binder resin.

[Release agent]
As the mold release agent, for example, paraffin wax, microcrystalline wax, Fishertropus wax, polyethylene wax, polypropylene wax, carnauba wax, synthetic ester wax and the like can be used. The amount of the release agent used is not particularly limited and can be appropriately selected from a wide range, but is preferably 2.0 parts by weight or more and 6.0 parts by weight or less with respect to 100 parts by weight of the binder resin. If the amount of the release agent added is less than 2.0 parts, the release agent is less likely to seep out when the toner 100 is fixed, and high temperature offset is likely to occur. Further, when the amount of the release agent added is more than 6.0 parts, the release agent may be exposed on the surface of the toner core particles 101, and the fluidity of the toner core particles 101 may deteriorate.

[Charge control agent]
A charge control agent may be added to the toner core particles 101 as needed. As the charge control agent, charge control agents for positive charge control and negative charge control commonly used in this field can be used.

As the charge control agent for positive charge control, for example, a quaternary ammonium salt, a pyrimidine compound, a triphenylmethane derivative, a guanidine salt, an amidine salt and the like can be used.

As the charge control agent for negative charge control, metal-containing azo compounds, azo complex dyes, metal complexes and metal salts of salicylic acid and its derivatives (metals are chromium, zinc, zirconium, etc.), organic bentonite compounds, boron compounds, etc. are used. can.

The amount of the charge control agent used is not particularly limited and can be appropriately selected from a wide range, but is preferably 0.5 parts by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the binder resin.

[Volume average particle size of toner core particles]
The volume average particle size of the toner core particles 101 is preferably 5 μm or more and 10 μm or less. When the volume average particle size is 5 μm or more and 10 μm or less, a high-definition image can be stably formed for a long period of time. Further, by reducing the particle size of the toner core particles 101 within this range, a high image density can be obtained even if the amount of adhesion is small, and the effect of reducing the toner consumption can also be obtained. If the volume average particle size of the toner core particles 101 is less than 5 μm, the particle size of the toner core particles is small, so that there is a risk of high charge and low fluidity. When the toner becomes highly charged and has a low fluidity, the toner cannot be stably supplied to the photoconductor, and there is a possibility that the background fog and the decrease in image density may occur. When the volume average particle size of the toner core particles 101 exceeds 10 μm, the layer thickness of the formed image becomes large due to the large particle size of the toner core particles 101, resulting in an image having remarkable graininess, and a high-definition image cannot be obtained. Further, as the particle size of the toner core particles 101 increases, the specific surface area decreases and the amount of charge of the toner decreases. If the amount of charge of the toner becomes small, the toner is not stably supplied to the photoconductor, and there is a possibility that in-machine contamination due to toner scattering may occur.

[Shell layer]
The shell layer 103 is formed of an acrylic resin on the outside of the toner core particles 101. As the acrylic resin, a resin obtained by polymerizing or copolymerizing a single or a plurality of monomers containing at least one of an acrylic monomer and a methacrylic monomer can be used.

As the acrylic monomer, for example, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, octyl acrylate, 2-chlorethyl acrylate, phenyl acrylate and the like can be used. ..

Examples of the methacrylic monomer include methacrylic acid, methyl methacrylic acid, ethyl methacrylic acid, propyl methacrylic acid, n-butyl methacrylic acid, isobutyl methacrylic acid, n-octyl methacrylic acid, and 2 methacrylic acid. -Acrylic acid derivatives such as ethylhexyl, phenyl methacrylic acid, and dimethylaminoester methacrylic acid and methacrylic acid derivatives can be used.

Styrene such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, and 2,4-dimethylstyrene as monomers that can be used in addition to acrylic monomers or methacrylic monomers. Derivatives can be used.

[Fragrance microcapsules]
The fragrance microcapsule 102 contains the fragrance 102b with a thermosetting resin 102a (a wall film formed of the thermosetting resin 102a). As the fragrance 102b, a liquid scent component (liquid fragrance) can be typically exemplified.

The liquid scent component is not particularly limited, and examples thereof include a general oily scent component or a diluted solution of the scent component. Examples of the oily scent component include bromstyrol, phenylethyl alcohol, linalool, hexyl cinnamic aldehyde, α-limonene, benzyl aldehyde, eugenol, borneyl aldehyde, citronellal, colorar, terpineol, geraniol, menthol, silicic acid and the like. Natural or synthetic scent components of. As the fragrance 102b, a case where one kind is used alone or a case where two or more kinds are used in combination can be exemplified.

Examples of the diluted solution of the scent component include a diluted solution obtained by diluting the above-mentioned scent component with an odorless solvent such as benzylbenzoates.

Examples of the thermosetting resin 102a include urea / formaldehyde resin, melamine / formaldehyde resin, guanamine / formaldehyde resin, sulfoamide / aldehyde resin, aniline / formaldehyde resin and the like. Among these resins, a melamine / formaldehyde resin can be preferably used in that it is excellent in water resistance, chemical resistance, solvent resistance, and aging resistance.

2. 2. Toner Manufacturing Method FIG. 2 is a process diagram showing a part of the toner 100 manufacturing method according to the present embodiment. The method for manufacturing the toner 100 for manufacturing the toner 100 according to the present embodiment includes the first step P1 and the second step P2.

In the first step P1, the shell particles 110 are attached to the surface 102c of the perfume microcapsules 102. The shell particles 110 may also be referred to as shell materials or resin fine particles. In the second step P2, the perfume microcapsules 102 to which the shell particles 110 are attached to the surface 102c are attached to the surface 101a of the toner core particles 101.

According to the method for producing the toner 100 according to the present embodiment, the surface 102c of the perfume microcapsules 102 can be covered with the shell particles 110 in the first step P1. Further, by carrying out the second step P2 after the first step P1, the surface 102c is covered with the shell particles 110 before the shell particles 110 are attached to the surface 101a of the toner core particles 101 in the second step P2. The perfume microcapsules 102 can be attached to the surface 101a of the toner core particles 101. As a result, in the second step P2, the perfume microcapsules 102 in which the surface 102c is completely covered with the shell particles 110 and the toner core particles 101 are mixed, and the surface 102c is covered with the shell particles 110. 102 can be attached to the surface 101a of the toner core particles 101.

The method for manufacturing the toner 100 according to the present embodiment further includes the third step P3. In the third step P3, the shell layer 103 is formed from the shell particles 110, and the fragrance microcapsules 102 are fixed to the toner core particles 101 by the formed shell layer 103. Specifically, in the third step P3, the perfume microcapsules 102 are fixed to the outside of the toner core particles 101 by the formed shell layer 103. By doing so, the perfume microcapsules 102 can be reliably immobilized on the toner core particles 101.

FIG. 3A is a schematic view showing how the shell particles 110 adhering to the surface 102c of the fragrance microcapsules 102 are deformed in the method for producing the toner 100 according to the present embodiment. Further, FIG. 3B shows a shell formed from the shell particles 110 on the surface 101a of the toner core particles 101 by deforming the shell particles 110 adhering to the surface 102c of the perfume microcapsules 102 in the method for producing the toner 100 according to the present embodiment. It is a schematic diagram which shows the state which covers the layer 103.

In the method for producing the toner 100 according to the present embodiment, as shown in FIGS. 3A and 3B, in the third step P3, a mixture of the toner core particles 101, the shell particles 110, and the perfume microcapsules 102 will be described later. The hybridization system 201 (see FIGS. 7A and 7B) disperses the annular flow path into the circulating airflow. Next, the surface 101a of the toner core particles 101 is coated with the shell layer 103 formed from the shell particles 110 by the mechanical treatment of the rotary stirring unit provided in the middle of the flow path. Then, the fragrance microcapsules 102 are fixed to the toner core particles 101 by the coated shell layer 103. By doing so, the shell particles 110 can be deformed to form the shell layer 103, whereby the perfume microcapsules 102 can be easily fixed to the toner core particles 101.

By the way, as the volume average particle size of the fragrance microcapsules 102 is smaller, the amount of the fragrance 102b that can be stored in the fragrance microcapsules 102 is relatively reduced. Further, if the volume average particle size of the perfume microcapsules 102 becomes too small, the perfume microcapsules 102 are less likely to be broken by an external force, and thus the ability to generate a scent from the perfume microcapsules 102 is reduced. On the other hand, if the volume average particle size of the fragrance microcapsules 102 becomes too large, the ability of the shell layer 103 to immobilize the fragrance microcapsules 102 decreases, and the fragrance microcapsules 102 are easily detached from the shell layer 103. That is, if the volume average particle size of the fragrance microcapsules 102 becomes too large, the fragrance microcapsules 102 tend to separate from the shell layer 103 even if the coating thickness of the shell layer 103 is increased. Then, the particles of the fragrance microcapsules 102 are present alone. For example, if the perfume microcapsules 102 that exist alone adhere to an image carrier such as a photoconductor drum or a transfer belt, the toner 100 easily slips through the cleaning blade that cleans the image carrier. As a result, it causes poor cleaning.

In this respect, in the present embodiment, the volume average particle size of the fragrance microcapsules 102 can be exemplified by about 0.4 μm to 1.9 μm. By setting the volume average particle size of the fragrance microcapsules 102 to 0.4 μm or more, it is possible to secure an appropriate amount of the fragrance 102b that can be stored in the fragrance microcapsules 102, and the fragrance microcapsules 102 are broken by an external force. This can improve the effect of generating a scent from the fragrance microcapsules 102. Further, by setting the volume average particle size of the fragrance microcapsules 102 to 1.9 μm or less, it is possible to make it difficult to separate from the shell layer 103, which is effective in the presence of the particles of the fragrance microcapsules 102 alone. Can be prevented. Cleaning defects can be reduced or eliminated accordingly.

In the method for producing toner according to the present embodiment, as shown in FIG. 2, in the first step P1, the shell particles 110 are attached to the surface 102c of the fragrance microcapsules 102 by using the dispersion liquid 120 of the shell particles 110. Here, the dispersion liquid 120 of the shell particles 110 is housed in the container V together with the water W. By doing so, the perfume microcapsules 102 can be mixed with the dispersion liquid 120 of the shell particles 110. As a result, the shell particles 110 can be uniformly adhered to the surface 102c of the fragrance microcapsules 102. That is, the shell particles 110 can be attached to the surface 102c of the fragrance microcapsules 102 in a state where the shell particles 110 do not aggregate due to drying. In the second step P2, the perfume microcapsules 102 to which the shell particles 110 are attached to the surface 102c in the dispersion liquid 120 are attached to the surface 101a of the toner core particles 101. By doing so, uniform immobilization of the fragrance microcapsules 102 on the surface 101a of the toner core particles 101 by the shell layer 103 can be realized.

For example, since the size of the fragrance microcapsules 102 increases due to the amount of the liquid fragrance contained therein, it is difficult to immobilize the fragrance microcapsules 102 on the surface 101a of the toner core particles 101 by the shell layer 103. Dispersion liquid (emulsion) of a complex (fragrance microcapsules-shell particle complex 130) composed of fragrance microcapsules 102 and shell particles 110 (specifically, shell particles of a soft material) mixed with water W in step P1. Is mixed with the toner core particles 101 in the second step P2 to form a film. By doing so, the perfume microcapsules 102 can be uniformly and stably immobilized on the surface 101a of the toner core particles 101.

By the way, if the proportion of the perfume microcapsules 102 present on the surface 101a of the toner core particles 101 is too large, the perfume microcapsules 102 overlap on the surface 101a of the toner core particles 101 and are easily detached from the shell layer 103. On the other hand, if the proportion of the perfume microcapsules 102 present on the surface 101a of the toner core particles 101 is too small, the heat-resistant storage stability of the toner 100 tends to decrease.

In this regard, in the present embodiment, the particle weight of the toner core particles 101 is set to Ma1 by using the area ratio of the total particle projection area of the fragrance microcapsules 102 present on the surface 101a of the toner core particles 101 to the surface area of the toner core particles 101. When the particle weight of the fragrance microcapsules 102 is Ma2, the volume average particle size of the toner core particles 101 is Da1, and the particle projection particle size of the fragrance microcapsules 102 is Da2, the specific gravity of the toner core particles 101 is 1, and the specific gravity of the toner core particles 102 is 1. The simple first coverage θt of the following equation (1) when the specific gravity is assumed to be 1 is within the range of 9% ≦ (θt) ≦ 133%.

θt = (1/4) × (Ma2 / Ma1) × (Da1 / Da2) ... Equation (1)
By doing so, the perfume microcapsules 102 can be appropriately present on the surface 101a of the toner core particles 101, whereby the toner 100 having high heat-resistant storage stability can be obtained.

By the way, if the proportion of the shell particles 110 present on the surface 102c of the fragrance microcapsules 102 is too large, the ability to generate the scent from the fragrance microcapsules 102 is reduced. On the other hand, if the proportion of the shell particles 110 present on the surface 102c of the fragrance microcapsules 102 is too small, there is an adverse effect of the charge polarity opposite to the charge polarity of the shell particles 110 due to the material of the thermosetting resin 102a in the fragrance microcapsules 102. Invites the occurrence of.

In this regard, in the present embodiment, the particle weight of the fragrance microcapsules 102 is determined by using the area ratio of the total particle projection area of the shell particles 110 present on the surface 102c of the fragrance microcapsules 102 to the surface surface of the fragrance microcapsules 102. When the particle weight of Mb1 and the shell particles 110 is Mb2, the volume average particle size of the fragrance microcapsules 102 is Db1, and the particle projection particle size of the shell particles 110 is Db2, the specific gravity of the fragrance microcapsules 102 is 1 and the shell particles 110. The second simple second coverage θmc of the following equation (2) when the specific gravity of 1 is assumed to be 1 is within the range of 23% ≦ (θmc) ≦ 324%.

θmc = (1/4) × (Mb2 / Mb1) × (Db1 / Db2) ... Equation (2)
By doing so, the shell particles 110 can be appropriately present on the surface 102c of the perfume microcapsules 102, whereby the toner 100 which is easy to control in the electrophotographic process can be obtained.

Here, the above-mentioned simple first coverage θt [Equation (1)] and the simple second coverage θmc [Equation (2)] were derived as follows.

[Calculation of coverage]
First, the coverage rate θ is calculated with the coverage rate as θ.

-For the center particle 1 (center particle), the radius is obtained as a sphere by the representative value "volume average particle size D50 (median particle size)" obtained as the particle size, and the center particle 1 when the radius of the center particle 1 is r1. The surface area S1 = 4 × π × (r1) ² of

-For the coated particles 2 (particles to be coated), the projected area S2 = π × (r2) ² of the coated particles 2 is calculated when the coated particles 2 are circular and the radius is r2.

-When the ratio is calculated by summing up the average number of particles n existing around the sphere, the coverage θ is as shown in the following equation (3).

θ = (n × S2) / S1 = {n × π × (r2) ² } / {4 × π × (r1) ² }
= N / 4 × (r2 / r1) ² ... Equation (3)
[Calculation of particle weight ratio]
Next, the particle weights of the center particles 1 and the coated particles 2 are M1 and M2, respectively, and the specific gravity of the center particles 1 and the coated particles 2 are ρ1 and ρ2, respectively. The particle weight ratio (M2 / M1) to M1 is calculated.

The particle weight M1 of the central particle 1 is
M1 = (4/3) × π × (r1) ³ × ρ1 ... Equation (4)
Will be.

The particle weight M2 of the coated particles 2 is
M2 = n × {(4/3) × π × (r2) ³ × ρ2} ・ ・ ・ Equation (5)
Will be.

・ When M2 / M1 is solved from Eqs. (4) and (5),
(M2 / M1) = n × {(4/3) × π × (r2) ³ × ρ2} ÷ {(4/3) × π × (r1) ³ × ρ1}
= N × {(r2) ³ × ρ2} / {(r1) ³ × ρ1}
= N × (ρ2 / ρ1) × (r2 / r1) ³
= 4 × n / 4 × (r2 / r1) ² × (ρ2 / ρ1) × (r2 / r1) ... Equation (6)
Substituting equation (3) into equation (6),
(M2 / M1) = 4 × θ × (ρ2 / ρ1) × (r2 / r1) ... Equation (7)
Will be.

[Simple calculation of coverage]
Next, since the specific densities ρ1 and ρ2 of the central particles 1 and the covering particles 2 used this time are both close to about 1, the simple covering ratio θ S with ρ1 = ρ2 = 1 is used as the simple covering ratio θ _S , and the simple covering ratio θ _S is calculated. do.

When the radius r1 of the central particle 1 is replaced with the diameter D1 = 2 × r1 and the radius r2 of the coated particle 2 is replaced with the diameter D2 = 2 × r2, the equation (7) is:
(M2 / M1) = 4 × θ _S × (D2 / D1) ... Equation (8)
Will be.

-By transforming equation (8), the simple coverage θ _S is
θ _S = (1/4) × (M2 / M1) × (D1 / D2) ... Equation (9)
Is simplified.

That is, the particle weight ratio (D1 / D2) particle size ratio of the diameter D1 of the central particle 1 to the diameter D2 of the coated particle 2 and the particle weight ratio (M2 /) of the particle weight M2 of the coated particle 2 to the particle weight M1 of the central particle 1. A simple coverage rate θ _S can be obtained from M1) (the number of particles or the number of copies). Here, "simple" means that uniform spherical particles with a median particle size are assumed and that the specific gravity is ≈1.

[Simple first coverage]
In the formula (9), the particle weight M1 of the central particle 1, the particle weight M2 of the coated particle 2, the diameter D1 of the central particle 1, and the diameter D2 of the coated particle 2 are respectively, the particle weight Ma1 of the toner core particle 101 and the fragrance microcapsule. Let the simple coverage rate θ _S having the particle weight Ma2 of 102, the volume average particle size Da1 of the toner core particles 101, and the particle projection particle size Da2 of the fragrance microcapsule 102 be the simple first coverage rate θt.
θt = (1/4) × (Ma2 / Ma1) × (Da1 / Da2) ... Equation (1)
Will be.

[Simple second coverage]
In the formula (9), the particle weight M1 of the central particle 1, the particle weight M2 of the coated particle 2, the diameter D1 of the central particle 1, and the diameter D2 of the coated particle 2 are respectively, the particle weight Mb1 of the fragrance microcapsule 102 and the shell particle. Let the simple coverage rate θ _S having the particle weight Mb2 of 110, the volume average particle size Db1 of the fragrance microcapsule 102, and the particle projection particle size Db2 of the shell particles 110 be the simple second coverage rate θmc.
θmc = (1/4) × (Mb2 / Mb1) × (Db1 / Db2) ... Equation (2)
Will be.

Next, the details of the method for manufacturing the toner 100 will be described below.

FIG. 4 is a process diagram showing the entire manufacturing method of the toner 100 according to the present embodiment. The method for producing the toner 100 according to the present embodiment includes a toner core particle preparation step Pa, a shell particle dispersion liquid preparation step Pb, a fragrance microcapsule dispersion preparation step Pc, and a fragrance microcapsule-shell particle composite formation step Pd. (1st step P1), a composite particle forming step Pe (2nd step P2), a capsule particle forming step Pf (3rd step P3), and an external addition step Pg are included.

(1) Toner core particle manufacturing process Pa
The toner core particle manufacturing step Pa is a step of manufacturing the toner core particles 101. Examples of the method for producing the toner core particles 101 include a dry method such as a kneading and pulverizing method, and a wet method such as a suspension polymerization method, an emulsification aggregation method, a dispersion polymerization method, a dissolution suspension method and a melt emulsification method. .. Hereinafter, a method for producing the toner core particles 101 by a kneading and pulverizing method will be described.

In the production of the toner core particles 101 by the pulverization method, the toner core particle raw materials containing the binder resin, the colorant and other additives are dry-mixed by a mixer and then melt-kneaded by a kneader to obtain a melt-kneaded product. The melt-kneaded product is cooled and solidified, and the solidified product is pulverized with a pulverizer to obtain a finely pulverized product. After that, the toner core particles 101 are obtained by adjusting the particle size such as classification as necessary.

As the mixer, a known mixer can be used, and examples thereof include a Henschel mixer (trade name, manufactured by Mitsui Mining Co., Ltd.) and a super mixer (trade name, manufactured by Kawata Co., Ltd.).

A known kneader can be used, for example, a twin-screw kneader such as PCM-65 / 87, PCM-30 (all of the above are trade names, manufactured by Ikegai Corp.), and Kneedex (trade name, Mitsui Mine). An open roll kneader such as (manufactured by Co., Ltd.) can be mentioned.

Examples of the crusher include a counter jet mill AFG (trade name, manufactured by Hosokawa Micron Co., Ltd.) that crushes using a supersonic jet stream. Examples of the classifier include a rotary type classifier TSP separator (trade name, manufactured by Hosokawa Micron Co., Ltd.).

(2) Shell particle dispersion liquid preparation step Pb
The shell particle dispersion liquid preparation step Pb is a step of preparing a dispersion liquid of shell particles 110 (resin fine particles). As a method for producing a dispersion liquid of shell particles 110 (resin fine particles), for example, a method of emulsifying and dispersing a resin which is a raw material of shell particles with a homogenizer or the like, or a method of polymerizing a monomer by a method such as emulsion polymerization or soap-free emulsion polymerization. Therefore, a dispersion liquid of the shell particles 110 can be obtained by forming the shell particles 110 having a particle diameter of 0.05 μm or more and 1 μm or less.

The volume average particle size of the shell particles 110 (primary particles) needs to be sufficiently smaller than the average particle size of the toner core particles 101, and is preferably 0.05 μm or more and 1 μm or less. Further, the volume average particle size of the shell particles 110 (primary particles) is more preferably 0.1 μm or more and 0.2 μm or less. When the volume average particle size of the shell particles 110 (primary particles) is 0.05 μm or more and 1 μm or less, the shell layer 103 (resin coating layer) having a suitable thickness can be formed on the surface of the toner core particles 101. As a result, the toner 100 produced by the method of the present embodiment can be easily caught by the cleaning blade during cleaning. Thereby, the cleaning property of the toner 100 can be improved.

Further, the softening temperature of the resin used as the raw material for the shell particles is preferably higher than the glass transition temperature of the binder resin contained in the toner core particles 101, and more preferably 60 ° C. or higher. This makes it possible to prevent the toners 100 produced by the method of the present embodiment from being fused with each other during storage. Thereby, the storage stability of the toner 100 can be improved.

(3) Perfume microcapsule dispersion preparation step Pc
The fragrance microcapsule dispersion liquid preparation step Pc is a step of preparing a dispersion liquid of the fragrance microcapsule 102. Examples of the method for producing the dispersion liquid of the fragrance microcapsules 102 include an interfacial polymerization method, a core selvation method, an in-situ polymerization method, an in-liquid drying method, and an in-liquid curing coating method. Among these production methods, an in-situ method using a melamine resin as a wall film and an interfacial polymerization method using a urethane resin as a wall film can be preferably used.

The content of the thermosetting resin 102a is, for example, about 0.1 part by weight to 1 part by weight, more preferably about 0.2 part by weight to 0.5 part by weight with respect to 1 part by weight of the fragrance (102b). Can be mentioned.

The content of the fragrance microcapsules 102 may be, for example, about 0.5 parts by weight to 30 parts by weight, more preferably about 1 part by weight to 15 parts by weight, based on 100 parts by weight of the toner core particles (101). can.

(4) Perfume microcapsule-shell particle complex forming step Pd (first step P1)
In the perfume microcapsule-shell particle complex forming step Pd, the shell particles 110 are attached to the surface 102c of the perfume microcapsule 102. Thus, the perfume microcapsule-shell particle complex 130 is formed by combining the perfume microcapsules 102 and the shell particles 110. Here, the perfume microcapsule-shell particle complex 130 is a shell particle-coated microcapsule in which the perfume microcapsule 102 is covered with the shell particle 110.

FIG. 5 is a schematic view of the stirrer 300 used in the fragrance microcapsule-shell particle complex forming step Pd.

In the fragrance microcapsule-shell particle complex forming step Pd, for example, a stirrer 300 as shown in FIG. 5 (in the example shown in FIG. 5 having a propeller-type stirring blade 310) is used with the slurry of the fragrance microcapsules 102. , The dispersion liquid (emulsion) of the shell particles 110 is put into the container V, and the mixture is stirred at a low speed (for example, the rotation speed of the stirring blade is 60 rpm to 180 rpm) to form the fragrance microcapsule-shell particle complex 130. The example of the value of the rotation speed of the blade is an example, and it is sufficient that the liquid and the liquid are simply mixed, and the value is not limited to this value.

(5) Composite particle forming step Pe (second step P2)
In the composite particle forming step Pe, the surface 101a of the toner core particles 101 is coated with the shell particles 110, and the perfume microcapsules 102 (perfume microcapsules-shell particle composite 130) covered with the shell particles 110 are coated on the surface 101a of the toner core particles 101. Attach to. Thus, the composite particles 140 are formed by combining the toner core particles 101 and the perfume microcapsule-shell particle composite 130.

In the composite particle forming step Pe, for example, the following method can be used as a method for forming the composite particles 140.

FIG. 6 is a schematic diagram of a Henschel mixer type dryer 400 used in the composite particle forming step Pe.

In the composite particle forming step Pe, a Henschel mixer type dryer 400, for example, a Henschel mixer vacuum drying system (trade name: FM20C, manufactured by Nippon Coke Industries Co., Ltd.) as shown in FIG. 6 can be used. Toner core particles 101 (fill: 2.5 kg) and perfume microcapsules-shell obtained in the perfume microcapsule-shell particle complex forming step Pd (first step P1) in a Henshell mixer type dryer 400. The particle composite 130 (specified by the number of copies) is charged.

The toner core particles 101 and the fragrance microcapsule-shell particle composite 130 (drying hydrous particles or particle dispersion liquid) are stirred so that the peripheral speed of the tip portion 411 of the stirring blade 410 is 10 m / sec to 20 m / sec. However, it can be dried by introducing dry air. Further, the pressure inside the mixer tank 420 may be reduced as long as the scent does not disappear from the fragrance microcapsules 102. In this case, the water content can be dried to less than 1% by weight by mixing and drying the toner core particles 101 and the perfume microcapsule-shell particle composite 130 under reduced pressure.

Although it is possible to dry quickly by raising the jacket temperature of the dryer 400, it is preferable to operate at a lower temperature than the oil containing the fragrance in the fragrance microcapsules 102 to boil, and the temperature is 30 ° C to 80. It is preferable to set it to about ° C. Further, if the temperature is near the glass transition point (Tg) of the shell particles 110, the effect of immobilizing the shell particles 110 on the toner core particles 101 when the shell particles 110 are dried can be expected.

The coating state of the perfume microcapsule-shell particle composite 130 with respect to the toner core particles 101 changes depending on the timing of drying in the process. For example, after drying, agglomeration by the shell particles 110 occurs and uniform coating becomes difficult, but a liquid cross-linking force by water is generated during drying, which has an effect of helping the shell particles 110 to be immobilized on the toner core particles 101.

The mixing ratio of the toner core particles 101 and the shell particles 110 is preferably such that the surface 101a of the toner core particles 101 is completely and thinly covered with the shell particles 110, and the mixing ratio of the toner core particles 101 and the shell particles 110 is as follows. For example, the ratio of 5 parts by weight to 15 parts by weight of the shell particles (110) to 100 parts by weight of the toner core particles (101) can be mentioned. When the compounding ratio of the shell particles 110 is less than 5 parts by weight, it is difficult to sufficiently coat the toner core particles 101, and the storage stability tends to be insufficient. If it exceeds 15 parts by weight, the amount of the film is excessive, it is difficult to thin the shell layer 103, and the low temperature fixability tends to deteriorate. As the compounding ratio of the toner core particles 101 and the perfume microcapsules 102, for example, the ratio of 0.5 parts by weight to 35 parts by weight of the perfume microcapsules (102) to 100 parts by weight of the toner core particles (101) can be mentioned. ..

(6) Capsule particle forming step Pf (third step P3)
In the capsule particle forming step Pf, the shell particles 110 are filmed on the surface of the toner core particles 101 to form capsule particles by applying a mechanical impact force to the composite particles 140.

FIG. 7A is a front view showing a schematic configuration of the hybridization system 201 used in the capsule particle forming step Pf. FIG. 7B is a schematic cross-sectional view of the hybridization system 201 shown in FIG. 7A as viewed from the cut plane lines A200-A200.

In the capsule particle forming step Pf, for example, the hybridization system 201 (trade name: NHS-3 type, manufactured by Nara Machinery Co., Ltd.) as shown in FIG. 7A was used to form the toner core particles 101 produced in the toner core particle producing step Pa. The composite particles 140 formed in the composite particle forming step Pe are attached, and the shell layer 103 (resin coating layer) is formed on the toner core particles 101 by the impact force due to the synergistic effect of circulation and stirring in the hybridization system 201. The hybridization system 201 is a rotary stirring device, and includes a powder flow path 202, a rotary stirring means 203 (rotary stirring section), a temperature control jacket (not shown), a powder charging section 206, and a powder recovery section 207. Consists of including. The rotary stirring means 203 and the powder flow path 202 form a circulation means.

The powder flow path 202 is composed of a stirring unit 208 and a powder flow unit 209. The stirring unit 208 is a cylindrical container-shaped member having an internal space. Openings 210 and 211 are formed in the stirring unit 208, which is a rotary stirring chamber. The opening 210 is formed so as to penetrate the side wall including the surface 208a of the stirring unit 208 in the thickness direction at a substantially central portion of the surface 208a on one side in the axial direction of the stirring unit 208. Further, the opening 211 is formed so as to penetrate the side wall including the side surface 208b of the stirring unit 208 on the side surface 208b perpendicular to the surface 208a on one side in the axial direction of the stirring unit 208 in the thickness direction. One end of the powder flow portion 209, which is a circulation pipe, is connected to the opening 210, and the other end is connected to the opening 211. As a result, the internal space of the stirring portion 208 and the internal space of the powder flowing portion 209 are communicated with each other, and the powder flow path 202 is formed. The toner core particles 101, the composite particles 140, and the gas flow through the powder flow path 202. The powder flow path 202 is provided so that the powder flow direction, which is the direction in which the toner core particles 101 and the composite particles 140 flow, is constant.

The rotary stirring means 203 includes a rotary shaft member 212, a disk-shaped rotary disk 213, and a plurality of stirring blades 214. The rotary shaft member 212 has an axis line that coincides with the axis line of the stirring unit 208, and is formed in the surface 208c on the other side of the stirring unit 208 in the axial direction so as to penetrate the side wall including the surface 208c in the thickness direction. It is a cylindrical rod-shaped member provided so as to be inserted through 205 and rotated about an axis by a motor (not shown). The rotary disk 213 is a disk-shaped member that is supported by the rotary shaft member 212 so that its axis coincides with the axis of the rotary shaft member 212 and rotates with the rotation of the rotary shaft member 212. The plurality of stirring blades 214 are supported by the peripheral edge portion of the turntable 213 and rotate with the rotation of the turntable 213.

In the capsule particle forming step Pf, the peripheral speed of the outermost circumference of the rotary stirring means 203 is preferably set to 30 m / sec to 50 m / sec. The outermost circumference of the rotary stirring means 203 is a portion 203a of the rotary stirring means 203 having the longest distance from the axis of the rotary shaft member 212 in the direction perpendicular to the direction in which the rotary shaft member 212 of the rotary stirring means 203 extends. By setting the peripheral speed at the outermost circumference of the rotary stirring means 203 during rotation to 30 m / sec or more, the mixture of the toner core particles 101 and the composite particles 140 (fill: 0.5 kg to 0.7 kg) can be used. It can be dispersed in an air flow having a flow rate of 30 m / sec or more circulating in an annular flow path (powder flow path 202) at a treatment temperature of 40 ° C. to 60 ° C. for a treatment time of about 5 minutes. The composite particles 140 can be isolated and flowed by dispersing the composite particles 140 in an air flow having a flow velocity of 30 m / sec or more circulating in the annular flow path. If the peripheral speed at the outermost circumference is less than 30 m / sec, it is difficult to allow the composite particles 140 to flow in isolation, so that it is difficult to reliably fix the perfume microcapsules 102 to the toner core particles 101.

A temperature control jacket (not shown), which is a temperature control means, is provided in at least a part of the outside of the powder flow path 202, and a cooling medium or a heating medium is passed through the space inside the jacket to enter the powder flow path 202 and the rotary stirring means. Adjust 203 to a predetermined temperature. Thereby, the temperature inside the powder flow path and the outside of the rotary stirring means can be controlled to be lower than the temperature at which the toner core particles 101 and the composite particles 140 are not softened and deformed.

(7) External attachment process Pg
In the external addition step Pg, a step of adhering the external additive to the surface of the toner particles by mixing the toner particles to which the perfume microcapsules 102 are fixed by the shell layer 103 in the toner core particles 101 and the external additive with a mixer. Is. As the external additive, silica fine particles having a primary particle diameter of 7 nm to 20 nm treated with a silane coupling agent can be used.

As the mixer, a known mixer can be used, and examples thereof include a Henschel mixer (trade name, manufactured by Mitsui Mining Co., Ltd.) and a super mixer (trade name, manufactured by Kawata Co., Ltd.).

Examples and comparative examples will be given below, and the present embodiment will be specifically described.

[Preparation of shell particles]
In the shell particle dispersion liquid preparation step Pb described above, an aqueous dispersion (aqueous dispersion shell particle EM1: emulsion polymerization emulsion) which is a dispersion liquid of shell particles was prepared. Further, the aqueous dispersion shell particles EM1 produced in the shell particle dispersion liquid preparation step Pb are dried by adding 1 kg of the aqueous dispersion material by the above-mentioned dryer 400 in the drying process to obtain dried shell particles. By repeating this, the required amount was recovered, and dried shell particles EM2 for comparative examples were prepared.

Table 1 shows the physical property values of the aqueous dispersed shell particles EM1 and the dried shell particles EM2 used in Examples and Comparative Examples.

"Measurement method of volume median particle size"
Approximately 10 to 15 mg of the measurement sample is added to 10 mL of a 5% aqueous solution of an ether-type nonionic surfactant (polyoxylauryl ether, HLB = 13.6, manufactured by Kao Co., Ltd., product name: Emargen 109P), and ultrasonically. Dispersion processing is performed at a frequency of 20 kHz for 1 minute using a disperser (manufactured by SMT Co., Ltd., model: UH-50). The volume particle size distribution of about 1 mL of the obtained dispersion was measured with a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., model: Microtrac MT3000), and the volume median particle size (D50 volume average particle size) was obtained from the results. ..

"Thermal characteristics: Measurement method of glass transition point"
Using a differential scanning calorimeter (trade name: DSC220, manufactured by Seiko Electronics Inc.), 1 g of sample is heated at a heating rate of 10 ° C. per minute according to Japanese Industrial Standards (JIS) K7121-1987, and DSC (Differential Scanning). Calimotry: Differential scanning calorimetry) The curve was measured. Draw a straight line extending the baseline on the high temperature side of the heat absorption peak corresponding to the glass transition of the obtained DSC curve to the low temperature side, and a point where the gradient becomes maximum with respect to the curve from the rising portion of the peak to the apex. The glass transition point (Tg) was obtained from the intersection with the tangent line.

"Measurement method of solid content concentration"
Using an infrared moisture meter (trade name: FD-720, manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.), the sample is heated and dried by infrared irradiation, and the concentration of solid content is determined from the mass change due to the evaporation of the water contained in the sample. I asked.

[Making fragrance microcapsules]
A melamine / formaldehyde resin-coated fragrance microcapsule, a urea / formaldehyde resin-coated fragrance microcapsule, and a polyurethane resin-coated fragrance microcapsule were obtained by a conventionally known method (see, for example, paragraph [008] of Patent Document 2).

Table 2 shows the thermal characteristics and volume medium particle size D50 of the perfume microcapsules used in Examples and Comparative Examples.

"Measurement method of heat distortion temperature"
The deflection temperature under load was measured according to JIS standard K6911-1995 (5.35 deflection temperature under load).

[Preparation of fragrance microcapsules]
By classifying the perfume microcapsules, perfume microcapsules having symbols MC1 to MC7 used in Examples and Comparative Examples were obtained.

An elbow jet classifier EJ-LABO (manufactured by Nittetsu Mining Co., Ltd.) was used as a rating device for classification, and perfume microcapsules MC1 to MC5 were obtained while adjusting the gap. Similarly, MC6 and MC7 were obtained by classification.

Table 3 shows the number average particle diameters of the perfume microcapsules MC1 to MC7 used in Examples and Comparative Examples.

"Measurement method of number average particle size"
The average particle size of the number of particles of the obtained fragrance microcapsules MC1 to MC7 was determined by the following method by SEM observation.

Three fields of view were measured at an image magnification of 10000 times, and the particle sizes of the spherical particles contained therein were measured and averaged to obtain a number average particle size. The total number of particles counted in the three fields of view was about 1000. Since the perfume microcapsules MC1 to MC7 were substantially spherical, the longest visible range was selected for the overlapping particles whose diameters could be discriminated, and the selected diameter (diameter by the particle circumscribed circle) was obtained. The average was calculated by excluding those whose diameters could not be determined.

[Preparation of toner core particles (kneading)]
A polyester (binding resin), a colorant, a mold release agent, and a charge control agent were mixed by kneading to prepare a colored resin composition.

The raw materials of the toner core particles and their addition amounts are as follows.
-Polyester resin (trade name: Diamond, manufactured by Mitsubishi Rayon Co., Ltd.)
Glass transition temperature 48 ° C, softening temperature 110 ° C 90.0 parts, carbon black (trade name: MA-77, manufactured by Mitsubishi Chemical Corporation)
5.0 parts, mold release agent (carnauba wax, melting point 82 ° C) 4.0 parts, charge control agent (trade name: Bontron E84, Orient Chemical Industry Co., Ltd.)
1.0 part [Preparation of toner core particles]
The above-mentioned colored resin composition (kneaded product) was pulverized and classified to prepare toner core particles MP1 and MP2.

Table 4 shows the number of copies of the toner core particles MP1 and MP2 used in Examples and Comparative Examples, the volume medium particle size D50, and the thermal characteristics.

In Table 4, the perfume MC internal toner core particles are toner core particles to which perfume microcapsules are added.

"Measurement method of volume median particle size"
The volume median particle size of the toner core particles was measured using Multisizer 3 (manufactured by Beckman Coulter, Inc.) and a 100 μm aperture.

The thermal characteristics (glass transition point Tg) of the toner core particles were measured using a differential scanning calorimeter (trade name: DSC220, manufactured by Seiko Electronics Co., Ltd.) in the same manner as the above-mentioned thermal characteristics.

[Examples and Comparative Examples]
Tables 5 to 11 are tables showing the results of Examples and Comparative Examples.

Examples and comparative examples were carried out as follows.
(1) In the first step P1, the shell particles and the fragrance microcapsules were mixed. Drying was also carried out in Examples 1 to 9, Comparative Example 1 and Comparative Example 2.
(2) In the second step P2, the intermediate material A (the one obtained in the first step P1) of the first step P1 and the core particles were mixed. In Examples 10 to 12, the mixture was dried.
(3) In the third step P3, the immobilization treatment may be carried out on the intermediate B (the product obtained in the second step P2) of the second step P2. The hybridization system 201 described above was used for the immobilization treatment. Further, in Comparative Example 4, the dried shell particles EM2 were added to the intermediate material C (the product obtained in the third step P3), and the fourth step was also carried out.
(4) In the external addition step Pg, an external additive was externally added to the obtained final product to obtain a toner (fragrance toner) for evaluation.

In Table 5, "liquid mixing (core pre-filled)" means the case where the toner core particles are put into the dispersion liquid of the fragrance microcapsule-shell particle complex, and "liquid mixing (core pre-filled)" means the toner core particles. "Dry powder mixing (without shell)" means that a dispersion of fragrance microcapsules-shell particle composite is added, and the dry powder of fragrance microcapsules and the dry powder of toner core particles are mixed. "Dry powder mixing" means the case where the dry powder of dried fragrance microcapsules, the dry powder of toner core particles, and the dry powder of shell particles are mixed, and also. "Kneading and mixing" means the case of kneading the toner core particles contained in the fragrance microcapsules.

Further, in Table 5, "water-dispersed shell" means "aqueous dispersion shell particles" in Table 1, "shell-free" means that shell particles are not used, and "shell post-insertion". Means the case where the shell particles are put into a mixture of the toner core particles and the fragrance microcapsules, and "dried shell" means the case where the shell particles are dried and used.

In Table 6, "MC-coated toner" means toner in which perfume microcapsules are adhered to the surface of toner core particles by a shell layer, and "MC-containing particle toner" is a mixture of toner core particles and dried perfume microcapsules. , Means toner in which perfume microcapsules are contained in the toner core particles. Here, in Comparative Example 3, the shell particle immobilization treatment was not performed, and in Comparative Example 4, the shell particle immobilization treatment was performed.

In Table 8, the "number of copies" is shown as the amount of the perfume microcapsules in the toner core particles obtained by the ratio of the input amount. By going through the kneading and crushing steps, the actual amount in the toner and the amount of fragrance generated change.

As the "external additive" shown in Table 8, hydrophobic silica fine particles having a volume average particle diameter of 7 nm (simply referred to as small silica in Table 9) were used. In the examples and comparative examples, only the above-mentioned hydrophobic silica fine particles were used, but other than that, titanium oxide, alumina, alumina-coated silica, strontium titanate, resin fine particles, etc. were also combined as needed. It is possible to use.

In Table 10, the "coating thickness of the shell layer" was determined as follows. That is, first, a cross-section sample of toner particles is prepared according to the <cross-section observation method> described later.

Subsequently, a cross-sectional sample of the toner particles is observed in 20 fields including the toner core particles (about 4 μm to 7 μm) at a magnification of 10000 times with a scanning transmission electron microscope (STEM).

Spherical particles (about 2 μm) contained in the toner particles including the toner core particles are used as fragrance microcapsules, and the distance from the fragrance microcapsules to the surface of the toner particles is measured as the thickness of the shell layer.

Next, how to take the thickness of the shell layer will be described. FIG. 11 is a cross-sectional view for explaining how to take the thickness of the shell layer 103 in the toner particles (100).

From the surface 102c of the perfume microcapsule 102 (the outer circumference of the circle indicating the perfume microcapsule 102), the first point Q1 in which the distance to the surface 100a of the toner particles (100) is the smallest is extracted. The second point Q2, which is the intersection of the virtual straight line α passing through the first point Q1 and the center point O of the perfume microcapsule 102 and the surface 102c on the opposite side of the first point Q1 of the perfume microcapsule 102, is extracted. Further, the third point Q3, which is the intersection of the virtual straight line α and the surface 100a on the first point Q1 side of the toner particles (100), is extracted. Then, the length L between the second point Q2 and the third point Q3 is measured.

The work of measuring this length L was performed on 20 or more particles of the fragrance microcapsules 102 to calculate the average length, and the obtained average length was taken as the thickness of the shell layer of one toner particle. do.

This was done for 20 fields of view (20 toner particles), and the average was taken as the thickness of the shell layer 103.

“Θt” is a simple first coverage rate θt, which is a value calculated by the above-mentioned equation (1), and “θmc” is a simple second coverage rate θmc, which is the above-mentioned equation (2). It was the value obtained by calculation.

Examples 10 and 11 are mainly examples for comparison with Example 3, and Example 12 is mainly for comparison with Example 1. Comparative Example 3 is a comparative example in which there is no shell layer and only fragrance microcapsules are used. Comparative Example 4 is a comparative example in which shell particles are added to a mixture of toner core particles and perfume microcapsules. Comparative Example 5 is a comparative example in which the toner core particles contained in the fragrance microcapsules are coated with a shell layer. Comparative Example 6 is a comparative example in which the toner core particles contained in the fragrance microcapsules are not coated with the shell layer.

<First step P1 to second step P2> and <Drying step>
You can also work continuously. At that time, the process is carried out by sequentially adding the materials after drying or mixing, and mixing and stirring. When drying was performed without removing from the inside, the weight calculated from the original solid content was displayed as the input amount, and the amount calculated from the final input amount was displayed as the number of copies. In the case of a mixing process that does not include drying, the total amount is entered as it is.

<Third step P3 and fourth step P4>
Immobilization treatment was performed by the hybridization system 201 using the intermediate B produced by the first step P1 to the second step P2. In order to recover the required amount for external attachment, the required amount was recovered by conducting multiple times under each condition.

<External process Pg>
1000 g of the particles produced in the third step P3 are weighed, mixed with 20 g of small silica, the externally added toner is collected, and the externally added toner (scented toner) is passed through a mesh having an opening of 45 μm. Obtained.

[Fog evaluation]
In Table 11, "fog evaluation" uses a whiteness meter (product name: manufactured by Nippon Denshoku Industries Co., Ltd.) to determine the difference between the whiteness of the paper before printing and the whiteness after printing (non-image area). It was evaluated by measuring. Judgment was made based on which range the difference in whiteness falls under.
⊚: 0.5 or less 〇: 0.5 or more and 1.0 or less Δ: 1.0 or more and 1.5 or less ×: 1.5 or more [evaluation of cleaning defects]
After the fog evaluation, the cleaning defect was evaluated. A solid band is created at the tip so that the print density is ID 1.3, and 2000 sheets are printed by vertical threading of A4 paper using a document whose image area is 5% of the paper surface. The stains on the white background caused by the stain were visually confirmed. Since the stain is generated by the slipping of the spherical particles, the portion where the cleaning failure in the paper passing direction occurs linearly stains the paper surface.
◎: No dirt generated ×: Dirt generated [Storage stability]
100 g of toner was sealed in a wide-mouthed plastic container having a capacity of 250 mL, and the toner was kept under the condition of a temperature of 60 ° C. for 120 hours, then the container was taken out and the storage stability was evaluated. The storage stability was evaluated by confirming the aggregated state by the following method. A cylindrical plastic container was placed on a rotating roller (diameter 10 cm) and stirred at 120 rpm for 3 minutes. After that, it was discharged upside down from the container and the aggregated state was confirmed.
⊚: Same as before input, no problem with liquidity.
〇: There is soft agglomeration, but it can be loosened with a finger.
Δ: Discharged from the container, but there is hard agglomeration.
×: Even if it is turned upside down, it is not discharged from the container.

[Aroma evaluation]
In this example, the "scent evaluation" was performed based on whether or not there was a scent at the time of fixing. A commercially available copying machine (trade name: MX-2300G, manufactured by Sharp Corporation) was used for the "fragrance evaluation". A solid band is created at the rear end so that the print density is ID 1.3, and 10 sheets are printed with a vertical thread for A4 paper using a manuscript whose image area is 20% of the paper surface, and the scent of paper is scented. I confirmed the strength. A sensory test was carried out by confirming 10 printed matter immediately after printing, 2 for each of 5 different persons. The scents of the imaged and non-imaged parts of the paper were confirmed and evaluated in the following four stages. Judgment was made on each paper, and the intermediate evaluation result out of 10 sheets was used for the judgment.
◎: Smell only in the printed part 〇: Smell is also generated in the non-printed part △: Weak scent ×: No scent at the time of fixing Here, “weak scent” means a big difference between the non-printed part and the printed part. If not.

In Table 11, "comprehensive evaluation" is the worst evaluation among the evaluations of quality performance and image evaluation (image quality). That is, the "comprehensive evaluation" is the case where "◎" is not included in the evaluations of "quality performance" and "image quality", and "○" is included in the case of "◎". Is "○", "△" when there is no "×" and "△" is included, and "×" when there is even one "×".

As shown in Table 11, generally good results were obtained in Examples 1 to 12, but in particular, in Examples 10 and 11, the storage stability was improved by changing the drying process. On the other hand, in Comparative Example 2, it was found that the coating thickness of the shell layer also decreased due to the desorption of large particles. In Comparative Example 3, the perfume microcapsules were not immobilized. In Comparative Example 4, the immobilization of the perfume microcapsules was not perfect, and slip-through occurred due to spherical desorbed particles. In Comparative Example 5, the toner core particles were internally impregnated with fragrance microcapsules, and only the shell layer was formed on the surface of the toner core particles, so that the storage stability was insufficient. Further, in Comparative Example 6, the toner core particles in which the fragrance microcapsules were added did not have a shell layer, so that the storage stability was insufficient. Kneading → The aroma was lost during crushing.

[Inconvenience due to the size of the particle size of the fragrance microcapsules]
Next, the inconvenience due to the size of the particle size of the perfume microcapsules 102 in the toner 100 according to the present embodiment will be considered.

FIG. 8A is a cross-sectional view showing the size of the particle size of the fragrance microcapsules 102. FIG. 8B is a cross-sectional view showing the size of the particle size of the fragrance microcapsules 102 in the toner 100.

Since the perfume microcapsule 102 (specifically, the thermosetting resin perfume microcapsule) is obtained by encapsulating the perfume 102b with the thermosetting resin 102a, it is not easily deformed and has excellent heat resistance.

The volume average particle size of the fragrance microcapsules is preferably 0.4 μm to 1.9 μm, but as shown in FIG. 8A, when the volume average particle size of the fragrance microcapsules 102 is smaller than 0.4 μm. The content of the fragrance 102b per weight is reduced, the strength of the shell layer 103 is increased, the fragrance is less likely to be cracked, the fragrance is less likely to be generated, and the ability to generate the fragrance is likely to be reduced accordingly. Further, as shown in FIG. 8B, when the toner 100 is used in combination with the shell particles 110, the fragrance microcapsules 102 tend to be non-sphericized when the volume average particle size is less than 0.4 μm.

On the other hand, when the volume average particle size of the fragrance microcapsules 102 becomes a large particle size exceeding 1.9 μm, the fragrance microcapsules 102 become spherical and difficult to handle, and the fragrance microcapsules 102 are easily separated from the shell layer 103, resulting in poor cleaning. Easy to do. Further, as shown in FIG. 8B, in the toner 100, large particles having a volume average particle size of more than 1.9 μm of the perfume microcapsules 102 tend to exist as spherical particles, and the adhesiveness to the toner core particles 101 is increased accordingly. Easy to drop.

Here, the cross-section observation method will be described below.

<Cross-section observation method>
(1) Embed the toner with the embedding resin.

Put one cup of toner in a silicon mold and pour Aronix D-800 (manufactured by Toagosei Co., Ltd.). Stir the toner and D-800 well so that the toner is evenly dispersed. After degassing to remove air bubbles, the resin is cured by irradiating it with the light of a halogen lamp for 1 minute and incubating it in a constant temperature bath at 40 ° C. for 30 minutes or more.

As the embedding resin, in addition to D-800, epoxy resins for electron microscopes (EPON series manufactured by EM Japan Co., Ltd., EpixiCure manufactured by BUEHLER Co., Ltd., etc.), UV curable resins, adhesives, etc. can also be used. .. Since D-800 is cured by visible light, heat is less likely to be generated during curing, and denaturation of toner can be suppressed.

(2) Prepare a cross-section sample with a microtome.

The tip of the resin-embedded toner sample is surfaced to a size of approximately 0.5 mm square using a double-edged razor. An ultrathin section is prepared using a microtome (manufactured by Leica Microsystems, Inc.) (thickness of about 100 nm).

(3) Stain the cross-section sample.

If the core and shell can be dyed separately as needed, more accurate observation will be possible. The ultrathin sections recovered on the grid are stained with a 4% osmium tetroxide aqueous solution (or ruthenium tetroxide aqueous solution is also acceptable).

(4) Observe with an electron microscope.

Observation is performed with a transmission electron microscope (TEM: Transmission Electron Microscope) or a scanning transmission electron microscope (STEM).

[Impact on image quality]
Next, the effect on image quality will be considered. FIG. 9 is an explanatory diagram for explaining the influence on the image quality.

As shown in FIG. 9, the perfume microcapsules 102 are immobilized by the shell layer 103, and the forward-charged good perfume MC-coated toner (toner having good coverage of the shell layer 103 on the perfume microcapsules 102) has "image quality". Is good (〇).

[Impact on performance and quality]
Next, the impact on performance and quality will be considered. FIG. 10 is an explanatory diagram for explaining the influence on performance and quality.

As shown in FIG. 10, the fragrance microcapsules 102 are immobilized by the shell layer 103, and a good core (toner core particle) coated toner having a small particle size (toner having good coating property to the toner core particles 101 of the shell layer 103) has a small particle size. Both "fragrance" and "preservation" are excellent (◎).

The present invention is not limited to the embodiments described above, and can be implemented in various other forms. Therefore, such embodiments are merely exemplary in all respects and should not be construed in a limited way. The scope of the present invention is set forth by the claims and is not bound by the text of the specification. Further, all modifications and modifications that fall within the equivalent scope of the claims are within the scope of the present invention.

100 Toner 101 Toner core particles 101a Surface 102 Perfume microcapsules 102a Thermocurable resin 102b Fragrance 102c Surface 103 Shell layer 110 Shell particles 120 Dispersion liquid 130 Perfume microcapsules-Shell particle composite 140 Composite particles 201 Hybridization system 202 Powder flow path 203 Rotating stirring means 205 Through hole 206 Powder charging part 207 Powder collecting part 208 Stirring part 209 Powder flow part 210 Opening part 211 Opening part 212 Rotating shaft member 213 Rotating plate 214 Stirring blade 300 Stirrer 310 Propeller type stirring blade 400 Dryer 410 Stirring blade 411 Tip part 420 Mixer tank P1 First step P2 Second step P3 Third step Pa Toner core particle preparation step Pb Shell particle dispersion preparation step Pc Perfume microcapsule dispersion preparation step Pd Perfume microcapsule-shell Particle composite formation step Pe Composite particle formation step Pf Capsule particle formation step Pg External step V Container W Water θmc Simple second coverage θt Simple first coverage

Claims (11)

A toner containing toner core particles and fragrance microcapsules in which a fragrance is encapsulated in a thermosetting resin and microencapsulated.
The perfume microcapsule is a toner characterized in that it is fixed to the toner core particles by a shell layer that covers the surface of the toner core particles. The toner according to claim 1.
A toner characterized by having a coating thickness of the shell layer of 0.8 μm to 2.2 μm. The toner according to claim 1 or 2.
A toner characterized by having a heat distortion temperature of the perfume microcapsules of 70 ° C to 180 ° C. The toner according to any one of claims 1 to 3.
The perfume microcapsule is a toner characterized in that it is microencapsulated with a thermosetting resin selected from a urea resin, a melamine resin, and a polyurethane resin. The method for manufacturing toner according to any one of claims 1 to 4, wherein the toner is manufactured.
The first step of adhering the shell particles to the surface of the perfume microcapsules,
A method for producing a toner, which comprises a second step of adhering the perfume microcapsules to which the shell particles have adhered to the surface to the surface of the toner core particles. The toner manufacturing method according to claim 5.
A method for producing a toner, which further comprises a third step of forming the shell layer from the shell particles and fixing the perfume microcapsules to the toner core particles by the formed shell layer. The method for manufacturing toner according to claim 6.
In the third step, the mixture of the toner core particles, the shell particles, and the fragrance microcapsules is dispersed in an air stream circulating in the annular flow path, and a rotary stirring unit provided in the middle of the flow path. A method for producing toner, which comprises coating the surface of the toner core particles with a shell layer formed from the shell particles by the mechanical treatment of the above, and fixing the perfume microcapsules to the toner core particles by the coated shell layer. .. The toner manufacturing method according to any one of claims 5 to 7.
A method for producing a toner, wherein the volume average particle size of the fragrance microcapsules is 0.4 μm to 1.9 μm. The toner manufacturing method according to any one of claims 5 to 8.
In the first step, the shell particles are adhered to the surface of the perfume microcapsules using the dispersion liquid of the shell particles.
The second step is a method for producing a toner, which comprises attaching the perfume microcapsules to which the shell particles are attached to the surface in the dispersion liquid to the surface of the toner core particles. The toner manufacturing method according to any one of claims 5 to 9.
The simple first coverage rate θt calculated from the area ratio of the total particle projection area of the perfume microcapsules present on the surface of the toner core particles to the surface area of the toner core particles is in the range of 9% ≦ (θt) ≦ 133%. A method of manufacturing a toner, which is characterized by being inside. The method for manufacturing a toner according to any one of claims 5 to 10.
The simple second coverage rate θmc calculated from the area ratio of the total particle projection area of the shell particles present on the surface of the perfume microcapsules to the surface area of the perfume microcapsules is 23% ≤ (θmc) ≤ 324%. A method for producing a toner, which is characterized by being within the range.

Images