JP2010044196A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve developing properties, fixing properties and storage property of a toner. <P>SOLUTION: The toner includes toner particles, containing at least a binder resin, polar resin, a colorant and wax, and is such that when a UV photo-curable composition is made to permeate the toner, the permeation film thickness is L (μm) with 5 seconds of permeation time, the average permeation rate is Va (μm/s) of a period of 5 seconds to 10 seconds, and the average permeation rate is Vb (μm/s) of a period of 10 seconds to 15 seconds satisfy predetermined conditions, L, Va and Vb satisfy predetermined conditions, and the viscosity of the toner at 100°C lies in a predetermined range. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner used in a recording method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method, or a toner jet method.

  In the conventional electrophotographic method, after charging on a photosensitive drum by various means, an electrical latent image is formed, then toner is developed on the latent image, and the toner image is transferred to a transfer material such as paper. The toner image is fixed by heating and pressing means.

  In recent years, in printers and copiers, there are increasing demands for high reliability that remains unchanged even after printing for a long period of time, quality stability during long-term storage, and response to the environment.

  High reliability means providing an excellent user-friendly machine in addition to continuing to output the same level as the initial image even when printed over a long period of time. Specifically, good developability is maintained even in various environments and various transfer materials.

  Moreover, the response | compatibility to an environment shows the energy-saving response | compatibility by low power consumption, specifically, shows favorable low-temperature fixability and winding resistance.

  Further, quality stability means that the toner has little deterioration even during long-term storage, and exhibits development characteristics and fixing characteristics at levels that do not change before and after storage. Specifically, the toner physical properties do not change even before and after long-term storage in each environment.

  To provide an electrophotographic toner composition that can be fixed at a low temperature in a heat fixing method and has good storage stability, and to provide an electrophotographic toner composition in which offset is prevented in a heat roll fixing method. In order to achieve this, the resin constituting the resin outer shell is polyurea and / or polyurethane having a glass transition point of 80 to 140 ° C., and the average thickness of the resin outer shell is 0.005 to 0.5 μm. There has been proposed a toner containing toner particles that is characterized (see Patent Document 1).

  In addition, it has excellent blocking resistance even in high temperature and high humidity environments, fixing at low temperature, excellent releasability, stable and high developability, high image density, and changes in performance over long periods of use. A toner having no toner is known (see Patent Document 2). The toner contains at least two components, a high softening point resin (A) and a low softening point substance (B), and the A phase mainly composed of the high softening point resin (A); In the vicinity of the surface from the toner particle surface to a depth of 0.15 times the toner particle diameter, the B phase is separated from the B phase mainly composed of the low softening point substance (B). The component ratio between the high softening point resin (A) and the low softening point substance (B) of the toner particles is A: B = 50: 50 to 95: 5, and the low softening point substance (B ) Has a wax having a melting point of 30 to 130 ° C., and the total content of the organic solvent and the polymerizable monomer in the toner particles is 1,000 ppm or less. Toners have been proposed (see Patent Document 2).

In addition, it provides a polymerized toner having a low fixing temperature and uniform meltability, and excellent storage stability (blocking resistance), and a method for producing the same, and supports high speed copying and printing, full color, and energy saving. Polymerized toner capable of forming a toner image exhibiting excellent transparency (OHP permeability) when printed on an OHP sheet and fixed is known. (See Patent Document 3). As such a toner, a polymerizable monomer containing at least a colorant and a core polymerizable monomer capable of forming a polymer having a glass transition temperature of 70 ° C. or lower in an aqueous dispersion medium containing a dispersant. The volume average particle size (dv) obtained by suspension polymerization of the composition in the presence of a macromonomer is 0.5 to 20 μm, and the volume average particle size (dv) and the number average particle size (dp) Core particles made of colored polymer particles having a ratio (dv / dp) of 1.7 or less are obtained by suspension polymerization of a polymerizable monomer for shells in the presence of the core particles. It has a glass transition temperature higher than the glass transition temperature of the constituent polymer component, is covered with a shell made of a polymer layer having an average film thickness of 0.005 to 0.05 μm, and has a toluene insoluble content of 50% or less. Suspension polymerization toners with a core-shell structure have been proposed. See Permissible Literature 3).

  For the purpose of providing an appropriate image gloss, imparting good color reproducibility, and ensuring uniform stability of the image gloss, the binder resin has a weight average molecular weight of 8,000 to 50,000 and a glass transition point of 40. A toner has been proposed in which a thermoplastic resin having a weight average molecular weight of at least twice as high as that of the binder resin and a glass transition point of 5 ° C. or more is present in the vicinity of the surface at 55 ° C. (see Patent Document 4).

  As described above, many studies have been made to achieve both durability and fixability by protecting the relatively soft (low Tg, low softening point) toner inner layer with the relatively hard (high Tg, high softening point) toner outer layer. It has been broken. In any of the toners of the above patent documents, there is an interface between the toner inner layer and the toner outer layer, and the toner inner layer is protected by a relatively thin toner outer layer. For this reason, when the toner is continuously stressed, such as when images are continuously output at high speed, the outer layer is likely to be peeled off or scraped off, and the toner inner layer is exposed and the surface property of the toner changes abruptly. there were. In addition, when the toner outer layer is designed to be thick in order to solve the above problems, there is a problem that the low temperature fixing property and the image glossiness are adversely affected.

Under the present circumstances, further increase in output speed is demanded, and a toner that sufficiently satisfies high durability and storage stability while maintaining good fixability and high image gloss is desired.
Japanese Patent No. 2827697 Japanese Patent No. 3184626 Japanese Patent No. 3429986 JP 2006-053353 A

  The problem to be solved by the present invention is to achieve improvement in toner developability, toner fixability and toner storage stability.

The toner of the present invention is a toner having toner particles containing at least a binder resin, a polar resin, a colorant, and a wax, and the penetration time is 5 seconds when the UV photocurable composition is infiltrated into the toner. When the osmotic film thickness is L (μm), the average osmotic rate at 5 seconds to 10 seconds is Va (μm / s), and the average osmotic rate at 10 seconds to 15 seconds is Vb (μm / s), L , Va and Vb are the following conditions:
0.30 ≦ L ≦ 0.60 Formula (1)
0.040 ≦ Va ≦ 0.070 Formula (2)
Va <Vb Formula (3)
The viscosity of the toner at 100 ° C. is 3.0 × 10 ^{3 to} 4.5 × 10 ⁴ Pa · s.

  According to the present invention, improvement in toner developability, toner fixability, and toner storage stability are achieved.

The present invention satisfies the improvement of the developing property of the toner, the improvement of the fixing property of the toner and the improvement of the storage stability of the toner at the same time.
<1> Improvement of toner developability means the following three points.
(I) Toughness due to rubbing between the toner regulating member and the toner carrier is large, and even when images are continuously output, there is little change in the charging characteristics of the toner, and high development efficiency can be obtained.
(Ii) No circumferential streaking due to foreign matter pinching between the toner restricting member and the toner carrying member due to toner destruction or fusion, and no toner scattering due to foreign matter pinching between the toner carrying member and the toner end seal.
(Iii) The toner coat amount in the longitudinal direction of the toner carrier is uniform, and the development on the photoreceptor is uniform.
<2> Improvement of toner fixability means the following two points.
(I) To ensure low-temperature fixability of toner in a light pressure fixing system.
(Ii) Ensuring the wrapping resistance of the transfer material at a high temperature between the transfer material and the fixing member.
<3> Improvement in the storage stability of the toner means the following.
There is little aggregation of toner even after leaving at 50 ° C. for 3 days.

The features of the present invention are as follows.
Although the mechanism is not clear, the present inventors believe that the magnitude of the penetration rate (hereinafter also referred to as VUV) of the _UV photocurable composition with respect to the resin is caused by the mobility of the molecular chain of the resin. That, V _UV higher mobility of the molecular chain of the resin is large, V _UV lower the mobility is estimated to be small. Therefore, the present inventors presume that the Tg, the degree of crosslinking, the molecular weight, etc. of the resin act in a complex manner as factors determining V _UV .

At this time, the mobility of the molecular chain of the resin is larger, and the larger V _UV is, the easier the toner melts during heating and pressurization, and the wax is more likely to ooze out to the surface. On the other hand, stress resistance and heat resistance are low. On the other hand, the lower the molecular chain mobility of the resin and the lower the V _UV , the higher the stress resistance and heat resistance. On the other hand, the toner is difficult to melt during heating and pressurization, and the wax is difficult to ooze out to the surface. That is, the toner inner layer it is preferable to use a large resin V _UV, the toner layer is estimated to be preferable to use a resin having a low V _UV.

L, Va and Vb of the present invention are the penetration film thickness at a penetration time of 5 seconds when the UV photocurable composition penetrates into the toner, the average penetration speed at 5 seconds or more and 10 seconds or less, and at 10 seconds or more and 15 seconds or less. Each represents the average penetration rate. That is, L is related to the V _UV near the toner surface layer, and Va and Vb are more related to the V _UV of the toner inner layer.

Here, in this invention, it is estimated that L, Va, and Vb satisfy | fill the relationship of Formula (1), (2), (3) represents the following. That is, it is presumed that in a toner composed of a low-V _UV polar resin and a high-V _UV binder resin, the polar resin concentration is present in a concentration gradient that is high in the outer layer of the toner and thin in the inner layer of the toner. The

That is, when considering a toner having a core-shell structure in which the outer layer is made of a low-V _UV resin, the inner layer is made of a high-V _UV resin, and the outer layer and the inner layer are partially compatible, the permeation rate gradually changes from the outer layer to the inner layer. It is expected to show At this time, the penetration rate at a penetration time of 5 seconds is expected to be between the penetration rate in the outer layer and the penetration rate in the inner layer. At this time, the value of L becomes larger as compared with the case of the core-shell structure clearly phase-separated. In addition, Va <Vb is expected because the penetration rate gradually changes.

  Therefore, by setting L, Va and Vb of the toner within the range of the present invention, the adhesion between the binder resin mainly existing in the toner inner layer and the polar resin mainly existing in the toner outer layer is improved. It will be. Further, the resin constituting the toner outer layer exists with a density gradient from the vicinity of the toner surface layer toward the inside. For this reason, when the toner is stressed by continuous output, the outer layer of the toner is not easily peeled off or scraped off, and the surface property change is small even when a defect occurs on the toner surface. Therefore, high development efficiency, reduction in circumferential streaks, and reduction in toner scattering can be achieved. Further, from the above characteristics, the toner inner layer is difficult to be exposed even when the toner is continuously stressed by the continuous output, and therefore the toner inner layer can be designed to be sufficiently soft. Furthermore, the absence of an interface between the toner inner layer and the toner outer layer improves the bleedability of the wax during fixing. Therefore, it is possible to achieve good low-temperature fixability and anti-winding property at a high temperature of the transfer material without deteriorating development characteristics and storage stability.

Specifically, the toner L is in the range of 0.30 to 0.60 μm. Preferably it exists in 0.30 to 0.50 μm.
When the L is in the range of 0.30 to 0.60 μm, the adhesion between the toner inner layer and the toner outer layer is enhanced for the reasons described above. Therefore, sufficient toner toughness can be obtained. Moreover, the bleeding property of the wax at the time of fixing is improved. Therefore, development characteristics and fixing characteristics are improved. Further, the thickness of the toner outer layer and the mobility of the resin molecular chain are in the optimum range. Therefore, the storage stability is improved.

  When L is in the range of 0.30 to 0.60 μm, the adhesion between the toner inner layer and the toner outer layer is optimal, and the mobility of the molecular chain of the resin in the toner outer layer is optimal. As a result, adverse effects on development characteristics and fixing characteristics can be prevented. When L is in the range of 0.30 to 0.50 μm, the above effect is further improved.

The Va of the toner is in the range of 0.040 to 0.070 μm / s.
When Va is in the range of 0.040 to 0.070 μm / s, the mobility of the molecular chains of the resin in the toner inner layer and the toner outer layer is in the optimum range. Further, the adhesion between the toner inner layer and the toner outer layer is improved. Therefore, sufficient toner toughness can be obtained. Moreover, the bleeding property of the wax at the time of fixing is improved. Therefore, development characteristics and fixing characteristics are improved.
When the Va is 0.040 μm / s or more, the mobility of the molecular chain of the resin in the toner outer layer is suitable, and the adhesion between the toner inner layer and the toner outer layer is favorable. Thereby, adverse effects on development characteristics and low-temperature fixability can be prevented.
When the Va is 0.070 μm / s or less, the mobility of the molecular chain of the resin of the toner outer layer becomes favorable. Further, the adhesiveness between the toner inner layer and the toner outer layer is suitable. Thereby, adverse effects on development characteristics and storage stability can be prevented.

The Va and Vb of the toner satisfy the relationship Va <Vb.
When the relationship between Va and Vb is Va <Vb, the resin constituting the toner outer layer exists with a density gradient from the vicinity of the toner surface layer toward the inside. Further, the adhesion between the toner inner layer and the toner outer layer is high. Therefore, development characteristics and low-temperature fixability are improved.

  The above conditions relating to L, Va and Vb of the toner adjust the composition ratio of the polymerizable monomer and reduce the compositional difference such as the resin type and copolymerization ratio between the binder resin and the polar resin. Can be satisfied.

By setting the viscosity of the toner at 100 ° C. within the range of the present invention, the bleedability of the wax at the time of heating and pressurizing the toner increases, and the bleeding of the wax at the time of fixing is promoted. Therefore,
It is possible to improve the low-temperature fixability of the toner and the winding resistance of the transfer material at high temperatures.

Specifically, the viscosity of the toner at 100 ° C. is 3.0 × 10 ^{3 to} 4.5 × 10 ⁴ Pa · s. The viscosity of the toner at 100 ° C. is preferably 5.0 × 10 ^{3 to} 2.5 × 10 ⁴ Pa · s.
When the viscosity of the toner at 100 ° C. is 3.0 × 10 ^{3 to} 4.5 × 10 ⁴ Pa · s, high-temperature wrapping resistance is improved due to moderate wax bleeding. Furthermore, the adhesion to paper is improved and the low-temperature fixability is improved.
When the viscosity of the toner at 100 ° C. is 5.0 × 10 ^{3 to} 2.5 × 10 ⁴ Pa · s, the above effect is further improved.

When the viscosity of the toner at 100 ° C. is 3.0 × 10 ³ Pa · s or more, the Tg of the toner is suitable. Therefore, adverse effects on development characteristics and storage stability can be prevented.
When the viscosity of the toner at 100 ° C. is 4.5 × 10 ⁴ Pa · s or less, the Tg of the toner is suitable. Therefore, it is possible to prevent adverse effects on the high-temperature wrapping resistance due to a decrease in the bleedability of the wax. In addition, the adhesion to paper is reduced, and adverse effects on low-temperature fixability can be prevented.

  In addition, the above-mentioned conditions relating to the viscosity of the toner at 100 ° C. can be satisfied by adjusting the composition ratio of the polymerizable monomer.

  By setting the ratio of Va to Vb of the toner within the following range, the adhesion between the toner outer layer and the toner inner layer can be further enhanced.

In particular
The Va and Vb of the toner are the following conditions:
1.2 ≦ Vb / Va ≦ 2.0
Preferably, the following conditions are satisfied:
1.4 ≦ Vb / Va ≦ 1.8
It is more preferable to satisfy this relationship.

When the relationship between Va and Vb of the toner satisfies 1.2 ≦ Vb / Va ≦ 2.0, the resin constituting the toner outer layer exists with a density gradient from the vicinity of the toner surface layer toward the inside. . Further, the adhesion between the toner inner layer and the toner outer layer is high. Therefore, development characteristics and low-temperature fixability are improved.
The above effect is further improved when the relationship between Va and Vb of the toner satisfies 1.4 ≦ Vb / Va ≦ 1.8.
When the relationship between Va and Vb of the toner is 1.2 ≦ Vb / Va, adverse effects on development characteristics and storage stability can be prevented.
When the relationship between Va and Vb of the toner is Vb / Va ≦ 2.0, adverse effects on storage stability can be prevented.

By setting the R (25) of the toner within the following range, the outer layer of the toner can be designed to have an optimum hardness. Therefore, the toughness of the toner can be further enhanced, and high development efficiency, reduction in circumferential streaks, and reduction in toner scattering can be achieved. Here, R (25) of the toner in the present invention is, as will be described later, after a load of 2.94 × 10 ⁻⁴ N is applied to the toner at a load speed of 9.8 × 10 ⁻⁵ N / sec at 25 ° C. In the displacement curve until unloading, it refers to the slope of the displacement curve from the beginning to the end of loading.

Specifically, in the displacement curve from applying a load of 2.94 × 10 ⁻⁴ N to the toner at 25 ° C. at a load speed of 9.8 × 10 ⁻⁵ N / sec, starting to apply the load. The slope R (25) of the displacement curve from the end to the end is as follows:
4.90 × 10 ⁻⁴ ≦ R (25) ≦ 1.27 × 10 ⁻³
It is preferable to satisfy.
When R (25) of the toner is 4.90 × 10 ⁻⁴ or more, the mechanical strength of the toner outer layer becomes favorable. Therefore, the toner outer layer is less likely to be crushed by mechanical stress, so that adverse effects on development characteristics can be prevented.
When the R (25) of the toner is 1.27 × 10 ⁻³ or less, the mechanical strength of the toner surface layer is favorable. Therefore, the toner outer layer is less likely to be lost due to mechanical stress, and adverse effects on development characteristics can be prevented.
As a result, the toughness of the toner is increased and the development characteristics are improved.

  Further, the above-described conditions relating to the R (25) of the toner can be satisfied by adjusting the composition ratio of the polymerizable monomer and appropriately selecting the binder resin and the polar resin.

  By setting the weight average particle diameter (D4) of the toner within the following range, the relationship between the thickness of the outer layer of the toner and the weight average particle diameter (D4) of the toner can be made a suitable range. Therefore, improvement in storage stability and development characteristics can be achieved.

Specifically, it is preferable that the weight average particle diameter (D4) of the toner is 4.0 to 9.0 μm.
When the weight average particle diameter (D4) of the toner is 4.0 μm or more, the thickness of the toner outer layer is sufficient. Therefore, adverse effects on developability and storage stability due to the toner inner layer not being properly protected by the toner outer layer can be prevented. Further, when the weight average particle diameter (D4) of the toner is 9.0 μm or less, the toner outer layer becomes suitable. Therefore, since the exudation of the wax at the time of heating and pressing becomes good, it is possible to prevent adverse effects on the low-temperature fixability and the high-temperature wrapping property.
As a result, the inner layer of the toner is protected by the outer layer of the toner without hindering the exudation of wax during heating and pressurization, so that development characteristics, fixing characteristics and storage stability are improved. In the present invention, for the weight average particle diameter (D4) of the toner, for example, when a suspension polymerization method is used as a method for producing toner particles, a stirring condition during granulation is adjusted, and a pulverization method is used. In some cases, it can be adjusted by adjusting the grinding strength and time.

  By setting the number of polar resins in the toner to 100 parts by mass of the binder resin within the following range, the thickness of the outer layer of the toner can be optimally designed. Accordingly, development characteristics, storage stability, transfer characteristics and fixing characteristics can be improved.

Specifically, the polar resin is preferably contained in a total of 10 to 50 parts by mass with respect to 100 parts by mass of the binder resin.
When the polar resin is contained in a total amount of 10 to 50 parts by mass with respect to 100 parts by mass of the binder resin, the thickness of the toner outer layer is in a suitable range. Therefore, the inner layer of the toner is protected by the outer layer of the toner without hindering the seepage of the wax during heating and pressurization, so that the development characteristics, fixing characteristics and storage stability are improved.
When the polar resin is contained in a total of 10 parts by mass or more with respect to 100 parts by mass of the binder resin, the toner outer layer has a sufficient thickness. Therefore, adverse effects on development characteristics and storage stability due to the toner inner layer not being properly protected by the toner outer layer can be prevented.
When the polar resin is contained in a total amount of 50 parts by mass or less with respect to 100 parts by mass of the binder resin, the thickness of the toner outer layer is suitable. Therefore, since the seepage of wax during heating and pressing is not hindered, adverse effects on the fixing characteristics can be prevented.

By setting the glass transition point (Tg) of the polar resin in the toner within the following range, the heat resistance of the toner outer layer becomes favorable. Therefore, the storage stability is improved.
Specifically, the glass transition point (Tg) of the polar resin is preferably 70 to 120 ° C.
When the Tg of the polar resin is 70 to 120 ° C., it is possible to protect the toner inner layer without hindering the exudation of wax during heating and pressurization. Therefore, the storage stability is improved.
By making Tg of polar resin 70 degreeC or more, the bad influence on storage stability can be prevented.
By setting the Tg of the polar resin to 120 ° C. or less, it is possible to prevent adverse effects on the fixing characteristics.

In the present invention, when x types of polar resins are included in the toner, the weight fraction of the k-th type polar resin with respect to the total weight of the polar resin contained in the toner is w _k , and Tg is t _k (K). And At that time, Tg (K) of the polar resin in the present invention is defined by the following formula.

1 / Tg = (w ₁ / t ₁ + w ₂ / t ₂ +... + W _x / t _x )

Also,
Tg (° C.) = Tg (K) −273
It is defined as
In addition, the glass transition point (Tg) of polar resin used by this invention can be adjusted by adjusting the monomer composition of polar resin, for example.

  By setting the acid value of the polar resin in the toner within the following range, the adhesion between the toner outer layer and the toner inner layer can be designed to be suitable. Therefore, the toughness when the toner is stressed by continuous output is increased, and high development efficiency, reduction in circumferential streaks, and reduction in toner scattering can be achieved.

Specifically, the acid value of the polar resin is 3.0 to 30.0 mgKOH / g.
Is preferred.
When the acid value of the polar resin is 3.0 mgKOH / g or more, the toner outer layer is easily formed, and when it is 30.0 mgKOH / g or less, the adhesion between the toner inner layer and the toner outer layer is increased. As a result, the toughness of the toner is increased and the development characteristics are improved.

In the present invention, when x types of polar resins are contained in the toner, the weight fraction of the k-type polar resin with respect to the total weight of the polar resin contained in the toner is w _k , and the acid value is Av _k (mgKOH / G). At that time, Av (mg KOH / g) of the polar resin in the present invention is defined by the following formula.

Av = w ₁ Av ₁ + w ₂ Av ₂ +... + W _x Av _x

Examples of polar resins include polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, or copolymers of nitrogen-containing monomers and styrene-unsaturated carboxylic acid esters; nitriles such as acrylonitrile Monomer; Halogen-containing monomer such as vinyl chloride; Unsaturated carboxylic acid such as acrylic acid and methacrylic acid; Unsaturated dibasic acid; Unsaturated dibasic acid anhydride; Polymer of nitro monomer or Examples thereof include copolymers of styrene monomers and polyesters; epoxy resins. More preferable is a vinyl polymer for improving the adhesion between the polar resin and the binder resin.
The acid value of the polar resin used in the present invention can be adjusted by adjusting the amount of the acid component in the monomer, for example.

  Examples of the binder resin used in the present invention include polystyrene; a styrene-substituted homopolymer such as poly-p-chlorostyrene and polyvinyltoluene; a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer, Styrene-vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacrylic acid methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether Styrene copolymer such as copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Coalescence; acrylic resin; methacrylic tree ; Polyvinyl acetate; silicone resins; polyester resins; polyamide resin; furan resins, epoxy resins, xylene resins. These resins are used alone or in combination.

  The comonomer for the styrene monomer of the styrene copolymer includes acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, doditer acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methacrylic acid. Monocarboxylic acid having a double bond such as methyl acid, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; maleic acid, butyl maleate, methyl maleate, maleate Dicarboxylic acids having a double bond such as dimethyl acid and its substitutes; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene and butylene; Sulfonyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

As the polymerizable monomer used when the toner of the present invention is produced by the polymerization method, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p A styrene derivative such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl accelerator Acrylic polymer such as n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Mer: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n -Octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl meta Methacrylic polymerizable monomers such as relate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinylmethyl And vinyl ethers such as ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxy / polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  In the present invention, the above-described monofunctional polymerizable monomers are used alone or in combination of two or more, or the above-mentioned monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. . The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

  In particular, as the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used. The following aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline And divinyl compounds such as divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups. These can be used alone or as a mixture. A preferable addition amount is 0.001 to 15% by mass with respect to 100 parts by mass of the binder resin.

  Examples of the wax used in the present invention include the following. Petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax, petrolactam; montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method; polyolefin waxes and derivatives thereof such as polyethylene wax and polypropylene wax; carnauba wax Natural waxes such as candelilla wax and derivatives thereof. Examples of the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, the following are mentioned. Higher fatty alcohols; fatty acids such as stearic acid and palmitic acid; acid amide waxes; ester waxes; hardened castor oil and its derivatives; plant waxes; Among these, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability.

The wax preferably contains 1 to 40% by mass with respect to 100 parts by mass of the binder resin. More preferably, the content is 3 to 25% by mass.
When the amount of the wax is 1 to 40% by mass, the winding resistance at a high temperature is improved by having a suitable wax bleeding property when the toner is heated and pressurized. Further, even when the toner is subjected to stress during development or transfer, the exposure of the wax to the toner surface is small, and uniform chargeability of each toner can be obtained.

In the present invention, it is preferable to use a polymer having a sulfonic acid group in the side chain mainly for charge control and stabilization of granulation in an aqueous medium. Among them, it is particularly preferable to use a polymer or copolymer containing a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group.

Examples of the monomer having a sulfonic acid group for producing the polymer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid, vinyl sulfonic acid, methacrylic acid. A sulfonic acid can be illustrated.
The polymer containing a sulfonic acid group and the like used in the present invention may be a homopolymer of the above monomer, but is a copolymer of the above monomer and another monomer. It doesn't matter. As a monomer that forms a copolymer with the above monomer, there is a vinyl polymerizable monomer, and a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Monofunctional polymerizable monomers include the following styrene: α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn -Butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene Styrene-based polymerizable monomers such as p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate , N-hexyl acrylate, 2-ethylhexyl Acrylic polymerizable monomers such as polyacrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Mer: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n -Octyl methacrylate, n-nonyl methacrylate, diethyl phosphate Methacrylic polymerizable monomers such as til methacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl methyl ether And vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  The following polyfunctional polymerizable monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, Propylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tri Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Coal dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane 2,2′-bis (4-methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like.

And it is preferable that the polymer which has the said sulfonic acid group etc. contains 0.01 thru | or 5.00 mass% with respect to 100 mass parts of polymerizable monomers or binder resins. More preferably, it is 0.1 to 3.0% by mass.
When the polymer having a sulfonic acid group or the like is 0.01 to 5.00% by mass, sufficient chargeability can be obtained and uniform transferability can be obtained. Furthermore, in the granulation step in an aqueous medium using a dispersion stabilizer having a positive component, a sharp distribution of toner particle size can be obtained in order to enhance the formation of an electric double layer.

  In addition to the polymer having a sulfonic acid group in the side chain, a charge control agent may be blended in the toner of the present invention in order to stabilize charging characteristics. As the charge control agent, known ones can be used, and in particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable. Specific compounds include metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, boron compounds as negative charge control agents , Silicon compounds, calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, a nigrosine compound, and an imidazole compound.

  The amount of these charge control agents to be used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. When added internally, it is preferably used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. Further, when added externally, the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.3 part by mass with respect to 100 parts by mass of the toner.

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

  Examples of the yellow colorant used in the present invention include compounds represented by monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 214, C.I. I. Solvent yellow 93, 162 etc. can be illustrated.

Examples of the magenta colorant used in the present invention include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. It is done. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment violet 19 etc. can be illustrated.
Examples of the cyan colorant used in the present invention include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like.

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

  Furthermore, the toner of the present invention may be a magnetic toner containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. Magnetic materials include the following iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium and bismuth of these metals. And alloys of metals such as cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

The magnetic material is more preferably a surface-modified magnetic material. When the magnetic toner is prepared by a polymerization method, it is preferable that the toner is subjected to a hydrophobic treatment with a surface modifier that is a substance that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.
These magnetic materials have a number average particle diameter of 2 μm or less, preferably 0.1 to 0.5 μm. The amount contained in the toner particles is 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin.

Furthermore, in the toner of the present invention, a fluidity improver may be added to the toner particles for the purpose of improving the fluidity of the toner particles. As the fluidity improver, the following fluororesin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fatty acid metal salts such as zinc stearate, calcium stearate and lead stearate; titanium oxide powder, oxidation Metal powder such as aluminum powder and zinc oxide powder, or powder obtained by hydrophobizing the above metal oxide; and silica fine powder such as wet process silica and dry process silica, or silica with silane coupling agent and titanium coupling. Examples thereof include fine particles of surface-treated silica that have been surface-treated with a treating agent such as an agent and silicone oil.
The fluidity improver is preferably used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the toner particles.

  Examples of the method for producing the toner of the present invention include the following methods. Conventional pulverization method; emulsion aggregation method in which an emulsion composed of essential toner components is aggregated in an aqueous medium; after dissolving essential toner components in an organic solvent, the organic solvent is volatilized after granulation in an aqueous medium Suspension granulation method; Suspension polymerization method or emulsion polymerization method in which a polymerizable monomer in which essential toner components are dissolved is directly granulated in an aqueous medium and then polymerized; Then, seed polymerization is used to provide an outer layer on the toner. Method: Microcapsule method represented by interfacial polycondensation and drying in liquid.

  Among these, the suspension polymerization method is particularly preferable as the one that easily exhibits the effects of the present invention. In this suspension polymerization method, a polymerizable monomer is uniformly dissolved or dispersed with a wax and a colorant (and a polymerization initiator, a crosslinking agent, a charge control agent, and other additives as necessary) to achieve polymerization. A monomer composition is used. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using a suitable stirrer, and a polymerization reaction is performed to obtain toner particles having a desired particle size. is there. After the polymerization, the toner particles are filtered, washed and dried by a known method, and if necessary, a fluidity improver is mixed and adhered to the surface to obtain the toner of the present invention.

For the purpose of efficiently proceeding the polymerization reaction, it is preferable to manage the dissolved oxygen in the reaction vessel. If there is little dissolved oxygen, the polymerization reaction will be more efficient. As a result, low molecular weight components that adversely affect developability and transferability can be suppressed, and excellent high development efficiency, high transfer efficiency, and uniformity can be obtained.
When the toner is produced by this suspension polymerization method, since the individual toner particle shapes are almost spherical, the distribution of charge amount is relatively uniform, and it is easy to obtain a toner satisfying development characteristics. In addition, it is easy to obtain a toner that maintains a high transferability with little dependence on external additives.
Examples of the polymerizable monomer for producing the toner by the suspension polymerization method include the monofunctional polymerizable monomer and the polyfunctional polymerizable monomer.

  As the polymerization initiator used in the present invention, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. When the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 10,000 and 100,000 is usually obtained. A toner having strength and melting characteristics can be obtained.

As polymerization initiators, the following 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbohydrate) were used. Nitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2- Ethyl hexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, Peroxides such as 2,4-dichlorobenzoyl peroxide and lauroyl peroxide Examples thereof include initiators.
In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

A dispersion stabilizer is added to the aqueous medium. Inorganic compounds used as dispersion stabilizers include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, sulfuric acid. Examples include calcium, barium sulfate, bentonite, silica, alumina and the like.
Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

Further, 0.001 to 0.1 parts by mass of a surfactant may be used for fine dispersion of these dispersion stabilizers. This is to promote the intended action of the dispersion stabilizer. Specific examples include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like.
When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be generated and used in an aqueous medium.
For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high stirring.

  The physical property value measuring method of the present invention will be described below.

<Measurement of L, Va and Vb of toner>
In the present invention, when the UV photocurable composition is infiltrated, the osmotic film thickness L (μm) at an osmosis time of 5 seconds, the average penetration speed Va (μm / s) at 5 seconds to 10 seconds, and 10 seconds or more The average penetration speed Vb (μm / s) at 15 seconds or less is measured by the following method.

  The measurement sample was produced as follows.

  The toner to be measured was placed in, for example, a UV photocurable composition D-800 (manufactured by Toagosei Co., Ltd.), and the UV photocurable composition was infiltrated for 5 seconds. After that, for example, a sample is placed at a distance of 3.0 ± 0.1 cm from the irradiation part of the irradiator LUXSPOT-II (manufactured by JEOL Detam Co., Ltd.), and irradiated with UV light at an output of 150 W for 30 seconds. The curable composition was cured in the toner. The toner after penetration and curing of the UV photocurable composition was made into a toner slice having a thickness of 50 to 100 nm using, for example, ULTRACUT UCT (manufactured by Leica Microsystems). The toner slice was observed using, for example, a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Tech Co., Ltd.) to obtain a transmission electron image (STEM image) of the toner slice.

The penetration film thickness of the UV photocurable composition in the transmission electron image was L. The osmotic film thickness is defined as Lx is the osmotic film thickness of the UV photocurable composition in the major axis direction in the toner slice, and Ly is the osmotic film thickness in the minor axis direction of the UV photocurable composition.
L = (Lx + Ly) / 2
Defined.

  Further, in order to eliminate the measurement error as much as possible, a toner having a number average particle diameter D1 of ± 0.2 μm was selected and measured. Regarding the measurement, 100 arbitrary particles were selected and measured, and with respect to L obtained as a measurement result, the remaining 80 particles obtained by removing 10 from the maximum value and the minimum value were used as data. L was determined as an arithmetic mean value.

Similarly, a section was prepared for a toner impregnated with the UV photocurable composition for 10 seconds. The penetration thickness of the UV light curable composition in the toner slice was L _10. At this time, Va is
Va = (L ₁₀ −L) / 5
Defined.

Similarly, a section was prepared for a toner impregnated with a UV photocurable composition for 15 seconds. The penetration thickness of the UV light curable composition in the toner slice was L _15. At this time, Vb is
_{Vb = (L 15 -L 10)} / 5
Defined.

  An image of the relationship between the osmotic film thickness and the osmotic time at this time is shown in FIG. Here, in FIG. 1, the osmotic film thickness at the osmosis time of 0 second is not 0 μm, which is considered to be due to the penetration of the UV photocurable composition during UV light irradiation.

  In addition, as a UV photocurable composition used for this invention, the mixture containing a (meth) acrylic acid ester, a (meth) acryl modified oligomer, and a photoinitiator at least is used. Preferably, the composition contains 50 to 200 parts by mass of a polyester (meth) acrylate and 0.1 to 20 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the (meth) acrylic acid ester.

  Examples of the (meth) acrylic acid ester include the following triethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and isoboronyl (meth) acrylate. 2-hydroxy-3-phenoxypropyl (meth) acrylate, isostearyl (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, dioxane glycol di (meth) acrylate, Tricyclodecane dimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethoxylation Limethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, nonylphenol EO modified (Meth) acrylate, bisphenol AEO-modified di (meth) acrylate, tripropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpro Ntetora (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like. Of these, triethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaerythritol tris are particularly preferred from the viewpoint of excellent UV photocurability. It is preferable to use (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tri (ethylene glycol) di (meth) acrylate. More preferably, it is used.

  Examples of the acrylic modified oligomer include the following (meth) acryl modified polyester oligomer, (meth) acryl modified polyurethane oligomer, (meth) acryl modified epoxy oligomer, (meth) acryl modified polyethylene glycol oligomer, and (meth) acryl modified polypropylene glycol oligomer. Etc. can be exemplified. Among these, it is particularly preferable to use an acrylic-modified polyurethane oligomer from the viewpoint of excellent UV light curability.

  Examples of the photopolymerization initiator include the following 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane- 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- Alkylphenone photopolymerization initiators such as 4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Acylphosphine oxide photopolymerization initiator such as oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl ) A titanocene photopolymerization initiator such as titanium can be exemplified.

  The UV photocurable composition may contain an ultraviolet absorber and a polymerization accelerator.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4, 5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy- Examples thereof include 5-t-octylphenyl) benzotriazole and 2- (2-hydroxy-3,5-di-t-pentylphenyl) benzotriazole.

  Examples of the polymerization accelerator include the following aminobenzoate polymerization accelerators such as ethyl-4-dimethylaminobenzoate and 2-ethylhexyl-4-dimethylaminobenzoate.

<Measurement of viscosity>
The viscosity of the toner at 100 ° C. is measured by the following method.
For example, a flow tester CFT-500D (manufactured by Shimadzu Corporation) is used as an apparatus, and measurement is performed under the following conditions in accordance with the operation manual of the apparatus.
Sample: About 1.0 g of toner is weighed and molded with a pressure molding machine to obtain a sample.
・ Die hole diameter: 0.5mm
-Die length: 1.0mm
・ Cylinder pressure: 9.807 × 10 ⁵ (Pa)
Measurement mode: Temperature rising method Temperature rising rate: 4.0 ° C./min
By the above method, the viscosity of the toner at a temperature of 50 ° C. to 200 ° C. is measured, and the viscosity at a temperature of 100 ° C. is obtained.

<Micro compression test>
In the displacement curve from applying a load of 2.94 × 10 ⁻⁴ N to the toner at a load speed of 9.8 × 10 ⁻⁵ N / sec in the toner micro-compression test until the load is removed, the load ends. The slope R (25) of the displacement curve up to is measured by the following method.

A measurement method of the micro compression test will be described with reference to FIG.
FIG. 2 shows a profile (displacement curve) when the toner is measured in the micro-compression test of the present invention. The horizontal axis represents the amount of displacement of the toner and the vertical axis represents the amount of load applied to the toner.

  As an apparatus, for example, an ultra micro hardness meter ENT1100 (manufactured by Elionix Co., Ltd.) was used. The working indenter was measured using a 20 μm × 20 μm square flat indenter.

1-1 is the initial state before starting the test, to the maximum load 2.94 × ^{10 -4} N, applying a load at a speed of 9.8 × ¹⁰ -5 N / sec. Immediately after reaching the maximum load, the state is 1-2, and the amount of displacement at this time is X ₂ (μm). In the state of 1-2, leave with the load for 0.1 sec. The state immediately after the end of standing is 1-3, and the maximum displacement at this time is X ₃ (μm), and further unloads at a speed of 9.8 × 10 ⁻⁵ N / sec through the maximum load, When the load becomes 0, the state is 1-4. The amount of displacement at this time is X ₄ (μm).
The slope R (25) of the displacement curve approximates the displacement curve from 1-1 to 1-2 as a linear line, and is calculated as the slope X ₂ /(2.94×10 ⁻⁴ ) (μm / N) of the straight line. did.

In actual measurement, a toner is applied on a ceramic cell, and minute air is blown so that the toner is dispersed on the cell. The cell is set in the apparatus and measured.
In the measurement, the cell was brought into a temperature-controllable state, and the temperature of this cell was taken as the measurement temperature. That is, R (25) was measured at a cell temperature of 25 ° C. In the micro compression test according to the present invention, the toner is dispersed on the cell, and then the cell is placed on the main body. Thereafter, after the cell reaches the measurement temperature, it is left for 10 minutes or more, and then the measurement is started.
For the measurement, while looking through the microscope attached to the apparatus, select the measurement screen (horizontal width: 160 μm, vertical width: 120 μm) in which one toner exists. In order to eliminate the displacement error as much as possible, a toner having a number average particle diameter D1 of ± 0.2 μm is selected and measured. An arbitrary toner is selected from the measurement screen. As the means for measuring the toner particle diameter on the measurement screen, the major and minor diameters of the toner particles were measured using software attached to an ultra-micro hardness meter ENT1100. Then, a toner having an aspect ratio [(major axis + minor axis) / 2] determined from them having a D1 of ± 0.2 μm was selected and measured.

  Regarding the measurement data, 100 arbitrary particles were selected and measured, and the R (25) obtained as a measurement result was used as the data, with the remaining 80 values excluding 10 from the maximum and minimum values, respectively. And R (25) was calculated | required as the arithmetic mean value of the 80 pieces.

<Measurement of Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are measured by a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman 2) Effective measurement channel number 25,000 using “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter) Measurement was performed on the channel, and the measurement data was analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

Prior to measurement and analysis, the dedicated software was set as follows.
In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion Sys” with an electric output of 120 W is provided.
A predetermined amount of ion-exchanged water is placed in a water tank of “tem Tetora 150” (manufactured by Nikka Ki Bios), and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the analysis / number statistic (arithmetic average) screen is the number average particle diameter (D1).

<Measurement of glass transition point (Tg) of polar resin>
The glass transition point (Tg) of the polar resin in the present invention is measured under the following conditions and determined from the peak position of the DSC curve at the first temperature increase.
<Measurement conditions>
・ Equilibrium at 20 ° C. for 5 minutes ・ Modulation of 1.0 ° C./min is applied and the temperature is raised to 140 ° C. at 1 ° C./min. ・ Equilibrium is maintained at 140 ° C. for 5 minutes.

A differential scanning calorimeter (DSC measuring apparatus) is measured as follows according to ASTM D3418-82 using DSC-7 (manufactured by PerkinElmer), DSC2920 (manufactured by TA Instruments Japan) and the like. The sample to be measured is precisely weighed from 2 to 5 mg, preferably 3 mg. It is put in an aluminum pan, and an empty aluminum pan is used as a control, and measurement is performed at a temperature rising rate of 1 ° C./min in a measurement range of 20 to 140 ° C.
The glass transition point here is determined by the midpoint method.

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

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

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

(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

  Next, an example of an image forming method using the toner manufactured using the toner particle manufacturing method of the present invention will be described with reference to FIGS. 3, 4, 5 and 6. FIG.

FIG. 4 shows the configuration of the image forming apparatus (contact single component development system) used in this embodiment. The image forming apparatus is a laser beam printer using a transfer type electrophotographic process.
FIG. 4 is a schematic cross-sectional view showing an example of an image forming apparatus to which the image forming method of the present invention is applied.
The image forming apparatus 100 has four image forming stations Pa, Pb, Pc, and Pd arranged in parallel in the vertical direction. The process cartridges 7 (7a, 7b, 7c, 7d) are detachably attached to the image forming stations Pa, Pb, Pc, Pd by attachment means (not shown). The magenta, cyan, yellow, and black cartridges 7a, 7b, 7c, and 7d have the same configuration.

In this schematic diagram, the image forming stations Pa, Pb, Pc, and Pd are arranged side by side with a slight inclination in the vertical direction, but they may be arranged in the vertical direction without being inclined. Further, the process cartridge 7 may be the same as that illustrated in FIG. 3 or may be different.
Each cartridge 7 (7a, 7b, 7c, 7d) includes a photosensitive drum 1 (1a, 1b, 1c, 1d). The photosensitive drum 1 is driven to rotate counterclockwise in the drawing by a driving means (not shown). The following means are provided around the photosensitive drum 1 in order according to the rotation direction. (A) Charging means 2 (2a, 2b, 2c, 2d) for uniformly charging the surface of the photosensitive drum 1. (B) A scanner unit 3 (3a, 3b, 3c, 3d) that irradiates a laser beam based on image information to form an electrostatic latent image on the photosensitive drum 1. (C) Developing means 4 (4a, 4b, 4c, 4d) for developing a toner image by attaching a developer (hereinafter referred to as “toner”) to the electrostatic latent image. (D) A transfer device 5 that transfers the toner image on the photosensitive drum 1 to the recording medium S. (E) Cleaning means 6 (6a, 6b, 6c, 6d) for removing toner remaining on the surface of the photosensitive drum 1 after transfer.

Here, the photosensitive drum 1 and the charging means 2, the developing means 4, and the cleaning means 6, which are process means, are integrally constituted by a cartridge frame to form a cartridge to constitute a cartridge 7.
The photosensitive drum 1 (1a, 1b, 1c, 1d) is configured by providing a photosensitive layer on the outer peripheral surface of a cylinder. Both ends of the photosensitive drum 1 are rotatably supported by support members. Then, when a driving force from a driving motor (not shown) is transmitted to one end portion, it is rotationally driven counterclockwise.

As the photoconductor, a photoconductor drum having a photoconductive insulating material layer such as a-Se, CdS, ZnO ₂ , OPC, or a-Si is preferably used. Further, the binder resin of the organic photosensitive layer in the OPC photoreceptor is not particularly limited. Among them, polycarbonate resin, polyester resin, and acrylic resin are particularly preferable because they are excellent in transferability and hardly cause toner fusion to the photoreceptor and filming of external additives.

  As the charging means 2 (2a, 2b, 2c, 2d), a contact charging type is used. The charging means 2 is a conductive roller formed in a roller shape. The roller is brought into contact with the surface of the photosensitive drum 1 and a charging bias voltage is applied to the roller. As a result, the surface of the photosensitive drum 1 is uniformly charged.

  As a preferable process condition when the charging roller is used, the contact pressure of the roller is 0.05 to 5 N / cm as a linear pressure. As the applied voltage, a DC voltage or a DC voltage superimposed with an AC voltage is preferably used. When a DC voltage superimposed with an AC voltage is used, it is preferable that AC voltage = 0.5 to 5 dVpp, AC frequency = 50 Hz to 5 kHz, and DC voltage = ± 0.2 to ± 1.5 kV. When a DC voltage is used, the DC voltage is preferably ± 0.2 to ± 5 kV.

  As charging means other than the charging roller, there are a method using a charging blade and a method using a conductive brush. These contact charging means have an effect that a high voltage is unnecessary and generation of ozone is reduced as compared with non-contact corona charging. The material of the charging roller and charging blade as the contact charging means is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), and the like are applicable.

In the scanner unit 3 (3a, 3b, 3c, 3d), a laser diode (not shown) passes image light corresponding to an image signal through a polygon mirror (not shown) and an imaging lens (not shown) rotated at high speed. Then, the surface of the charged photosensitive drum 1 is exposed according to image information. As a result, an electrostatic latent image is formed on the photosensitive drum.
The developing means 4 (4a, 4b, 4c, 4d) is composed of a toner container 41 that stores magenta, cyan, yellow, and black toners, respectively, and feeds toner in the toner container 41. To the toner supply roller 43.
The toner supply roller 43 rotates in the clockwise direction in the figure, and supplies toner to the developing roller 40 as a toner carrying member and does not contribute to the development of the electrostatic latent image. Perform stripping.

  The toner supplied to the developing roller 40 is applied to the outer periphery of the developing roller 40 (rotated clockwise) by the toner regulating member 44 pressed against the outer periphery of the developing roller 40, and is given an electric charge. Then, a developing bias is applied to the developing roller 40 facing the photosensitive drum 1 on which the latent image is formed. Then, toner development is performed on the photosensitive drum 1 in accordance with the latent image.

The transfer device 5 is provided with an electrostatic transfer belt 11 which circulates and moves so as to face and contact all the photosensitive drums 1 (1a, 1b, 1c, 1d). The transfer belt 11 is stretched around a driving roller 13, driven rollers 14a and 14b, and a tension roller 15, and electrostatically attracts the recording medium S to the outer peripheral surface on the left side in the drawing. Then, the transfer belt 11 circulates and moves so as to bring the recording medium S into contact with the photosensitive drum 1. As a result, the recording medium S is conveyed to the transfer position by the transfer belt 11 and the toner image on the photosensitive drum 1 is transferred.
The four photosensitive drums 1 (1a, 1b, 1c, 1d) are in contact with the inside of the transfer belt 11.
), Transfer rollers 12 (12a, 12b, 12c, 12d) are arranged in parallel. A bias is applied to the transfer rollers 12 at the time of transfer, and an electric charge is applied to the recording medium S via the electrostatic transfer belt 11. The toner image on the photosensitive drum 1 is transferred to the recording medium S in contact with the photosensitive drum 1 by the electric field generated at this time.

  The feeding unit 16 feeds and transports the recording medium S to the image forming stations Pa, Pb, Pc, and Pd. A plurality of recording media S are stored in the cassette 17 in the feeding unit 16. At the time of image formation, the feeding roller 18 (half-moon roller) and the registration roller 19 are driven and rotated according to the image forming operation. The feeding roller 18 separates and feeds the recording medium S in the cassette 17 one by one, and then stops the recording medium S by abutting against the registration roller 19. Thereafter, the registration roller 19 feeds the recording medium S to the electrostatic transfer belt 11 in synchronization with the rotation of the transfer belt 11 and the image writing position.

  The fixing unit 20 fixes the toner images of a plurality of colors transferred to the recording medium S. The fixing unit 20 includes a heating roller 21a and a pressure roller 21b that presses against the heating roller 21a and applies heat and pressure to the recording medium S. That is, the recording medium S to which the toner image formed on the photosensitive drum 1 has been transferred is conveyed by the pressure roller 21b and applied with heat and pressure by the heating roller 21a when passing through the fixing unit 20. As a result, a plurality of color toner images are fixed on the surface of the recording medium S.

As an image forming operation, the cartridges 7 (7a, 7b, 7c, 7d) are sequentially driven in accordance with the image forming timing. In response to the driving, the photosensitive drums 1a, 1b, 1c, and 1d are rotationally driven in the counterclockwise direction. The scanner units 3 corresponding to the cartridges 7 are sequentially driven. By this driving, the charging roller 2 applies a uniform charge to the peripheral surface of the photosensitive drum 1. Then, the scanner unit 3 exposes the circumferential surface of the photosensitive drum according to an image signal to form an electrostatic latent image on the circumferential surface of the photosensitive drum. The developing roller 40 in the developing means 4 forms (develops) a toner image on the circumferential surface of the photosensitive drum 1 by transferring the toner to the low potential portion of the electrostatic latent image.
At the timing when the leading edge of the toner image formed on the peripheral surface of the most upstream photosensitive drum 1 is rotated and conveyed to a point facing the transfer belt 11, the printing start position of the recording medium S coincides with that point. The registration roller 19 rotates to feed the recording medium S to the transfer belt 11.

  The recording medium S is pressed against the outer periphery of the transfer belt 11 so as to be sandwiched between the suction roller 22 and the transfer belt 11. A voltage is applied between the transfer belt 11 and the suction roller 22. Electric charges are induced in the recording medium S that is a dielectric and the dielectric layer of the transfer belt 11, and the recording medium S is electrostatically adsorbed on the outer periphery of the transfer belt 11. Thereby, the recording medium S is stably adsorbed to the electrostatic transfer belt 11 and conveyed to the most downstream transfer unit.

While being conveyed in this manner, the toner image on each photoconductive drum 1 is sequentially transferred to the recording medium S by an electric field formed between each photoconductive drum 1 and the transfer roller 12.
The recording medium S to which the four color toner images are transferred is separated from the electrostatic transfer belt 11 by the curvature of the belt driving roller 13 and is carried into the fixing unit 20. After the toner image is thermally fixed by the fixing unit 20, the recording medium S is discharged out of the main body by the paper discharge roller 23 with the image surface facing down from the paper discharge unit 24.

  In FIG. 2, a method using a heating roller for the fixing unit 20 is illustrated, but other fixing methods can also be suitably used for the image forming method of the present invention. 5 and 6 show an apparatus for fixing a toner image by heating a heat-resistant polymer film using a heating element.

FIG. 5 shows a fixing device having a structure in which tension is always applied to the film.
In the present invention, the heating element has a small heat capacity and has a linear or planar heating section, and the maximum temperature of the heating section is preferably 100 to 300 ° C.
The film is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. As these heat-resistant sheets, polyester, PET (polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether) having high heat resistance are used. Copolymers), PTFE (polytetrafluoroethylene), polyimide, polyamide and other polymer sheets, metal sheets such as aluminum, and laminate sheets composed of metal sheets and polymer sheets are used.
A more preferable film structure is that these heat-resistant sheets have a release layer and / or a low resistance layer.

Reference numeral 51 denotes a heating element fixedly supported by the apparatus, and includes a heater substrate 52, an energization heating resistor (heating element) 53, a temperature detecting element 54, and the like.
The heater substrate 52 is a member having heat resistance, insulation, low heat capacity, and high heat conductivity, and is, for example, an alumina substrate having a thickness of 1 mm, a width of 10 mm, and a length of 240 mm.
The heating element 53 is formed by screen printing or the like in an approximately 10 μm thickness and 1 to 3 mm wide linear or narrow strip of an electric resistance material along the longitudinal direction at a substantially central portion of the lower surface of the heater substrate 52 (on the side facing the film 55). It has been applied. For example, Ag / Pd (silver palladium), Ta ₂ N, RuO ₂ or the like is used as the electrical resistance material.

The temperature measuring element 54 is, for example, a temperature measuring resistor having a low heat capacity, such as a Pt film, which is provided by applying screen printing or the like on the substantially central portion of the upper surface of the heater substrate 52 (the side opposite to the surface on which the heating element 53 is provided). Is the body. A thermistor with a low heat capacity can also be used.
In the case of the heating element 51 of the present example, the heating element 53 having a linear or planar shape is energized at a predetermined timing by an image formation start signal to cause the heating element 53 to generate heat over substantially the entire length. The energization is AC 100 V, and the supplied power is controlled by controlling the phase angle of energization by an energization control circuit (not shown) including a triac in accordance with the temperature detected by the temperature sensing element 54.

When the heating element 51 is energized, the heat capacity of the heater substrate 52 and the heating element 53 is small, so that the surface of the heating element rapidly rises to a required fixing temperature (for example, 140 to 200 ° C.).
The heat-resistant film 55 is in contact with the heating body 51.

To reduce the heat capacity and improve the quick start performance, the film 55 is a single layer or composite layer film with a total thickness of 100 μm or less and heat resistance / release properties, strength / durability of 20 μm or more. it can.
For example, polyimide, polyetherimide (PEI), polyethersulfone (PES), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), polyetheretherketone (PEEK), polyparabanic acid (PPA), Alternatively, a composite layer film such as a polyimide film having a thickness of 20 μm, on at least the image contact surface side, PTFE (tetrafluoroethylene resin), fluororesin such as PAF / FEP, silicon resin, etc., and further, a conductive material (carbon black, graphite, And a releasable coating layer to which a conductive whisker or the like is added is applied to a thickness of 10 μm.
The support roller 58, which is a rotating body, is made of a rubber elastic body having good releasability such as silicon rubber, and is pressed against the heating body 51 via the film 55 to form a nip portion, and the film 55 is moved and driven at a predetermined speed. To do. When a recording material sheet as a material to be heated is introduced between the film 55 and the film 55, the recording material sheet is brought into close contact with the surface of the film 55, pressed against the heating body 51, and moved and driven together with the film 55.

Another embodiment of a device for fixing a toner image by heating a heat-resistant polymer film using a heating element will be described.
FIG. 6 shows a fixing device having a structure in which no tension is applied to the film (tension-free type).

In the present invention, the heating element has a small heat capacity and has a linear or planar heating section, and the maximum temperature of the heating section is preferably 100 to 300 ° C.
The film is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. As these heat-resistant sheets, polyester, PET (polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether) having high heat resistance are used. Copolymers), PTFE (polytetrafluoroethylene), polyimide, polyamide and other polymer sheets, metal sheets such as aluminum, and laminate sheets composed of metal sheets and polymer sheets are used.
A more preferable film structure is that these heat-resistant sheets have a release layer and / or a low resistance layer.

Reference numeral 64 denotes a low heat capacity linear heater fixedly supported by the apparatus, which includes a heater substrate 64a, an energizing heating resistor (heating element) 64b, a surface protective layer 64c, a temperature detecting element 64d, and the like.
The heater substrate 64a is a member having heat resistance, insulation, low heat capacity, and high heat conductivity, and is, for example, an alumina substrate having a thickness of 1 mm, a width of 10 mm, and a length of 240 mm.

The heating element 64b is coated with an electric resistance material in a linear or narrow strip shape having a thickness of about 10 μm and a width of 1 to 3 mm along the longitudinal direction at a substantially central portion of the lower surface (the side facing the film 65) of the heater substrate 64a. The surface protective layer 64c is coated thereon with a heat resistant glass of about 10 μm. For example, Ag / Pd (silver palladium), Ta ₂ N, RuO ₂ or the like is used as the electrical resistance material. Moreover, as a coating method of the electrical resistance material, a screen printing method or the like is used.

The temperature measuring element 64d is, for example, a low-temperature-capacitance resistance measuring resistor such as a Pt film that is applied by screen printing or the like on the substantially central portion of the upper surface of the heater substrate 64a (the side opposite to the surface on which the heating element 64b is provided). Is the body. A thermistor with a low heat capacity can also be used.
In the case of the heating element 64 of this example, the heating element 64b having a linear or planar shape is energized at a predetermined timing by an image formation start signal to cause the heating element 64b to generate heat over substantially the entire length. The energization is AC 100 V, and the supplied power is controlled by controlling the phase angle of energization by an energization control circuit (not shown) including a triac according to the temperature detected by the temperature sensing element 64d. Since the heating element 64 has a small heat capacity of the heater substrate 64a, the heating element 64b, and the surface protective layer 64c by energizing the heating element 64b, the surface of the heating element rapidly rises to a required fixing temperature (for example, 140 to 200 ° C.). To do.
The heat resistant film 65 is in contact with the heating body 64.

To reduce the heat capacity and improve the quick start performance, the film 65 is a single layer or composite layer film with a total thickness of 100 μm or less and heat resistance / release properties, strength / durability of 20 μm or more. it can.
For example, polyimide, polyetherimide (PEI), polyethersulfone (PES), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), polyetheretherketone (PEEK), polyparabanic acid (PPA), Alternatively, a composite layer film such as a polyimide film having a thickness of 20 μm, on at least the image contact surface side, PTFE (tetrafluoroethylene resin), fluororesin such as PAF / FEP, silicon resin, etc., and further, a conductive material (carbon black, graphite, And a releasable coating layer to which a conductive whisker or the like is added is applied to a thickness of 10 μm.

The support roller 62, which is a rotating body, is made of a rubber elastic body having good releasability such as silicon rubber, and is pressed against the heating body 64 via the film 65 to form a nip portion, and the film 65 is moved and driven at a predetermined speed To do. When a recording material sheet as a material to be heated is introduced between the film 65 and the recording material sheet, the recording material sheet is brought into close contact with the surface of the film 65, pressed against the heating body 64, and moved and driven together with the film 65.

FIG. 3 is a schematic cross-sectional view of a process cartridge 7 (hereinafter also referred to as a cartridge) that can be suitably used in an image forming apparatus to which the image forming method of the present invention is applied.
The cartridge 7 includes a photosensitive drum 1, a cleaner unit 50 including a charging unit 2 and a cleaning unit 6, and a developing unit 4 </ b> A having a developing unit 4 that develops an electrostatic latent image formed on the photosensitive drum 1. Have. The photosensitive drum 1 is rotatably attached to the cleaning frame 31 constituting the cleaner unit 50 via a bearing member (not shown).

  The photosensitive drum 1 has a charging roller 2 for uniformly charging the photosensitive layer provided on the outer peripheral surface of the photosensitive drum 1, and a developer (residual toner) remaining on the photosensitive drum 1 after transfer is removed. The cleaning blade 60 for making contact is in contact. The toner (removed toner) removed from the surface of the photosensitive drum 1 by the cleaning blade 60 is stored in a removed toner storage chamber 35 provided in the cleaning frame 31.

The developing unit 4A has a developing frame body 45 (45a, 45b, 45e) that accommodates toner, and the developing roller 40 (rotated in the direction of arrow Y) is rotatably attached to the developing frame body 45 via a bearing member. It is supported. Further, a toner supply roller 43 (rotated in the arrow Z direction) and a toner regulating member 44 are provided in contact with the developing roller 40. Further, the developing device frame 45 is provided with a toner transport mechanism 42 for stirring the toner contained therein and transporting the toner to the toner supply roller 43.
The developing unit 4A is supported so as to be swingable with respect to the cleaner unit 50. That is, the coupling holes 47 and 48 provided at both ends of the developing device frame 45 are aligned with the support holes (not shown) provided at both ends of the cleaning frame 31 of the cleaner unit 50, and pins (not shown) are inserted from both ends of the cleaner unit 50. It is out.

Further, the developing unit 4A is always urged by a pressure spring (not shown) so that the developing roller 40 contacts the photosensitive drum 1 with the support hole as the rotation axis.
At the time of development, the toner stored in the toner container 41 is conveyed to the toner supply roller 43 by the toner stirring mechanism 42. The toner supply roller 43 supplies toner to the developing roller 40 by rubbing with the developing roller 40, and causes the toner to adhere on the developing roller 40. The toner adhered on the developing roller 40 reaches the toner regulating member 44 as the developing roller 40 rotates. Then, the toner regulating member 44 regulates the toner to form a predetermined toner thin layer, and gives a desired charge amount. The toner thinned on the developing roller 40 is conveyed to the developing unit in which the photosensitive drum 1 and the developing roller 40 come close as the developing roller 40 rotates. Then, in the developing unit, the latent image is developed by attaching to the electrostatic latent image formed on the surface of the photosensitive drum 1 by a developing bias applied to the developing roller 40 from a power source (not shown). The toner remaining on the surface of the developing roller 40 without contributing to the development of the electrostatic latent image is returned into the developing frame 45 as the developing roller 40 rotates. Then, it is peeled off and collected from the developing roller 40 at the rubbing portion with the toner supply roller 43. The collected toner is stirred and mixed with the remaining toner by the toner stirring mechanism 42.
Here, an elastic roller is used as the developing roller 40, and a method of bringing the roller into contact with the surface of the photosensitive drum 1 can be used. In general, in a developing method in which a toner carrier and a photoreceptor are in contact with each other, toner is easily damaged or deformed. However, when the toner described in the present invention is used, such a change can be effectively suppressed. preferable.

In the developing method in which the toner carrying member and the photosensitive member are in contact with each other, development is performed by an electric field acting between the photosensitive member and the elastic roller facing the surface of the photosensitive member through the toner. Therefore, the surface of the elastic roller or the vicinity of the surface has a potential, and it is necessary to have an electric field in a narrow gap between the surface of the photosensitive member and the surface of the toner carrying member. Therefore, it is possible to use a method in which the elastic rubber of the elastic roller is resistance-controlled in the middle resistance region to keep the electric field while preventing conduction with the surface of the photoreceptor, or a method of providing a thin insulating layer on the surface layer of the conductive roller. . Further, a conductive resin sleeve in which the side facing the surface of the photoconductor is coated with an insulating material on the conductive roller, or a conductive layer is provided on the side not facing the photoconductor with an insulating sleeve is also possible. . Further, it is possible to employ a configuration in which a rigid roller is used as the toner carrying member and the photosensitive member is a flexible material such as a belt. The resistance value of the roller as the toner carrier is preferably in the range of 10 ² to 10 ⁹ Ω · cm.

  As the surface shape of the toner carrier, when the surface roughness Ra (μm) is set to 0.1 to 3.0, both high image quality and high durability can be achieved. The surface roughness Ra correlates with the toner conveying ability and the toner charging ability. When the surface roughness Ra of the toner carrier exceeds 3.0, it is difficult not only to make the toner layer on the toner carrier thin, but also the chargeability of the toner is not improved, so that improvement in image quality cannot be expected. . Since the toner carrying ability on the surface of the toner carrier is suppressed by setting it to 3.0 or less, the toner layer on the toner carrier is thinned, and the number of contact between the toner carrier and the toner increases. Since the chargeability of the toner is also improved, the image quality is synergistically improved. On the other hand, when the surface roughness Ra is smaller than 0.1, it becomes difficult to control the toner coat amount.

  In the present invention, the surface roughness Ra of the toner carrier is in accordance with Japanese Industrial Standard (JIS) B06014.2.1 (revision date January 20, 2001, confirmation date July 20, 2005). Arithmetic mean roughness determined. In the present invention, a surface roughness measuring device (Surfcoder SE3500 manufactured by Kosaka Laboratory Co., Ltd.) was used to measure from an arbitrary point on the surface of the toner carrier in a direction parallel to the rotation axis of the toner carrier. The cut-off value was 0.8 mm, the measurement length was 2.5 mm, and the measurement speed was 0.1 mm / second.

  The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. The toner production method will be described below. Unless otherwise specified, all parts and% in the examples and comparative examples are based on mass.

(Example of toner production)
<Cyan toner 1>
A suspension polymerization toner was prepared according to the following procedure.
The following materials were stirred at 10,000 r / min at a temperature of 60 ° C. using a TK homomixer (manufactured by Tokushu Kika Kogyo) to prepare an aqueous medium having a pH of 5.2. The following polar resin 1 and polar resin 2 were obtained by solution polymerization of the monomers shown in Table 4 in xylene at the composition ratio (based on parts by mass) shown in Table 4, respectively.
-Ion-exchanged water 1300.0 parts by mass-Tricalcium phosphate 9.0 parts by mass-10% hydrochloric acid 11.0 parts by mass In addition, the following materials are dissolved at 100 r / min with a propeller-type stirrer to obtain a solution. Prepared.
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Chemical Co., Ltd.) 2.0 parts by mass Polar resin 1 10.0 parts by mass Polar resin 2 10.0 parts by mass Next, the following materials were added to the solution.
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Thereafter, the mixture was heated to a temperature of 60 ° C. and then stirred and dissolved and dispersed at 9,000 r / min with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
Into this, 8.0 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition was charged into the aqueous medium, and stirred at 10,000 r / min for 30 minutes at a temperature of 60 ° C. using a TK homomixer, and granulated.

Thereafter, the mixture was transferred to a propeller type stirring device and reacted at a temperature of 70 ° C. for 5 hours while stirring at 100 r / min, then heated to a temperature of 80 ° C. and further reacted for 5 hours to produce cyan toner particles. After completion of the polymerization reaction, the slurry containing the particles was cooled, washed with an amount of water 10 times that of the slurry, filtered and dried, and the particle size was adjusted by classification to obtain cyan toner particles.
Hydrophobic silica fine powder (number average 1) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts by mass of the toner particles. Cyan toner 1 was obtained by mixing 2.0 parts by mass of secondary particle size: 10 nm, BET specific surface area: 170 m ² / g) with a Henschel mixer (manufactured by Mitsui Miike) at 3,000 r / min for 15 minutes. Table 1 shows the physical properties of cyan toner 1, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 2>
-Styrene 70.0 parts by mass-n-butyl acrylate 30.0 parts by mass-Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass-Polar resin 1 15.0 parts by mass-Polar resin 2 5.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 2 was obtained in the same manner as cyan toner 1 except that the above materials were used.
Table 1 shows the physical properties of the cyan toner 2, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 3>
-Styrene 70.0 parts by mass-n-butyl acrylate 30.0 parts by mass-Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass-Polar resin 1 5.0 parts by mass-Polar resin 2 15.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 3 was obtained in the same manner as cyan toner 1 except that the above materials were used.
The physical properties of cyan toner 3 are shown in Table 1, the evaluation results are shown in Table 3, and the physical properties of the polar resin used are shown in Table 4.

<Cyan toner 4>
Styrene 73.0 parts by mass n-butyl acrylate 27.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Chemical Co., Ltd.) 2.0 parts by mass Polar resin 1 10.0 parts by mass Polar resin 2 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 4 was obtained in the same manner as cyan toner 1 except that the above materials were used.
Table 1 shows the physical properties of the cyan toner 4, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 5>
Styrene 67.0 parts by mass n-butyl acrylate 33.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Kasei) 2.0 parts by mass Polar resin 1 10.0 parts by mass Polar resin 2 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 5 was obtained in the same manner as cyan toner 1 except that the above materials were used.
The physical properties of cyan toner 5 are shown in Table 1, the evaluation results are shown in Table 3, and the physical properties of the polar resin used are shown in Table 4.

<Cyan toner 6>
Styrene 67.0 parts by mass n-butyl acrylate 33.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Kasei) 2.0 parts by mass Polar resin 3 10.0 parts by mass Polar resin 4 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 6 was obtained in the same manner as cyan toner 1 except that the above materials were used. The polar resin 3 and the polar resin 4 were obtained by subjecting the monomers shown in Table 4 to solution polymerization in xylene at the composition ratio (part by mass) shown in Table 4, respectively.
Table 1 shows the physical properties of the cyan toner 6, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 7>
-Styrene 73.0 parts by mass-n-Butyl acrylate 27.0 parts by mass-Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass-Polar resin 5 10.0 parts by mass-Polar resin 6 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 7 was obtained in the same manner as cyan toner 1 except that the above materials were used. In addition, the said polar resin 5 and the polar resin 6 used what was obtained by solution-polymerizing the monomer shown in Table 4 in xylene with the composition ratio (mass part basis) shown in Table 4, respectively.
Table 1 shows the physical properties of the cyan toner 7, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 8>
-Styrene 70.0 parts by mass-n-butyl acrylate 30.0 parts by mass-Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass-Polar resin 1 7.5 parts by mass-Polar resin 2 7.5 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 8 was obtained in the same manner as cyan toner 1 except that the above materials were used.
Table 1 shows the physical properties of the cyan toner 8, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 9>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass Polar resin 1 12.5 parts by mass Polar resin 2 12.5 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 9 was obtained in the same manner as cyan toner 1 except that the above materials were used.
Table 1 shows the physical properties of cyan toner 9, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 10>
-Styrene 70.0 parts by mass-n-butyl acrylate 30.0 parts by mass-Charge control agent FCA1001NS (manufactured by Fujikura Chemical Co., Ltd.) 2.0 parts by mass-Polar resin 5 5.0 parts by mass-Polar resin 6 3.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass A cyan toner 10 was obtained in the same manner as the cyan toner 1 except that the above materials were used.
Table 1 shows the physical properties of the cyan toner 10, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 11>
-Styrene 70.0 parts by mass-n-Butyl acrylate 30.0 parts by mass-Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass-Polar resin 3 22.0 parts by mass-Polar resin 4 30.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass A cyan toner 11 was obtained in the same manner as the cyan toner 1 except that the above materials were used.
Table 1 shows the physical properties of the cyan toner 11, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 12>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (Fujikura Kasei Co., Ltd.) 2.0 parts by mass Polar resin 7 10.0 parts by mass Polar resin 8 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass A cyan toner 12 was obtained in the same manner as the cyan toner 1 except that the above materials were used. The following polar resin 7 and polar resin 8 were obtained by subjecting the monomers shown in Table 4 to solution polymerization in xylene at the composition ratio (part by mass) shown in Table 4, respectively.
Table 1 shows the physical properties of the cyan toner 12, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 13>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Kasei) 2.0 parts by mass Polar resin 9 10.0 parts by mass Polar resin 10 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 13 was obtained in the same manner as cyan toner 1 except that the above materials were used. In addition, the following polar resin 9 and polar resin 10 used what was obtained by solution-polymerizing the monomer shown in Table 4 in xylene by the composition ratio (mass part basis) shown in Table 4, respectively.
Table 1 shows the physical properties of the cyan toner 13, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 14>
Styrene 75.0 parts by mass n-butyl acrylate 25.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass Polar resin 11 10.0 parts by mass Polar resin 12 20.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 14 was obtained in the same manner as cyan toner 1 except that the above materials were used. The polar resin 11 and the polar resin 12 were obtained by subjecting the monomers shown in Table 4 to solution polymerization in xylene at the composition ratio (parts by mass) shown in Table 4, respectively.
Table 1 shows the physical properties of the cyan toner 14, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 15>
-Styrene 65.0 parts by mass-n-butyl acrylate 35.0 parts by mass-Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass-Polar resin 13 7.0 parts by mass-Polar resin 14 3.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass A cyan toner 15 was obtained in the same manner as the cyan toner 1 except that the above materials were used. The polar resin 13 and the polar resin 14 were obtained by subjecting the monomers shown in Table 4 to solution polymerization in xylene at the composition ratio (part by mass) shown in Table 4, respectively.
Table 1 shows the physical properties of the cyan toner 15, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 16>
-Styrene 70.0 parts by mass-n-butyl acrylate 30.0 parts by mass-Charge control agent FCA1001NS (manufactured by Fujikura Chemical Co., Ltd.) 2.0 parts by mass-Polar resin 6 10.0 parts by mass-Polar resin 15 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 16 was obtained in the same manner as cyan toner 1 except that the above materials were used. In addition, the said polar resin 15 used what was obtained by solution-polymerizing the monomer shown in Table 4 in xylene by the composition ratio (mass part basis) shown in Table 4.
Table 1 shows the physical properties of the cyan toner 16, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 17>
-Styrene 70.0 parts by mass-n-butyl acrylate 30.0 parts by mass-Charge control agent FCA1001NS (manufactured by Fujikura Chemical Co., Ltd.) 2.0 parts by mass-Polar resin 6 10.0 parts by mass-Polar resin 16 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 17 was obtained in the same manner as cyan toner 1 except that the above materials were used. In addition, the said polar resin 16 used what was obtained by solution-polymerizing the monomer shown in Table 4 in xylene by the composition ratio (mass part basis) shown in Table 4.
Table 1 shows the physical properties of the cyan toner 17, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 18>
(Production example of polar resin)
The polar resin 17 used for the cyan toner 18 was manufactured by the following method.
The following materials were mixed in a flask to prepare an aqueous medium.
・ Ion-exchanged water 500.0 parts by mass Nonionic surfactant Nonipol 400 (manufactured by Kao) 6.0 parts by mass Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku) 10.0 parts by mass Were mixed to obtain a mixed solution.
-74.8 parts by mass of styrene-15.0 parts by mass of α-methylstyrene-1.7 parts by mass of methacrylic acid-2.5 parts by mass of methyl methacrylate The above mixed solution is dispersed and emulsified in the aqueous medium. While slowly stirring and mixing for 10 minutes, 50 parts by mass of an ion exchange aqueous solution in which 4 parts by mass of ammonium persulfate was dissolved was added. Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the temperature in the system reached 70 ° C. to initiate polymerization. Thereafter, 6.0 parts by mass of n-butyl acrylate was added dropwise over 1 hour at a dropping rate of 0.1 parts by mass / min. Reaction was continued for 4 hours after completion | finish of dripping, and the fine particle dispersion of polar resin 17 was obtained. A polar resin 17 was obtained by centrifuging the obtained dispersion.

(Example of toner production)
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass Polar resin 17 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 18 was obtained in the same manner as cyan toner 1 except that the above materials were used.
Table 1 shows the physical properties of the cyan toner 18, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 19>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Chemical Co., Ltd.) 2.0 parts by mass Polar resin 1 7.0 parts by mass Polar resin 2 6.0 parts by mass Part / polar resin 18 7.0 parts by mass / C.I. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 19 was obtained in the same manner as cyan toner 1 except that the above materials were used. In addition, the said polar resin 18 used what was obtained by solution-polymerizing the monomer shown in Table 4 in xylene by the composition ratio (mass part basis) shown in Table 4.
Table 1 shows the physical properties of the cyan toner 19, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 20>
An emulsion aggregation method toner was produced by the following procedure.

(Preparation of resin fine particle dispersion)
The following materials were mixed in a flask to prepare an aqueous medium.
・ Ion-exchanged water 500.0 parts by mass Nonionic surfactant Nonipol 400 (manufactured by Kao) 6.0 parts by mass Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku) 10.0 parts by mass Were mixed to obtain a mixed solution.
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass The above mixed solution is dispersed and emulsified in the aqueous medium. While slowly stirring and mixing for 5 minutes, 50 parts by mass of an ion exchange aqueous solution in which 4 parts by mass of ammonium persulfate was dissolved was added. Next, after sufficiently replacing the system with nitrogen, the system was heated in an oil bath while stirring the flask until the temperature reached 70 ° C., and emulsion polymerization was continued for 5 hours. Thereby, an anionic resin fine particle dispersion was obtained.

(Preparation of colorant particle dispersion)
-Ion exchange water 100.0 parts by mass-C.I. I. Pigment Blue 15: 3 7.0 parts by mass / nonionic surfactant Nonipol 400 (manufactured by Kao) 1.0 part by mass The above components are mixed and dissolved, and dispersed for 10 minutes with a homogenizer (Ultra Turrax manufactured by IKA). An agent particle dispersion was obtained.

(Preparation of release agent particle dispersion)
・ Ion-exchanged water 100.0 parts by mass Wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cationic surfactant Sanisol B50 (made by Kao) 5.0 parts by mass The mixture was heated to 95 ° C. and sufficiently dispersed with IKA Ultra Turrax T50, and then dispersed with a pressure discharge homogenizer to obtain a release agent particle dispersion.

(Preparation of fine particle dispersion 1 for shell formation)
-Ion exchange water 100.0 mass parts-Ethyl acetate 50.0 mass parts-Polar resin 1 10.0 mass parts The said component was mixed and stirred. Solvent was removed by heating at 80 ° C. and holding for 6 hours while emulsifying the solution with IKA Ultra Turrax T50 to obtain a fine particle dispersion 1 for shell formation.

(Preparation of fine particle dispersion 2 for shell formation)
-Ion-exchange water 100.0 mass parts-Ethyl acetate 50.0 mass parts-Polar resin 2 10.0 mass parts The said component was mixed and stirred. The emulsified solution was emulsified with IKA Ultra Turrax T50, and the solvent was removed by heating at 80 ° C. and holding for 6 hours to obtain a shell-forming fine particle dispersion 2.

(Create toner particles)
The resin fine particle dispersion, the colorant particle dispersion, the release agent particle dispersion, and 1.2 parts by weight of polyaluminum chloride are mixed, and an IKA Ultra Turrax T50 is prepared in a round stainless steel flask. After mixing and dispersing sufficiently, the flask was heated to a temperature of 51 ° C. with stirring in a heating oil bath. After maintaining at a temperature of 51 ° C. for 60 minutes, the shell-forming fine particle dispersion 1 and the shell-forming fine particle dispersion 2 were added thereto. Then, after adjusting the pH in the system to 6.5 using a sodium hydroxide aqueous solution having a concentration of 0.5 mol / L, the stainless steel flask is sealed, and the stirring shaft seal is magnetically sealed and stirred. Was continued and heated to a temperature of 97 ° C. and held for 3 hours. Thereafter, the resulting slurry was transferred to an autoclave and heated and stirred at a pressure of 3.0 × 10 ⁵ Pa and a temperature of 120 ° C. for 3 hours. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then solid-liquid separation was performed by Nutsche suction filtration. This was further redispersed using 3 L of ion exchange water at a temperature of 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 5 times, and then No. 1 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain toner particles. Hydrophobic silica fine powder (primary particles) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts by mass of the toner particles. Cyan toner 20 was obtained by mixing 2.0 parts by mass (diameter: 10 nm, BET specific surface area: 170 m ² / g) with a Henschel mixer (manufactured by Mitsui Miike) at 3,000 r / min for 15 minutes.

  Table 1 shows the physical properties of the cyan toner 20, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 21>
A pulverized toner was produced according to the following procedure.
Styrene-butyl acrylate copolymer 100.0 parts by mass (styrene-butyl acrylate copolymer ratio = 70: 30, Mp = 22,000, Mw = 35,000, Mw / Mn = 2.4, TgA = 45 ° C. )
-Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass The above materials were dissolved and kneaded and pulverized. After that, classification was performed with a wind classifier. Further, 10.0 parts by mass of resin fine particles (number average particle diameter: 300 nm) having the same composition as that of the polar resin 1 are added, and the shell of the polar resin 1 is processed by the “hybridization system” (manufactured by Nara Machinery). A structure was formed. Subsequently, in the same manner, 10.0 parts by mass of resin fine particles (number average particle diameter: 300 nm) having the same composition as that of the polar resin 2 are added and treated with a “hybridization system” (manufactured by Nara Machinery). Two shell structures were formed. Thereafter, the obtained particles were dispersed in 500 parts by mass of ion-exchanged water, and heated and stirred for 3 hours at a pressure of 3.0 × 10 ⁵ Pa and a temperature of 120 ° C. in an autoclave. Subsequently, toner particles were obtained by filtration and drying. Hydrophobic silica fine powder (number average 1) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts by mass of the toner particles. Cyan toner 21 was obtained by mixing 2.0 parts by mass of secondary particle size: 10 nm, BET specific surface area: 170 m ² / g) with a Henschel mixer (manufactured by Mitsui Miike) at 3,000 r / min for 15 minutes.

  Table 1 shows the physical properties of the cyan toner 21, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 22>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (Fujikura Chemical Co., Ltd.) 2.0 parts by mass Polar resin 19 10.0 parts by mass Polar resin 20 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 22 was obtained in the same manner as cyan toner 1 except that the above materials were used. The polar resin 19 and the polar resin 20 were obtained by subjecting the monomers shown in Table 4 to solution polymerization in xylene at the composition ratio (parts by mass) shown in Table 4, respectively.
Table 1 shows the physical properties of the cyan toner 22, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 23>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Chemical Co., Ltd.) 2.0 parts by mass Polar resin 21 10.0 parts by mass Polar resin 22 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 23 was obtained in the same manner as cyan toner 1 except that the above materials were used and that 9.0 parts by mass of tricalcium phosphate was changed to 30.0 parts by mass. The polar resin 21 and the polar resin 22 were obtained by subjecting the monomers shown in Table 4 to solution polymerization in xylene at the composition ratio (part by mass) shown in Table 4, respectively.
Table 1 shows the physical properties of the cyan toner 23, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 24>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass Polar resin 23: saturated polyester resin [terephthalic acid and propylene oxide modified bisphenol A 20.0 parts by mass (Mp = 9000, Tg = 72 ° C., acid value = 12.0)
mgKOH / g)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 24 was obtained in the same manner as cyan toner 1 except that the above materials were used.
Table 1 shows the physical properties of the cyan toner 24, and Table 3 shows the evaluation results.

<Cyan toner 25>
-Styrene 78.0 parts by mass-n-butyl acrylate 22.0 parts by mass-Charge control agent FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) 2.0 parts by mass-Polar resin 1 10.0 parts by mass-Polar resin 2 10.0 parts by mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 25 was obtained in the same manner as cyan toner 1 except that the above materials were used.
Table 1 shows the physical properties of the cyan toner 25, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 26>
Styrene 62.0 parts by mass n-butyl acrylate 38.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Chemical Co., Ltd.) 2.0 parts by mass Polar resin 1 10.0 parts by mass Polar resin 2 10.0 mass Part ・ C. I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 26 was obtained in the same manner as cyan toner 1 except that the above materials were used.
Table 1 shows the physical properties of the cyan toner 26, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 27>
Styrene 78.0 parts by mass n-butyl acrylate 22.0 parts by mass Charge control agent FCA1001NS (Fujikura Kasei Co., Ltd.) 2.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 8.0 parts by mass Cyan toner 27 was obtained in the same manner as cyan toner 1 except that the above materials were used, polar resin 1 and polar resin 2 were not used, and 9.0 parts by mass of tricalcium phosphate was changed to 30.0 parts by mass. It was.
Table 1 shows the physical properties of the cyan toner 27, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 28>
Cyan toner 28 was obtained in the same manner as cyan toner 20 except that heating and stirring were not performed in the autoclave.
Table 1 shows the physical properties of the cyan toner 28, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Cyan toner 29>
Cyan toner 29 was obtained in the same manner as cyan toner 21 except that heating and stirring were not performed in the autoclave.
The physical properties of the cyan toner 29 are shown in Table 1, the evaluation results are shown in Table 3, and the physical properties of the polar resin used are shown in Table 4.

<Magenta toner 1>
C. I. Pigment Blue 15: 3 7 parts by mass, C.I. I. Pigment Red 122 Magenta Toner 1 was obtained in the same manner as Cyan Toner 1 except for changing to 10 parts by mass.
Table 1 shows the physical properties of the magenta toner 1, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Yellow Toner 1>
C. I. Pigment Blue 15: 3 7 parts by mass, C.I. I. Pigment Yellow 93 A yellow toner 1 was obtained in the same manner as cyan toner 1 except that the amount was changed to 7 parts by mass.
Table 1 shows the physical properties of Yellow Toner 1, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

<Black toner 1>
C. I. Black toner 1 was obtained in the same manner as cyan toner 1 except that 7 parts by mass of Pigment Blue 15: 3 was changed to 8 parts by mass of carbon black.
Table 1 shows the physical properties of the black toner 1, Table 3 shows the evaluation results, and Table 4 shows the physical properties of the polar resin used.

(Examples 1 to 24, Comparative Examples 1 to 8)
The toners shown in Table 1 were evaluated in combination as shown in Table 2.
The results are listed in Table 3.

The evaluation method and evaluation criteria of the present invention will be described below.
(1) Development efficiency / circumferential streak / toner scattering / toner coat uniformity In the modified image forming apparatus LBP-5400 (manufactured by Canon Inc.) of the contact one-component development system shown in FIG. 4, the development shown in FIG. The container is filled with 190 g of the toner described in the examples and comparative examples. It is left for 24 hours in a low temperature and normal humidity environment (10 ° C./50% RH) and a high temperature and high humidity environment (30 ° C./85% RH). At this time, the transfer paper is also left as it is. Thereafter, density detection correction is performed, and continuous output is performed using a chart with a printing ratio of 1%. When the total number of output sheets is 100 sheets and 5000 sheets, the development efficiency / circumferential streak / toner scattering / toner coat uniformity is confirmed.
When measuring the development efficiency, the main body power supply is forcibly turned off while outputting the entire solid image (toner loading amount 0.55 mg / cm ² ) after the continuous output of the 100 sheets and 5000 sheets. The weight per unit area of the toner before development on the toner carrier and the toner developed on the photosensitive drum is measured, and the development efficiency is measured by the following equation.
Development efficiency = toner developed on photosensitive drum / toner before development on toner carrier × 100
Evaluation conforms to the following judgments A, B, C, and D.

A: The development efficiency is 95% or more in both a low temperature and normal humidity environment and a high temperature and high humidity environment, and there is no problem in practical use.
B: The development efficiency is 88% or more and less than 95% in both a low temperature and normal humidity environment and a high temperature and high humidity environment, and there is no problem in practical use.
C: A development efficiency of 80% or more and less than 88% in a high temperature and high humidity environment, but a level that is not likely to cause a problem in actual use.
D: The development efficiency is 80% or more and less than 88% or lower than that in both a low temperature and normal humidity environment and a high temperature and high humidity environment, and it is highly likely to cause a problem in practical use.

When confirming circumferential streaks and toner scattering, after outputting 100 sheets and 5000 sheets continuously, a solid whole image (toner loading amount 0.55 mg / cm ² ) is output, and then the developing container is disassembled. The surface and edges of the toner carrier were visually observed. The criteria are shown below.

A: In the evaluation after outputting 5000 sheets, the surface and edges of the toner carrying member are circumferential streaks caused by foreign matter sandwiched between the toner regulating member and the toner carrying member due to toner destruction or fusion, and the toner carrying member and the toner. There is no scattering of toner due to foreign matter caught between the end seals, and there is no problem in actual use.
B: In the evaluation after outputting 5000 sheets, although toner scattering due to foreign matter pinching between the toner carrier and the toner end seal is slightly seen, there is no problem in practical use.
C: In the evaluation after outputting 5000 sheets, toner scattering is slightly observed, and 1 to 4 circumferential streaks are also observed at the end, but the level that is not likely to cause a problem in actual use.
D: In the evaluation after outputting 5000 sheets, toner scattering is observed, and five or more streaks in the circumferential direction are observed in the entire region, which is highly likely to cause a problem in practical use.

When confirming the toner coat uniformity, the main body power is forcibly turned off during the output of one halftone whole image (toner loading amount 0.20 mg / cm ² ) after the continuous output of 100 sheets and 5000 sheets, The dot reproducibility on the developed photosensitive drum was confirmed. Evaluation was performed while visually observing an image magnified 100 times with an optical microscope. The criteria are shown below.

A: Even in the evaluation after outputting 5000 sheets, the dot reproducibility is good and there is no problem in actual use.
B: Although the dot reproducibility is slightly disturbed in the evaluation after outputting 5000 sheets, there is no problem in practical use.
C: In the evaluation after outputting 100 sheets and 5000 sheets, the dot reproducibility is slightly disturbed, but is unlikely to cause a problem in actual use.
D: In the evaluation after outputting 100 sheets and 5000 sheets, the dot reproducibility is greatly disturbed, and there is a high possibility of causing a problem in use.

(2) Low-temperature fixability / high-temperature wrapping property In the image forming apparatus of the contact one-component development system shown in FIG. 4, the developer shown in FIG. 3 is filled with 190 g of the toner described in the examples and comparative examples. The sample is allowed to stand for 48 hours in a low temperature and normal humidity environment (10 ° C./50% RH). Thereafter, an unfixed image having an image pattern in which 9 mm × 10 mm square images are evenly arranged on the entire transfer paper is output. A monochrome toner loading amount outputs a halftone image of 0.2 mg / cm ² . The fixing start temperature was evaluated using the unfixed image. For the evaluation of the fixing area, Fox River Bond (90 / cm ² ) was used as the paper type.
The fixing machine was an external fixing machine capable of controlling the temperature of a 40 mmφ heat roller without an oil application function, and measurement was performed under a fixing condition of 150 mm / sec. As the roller material at this time, PFA was used for both the upper part and the lower part. The nip width was 6 mm.
Further, the determination of the start of fixing is performed by applying a load of 50 g / cm ² to the fixed image (including the image offset at a low temperature), and using a Sylbon paper [Lenz Cleaning Paper “dasper (R)” (Ozu Paper Co. Ltd)]. Rubbing. The temperature at which the density reduction rate before and after rubbing was less than 20% was defined as the fixing start point, and this temperature was used for the evaluation of the low temperature fixability.
Further, the winding property at high temperature was confirmed visually. The maximum temperature at which paper could be passed without winding was defined as the temperature for evaluating “high-temperature winding property”.

(3) Storage stability 5 g of toner was weighed in a 50 ml polycup and left in a thermostatic bath at a temperature of 50 ° C. for 72 hours. Thereafter, the state of the toner was visually evaluated. The criteria are shown below.
A: A level at which no aggregation occurs and there is no problem in actual use.
B: Slight agglomeration is observed, but it collapses with a slight external force, and there is no problem in practical use.
C: A level that is slightly agglomerated but is broken by loosening with hands and is unlikely to cause a problem in actual use.
D: A level that is highly agglomerated and does not collapse even if it is loosened by hand, and is likely to cause a problem in actual use.

It is a figure which shows L, Va, and Vb in the penetration time-penetration film thickness curve at the time of UV photocurable composition penetration of a toner, and this invention. It is a load-displacement curve in the micro compression test of toner. FIG. 4 is a cross-sectional explanatory view of a process cartridge according to the present invention. It is a schematic block diagram of an example of the apparatus which implements the image forming method of this invention. It is a schematic block diagram of the other fixing apparatus which concerns on this invention. It is a schematic block diagram of the other fixing apparatus which concerns on this invention.

Explanation of symbols

Pa, Pb, Pc, Pd Image forming station 1 (1a to 1d) Photosensitive drum (image carrier)
2 (2a to 2d) Charging means 3 (3a to 3d) Scanner unit 4 (4a to 4d) Developing means 4A Developing unit 5 Electrostatic transfer device 6 (6a to 6d) Cleaning means 7 (7a to 7d) Process cartridge 11 Static Electrotransfer belt 12 (12a to 12d) Transfer roller 13 Belt drive rollers 14a and 14b Driven roller 15 Tension roller 16 Feeding unit 17 Cassette 18 Feeding roller 19 Registration roller 20 Fixing unit 21a Heating roller 21b Pressure roller 22 Adsorption roller 23 Paper discharge roller 24 Paper discharge unit 31 Cleaning frame (cartridge frame)
35 Removal toner storage chamber 40 Developing roller (toner carrier)
41 Toner container (developer storage part)
42 Toner transport mechanism 43 Toner supply roller 44 Toner regulating member (blade)
45 (45a, 45b, 45e) Development frame (cartridge frame)
47, 48 Coupling hole 50 Cleaner unit 51, 64 Heating body 52, 64a Heater substrate 53, 64b Energizing heating resistor (heating element)
54, 64d Temperature detecting element 55, 65 Heat resistant film 56, 57 Belt support roller 58 Support roller 60 Cleaning blade 62 Support roller (rotating body)
63 Belt support 64c Surface protective layer 100 Image forming apparatus main body S Recording medium (recording material sheet)

Claims (10)

A toner having toner particles containing at least a binder resin, a polar resin, a colorant, and a wax, and the penetration film thickness at a penetration time of 5 seconds when the UV photocurable composition is penetrated into the toner is expressed as L (Μm) When Va (μm / s) is the average penetration rate at 5 seconds to 10 seconds, and Vb (μm / s) is the average penetration rate at 10 seconds to 15 seconds, L, Va and Vb are as follows: conditions:
0.30 ≦ L ≦ 0.60 Formula (1)
0.040 ≦ Va ≦ 0.070 Formula (2)
Va <Vb Formula (3)
And the toner has a viscosity at 100 ° C. of 3.0 × 10 ^{3 to} 4.5 × 10 ⁴ Pa · s. Said Va and Vb are the following conditions:
1.2 ≦ Vb / Va ≦ 2.0
The toner according to claim 1, wherein: In the micro-compression test, a load curve of 2.94 × 10 ⁻⁴ N at a load speed of 9.8 × 10 ⁻⁵ N / sec at 25 ° C. was applied to the unloading curve until the load was started. When the slope of the displacement curve until the end is R (25), R (25) is the following condition:
4.90 × 10 ⁻⁴ ≦ R (25) ≦ 1.27 × 10 ⁻³
The toner according to claim 1, wherein the toner satisfies the following condition.   4. The toner according to claim 1, wherein the toner has a weight average particle diameter (D4) of 4.0 to 9.0 μm.   The toner according to claim 1, wherein the polar resin is contained in a total amount of 10 to 50 parts by mass with respect to 100 parts by mass of the binder resin.   6. The toner according to claim 1, wherein the acid value of the polar resin contained in the toner is 3.0 to 30.0 mg KOH / g.   The toner according to any one of claims 1 to 6, wherein the polar resin contained in the toner has a glass transition point (Tg) of 70 to 120 ° C.   The toner according to claim 1, wherein the toner particles are obtained by manufacturing in an aqueous medium.   The toner particles are obtained by dispersing and granulating a polymerizable monomer composition containing at least a polymerizable monomer, a polar resin, a colorant, and a wax in an aqueous medium to polymerize the polymerizable monomer. The toner according to claim 1, wherein the toner is obtained by:   The toner according to claim 1, wherein the polar resin is a vinyl polymer.

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