JP5448406B2 - toner - Google Patents

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, and a toner jet method.

Conventionally, in electrophotography, a photoconductive material is generally used, and an electrostatic charge image is formed on a photoreceptor by various means. Then, the electrostatic charge image is developed with toner, and if necessary. After the toner image is transferred to a transfer material such as paper, it is fixed by heating, pressing, heating and pressing, or solvent vapor to obtain a toner image.
In recent years, as a response to the global warming problem, there is an increasing demand for energy-saving fixing technology, and toners that exhibit high gloss and rich color reproducibility that satisfy high-quality image quality even at low set temperatures are desired. Yes.

  In order to achieve this, it is necessary to lower the glass transition point (Tg) of the toner binder resin or to lower the average molecular weight of the toner binder resin. However, if the Tg or average molecular weight of the toner binder resin is simply lowered, the storage stability of the toner is impaired, or the toner is offset to the fixing device and the image is easily contaminated. Further, when the image output is advanced, the developability deteriorates due to the external additive being embedded in the toner particle surface due to repeated stress in the developing device, and crushing and rolling due to the decrease in the toner particle strength itself increase. Usually, contamination is likely to be promoted.

Various proposals have been made to achieve both seemingly contradictory performances such as the low-temperature fixability of the toner as described above and the image stability when outputting a large number of sheets. For example, a toner technology having a so-called core-shell structure in which the average molecular weight and glass transition point of the binder resin of the toner are controlled to be low, and protected with a resin component having a higher average molecular weight and glass transition point than the binder resin in the vicinity of the toner particle surface. Is disclosed (for example, see Patent Documents 1, 2 and 3).
However, according to the study by the present inventors, although these toners certainly have the effect of low-temperature fixability, particularly when the development output operation was repeated using a one-component contact development system, embedded external additives, etc. It has been found that there is room for improvement in image quality deterioration due to toner deterioration.

  In the toner having a core-shell structure, a toner having a higher storage stability by further increasing the glass transition point of the shell layer has been proposed (for example, see Patent Document 4). However, although the storage stability of these toners and images increases, external components such as inorganic fine particles coated on the toner particles tend to be detached with development output. The current situation is that deterioration of quality is inevitable.

On the other hand, with the widespread use of electrophotographic technology, there is an increasing demand for technology that maintains image quality even in harsher usage environments. For the purpose of improving environmental stability, techniques for controlling the acid value and hydroxyl value of a binder resin have been disclosed (see, for example, Patent Documents 5 and 6).
However, as a result of studying the influence of the acid value and hydroxyl value of the binder resin on the environment dependency, the present inventors have found that the acid value and hydroxyl value of the polyester resin and the acid of the vinyl polymerization resin have. The effect differs depending on the valence and hydroxyl value, and the effect of the effect is recognized by the interaction with the main binder composition and other additives, leaving room for further improvement in environmental stability. I understood.
JP 2006-053353 A JP-A-8-314186 JP 2006-276307 A JP 2007-93637 A JP 2005-91813 A JP 2006-91318 A

  The problems to be solved by the present invention are to achieve long-term development quality maintenance by improving toner fixing characteristics, improving charging stability that is not easily affected by environmental differences, and improving resistance to member contamination. It is in.

The present invention is a toner having toner particles containing a binder resin, a colorant, a wax component, and a vinyl copolymer having a hydroxyl group , and an inorganic fine powder, wherein the toner particles are contained in the toner particles. The vinyl copolymer having a hydroxyl group has a hydroxyl value of 3 to 70 mgKOH / g, the glass transition temperature (TgA) measured by a differential scanning calorimeter of the toner is 40 to 60 ° C., and the tetrahydrofuran of the toner The glass transition temperature (TgB) of cyclohexane (CHX) insoluble matter in (THF) soluble matter is 80 to 120 ° C., and the relationship between TgA and TgB is 25 ° C. ≦ (TgB−TgA) ≦ 70 ° C. The present invention relates to a toner characterized in that the inorganic fine powder is an inorganic fine powder whose surface is treated with a surface treatment agent.

  According to the present invention, by effectively exhibiting the function of the resin component constituting the toner particles, low temperature fixing characteristics corresponding to an energy saving fixing device, charging stability in a high temperature and high humidity environment and a low temperature and low humidity environment, and toner The durability is improved by suppressing deterioration, and high-quality image quality can be stably provided over a long period of time.

The toner of the present invention includes an inorganic toner whose surface is treated with a binder resin, a colorant, a wax component, and toner particles containing at least a vinyl copolymer having a hydroxyl value of 3 to 70 mgKOH / g, and at least a surface treatment agent. A toner containing fine powder. Further, the toner of the present invention has a glass transition temperature (Tg) measured by a differential scanning calorimeter of the toner of at least 40 ° C. to 60 ° C., and cyclohexane (CHX) in the tetrahydrofuran (THF) soluble content of the toner. The toner has a glass transition temperature (TgB) in an insoluble content of at least 80 to 120 ° C., and the TgA and TgB satisfy a relationship of 25 ° C. ≦ TgB−TgA ≦ 70 ° C.
By adopting the above configuration, even in toner particles having a relatively low strength aiming at low-temperature fixing characteristics, the release of a large number of inorganic fine powders covering the toner particles during the development output operation is suppressed, and the toner particle protecting function The development characteristic maintaining function works to stabilize the image quality.

The reason why the toner of the present invention exhibits the above-mentioned effect is not necessarily clear, but the present inventors consider that the reason is as follows.
That is, the inorganic fine powder added externally for the purpose of imparting the function of toner to the fluidity and the uniformity of the charge originally has a polar group such as a hydroxyl group present on the surface of the inorganic fine powder by a coupling agent or silicone oil. Surface treatment is applied to protect the adsorption sites of water molecules. In reality, however, the hydrophobization degree is enhanced by the effect of such a treatment agent, but it is difficult to completely protect polar groups on the surface of inorganic fine particles having a large specific surface area in the order of nanometers. It is inevitable that the group is exposed on the surface.
According to the study by the present inventors, when a resin having a specific hydroxyl group is added to the toner particles, the hydroxyl groups present on the surface of the toner particles interact with the hydroxyl groups exposed on the surface of the added inorganic fine powder. It was found that the coating of the inorganic fine particles can be maintained over a long period of time because the affinity is superior to the desorption resistance against the stirring stress received in the developing unit.
In addition, it has been found that the toner having the above constitution can block the adsorption of water molecules because the hydroxyl groups on the surface of the toner particles and the hydroxyl groups on the surface of the inorganic fine powder are compatible with each other, and can exhibit excellent environmental stability. .

  Conventionally, when a resin having a hydroxyl value, such as polyester, is used as the binder resin for the toner, the polar hydroxyl group tends to adsorb water molecules in the air. There was a problem that the charge amount could not be reduced. However, when a vinyl copolymer having a hydroxyl value, which is an essential component of the present invention, is used as a component of the toner, the vinyl copolymer has pendant functional sites having a hydroxyl group from the main chain. Because of the structure, the hydroxyl group and the inorganic fine powder have a functional interaction on the surface of the toner particles, thereby increasing the contact point density. As a result, the anchor effect between the toner particles and the inorganic fine powder is enhanced, and the coating of the inorganic fine particles can be maintained for a long period of time, and the decrease in the charge amount due to the adsorption of water molecules can be overcome.

The desorption of inorganic fine powder causes a significant problem especially in a low humidity environment. The reason is considered to be that when the toner is stirred in a low humidity environment, the triboelectric charge amount tends to be excessive, and the charged toner particles and the inorganic fine particles repel each other. Against this problem, since the hydroxyl groups present on the surface of the toner particles have a good affinity with the inorganic fine powder, the toner particle surface is uniformly protected by the inorganic fine powder and becomes integral with the toner. The problem of charging up can be prevented.
As described above, the resin having a specific hydroxyl value contained in the toner of the present invention is a vinyl copolymer. The reason for this is not clear, but the present inventors consider as follows. (1) Since a polyester-based resin having a hydroxyl value has a polar group at the end of the main chain, it is not in a distribution state in which the hydroxyl group functions effectively on the toner particle surface. (2) The polyester resin has a carboxylic acid group, which contains many elements that are unstable in controlling charging, and the use of the polyester resin reduces the effect of the present invention.

As described above, the toner particles used in the toner of the present invention contain a vinyl copolymer having a hydroxyl value of 3 to 70 mgKOH / g.
When the hydroxyl value is less than 3 mgKOH / g, the external additive tends to detach at the time of development output of a large number of sheets under low temperature and low humidity. Therefore, the contamination of the member and the developability are liable to occur before the toner consumption life is reached.
On the other hand, when the hydroxyl value exceeds 70 mgKOH / g, the charging performance in a high-temperature and high-humidity environment is inferior, so that the development characteristics such as fog are deteriorated when a large number of sheets are developed.
The hydroxyl value of the vinyl copolymer is preferably 5 to 34 mgKOH / g, more preferably 10 to 25 mgKOH / g.

The content of the vinyl copolymer having a hydroxyl value of 3 to 70 mgKOH / g contained in the toner particles is preferably 3 to 30% by mass with respect to the total binder resin constituting the toner. It is more preferable that it is 27 mass%.
When the content of the vinyl copolymer having the specific hydroxyl value is less than 3% by mass, the detachment of the external additive is promoted as the developing operation is repeated, which may cause member contamination.
On the other hand, when the content exceeds 30% by mass, the vinyl-based copolymer having the specific hydroxyl value also serves to strengthen the toner structure by setting the glass transition temperature high, so that the low-temperature fixing characteristics are low. It tends to decrease.

The vinyl copolymer having a specific hydroxyl value is a toner tetrahydrofuran (TH).
F) A part thereof is extracted as the insoluble matter in cyclohexane (CHX) in the soluble matter. The hydroxyl value of the extract is preferably 1 to 70 mgKOH / g.
When the hydroxyl value of the resin extracted as the insoluble component of cyclohexane (CHX) in the tetrahydrofuran (THF) soluble component of the toner is less than 1 mgKOH / g, the polarity of the vinyl copolymer having a specific hydroxyl value is low. The amount of hydroxyl groups that function on the surface of the toner particles is insufficient and the development durability tends to decrease.
On the other hand, when the hydroxyl value of the extracted resin exceeds 70 mgKOH / g, it means that the vinyl copolymer having a specific hydroxyl value has a strong polarity, and has a slight compatibility with the main component of the binder resin. There is a tendency to be inferior, and the development performance may become unstable.

The inorganic fine powder used in the present invention is essential to be an inorganic fine powder having a surface treated with at least a surface treatment agent. Originally, the purpose of coating the surface of the inorganic fine powder with the treatment agent is to improve the hydrophobicity and improve the environmental characteristics. In the present invention, in addition to the above purpose, the removal of inorganic fine particles is prevented by utilizing the affinity between the slightly exposed surface polar groups of the surface-treated inorganic fine particles and the hydroxyl groups present on the toner particle surface. The main purpose is to do.
The surface treatment agent for inorganic fine powders in the present invention includes coupling agents such as silane coupling agents, titanium coupling agents, and aluminum coupling agents, silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, and silanes. Compounds and the like. Therefore, the inorganic fine powder is an inorganic fine powder whose surface is treated with at least one kind of surface treatment agent selected from these surface treatment agents.

  Among these, in particular, a treatment agent selected from silane coupling agents, silicone oils, and silane compounds (hexamethyldisilazane, etc.) can treat inorganic fine powder uniformly and has excellent affinity with hydroxyl groups on the surface of toner particles. This is preferable because a rough surface state can be created.

  Examples of the silane coupling agent and silane compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, and benzyl. Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyl Examples include tetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having 2 to 12 siloxane units per molecule, and having one hydroxyl group in Si at the terminal unit. . These are used alone or in a mixture of two or more.

  In addition, the processing method of the inorganic fine powder using the said silane coupling agent and a silane compound (surface treatment agent) can be a dry processing method or a wet processing method. As an example of the dry treatment method, there is used a method of uniformly dispersing the surface treatment agent diluted with water or an organic solvent in a well-stirred inorganic fine powder base. As the stirrer, a Henschel mixer, a super mixer, a V-type blender, a spartan luzer, or the like is used. As an example of the wet processing method, impregnating the raw material of the inorganic fine powder into a dilute solution of the above surface treatment agent, and separating the slurry from the solution by a method such as filtration, centrifugation, decantation, etc., and heat drying Process.

Preferred examples of the silicone oil include dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil represented by the following general formula. it can. Moreover, you may use these silicone oils in mixture of 2 or more types.

Ｒ：炭素数１〜炭素数３のアルキル基
Ｒ’：アルキル、ハロゲン変性アルキル、フェニル、変性フェニル、水素等のシリコーンオイル変性基
Ｒ”：炭素数１〜炭素数３のアルキル基又はアルコキシ基

R: alkyl group having 1 to 3 carbon atoms R ′: silicone oil-modified group such as alkyl, halogen-modified alkyl, phenyl, modified phenyl, hydrogen R ″: alkyl group or alkoxy group having 1 to 3 carbon atoms

  As a method for treating the inorganic fine powder using the silicone oil, for example, the inorganic fine powder and the silicone oil may be directly mixed using a mixer such as a Henschel mixer, or the base inorganic fine powder may be mixed with the silicone oil. It is good also by the method of stirring while spraying. Alternatively, it may be prepared by dissolving or dispersing silicone oil in an appropriate solvent (preferably adjusted to pH 4 with an organic acid or the like), mixing the base inorganic fine powder, and then removing the solvent. In addition, the inorganic fine powder is put in a reaction vessel, alcohol water is added with stirring in a nitrogen atmosphere, surface treatment is performed by introducing silicone oil into the reaction vessel, and the solvent is removed by heating and stirring. Good.

As a processing method of the inorganic fine powder using the silicone oil, a straight silicone having a viscosity of 10 to 300 cSt (mm ² / s) at 25 ° C. is added in an amount of 5 to 40% by mass based on the inorganic fine powder base. What surface-treated can be illustrated suitably.
When the viscosity of the silicone oil is less than 10 cSt (mm ² / s), the adhesive force of the oil to the surface of the inorganic fine powder is not sufficient, and a reliable effect is not recognized. On the other hand, when the viscosity of the silicone oil exceeds 300 cSt (mm ² / s), unevenness occurs in the adhesion state of the silicone oil on the surface of the inorganic fine powder, and fogging in a high humidity environment or inorganic fine powder in a low humidity environment Is easily induced to cause a decrease in developability.

  When the amount of silicone oil added is less than 5% by mass, the amount of silicone oil is small, so that the exposed surface area of the inorganic fine powder becomes large, the degree of hydrophobicity becomes insufficient, and the environmental chargeability deteriorates. On the other hand, when the amount of the silicone oil exceeds 40% by mass, there is a possibility that agglomeration due to excessive silicone oil or fogging due to non-uniform charging performance may occur.

  As the inorganic fine powder used in the toner of the present invention, one that has been treated with at least a coupling agent and then hydrophobized with silicone oil can be preferably used. By performing the coupling treatment, the surface of the inorganic fine powder raw material can be reliably increased in hydrophobicity, and further, by treating the silicone oil, an effect of suppressing excessive charging can be imparted. As a result, a toner having more excellent environmental characteristics can be obtained.

In the toner of the present invention, the content of the inorganic fine powder is preferably 0.05 to 6.0% by mass, more preferably 0.1 to 3.0% by mass, and still more preferably 0.00%, based on the toner. 2-1.
5% by mass. If the content of the inorganic fine powder is too small than the above range, it is difficult to obtain the effect of adding the inorganic fine powder. Since the fine powder shows a tendency to detach, there is a tendency that the risk of these detachment inorganic fine powders causing member contamination increases by repeating the developing operation.

Further, the inorganic fine powder preferably contains an inorganic fine powder having a number average primary particle size of 5 to 80 nm. When the number average primary particle size of the inorganic fine powder is within the above range, the interaction with the toner particles of the present invention works particularly well and the development durability stability is high.
If the number average primary particle size of the inorganic fine powder is less than 5 nm, the development tendency tends to cause the inorganic fine powder to be physically embedded on the surface of the toner particles as the developing operation proceeds, which may lead to a decrease in developability. . On the other hand, when the number average primary particle size of the inorganic fine powder exceeds 80 nm, depending on the interaction with the inorganic fine powder externally added in a low temperature and low humidity environment due to repeated stirring in the developing device, the inorganic fine powder There is a concern about the development stability because the cohesive force between the bodies works and tends to be detached from the toner particles.

  The number average primary particle size of the inorganic fine powder was obtained by taking a photograph of the toner particle surface magnified 100,000 times with FE-SEM S-4800 (manufactured by Hitachi, Ltd.) and using the enlarged photograph, 100 or more inorganic particles The particle size of the fine powder was measured and obtained from the arithmetic average. The particle diameter of the inorganic fine powder is counted as the particle diameter when the shape is spherical, and the longest diameter when the shape has a major axis and a minor axis.

The inorganic fine powder having a number average primary particle size of 5 to 80 nm preferably has a specific surface area of 40 to 300 m ² / g by nitrogen adsorption measured by the BET method, preferably 60 to 250 m ² / g. Is more preferable. The specific surface area can be calculated using the BET multipoint method by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics Co., Ltd.) according to the BET method.

Examples of the inorganic fine powder used in the present invention include inorganic fine powders such as double oxides such as silica, titanium oxide, alumina, and hydrotalcite. Silica has a particularly good balance between fluidity and charging characteristics. The effect of the above is most easily expressed and preferable.
Examples of the silica include both dry silica produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside of the silica fine powder and few production residues of Na ₂ O and SO ₃ ²⁻ is preferable. In addition, dry silica can also be used to produce composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. Silica also includes them.

The glass transition temperature (TgA) measured by the differential scanning calorimeter of the toner of the present invention is at least in the range of 40 to 60 ° C. TgA is preferably present at least at 45 to 55 ° C.
If the TgA is less than 40 ° C., it is not suitable because the risk of blocking increases depending on the storage environment and use conditions of the toner. On the other hand, when TgA exceeds 60 ° C., the energy-saving fixing device cannot exhibit satisfactory fixing characteristics.
The TgA can be adjusted to the above range by setting the glass transition temperature of the main component of the binder resin contained in the toner to 40 to 60 ° C. In the present invention, the main component of the binder resin contained in the toner means a binder resin component that is contained in an amount of 50% by mass or more in all resin components constituting the toner.

The glass transition temperature (TgB) of the cyclohexane (CHX) insoluble component in the tetrahydrofuran (THF) soluble component of the toner of the present invention is at least from 80 to 120 ° C. Further, TgB is preferably present at least at 86 to 110 ° C.
When the TgB is less than 80 ° C., the toner cannot withstand the stress that the toner receives in the developing device with the repeated developing operation when outputting a large number of sheets, and the deterioration is accelerated and the image quality is lowered. On the other hand, when TgB exceeds 120 ° C., the removal of the external additive easily proceeds as the number of development outputs increases, so that the external additive contamination on the toner layer thickness regulating member or the latent image carrier or the toner development It causes image quality deterioration due to performance degradation.
In the present invention, the resin corresponding to the cyclohexane (CHX) insoluble component in the tetrahydrofuran (THF) soluble component of the toner has a small amount of the resin added to the toner, or is compatible with the main component of the binder resin. In the case of a resin that easily dissolves, the glass transition point is often not observed even when the toner is measured with a differential scanning calorimeter (DSC). Therefore, the tetrahydrofuran (THF) soluble matter of the toner is extracted, and the resin recovered from the extract as the cyclohexane (CHX) insoluble matter is subjected to DSC measurement. The characteristics of the resin corresponding to the (CHX) insoluble matter can be clarified.

In the present invention, the above TgA and TgB satisfy the relationship of 25 ° C. ≦ TgB−TgA ≦ 70 ° C. The TgA and TgB preferably satisfy the relationship of 30 ° C. ≦ TgB−TgA ≦ 65 ° C.
In the toner of the present invention, when [TgB-TgA] is less than 25 ° C., the two-component resin functions having different glass transition temperatures are not effectively exhibited, and the offset performance in the fixing process is inferior. On the other hand, when [TgB−TgA] exceeds 70 ° C., the fixed image may cause uneven glossiness depending on the use environment, which is not preferable.

The toner particles used in the toner of the present invention are preferably toner particles produced by a technique such as suspension polymerization, that is, in an aqueous medium. When toner particles are produced in an aqueous medium, the polar hydroxyl group tends to segregate uniformly on the surface of the toner particle, that is, on the toner particle surface. Is considered to be more effective.
Further, by conducting polymerization in an aqueous medium, such as suspension polymerization, a nonpolar resin, for example, a binder resin having a low glass transition temperature is mainly contained in the core part of the toner particles. For example, a resin having a hydroxyl value and a high glass transition temperature can be present in the shell layer. As a result, the structure of the toner can be controlled, and the fastness and the effect of the hydroxyl group can be enhanced at the same time. The toner of the present invention can exhibit a superior hydroxyl value effect by controlling the polarity of the resin constituting the toner particles.

  In the present invention, when the compatibility of both components such that the main component of the binder resin is a styrene-acrylic copolymer and the resin having a hydroxyl value is also a styrene-acrylic copolymer, The interaction between the two resins is high, and the low-temperature fixing characteristics and the structural strength of the toner particles are preferably increased.

In the toner of the present invention, the cyclohexane (CHX) insoluble component in the soluble component in tetrahydrofuran (THF) preferably contains a vinyl copolymer having a hydroxyl group.
The property of the resin component that is soluble in THF and insoluble in CHX is generally that the solubility of the resin increases when the polarity of the solvent is close to the polarity of the resin, so that it is soluble in THF but insoluble in CHX. It shows that it is a resin component having a relatively small polarity. When the resin component that is soluble in THF and insoluble in CHX is a vinyl polymer having a hydroxyl group, the polarities of the binder resin component soluble in THF and the vinyl copolymer having a hydroxyl value are relatively This means that the toner particles having good compatibility and uniform toner particles are easily formed, and the low-temperature fixability and the effect of suppressing the detachment of the external additive can be exhibited without variation.

In the toner of the present invention, the cyclohexane (CHX) insoluble component in the soluble component in tetrahydrofuran (THF) is preferably a vinyl copolymer having a primary or secondary hydroxyl group. More preferred is a vinyl copolymer having a primary hydroxyl group.
A vinyl copolymer having a primary or secondary hydroxyl group has a large polarity, and the effects of the hydroxyl group of the present invention are more easily exhibited.
Although it does not specifically limit as a vinyl-type copolymer which has a hydroxyl group in this invention, For example, it is preferable that it is a vinyl-type copolymer which has at least repeating unit (I) shown by the following structural formula.

［式（Ｉ）中、Ｒ_１ は（ＣＨ_２）ｎ（但し、ｎ＝１〜４）、或いは炭素数が１〜６のアルキル基であり、繰り返し単位（Ｉ）は複数種類であっても良い。］

[In the formula (I), R ₁ is (CH ₂ ) n (where n = 1 to 4) or an alkyl group having 1 to 6 carbon atoms, and the repeating unit (I) may be of multiple types. good. ]

Examples of the repeating unit (I) include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, and hydroxyisobutyl methacrylate.
Examples of the polymer composition having the repeating unit (I) include styrene-hydroxymethyl methacrylate copolymer, α-methylstyrene-2-hydroxyethyl methacrylate copolymer, and styrene-α-methylstyrene-2- Hydroxyethyl methacrylate copolymer, styrene-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer, styrene-n-butyl acrylate-2-hydroxyethyl methacrylate-methyl methacrylate copolymer, styrene-α-methyl Examples thereof include a styrene-2-hydroxyethyl methacrylate-methyl methacrylate copolymer and a styrene-α-methylstyrene-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer.

  The binder resin constituting the toner of the present invention preferably contains a vinyl polymer as a main component. The toner of the present invention is for exhibiting a low-temperature fixing property and durable development stability in a well-balanced manner. The main component of the binder resin is a vinyl polymer having excellent charging stability. The effect which is required can be exhibited more stably. In the present invention, the main component of the binder resin means a resin component occupying 50% by mass or more of the binder resin. Furthermore, the content of the vinyl polymer in the binder resin is preferably 70% by mass or more, more preferably 90% by mass or more.

The toner of the present invention is subjected to a maximum load of 2.94 × 10 ⁻⁴ N at a load speed of 9.8 × 10 ⁻⁵ N / sec at a measurement temperature of 25 ° C. in a minute compression test for the toner. The amount of displacement (μm) obtained when finished is the amount of displacement X ₂ , and after the maximum load is applied, the amount of displacement (μm) obtained by leaving for 0.1 second at the maximum load is the amount of maximum displacement X ₃ after standing the 0.1 seconds, unloading rate of 9.8 × ¹⁰ -5 N / unloaded at an sec, displacement amount obtained when the load becomes 0 N a ([mu] m) and displacement _{X 4 when, (X 3 -X 4) /} X 3 recovery ratio Z represented by × 100 (25) is satisfied 40 ≦ Z (25) ≦ 80 , the relationship,
In the load-displacement curve in which the load and the amount of displacement in the micro-compression test for the toner are plotted, the slope of the load- displacement curve from the origin to the end of applying the maximum load is R (25) [ R (25) = 2. 94 × 10 ⁻⁴ (N) / displacement amount X ₂ (μm )], R (25) is 0.49 × 10 ⁻³ ≦ R (25) ≦ 1.70 × 10 ⁻³ , It is preferable to satisfy this relationship.
In the measurement of the micro-compression test for the toner, the anti-stress received in the developing device is evaluated by applying a small load of 2.94 × 10 ⁻⁴ N to the toner as compared with the conventional measurement method. It is possible to obtain a restoration rate that correlates with the characteristics and the physical characteristics of the toner obtained with the light load fixing device.

The value of Z (25) in the micro-compression test for the toner is an index representing how much the surface layer of the toner returns to its original state after unloading at a temperature of 25 ° C.
If Z (25) is less than 40, the toner particles themselves are likely to be plastically deformed due to repeated stress in the developing device, and as the number of development outputs increases, the toner is fused to the member or developable. Degradation tends to occur and it tends to be difficult to maintain image quality.
On the other hand, if the value of Z (25) exceeds 80, the vicinity of the toner surface layer becomes difficult to deform, so that low-temperature fixability tends to be inferior in light load fixing devices and energy saving fixing devices, or the fixing surface is smooth. It tends to be inferior.

The value of R (25) in the micro-compression test for the toner is an index that represents the amount of displacement when a small load of 2.94 × 10 ⁻⁴ N is applied at a temperature of 25 ° C. This is the monitored value.
When R (25) is less than 0.49 × 10 ⁻³ , the surface layer of the toner particles exhibits a relatively soft property. The fine powder is easily embedded in the toner surface, which may lead to a decrease in developability.
On the other hand, when the value of R (25) exceeds 1.70 × 10 ⁻³ , the toner particles exhibit a relatively hard property, and thus the inorganic fine powder tends to be detached with respect to the stress applied during the developing operation. The tendency which leads to the member contamination of inorganic fine powder and the fall of development performance is shown.
In order for the values of R (25) and Z (25) to satisfy the above range, a method of controlling the toner particles to a core-shell structure using a suspension polymerization method is preferably exemplified. When the values of R (25) and Z (25) satisfy the above relationship, the toner particles have a structure having a shell layer with an optimum hardness, so that the development durability is improved and the core layer is sufficiently formed. It can be designed softly, and improvement in low-temperature fixability, image glossiness, etc. can also be realized.

The toner of the present invention has a maximum endothermic peak temperature (P1) measured by a differential scanning calorimeter of 70 to 120 ° C., and the maximum endothermic peak temperature (P1) and the differential scanning calorimeter of the toner of the present invention. It is preferable that the glass transition temperature (TgA) measured by the above satisfies the relationship of 15 ° C. ≦ P1-TgA ≦ 80 ° C.
The maximum endothermic peak temperature (P1) in the toner of the present invention is an endothermic peak corresponding to a fixing aid typified by wax, and the maximum endothermic peak temperature (P1) is more preferably 70 ° C. or higher and 120 ° C. or lower. When present at 70 ° C. or higher and 110 ° C. or lower, better low-temperature fixing properties are exhibited in combination with the properties of the binder resin of the present invention.
When the P1 is less than 70 ° C., the low molecular weight contained in the wax component corresponding to the maximum endothermic peak when left in a high temperature and high humidity environment for a long time in the configuration of the binder resin aimed at the low temperature fixing characteristics of the present invention. Such impurities and the like tend to bleed on the toner particle surface, which may adversely affect development durability. On the other hand, when P1 exceeds 120 ° C., gloss control of the fixed image may be difficult.

In the present invention, when the above P1 and Tg satisfy the relationship of 15 ° C. ≦ P1-TgA ≦ 80 ° C., more preferably 15 ° C. ≦ P1-TgA ≦ 70 ° C., the wax bleeding property at the time of fixing is optimized. Therefore, the low-temperature fixing performance is improved.
When the value of [P1-TgA] is less than 15 ° C., in a resin showing a low glass transition temperature, plasticization of the resin is promoted, so that winding tends to occur at low temperature fixing. On the other hand, when the value of [P1-TgA] exceeds 80 ° C., the release effect during low-temperature fixing tends to be difficult to work.

The toner of the present invention preferably has a viscosity at 100 ° C. measured by a flow tester temperature rising method of 5,000 to 32,000 Pa · s, more preferably 5,000 to 22,000 Pa · s. . When the viscosity at 100 ° C. is in this range, particularly excellent fixing characteristics are exhibited.
When the viscosity at 100 ° C. is less than 5,000 Pa · s, the winding property in low-temperature fixing tends to be lowered. On the other hand, when the viscosity at 100 ° C. exceeds 32,000 Pa · s, the fixability during low-temperature fixing tends to decrease.
The viscosity at 100 ° C. is controlled by controlling the addition amount, molecular weight, and glass transition point of the binder resin of the toner and a specific hydroxyl value vinyl copolymer that is an essential component of the toner of the present invention. It is possible to adjust to the above range.

The toner of the present invention preferably has an average circularity measured by a flow type particle image analyzer of 0.960 to 1.000.
When the average circularity is less than 0.960, the inorganic fine powder tends to be detached with respect to the agitation stress that the toner receives in the developing device, so that the development durability tends to be lowered.
A more preferable range of the average circularity is 0.970 to 1.000, and a more preferable range is 0.975 to 1.000.

In the toner of the present invention, the number of particles having a particle diameter of 1/3 or less of the average equivalent circle diameter based on the number-based equivalent circle diameter distribution measured by a flow type particle image analyzer is the total number of particles to be measured. On the other hand (hereinafter sometimes referred to as a small particle ratio), it is preferably 20% by number or less.
It is difficult to control the developability of particles having a particle diameter equal to or less than 1/3 of the average equivalent circle diameter than particles having an average equivalent circle diameter.
When these small-diameter particles having poor developability accumulate in the developing device by repeated development operations, there is an increased risk of causing significant image damage due to member contamination or the like when the remaining amount of toner is reduced. Therefore, in order to exhibit development durability stability, the number of particles having a particle diameter of 1/3 or less of the average equivalent-circle diameter is 20% or less, more preferably 15 % Or less, more preferably 12% by number or less.

The toner particles used in the toner of the present invention preferably have a core-shell structure in which a binder resin containing a wax component is coated with a resin containing a vinyl copolymer having a hydroxyl value of 3 to 70 mgKOH / g. . By adopting this structure, particularly excellent development durability characteristics are exhibited.
In the toner of the present invention, the glass transition temperature of the main component of the binder resin is controlled to be low in order to achieve low temperature fixing characteristics. The resin having a low glass transition temperature tends to ooze out a low molecular weight component derived from the wax component added therein, particularly in a high temperature and high humidity environment, and there is a high risk of deteriorating development characteristics. Therefore, the wax component contained in the toner of the present invention is preferable because the structure present in the core layer inside the toner particles has the highest environmental stability.

  As a method for adjusting the average circularity and the small particle ratio to the above range and a method for achieving the core-shell structure, a method for producing toner particles in an aqueous medium can be suitably exemplified. When toner particles are produced in an aqueous medium, core-shell structure control using the difference in SP (solubility parameter) value of each constituent material of the toner particles and high circularity toner particles can be easily obtained. The particle size distribution is sharp and the small particle ratio can be controlled. Also, Z (25) and R (25) in the micro compression test described above can be adjusted to a desired range by forming the core-shell structure.

The toner particles used in the present invention may contain a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group (hereinafter also referred to as a polymer having a sulfonic acid group or the like). Furthermore, it is mentioned as a preferable form.
A polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group has a high ability to maintain the charge amount. Accordingly, although it is effective in suppressing fogging in a high temperature and high humidity environment, it tends to cause charge-up of toner particles in a low temperature and low humidity environment. However, in the toner of the present invention, when the toner particles contain a vinyl copolymer having a hydroxyl group and a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, a low-temperature and low-humidity environment. In this case, the amount of charge, which is considered to be an interaction between resins, can be stabilized, so that stable charging characteristics can be exhibited in all environments.

Examples of the monomer having a sulfonic acid group for producing the polymer having the sulfonic acid group and the like include styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-methacrylamide-2-methylpropane. Examples thereof include sulfonic acid, vinyl sulfonic acid, and methacryl sulfonic acid.
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.
The content of the polymer having the sulfonic acid group or the like is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin for constituting the binder resin. Preferably there is. More preferably, it is 0.1 to 3.0 parts by mass.
When the polymer having a sulfonic acid group or the like is 0.01 to 5.00 parts by mass, sufficient chargeability can be obtained and stable development characteristics can be obtained. Further, 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.

The toner particles used in the toner of the present invention further preferably include a polymer or copolymer having a carboxylic acid group (hereinafter also referred to as a polymer having a carboxylic acid group).
Since the polymer having a carboxylic acid group has almost the same polarity as the vinyl copolymer having the hydroxyl group, the compatibility with each other is extremely good, and the function of improving environmental characteristics without impairing the effects of the present invention. Fulfill.
The polymer having a carboxylic acid group that can be used in the present invention preferably contains the same composition as the binder resin from the viewpoint of compatibility with the binder resin. The polymer having a carboxylic acid group that can be used in the present invention is preferably a styrene-based acrylic acid copolymer, a styrene-based methacrylic acid copolymer, a styrene-based maleic acid copolymer, or the like. An acid-based copolymer is particularly preferable because the charge amount can be easily controlled.
When a styrene copolymer is used as the polymer having a carboxylic acid group, the residual styrene is in the range of 0 to 300 ppm, and the polymer having the carboxylic acid group and the binder resin are used. It is preferable for improving the familiarity.

The polymer having a carboxylic acid group has a main peak molecular weight (Mp) of 8,000 to 250,000 in a molecular weight distribution measured by gel permeation chromatography (GPC), and a weight average molecular weight (Mw). Is preferably 8,000 to 260,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 1.05 to 5.00. The glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of the polymer or the like having the carboxylic acid group is 80 to 120 ° C., and the acid value of the polymer or the like having the carboxylic acid group is 5 to 40 mgKOH / g is preferable for achieving the most effective function.
The content of the polymer having a carboxylic acid group is preferably 1 to 30% by mass with respect to all the resin components constituting the toner particles.

The toner of the present invention has a main peak molecular weight (MpA) of 10,000 to 40,000 in the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble content of the toner. Is preferred. More preferably, it is 15,000 to 35,000.
When the MpA is 10,000 to 40,000, the melt viscosity of the resin component and the bleed property of the wax are well balanced during low temperature fixing, and a stable fixable temperature range is obtained.
When MpA is 15,000 to 35,000, the above effect is further improved.
The MpA can be controlled within the above range by adjusting the polymerization conditions (temperature, initiator type, and initiator amount) at the time of manufacturing the binder resin or toner.

In the toner of the present invention, in the molecular weight distribution measured by gel permeation chromatography (GPC) of the cyclohexane (CHX) insoluble matter in the tetrahydrofuran (THF) soluble content of the toner, the main peak molecular weight (MpB) is 10, 000 to 250,000 is preferred. More preferably, it is 10,000 to 100,000.
The resin corresponding to MpB in the present invention is a vinyl copolymer having a hydroxyl group, having a high glass transition temperature of 80 to 120 ° C., and having a main peak molecular weight of 10,000 to 250,000. In this case, the compatibility with the binder resin is good, and the effect of increasing the strength of the toner particles and the effect of improving the development durability stability are effectively exhibited.
The above MpB is a polymerization condition (temperature, initiator species, initiator amount, etc.) at the time of production of a vinyl copolymer having a hydroxyl group, and a polymerization condition (temperature, initiator species, initiator amount, etc.) at the time of toner production. ) Etc. can be controlled within the above range.
Further, when the toner of the present invention contains the polymer having the carboxylic acid group, etc., since the polymer also contains CHX insoluble matter in the THF soluble matter, there is consideration when adjusting the MpB. is necessary.

  The toner of the present invention preferably further contains at least one ether compound selected from the group consisting of compounds represented by the following structural formulas (1) and (2).

〔前記構造式（１）及び（２）中、Ｒ_１乃至Ｒ_１１は、独立して、炭素数１乃至６までのアルキル基である。〕

[In the structural formulas (1) and (2), R _{1 to} R ₁₁ are each independently an alkyl group having 1 to 6 carbon atoms. ]

Although the reason is not clear, the ether compound described above has a polarity between the water molecule and the resin component, and the binder resin component contained in the toner of the present invention and the vinyl copolymer having a hydroxyl group. Since it has the property of increasing the compatibility with the polymer, it is considered that it is effective for stable charging characteristics with little environmental dependency.
In the compounds represented by the structural formulas (1) and (2), R _{1 to} R ₁₁ in the formula are preferably alkyl groups having 1 to 6 carbon atoms. More preferably, it is an alkyl group having 1 to 4 carbon atoms.
When R _{1 to} R ₁₁ are alkyl groups having 1 to 6 carbon atoms, the balance between hydrophobicity and hydrophilicity is good, and appropriate polarity can further enhance the compatibility effect of the resin component of the present invention. It is preferable because of excellent charge stabilization.

  On the other hand, since the ether compound is excellent in compatibility with the binder resin, it is considered that when the ether compound is contained in the toner, it is dispersed in a nearly uniform state. Further, since oxygen atoms are elements having high electronegativity, the negative charges generated in the toner are delocalized. Since the ether compound has these two characteristics, the presence of the ether compound stabilizes the negative charge of the toner. Therefore, the effect of containing the ether compound is particularly remarkable when the toner of the present invention is a negative triboelectrically chargeable toner. In addition, it has the effect of suppressing charge-up even in the case of positive frictional charging.

Furthermore, the ether compound has a tertiary carbon and has a bulky structure. Since the functional group centered on tertiary carbon functions as a steric hindrance, it is hardly affected by water and charge leakage is suppressed. However, since the carbon bonded to the oxygen atom rotates, the functional group that can become steric hindrance can move, and the water molecule involved in the leakage of triboelectric charge is a small molecule. Must not. As a result, the functional group centered on the tertiary carbon functions as an appropriate steric hindrance.
Therefore, by combining the resin having the above polarity and the ether compound, what has conventionally contributed to the charge stabilization effect of the entire inner layer resin can also contribute to the charge stabilization effect in the outer layer resin. Therefore, a toner having an excellent balance of triboelectric charge as a whole in a high temperature and high humidity environment and a low temperature and low humidity environment can be obtained.

  The ether compound is preferably contained in the toner in the range of 5 to 1,000 ppm in order to sufficiently exhibit the above effects. More preferably, it is 10 to 800 ppm. More preferably, it is 10 to 500 ppm. The ether compound preferably contains at least one compound having the above structure, and may contain an ether compound having another structure. The content at that time is the total amount of the ether compounds contained. When the content of the ether compound in the toner is 5 to 1000 ppm, a good triboelectric charge amount can be obtained.

  Examples of the structure of the ether compound include the following structures.

Next, a preferable configuration for exhibiting the effects of the present invention more stably will be described.
The toner of the present invention preferably has a weight average particle diameter (D4) of 4.5 μm or more and 8.5 μm or less. When the value of D4 is less than 4.5 μm, the proportion of fine particles increases, so that segregation of the constituent components is likely to occur in the toner particles, and depending on the environment, disturbance of charging stability and progression of member contamination may be promoted. is there. If the value of D4 exceeds 8.5 μm, the developability of minute latent image dots that satisfy high-definition image quality may be inferior.

Below, the material used by this invention is demonstrated.
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.

As the comonomer for the styrene monomer of the styrene copolymer, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, doditer acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, Monocarboxylic acid having a double bond such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; maleic acid, butyl maleate, methyl maleate, Dicarboxylic acids having a double bond such as dimethyl maleate and substituted products thereof; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene and butylene ; Vinyl 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 polymerizable monomers 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 Body; 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, 2,2′-bis (4- (methacryloxy polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate,
Tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like can be mentioned.

  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. It is possible. Since the polyfunctional polymerizable monomer also acts as a crosslinking agent, it is effective in controlling the degree of branching.

The toner of the present invention preferably uses a crosslinking agent during the synthesis of the binder resin as a means for controlling the molecular weight and branching degree of the binder resin component.
In the crosslinking agent used in the present invention, examples of the bifunctional crosslinking agent include the following. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and diacrylate above instead of diacrylate Thing.
The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the 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, 2,4- Peroxides such as dichlorobenzoyl peroxide and lauroyl peroxide Examples thereof include initiators.
Particularly preferred is a polymerization initiator that produces an ether compound upon decomposition during the polymerization reaction. The ether compound is preferably a compound represented by the structural formula (1) or (2).

In the production of the toner of the present invention, it is preferable to add a low molecular weight polymer in order to obtain a preferable molecular weight distribution of the toner of the present invention. The low molecular weight polymer can be added at the time of melt kneading with a binder resin or the like when the toner is produced by a pulverization method, and the polymerizable single monomer is produced when the toner is produced by a suspension polymerization method. It can be added to the body composition. The low molecular weight polymer has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) in the range of 2,000 to 5,000, and Mw / Mn of less than 4.5, preferably Those less than 3.0 are preferred.
Examples of the low molecular weight polymer include low molecular weight polystyrene, low molecular weight styrene-acrylic acid ester copolymer, and low molecular weight styrene-acrylic copolymer.
In the present invention, a polar resin such as a polyester resin or a polycarbonate resin can be used in combination with the above-described binder resin.

The following are mentioned as a wax component used for this invention.
Petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax, petrolactam; montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof according to 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; hydrogenated castor oil and derivatives thereof; plant waxes; Among these, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability. Further, in the toner of the present invention, when the toner is produced by a suspension polymerization method, the hydrocarbon is effective in maintaining the strength of the core-shell structure and suppressing the deterioration of the developability due to the exudation of the wax even in the development output under severe conditions. It is more preferable to use a system wax.

  The wax component is preferably contained in an amount of 4 to 25 parts by mass with respect to 100 parts by mass of the binder resin. When the wax component is 4 to 25 parts by mass, an excellent release effect is exhibited by having an appropriate bleed property of the wax component when the toner is heated and pressurized. Further, it is possible to suppress the wax component from seeping out on the toner surface due to various stresses applied to the toner in the developing device, and uniform triboelectric chargeability of each toner can be obtained.

The toner of the present invention contains a colorant as an essential component in order to impart coloring power. Examples of the colorant preferably used in the present invention include the following organic pigments or dyes, or inorganic pigments.
As the organic pigment or organic dye as the cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, or a basic dye lake compound can be used. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.

Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment Red 150
, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  As the organic pigment or organic dye as the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

  As the black colorant, carbon black, a magnetic material, and a color toned to black using the yellow, magenta, and cyan colorants are used.

When toner particles are produced using a polymerization method in the present invention, it is necessary to pay attention to the polymerization inhibition property and water phase transfer property of the colorant. Preferably, the colorant should be subjected to surface modification, for example, a hydrophobic treatment with a substance that does not inhibit polymerization. In particular, dyes and carbon blacks have many polymerization inhibiting properties, so care must be taken when using them. A preferable method for surface-treating the dye system includes a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and a method in which the obtained colored polymer is added to the monomer system.
Carbon black may be treated with a material that reacts with the surface functional group of carbon black, for example, polyorganosiloxane, in addition to the same treatment as the above dye.
These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. The colorant is preferably used by adding 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

In the toner of the present invention, a magnetic material can be used by 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 a magnetic toner is prepared by a polymerization method, it is preferable to apply a hydrophobic treatment with a surface modifier, which is a substance that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.

  These magnetic materials preferably have a number average particle diameter of 2 μm or less, more preferably 0.1 to 0.5 μm. The content of the magnetic material is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin, and more preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin. It is.

In the toner of the present invention, a charge control agent may be mixed with toner particles as necessary, separately from or together with the polymer having a sulfonic acid group or the like in the side chain described above. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.
As the charge control agent, known ones can be used, and in particular, a charge control agent that has a high frictional charging speed and can stably maintain a constant triboelectric charge amount is preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable.
Examples of charge control agents include those that control the toner to be negatively charged, such as organometallic compounds and chelate compounds. Specific examples include a monoazo metal compound, an acetylacetone metal compound, an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, an oxycarboxylic acid, and a dicarboxylic acid-based metal compound. Others include aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenols. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.
Examples of charge control agents include those that control the toner to be positively charged. Nigrosine modified products with nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Some onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid , Ferricyanides, ferrocyanides); metal salts of higher fatty acids; resin-based charge control agents.

The toner of the present invention can contain these charge control agents alone or in combination of two or more. Among these charge control agents, a metal-containing salicylic acid-based compound is preferable in order to sufficiently exhibit the effects of the present invention, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.
A preferable blending amount of the charge control agent is 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

The toner of the present invention is preferably produced by carrying out a polymerization reaction in an aqueous medium in order to obtain sufficient structural strength, high development durability characteristics, and low-temperature fixing characteristics, thereby producing toner particles having a core-shell structure.
Examples of the method for producing toner particles in an aqueous medium include the following methods. An emulsion aggregation method in which an emulsion composed of essential toner components is aggregated in an aqueous medium; a suspension granulation method in which the essential toner components are dissolved in an organic solvent and then the organic solvent is volatilized after granulation in the aqueous medium. A suspension polymerization method or an emulsion polymerization method in which a polymerizable monomer in which an essential toner component is dissolved is directly granulated in an aqueous medium and then polymerized; a method in which an outer layer is then formed on the toner by using seed polymerization; A microcapsule method represented by 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, polymerization is performed by uniformly dissolving or dispersing a wax component and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) in a polymerizable monomer. It is set as a polymerizable monomer composition. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersant 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 the inorganic fine powder whose surface is treated with a surface treatment agent is mixed and adhered to the surface, whereby the toner of the present invention can be obtained. it can.

  In addition, it is preferable to manage the dissolved oxygen in the reaction vessel as a method for efficiently proceeding the polymerization reaction. If there is little dissolved oxygen, the polymerization reaction will be more efficient. As a result, low molecular weight components that adversely affect development durability and fixability can be suppressed, and stable performance can be exhibited.

As the dispersant used in the preparation of the aqueous medium, known inorganic and organic dispersants can be used.
Specifically, examples of the inorganic dispersant include the following. Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina Is mentioned.
Examples of the organic dispersant include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, and starch.
Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.
As the dispersant used in preparing the aqueous medium used in the toner of the present invention, an inorganic poorly water-soluble dispersant is preferable, and it is preferable to use a poorly water-soluble inorganic dispersant that is soluble in an acid.

  In the present invention, when an aqueous medium is prepared using the above dispersant, the amount of these dispersants used is 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Preferably there is. In the present invention, it is preferable to prepare an aqueous medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.

  In the present invention, when preparing an aqueous medium in which the above dispersant is dispersed, a commercially available dispersant may be used as it is and dispersed. However, in order to obtain dispersant particles having a fine and uniform particle size, a water-based dispersion medium can be prepared by generating a poorly water-soluble inorganic dispersant as described above in a liquid medium such as water under high-speed stirring. Good. For example, when tricalcium phosphate is used as a dispersant, a preferred dispersant can be obtained by mixing aqueous sodium phosphate solution and aqueous calcium chloride solution at high speed to form fine particles of tricalcium phosphate. .

The toner of the present invention can be used in combination with fine powders such as silica, titanium oxide, alumina or their double oxides in addition to the inorganic fine powders whose surface is treated with the surface treatment agent.
In particular, when the inorganic fine powder whose surface is treated with the surface treatment agent is silica, it is preferable to use silica or titanium oxide having different particle diameters in combination.
When the inorganic fine powder whose surface is treated with the surface treatment agent is silica, the fine powder added in addition to the silica improves the fluidity of the toner, makes the toner particles triboelectrically charged, and develops the toner particles. Added to improve durability. These fine powders can also be hydrophobized to provide functions such as adjusting the triboelectric charge amount of toner, improving environmental stability, and improving characteristics under high-humidity environments. It is preferable to use the fine powder prepared. When the inorganic fine powder or the like added to the toner absorbs moisture, the amount of triboelectric charge as the toner decreases, and the developability and transferability tend to decrease.
Examples of the treatment agent for hydrophobizing the fine powder include the following. Unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treatment agents may be used alone or in combination.
Among these, fine powder treated with silicone oil is preferable. More preferably, the hydrophobized fine powder treated with silicone oil treated with silicone oil at the same time or after hydrophobizing the fine powder with a coupling agent increases the triboelectric charge amount of the toner particles even in a high humidity environment. It is good for maintaining and reducing selective developability.

Next, an example of an image forming method that can use the toner of the present invention will be described with reference to FIGS.
FIG. 3 is a cross-sectional view of a tandem color LBP (color laser printer) that employs a non-magnetic one-component contact development system as an example of an image forming apparatus suitable for image formation using the toner of the present invention. Show. FIG. 2 is a schematic cross-sectional view of a process cartridge that can be attached to the image forming apparatus.

  An example of the image forming method will be described below with reference to the drawings, but the present invention is not limited to this.

<Process cartridge>
FIG. 2 is a schematic cross-sectional view of a process cartridge 7 (hereinafter also referred to as “cartridge”) that can be used in an image forming apparatus suitable for image formation using the toner of the present invention.
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 that develops an electrostatic latent image formed on the photosensitive drum 1. . 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 and the support holes (not shown) provided at both ends of the cleaning frame 31 of the cleaner unit 50 are aligned, 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 carrier 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.

In the image forming method of FIG. 2, the toner carrier rotates in the same direction as the peripheral speed of the photosensitive member, but may rotate in the opposite direction. When the rotation is in the same direction, it is preferable to set the peripheral speed of the toner carrier to be 1.05 to 3.0 times the peripheral speed of the photosensitive member.
When the peripheral speed of the toner carrier is less than 1.05 times the peripheral speed of the photoreceptor, the stirring effect received by the toner on the photoreceptor is insufficient, and good image quality cannot be expected. On the other hand, when the peripheral speed ratio exceeds 3.0, toner deterioration due to mechanical stress and toner adhesion to the toner carrier are generated and promoted, which is not preferable.
When the toner carrier is an elastic roller, a structure having an elastic layer on the surface is preferably used. The hardness of the material of the elastic layer used for the elastic roller is preferably 30 to 60 degrees (ASKER-C / load 1 kg).
Further, the toner coating amount is controlled by the toner regulating member 44, and the toner regulating member 44 is in contact with the developing roller 40 through the toner layer. At this time, the contact pressure between the toner regulating member 44 and the developing roller 40 is preferably in a range of 0.05 N / cm to 0.5 N / cm as a linear pressure.
The linear pressure is a load applied per length of the toner regulating member. For example, when a 1.2 N load is applied to the toner regulating member having a contact length of 1 m and brought into contact with the developing roller. The linear pressure is 1.2 N / m. If the linear pressure is less than 0.05 N / cm, it is difficult to control the toner coating amount and uniform triboelectric charging, resulting in fogging. On the other hand, if the linear pressure is higher than 0.5 N / cm, the toner particles are subjected to an excessive load, and therefore, deformation of the particles and adhesion of the toner to the toner regulating member or the developing roller are likely to occur.
The free end portion of the toner regulating member 44 may have any shape. For example, in addition to a linear cross-sectional shape, an L-shape that is bent near the tip, or a shape that bulges in the vicinity of the tip. Etc. are preferably used.
As the toner regulating member, a material in which a metal elastic body such as stainless steel, steel, phosphor bronze or the like is used as a base material and a resin is adhered or coated on a portion that contacts the sleeve contact portion is preferably used.
Furthermore, by applying a DC electric field and / or an AC electric field to the toner regulating member, the uniform thin layer coating property and the uniform charging property are further improved due to the loosening action on the toner, and sufficient image density is achieved. A good quality image can be obtained.

<Image forming apparatus>
FIG. 3 is a schematic cross-sectional view showing an example of an image forming apparatus suitable for image formation using the toner of the present invention. The image forming apparatus 100 includes four image forming stations Pa, Pb, P
c and Pd are juxtaposed 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. 2 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) An electrostatic 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. Of these, polycarbonate resins, polyester resins, and acrylic resins 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 the toner in the toner container 41 is transferred to the toner transport mechanism. 42 is sent 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 electrostatic 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. The transfer belt 11 circulates so that the recording medium S is brought 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 transfer roller 12 (12a, 12b, 12c, 12d) is arranged in parallel at a position in contact with the inside of the transfer belt 11 and facing the four photosensitive drums 1 (1a, 1b, 1c, 1d). 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. Then, the scanner units 3 corresponding to the respective 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. The scanner unit 3 exposes the circumferential surface of the photosensitive drum in accordance with the image signal to form an electrostatic latent image on the circumferential surface of the photosensitive drum. The developing roller 40 in the developing unit 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 circumferential surface of the most upstream photosensitive drum 1 is rotated and conveyed to the point facing the transfer belt 11, the print start position of the recording medium S coincides with the point facing the transfer belt 11. Thus, 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 photosensitive drum 1 is sequentially transferred to the recording medium S by an electric field formed between each photosensitive 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 heat-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.

Below, the measuring method of the physical-property value concerning this invention is demonstrated.
(1) Extraction method and content measurement method of cyclohexane (CHX) insoluble matter in tetrahydrofuran (THF) soluble content of toner The extraction method and content of CHX insoluble content in THF soluble content in the toner of the present invention The following methods can be used for the measurement method.
The toner to be measured and THF are mixed at a concentration of 450 mg / ml, and the mixture is sufficiently shaken at room temperature for 10 hours until the sample is no longer united, and the THF and sample are mixed well, and then allowed to stand for 7 days. Thereafter, the lysate is separated into a supernatant and a sediment by centrifuging at 15000 r / min for 60 minutes in a 10 ° C. environment using a cooling high-speed centrifuge (for example, H-9R (manufactured by Kokusan Co., Ltd.)). Collect the supernatant. Further, the supernatant liquid is reduced by 50% while bubbling the supernatant liquid with nitrogen gas to produce a concentrated liquid [X].
Thereafter, 5 ml of the concentrated solution is added to 100 ml of cyclohexane to produce an insoluble matter. The liquid in which insoluble matter is generated is centrifuged at 15000 r / min for 60 minutes in a 10 ° C. environment using a cooling high-speed centrifuge (for example, H-9R (manufactured by Kokusan Co., Ltd.)). And the supernatant liquid is removed.
The precipitate after removal was allowed to stand at room temperature for 24 hours, then the solvent was removed in a vacuum dryer (40 ° C.) for 24 hours to remove THF, and the insoluble matter in cyclohexane in the THF-soluble matter. The resulting component (A) is collected.
The content of the cyclohexane insoluble component in the THF soluble component for the toner is calculated as follows.
CHX insoluble content (mass%) = (A) / toner mass × 100
Further, the resin component extracted by the above method can be identified as a vinyl resin or a polyester resin by using an analyzer such as IR or NMR.
In the present invention, the THF soluble content of the toner is obtained by air-drying the concentrated liquid [X] at room temperature for 24 hours and then removing the solvent in a vacuum dryer (40 ° C.) for 48 hours. It is an ingredient.

(2) Measurement of molecular weight of THF soluble matter and CHX insoluble matter of the toner The molecular weight of THF soluble matter and CHX insoluble matter of the toner is measured using gel permeation chromatography (GPC) under the following conditions. .
The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min. A sample (solid) is dispersed in THF, dissolved, and allowed to stand for 24 hours, and then filtered through a 0.2 μm filter, and the filtration is used as a sample. Measurement is performed by injecting 50 to 200 μl of a THF solution of a resin adjusted to a sample concentration of 0.05 to 0.6 mass%. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Or the molecular weight of Toyo Soda Industry Co., Ltd. is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 It is suitable to use a standard polystyrene sample of at least about 10 points using 9.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ . An RI (refractive index) detector is used as the detector.
As a column, in order to accurately measure a molecular weight region of 1 × 10 ³ to 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns, shodex KF-801, 802, 803 manufactured by Showa Denko K.K. , 804, 805, 806, and 807 are used in combination.

(3) Method for Measuring Hydroxyl Value of Vinyl Copolymer Having Hydroxyl Value and CHX Insoluble Content In the present invention, the vinyl copolymer having a hydroxyl value and the CHX insoluble content in the THF soluble content of the toner are used. The hydroxyl value (JIS hydroxyl value) is determined by the following method.
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value of the binder resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
(A) Preparation of reagent 25 g of special grade acetic anhydride is placed in a 100 ml volumetric flask, pyridine is added to make a total volume of 100 ml, and shaken sufficiently to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.
Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95% by volume), add ion exchanged water to make 100 ml, and obtain a phenolphthalein solution.
Dissolve 35 g of special grade potassium hydroxide in 20 ml of water and add ethyl alcohol (95 vol%) to make 1 liter (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 0.5 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 0.5 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(A) Operation (A) Main test A 1.0 g sample of the pulverized binder resin is precisely weighed into a 200 ml round bottom flask, and 5.0 ml of the acetylating reagent is accurately added to the sample using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.
A small funnel is placed on the mouth of the flask, and the bottom of the flask is immersed in a glycerin bath at about 97 ° C. and heated. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.
After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1 ml of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5 ml of ethyl alcohol.
Add several drops of the phenolphthalein solution as an indicator and titrate with 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 similar to the above operation is performed except that a sample such as resin is not used.
(C) Substituting the obtained results into the following equation to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D
Here, A: hydroxyl value (mg KOH / g), B: addition amount (ml) of potassium hydroxide solution in blank test, C: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Factor of solution, S: sample (g), D: acid value of binder resin (mgKOH / g).

(4) Glass transition temperature (TgA and TgB) of toner and CHX insoluble matter
The glass transition temperature (TgA) and maximum endothermic peak temperature (P1) of the toner in the present invention, and the glass transition temperature (TgB) insoluble in CHX are a differential scanning calorimeter (DSC measuring device) Q1000 (TA Instruments Japan). And manufactured in accordance with ASTM D3418-82.
Specifically, using the modulated mode of the differential scanning calorimeter, the measurement is performed under the following conditions, and is obtained from the peak position of the DSC curve at the first temperature increase. About 3 mg of the measurement sample is accurately weighed. It is placed in an aluminum pan, and an empty aluminum pan is used as a control, and measurement is performed between a measurement range of 20 to 140 ° C.
<Measurement conditions>
• Equilibrate at a temperature of 20 ° C for 5 minutes.
・ Modulation of 1.0 ° C / min was applied, and the temperature was increased to 140 ° C at 1 ° C / min. • Equilibrate at 140 ° C for 5 minutes.
・ Temperature drop to 20 ℃.
Here, the glass transition temperature is a midpoint glass transition temperature defined in Japanese Industrial Standard (JIS) K7121 9.3 (Established date: October 1, 1987, Confirmed date: March 25, 2006). is there. The maximum endothermic peak temperature (P1) is a melting peak defined in Japanese Industrial Standard (JIS) K7121 9.1 (established date: October 01, 1987, confirmed date: March 25, 2006). Among the temperatures, this is a peak temperature at which the peak height from the baseline on the high temperature side is maximized.

(5) Method for Measuring Restoration Rate Using Fine Compression Test for Toner A method for measuring the restoration rate using the micro compression test will be described with reference to FIG.
FIG. 1 shows a profile (displacement curve) obtained by a micro-compression test for the toner 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.
In the present invention, an ultra micro hardness tester ENT1100 manufactured by Elionix Co., Ltd. was used for the micro compression test. A 20 μm × 20 μm square flat indenter was used as the working indenter.
(1-1) is the initial state before starting the test, and a load is applied at a speed of 9.8 × 10 ⁻⁵ N / sec with respect to the maximum load of 2.94 × 10 ⁻⁴ N. 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. (1-3) shows a state immediately after the standing is finished, and the maximum displacement at this time is X ₃ (μm). Furthermore, when the load is unloaded at a speed of 9.8 × 10 ⁻⁵ N / sec through the maximum load and the load becomes 0 N , the state (1-4) is obtained. The amount of displacement at this time is X ₄ (μm).
The restoration rate Z (25) was determined as 100 × (X ₃ −X ₄ ) / X ₃ .
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, Z (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. The toner particle diameter measuring means on the measurement screen measures the major axis and minor axis of the toner particles using the software attached to the microhardness meter ENT1100. A toner having an aspect ratio [(major axis + minor axis) / 2] obtained from the formula (1) of D1 of ± 0.2 μm was selected and measured.
With respect to the measurement data, 100 arbitrary particles were selected and measured, and with respect to Z (25) obtained as a measurement result, the remaining 80 values obtained by excluding 10 from the maximum value and the minimum value were used as data. Z (25) was determined as an arithmetic mean value.
Further, in the load-displacement curve in which the load and the amount of displacement in the micro-compression test for the toner are plotted, the slope of the load- displacement curve from the origin (1-1) until the maximum load is finished is represented by R (25) [2. 94 × 10 ⁻⁴ / displacement amount X ₂ (N / μm)].

(6) Weight average particle diameter (D4) and number average particle diameter (D1) of the toner
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precision particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.
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 is set as follows.
In the screen for changing the standard measurement method (SOM) of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and the Kd value is “standard particles 10.0 μm” (manufactured by Beckman Coulter) 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 special software pulse to particle size conversion setting screen, 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.
(A) About 200 ml of the electrolytic solution is put 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, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(A) About 30 ml of the electrolytic solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(C) Two oscillators having an oscillation frequency of 50 kHz are built in with a phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank.
(D) The beaker of (a) 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.
(E) About 10 mg of toner is added to the electrolytic aqueous solution little by little in a state where ultrasonic waves are applied to the electrolytic aqueous solution in the beaker of (d). 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.
(F) To the round bottom beaker (A) installed in the sample stand, the electrolyte solution (O) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(G) 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).

(7) Measurement of average circularity and average equivalent circle diameter of toner The average circularity and average equivalent circle diameter of toner in the present invention are those calculated by a flow type particle image analyzer.
The measurement of the present invention uses a flow type particle image measuring apparatus.
The measurement principle of the flow type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex) is to take a flowing particle as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted, Projected area, perimeter, etc. are measured.
The image signal is A / D converted by the image processing unit, captured as image data, and image processing for determining the presence or absence of particles is performed on the stored image data.
Next, contour enhancement processing is performed as preprocessing for accurately extracting the contour of the particle image.
Next, the image data is binarized at an appropriate threshold level.
When the image data is binarized at a certain appropriate threshold level, each particle image becomes a binarized image as shown in FIG. Next, it is determined whether each of the binarized particle images is an edge point (contour pixel representing a contour), and in which direction there is an edge point adjacent to the target edge point. Information, that is, chain code is generated.
Next, the projected area S and the perimeter L of each particle image are obtained. Using the area S and the perimeter L, the equivalent circle diameter and the circularity are obtained. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity is a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. Defined and calculated by the following formula.

When the particle image is circular, the circularity is 1.000. The greater the degree of irregularities on the outer periphery of the particle image, the smaller the circularity.
After calculating the circularity of each particle, the range of the circularity of 0.2000 to 1.000 is divided into 800, and the average circularity is calculated using the center value of the division points and the number of measured particles.
Further, the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can also be measured. As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the particle size range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave).

As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and after adding alkylbenzene sulfonate as a dispersant, 0.02 g of a measurement sample is further added. , Uniformly disperse. As a dispersion means, an ultrasonic disperser UH-50 type (manufactured by SMT) equipped with a titanium alloy chip having a diameter of 5 mm as a vibrator is used, and a dispersion treatment is performed for 5 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not become 40 degree | times or more.
For the measurement of the circularity and equivalent circle diameter of the toner in the present invention, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner concentration at the time of measurement is 3000 to 10,000 / μl, Measure 1000 or more toners. After the measurement, the average circularity and the average equivalent circle diameter are obtained using this data.
Further, in the present invention, the total number of toner particles having a particle diameter equal to or less than 1/3 of the average equivalent circle diameter based on the number-based equivalent circle diameter distribution measured with a flow particle image analyzer is analyzed. The ratio to the number of particles (small particle ratio) is obtained by the following method.
That is, the number of particles having a particle diameter equal to or smaller than 1/3 of the average equivalent circle diameter is obtained with respect to the average number of equivalent circle diameters of the toner obtained by the measurement method, and the ratio to the total number of particles is expressed by number%. It is obtained by calculating.

(8) Method for quantifying ether compound The amount of the ether compound contained in the toner of the present invention is quantified by a multiple headspace extraction method.
(Devices and instruments)
The headspace sampler is manufactured by Perkin Elmer Japan Co., Ltd., HS40XL, and GC / MS is manufactured by ThermoQuest Co., Ltd., TRACEGC, and TRACE MS.
In addition, the calculation of the peak area by the multiple headspace extraction method is performed using the following approximate expression.

Sample vials are connected to gas chromatography (GC) and analyzed using multiple headspace extraction methods.
(A) Headspace sampler condition sample amount: 50 mg
Vials: 22 ml
Sample temperature: 120 ° C
Needle temperature: 150 ° C
Transfer line temperature: 180 ° C
Holding time: 60 min
Pressurization time: 0.25 min
Injection time: 0.08 min
(A) GC condition column: HP5-MS (0.25 mm, 60 m)
Column temperature: 40 ° C. (3 min), 70 ° C. (2.0 ° C./min), 150 ° C. (5.0 ° C./min), 300 ° C. (10.0 ° C./min)
Split ratio: 50: 1
(C) Instrument As a sealed container, a glass vial for headspace analysis (22 ml) manufactured by PerkinElmer Japan Co., Ltd. was used.
(D) Method (1) Preparation of Standard Sample First, as a standard sample for quantifying the ether compound, a methanol solution having an ether compound concentration of 1000 ppm is prepared, and 5 μl of this solution is used using a 10 μl volume microsyringe. It was placed in a 22 ml glass vial and quickly sealed with a high temperature analytical septum.
In addition, when the structure of the ether compound is unknown, the structure is identified by an analysis method such as gas chromatography mass spectrometry (GC-MS) or liquid chromatography-mass spectrometry (LC-MS), and the identified substance It is possible to quantify by the method described above.
(2) Preparation of Toner Sample 50 mg of toner was placed in a 22 ml glass vial and sealed with a high temperature analysis septum to prepare a sample.
(E) Analysis First, a standard sample of the ether compound was measured using a quantitative multiple headspace extraction method, and the total peak area per 0.005 μl of the ether compound was determined (Note that the sensitivity of GC varies from day to day. Therefore, the peak area per 0.005 μl of the ether compound needs to be checked for each measurement).
Next, the ether compound volume in the measurement sample is obtained by proportional calculation from the total peak area obtained by the quantitative multiple headspace extraction method of the toner and the total peak area of the ether compound standard sample, and the calculated value of the ether compound is calculated. The specific gravity was multiplied and converted into a weight, and the ether compound concentration in the toner was calculated.

(9) Method for Measuring Viscosity of Toner at 100 ° C. by Flow Tester Temperature Raising Method The viscosity of toner at 100 ° C. by the flow tester temperature raising method is determined as follows.
A flow tester CFT-500A type (manufactured by Shimadzu Corporation) is used. Weigh 1.00 g of sample. This is pressurized for 1 minute under a load of 10 MPa using a molding machine.
This pressure sample was subjected to flow tester measurement under the following conditions under normal temperature and normal humidity (temperature of about 20 to 30 ° C., humidity of 30 to 70% RH), and the viscosity at 100 ° C. was measured. The measurement mode was a temperature raising method.
RATE TEMP 4.0 D / M (℃ / min)
SET TEMP 50.0 DEG (℃)
MAX TEMP 200.0 DEG
INTERVAL 4.0 DEG
PREHEAT 300.0 SEC (seconds)
LOAD 10.0 KGF (kg)
DIE (DIA) 1.0 MM (mm)
DIE (LENG) 1.0 MM
PLUNGER 1.0 CM ² (cm ² )

  The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. In the following description, “part” and “%” are all based on mass unless otherwise specified.

(Toner Production Example 1)
A polymerized toner was produced according to the following procedure.
To 1300 parts by mass of ion-exchanged water heated to 60 ° C., 9 parts by mass of tricalcium phosphate and 11 parts by mass of 10% hydrochloric acid are added, and 10,000 r using a TK type homomixer (manufactured by Special Machine Industries). / Min, and an aqueous medium having a pH of 5.2 was prepared.
Moreover, the following material was melt | dissolved at 100 r / min with the propeller-type stirring apparatus, and the solution was prepared.
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Charge control agent FCA1001NS (manufactured by Fujikura Kasei) 1.0 part by mass Hydroxyl-containing vinyl polymer 1 (shown in Table 2) 20.0 parts by mass Part

Next, in the above solution, 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 part by mass, wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 10.0 parts by mass Di-t-butyl ether (ether compound 1) 0.05 part by mass Divinylbenzene 0.25 part by mass was added, and then the mixture was heated to a temperature of 60 ° C. ), And dissolved and dispersed at 9,000 r / min.
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 the mixture was granulated by stirring at 60 ° C. with a TK homomixer at 10,000 r / min for 30 minutes.
Thereafter, the mixture was transferred to a propeller type stirring device and reacted at 70 ° C. for 5 hours while stirring at 100 r / min, then heated to 80 ° C. and further reacted for 5 hours to produce toner particles. After the 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 then the particle diameter was adjusted by classification to obtain cyan toner particles.
Hydrophobic silica fine powder treated with 20% by mass of dimethyl silicone oil (50 cs) as a fluidity improver with respect to 100 parts by mass of the cyan toner particles (primary particle size: 7 nm, BET specific surface area: 130 m ² / g) 1.7 parts by mass were mixed with a Henschel mixer (manufactured by Mitsui Miike) at 3000 r / min for 15 minutes to obtain cyan toner No. 1 was obtained. Cyan toner no. The physical properties of 1 are shown in Table 3.

(Toner Production Example 2)
In Toner Production Example 1, the hydroxyl group-containing vinyl polymer 1 is changed to the hydroxyl group-containing vinyl polymer 2 shown in Table 2, and styrene-α-methylstyrene-methacrylic acid-methyl methacrylate copolymer is used as the carboxylic acid group-containing resin. Polymer (carboxylic acid group-containing vinyl polymer 1) (styrene / α-methylstyrene / methacrylic acid / methyl methacrylate = 80.85 / 15.00 / 1.65 / 2.50, Mp = 20,000, Mn = 7,900, Mw = 19,000, Mw / Mn = 2.4, Tg = 99 ° C, acid value = 11.0 mgKOH / g) Similarly, toner No. 2 was produced. The obtained toner No. Table 3 shows the physical properties of 2.

(Toner Production Example 3)
Toner No. 1 was produced in the same manner as in Toner Production Example 1 except that the hydroxyl group-containing vinyl polymer 1 was changed to the hydroxyl group-containing vinyl polymer 3 shown in Table 2. 3 was produced. The obtained toner No. The physical properties of 3 are shown in Table 3.

(Toner Production Example 4)
In Toner Production Example 3, the same procedure as in Toner Production Example 3 was performed except that no charge control agent FCA1001NS (Fujikura Kasei Co., Ltd.) was added. 4 was produced. The obtained toner No. The physical properties of 4 are shown in Table 3.

(Toner Production Example 5)
In Toner Production Example 3, the same procedure as in Toner Production Example 3 was performed except that di-t-butyl ether (ether compound 1) was not added. 5 was produced. The obtained toner No. The physical properties of 5 are shown in Table 3.

(Toner Production Example 6)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3 except that the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 4 shown in Table 2. 6 was produced. The obtained toner No. The physical properties of 6 are shown in Table 3.

(Toner Production Example 7)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3 except that the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 5 shown in Table 2. 7 was produced. The obtained toner No. The physical properties of 7 are shown in Table 3.

(Toner Production Example 8)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3 except that the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 6 shown in Table 2. 8 was produced. The obtained toner No. The physical properties of 8 are shown in Table 3.

(Toner Production Example 9)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3 except that the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 7 shown in Table 2. 9 was produced. The obtained toner No. The physical properties of 9 are shown in Table 3.

(Toner Production Example 10)
In Toner Production Example 3, the hydroxyl group-containing vinyl polymer 3 is changed to the hydroxyl group-containing vinyl polymer 8 shown in Table 2, and the addition amount of the polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) is set to 10. In the same manner as in Toner Production Example 3 except for changing to the mass part, the toner No. 10 was produced. The obtained toner No. The physical properties of 10 are shown in Table 3.

(Toner Production Example 11)
In Toner Production Example 3, the same procedure as in Toner Production Example 3 was performed, except that the addition amount of the polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was changed to 5.0 parts by mass. Toner No. 11 was produced. The obtained toner No. The physical properties of 11 are shown in Table 3.

(Toner Production Example 12)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3 except that the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 9 shown in Table 2. 12 was produced. The obtained toner No. The physical properties of 12 are shown in Table 3.

(Toner Production Example 13)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3, except that the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 10 shown in Table 2. 13 was produced. The obtained toner No. The physical properties of 13 are shown in Table 3.

(Toner Production Example 14)
In Toner Production Example 3, the wax HNP-51 to be added (melting point: 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) is changed to an ester wax having a melting point of 68 ° C. Except for adding 0.2 part by mass of hydrophobic silica fine powder (primary particle size: 50 nm, BET specific surface area: 45 m ^{2 /} g) treated with 15% by mass of disilazane, Similarly, toner No. 14 was produced. The obtained toner No. The physical properties of 14 are shown in Table 3.

(Toner Production Example 15)
In Toner Production Example 3, the amount of styrene added was changed to 72 parts by mass, the amount of n-butyl acrylate added was changed to 28 parts by mass, and the added wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) Is changed to ester wax of 68 ° C., and is a hydrophobic silica fine powder (primary particle diameter: 50 nm, BET specific surface area: newly treated with 20% by mass of methyltrimethoxysilane as an inorganic fine powder externally added to toner particles. 50 m ^{2 /} g) Toner no. 15 was produced. The obtained toner No. Table 3 shows the 15 physical properties.

(Toner Production Example 16)
In Toner Production Example 3, the hydroxyl group-containing vinyl polymer 3 is changed to the hydroxyl group-containing vinyl polymer 11 shown in Table 2, and the added wax HNP-51 (melting point 77 ° C .: Nippon Seiwa Co., Ltd.) has a melting point of 85 ° C. Hydrophobic silica fine powder (primary particle diameter: 12 nm, BET specific surface area) obtained by treating the hydrophobic silica fine powder externally added to the toner particles with 30% by mass of dimethyl silicone oil (50 cs). No .: 102 m ² / g), except that the toner No. 16 was produced. The obtained toner No. The physical properties of 16 are shown in Table 3.

(Toner Production Example 17)
In Toner Production Example 3, the addition amount of styrene was changed to 67 parts by mass, the addition amount of n-butyl acrylate was changed to 33 parts by mass, and the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 12 shown in Table 2. Wax HNP-51 to be added (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) is changed to HNPO 190 (melting point 90 ° C .: manufactured by Nippon Seiwa Co., Ltd.), and hexamethyldisilazane is newly added as an inorganic fine powder added externally to toner particles. Except for the addition of hydrophobic silica fine powder (primary particle size: 30 nm, BET specific surface area: 70 m ² / g) treated with 20% by weight of dimethyl silicone oil (100 cs) after being treated with 20% by weight. In the same manner as in Production Example 3 of Toner No. 17 was produced. The obtained toner No. The physical properties of 17 are shown in Table 3.

(Toner Production Example 18)
Styrene / n-butyl acrylate copolymer (mass ratio 80/20) 100 mass
(Mp = 23,000, Mn = 8,500, Mw = 25,500, Mw / Mn = 3.0, Tg = 52 ° C.)
Hydroxyl group-containing vinyl polymer 3 (shown in Table 2) 20 parts by mass Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 3 parts by mass C.I. I. Pigment Blue 15: 3 6.5 parts by mass polyethylene wax (endothermic peak = 126 ° C.) 5 parts by mass The above materials were mixed in a blender, melt-kneaded with a biaxial extruder heated to 110 ° C., and the cooled kneaded product was Coarsely pulverized with a hammer mill, the coarsely pulverized product was finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the resulting finely pulverized product was subjected to air classification to obtain toner particles (18) having a weight average particle diameter of 7.5 μm. .
Hydrophobic silica fine powder (primary particle size: 7 nm, BET specific surface area) treated with 20% by mass of dimethyl silicone oil (50 cs) as a fluidity improver with respect to 100 parts by mass of the cyan toner particles (18). 130 m ^{2 /} g) 1.7 parts by mass were mixed with a Henschel mixer (Mitsui Miike Co., Ltd.) at 3000 r / min for 15 minutes to obtain cyan toner No. 18 was obtained. Cyan toner no. The physical properties of 18 are shown in Table 3.

(Toner Production Example 19)
100 parts by mass of polyester resin (Mp = 20,000, Mn = 6,000, Mw = 18,000, Mw / Mn = 3.0, acid value = 18, hydroxyl value = 20, Tg = 55 ° C.)
Hydroxyl group-containing vinyl polymer 13 (shown in Table 2) 10 parts by mass Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.8 parts by mass C.I. I. Pigment Blue 15: 3 6.5 parts by mass Wax HNP-51 (melting point 77 ° C .: manufactured by Nippon Seiwa Co., Ltd.) 4 parts by mass The above components are melt-kneaded with a Banbury mixer, and after cooling, the kneaded product is coarsely pulverized with a hammer mill. The coarsely pulverized product is finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the resulting finely pulverized product is classified with an air classifier, and the toner particles having an average circularity of 0.923 and a weight average particle size of 8.0 μm (19) was obtained.
Hydrophobic silica fine powder (primary particle size: 7 nm, BET specific surface area) treated with 20% by mass of dimethyl silicone oil (50 cs) as a fluidity improver with respect to 100 parts by mass of the cyan toner particles (19). 130 m ^{2 /} g) 1.7 parts by mass was mixed with a Henschel mixer (manufactured by Mitsui Miike) at 3000 r / min for 15 minutes to obtain cyan toner No. 19 was obtained. Cyan toner no. The physical properties of 19 are shown in Table 3.

(Toner Production Example 20)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3 except that the amount of styrene added was changed to 64 parts by mass and the amount of n-butyl acrylate added was changed to 36 parts by mass. 20 was produced. The obtained toner No. The physical properties of 20 are shown in Table 3.

(Toner Production Example 21)
In Toner Production Example 3, the addition amount of styrene was changed to 74 parts by mass, the addition amount of n-butyl acrylate was changed to 26 parts by mass, and the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 14 shown in Table 2. In the same manner as in Toner Production Example 3, except that 21 was produced. The obtained toner No. The physical properties of 21 are shown in Table 3.

(Toner Production Example 22)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3 except that the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 15 shown in Table 2. 22 was produced. The obtained toner No. The physical properties of 22 are shown in Table 3.

(Toner Production Example 23)
In Toner Production Example 3, the addition amount of styrene was changed to 69 parts by mass, the addition amount of n-butyl acrylate was changed to 31 parts by mass, and the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 16 shown in Table 2. In the same manner as in Toner Production Example 3, except that 23 was produced. The obtained toner No. Table 3 shows the physical properties of 23.

(Toner Production Example 24)
In Toner Production Example 3, the addition amount of styrene was changed to 64 parts by mass, the addition amount of n-butyl acrylate was changed to 36 parts by mass, and the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 12 shown in Table 2. In the same manner as in Toner Production Example 3, except that 24 was produced. The obtained toner No. The physical properties of 24 are shown in Table 3.

(Toner Production Example 25)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3 except that the amount of styrene added was changed to 79 parts by mass and the amount of n-butyl acrylate added was changed to 21 parts by mass. 25 was produced. The obtained toner No. The physical properties of 25 are shown in Table 3.

(Toner Production Example 26)
In Toner Production Example 3, the addition amount of styrene was changed to 72 parts by mass, the addition amount of n-butyl acrylate was changed to 28 parts by mass, and the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 17 shown in Table 2. In the same manner as in Toner Production Example 3, except that 26 was produced. The obtained toner No. The physical properties of 26 are shown in Table 3.

(Toner Production Example 27)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3, except that the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 18 shown in Table 2. 27 was produced. The obtained toner No. The physical properties of 27 are shown in Table 3.

(Toner Production Example 28)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3 except that the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 19 shown in Table 2. 28 was produced. The obtained toner No. Table 3 shows the physical properties of 28.

(Toner Production Example 29)
Toner No. 3 was prepared in the same manner as in Toner Production Example 3 except that the hydroxyl group-containing vinyl polymer 3 was changed to the hydroxyl group-containing vinyl polymer 20 shown in Table 2. 29 was produced. The obtained toner No. The physical properties of 29 are shown in Table 3.

(Toner Production Example 30)
In toner production example 3, except that the number of added parts of the hydroxyl group-containing copolymer 3 is changed to 31 parts by mass and the silica fine powder added to the toner particles is removed from the surface treatment. In the same manner as in Example 3, the toner No. 30 was produced. The obtained toner No. Table 3 shows the 30 physical properties.

［表２において、Ｓｔはスチレン、ＢＡはｎ−ブチルアクリレート、α−ＭＳｔはα−メチルスチレン、ＭＭＡはメタクリル酸メチル、
ＭＡＡはメタクリル酸、２ＨＥＭＡはメタクリル酸２−ヒドロキシエチル、２ＨＰＭＡはメタクリル酸２−ヒドロキシプロピルを表す。
また、ＯＨｖは水酸基価（ｍｇＫＯＨ／ｇ）を、Ａｖは酸価（ｍｇＫＯＨ／ｇ）を表す。
さらに、モノマー組成における数字は組成比（質量基準）を表す。］

[In Table 2, St is styrene, BA is n-butyl acrylate, α-MSt is α-methylstyrene, MMA is methyl methacrylate,
MAA represents methacrylic acid, 2HEMA represents 2-hydroxyethyl methacrylate, and 2HPMA represents 2-hydroxypropyl methacrylate.
OHv represents a hydroxyl value (mgKOH / g), and Av represents an acid value (mgKOH / g).
Furthermore, the numbers in the monomer composition represent the composition ratio (mass basis). ]

<Examples 1 to 23 and Comparative Examples 1 to 7>
The toners produced in Toner Production Examples 1 to 30 were evaluated according to the following criteria. While the toners of Examples 1 to 23 exhibited excellent effects on the low temperature fixing characteristics and the development durability characteristics, the toners of Comparative Examples 1 to 7 had a poor balance between the low temperature fixing characteristics and the development durability characteristics. . The evaluation results are shown in Table 4.

The image evaluation method and evaluation criteria of the present invention will be described below.
<Low-temperature fixing characteristics>
(1) Fixability Using a surf fuser of LBP5400 (Canon), the first printout time is set to 20 seconds, and a solid image of 10 mm × 10 mm (toner applied amount 0.50 mg / cm ² ) is manufactured by Xerox. The image was output on Business 4200 (75 g / m ² ), and the minimum fixing temperature at which a stable fixed image was obtained was evaluated according to the following criteria. The stable fixed image of the present invention is obtained by measuring the density of the obtained fixed image and the image density after rubbing the fixed image with Sylbon paper applied with a load of 50 g / cm ² five times. It is defined as a fixing state with a rate of 10% or less.
A: A stable fixed image can be obtained when the minimum fixable temperature is 150 ° C. or more and 160 ° C. or less. B: A stable fixed image can be obtained when the minimum fixable temperature is higher than 160 ° C. but not more than 170 ° C. C: Minimum fixable A stable fixed image can be obtained when the temperature is higher than 170 ° C. and lower than 190 ° C. D: The minimum fixing temperature is higher than 190 ° C. or has no fixing temperature.

(2) Gloss quality A solid whole area image (tip margin: 5 mm, toner applied amount 0.50 mg / cm ² ) is output on a Xerox business 4200 (75 g / m ² ) at a fixing temperature of 170 ° C. The 75 ° gloss (glossiness) of each section divided into 9 equal parts was measured, and an average value was obtained and evaluated according to the following criteria. The glossiness measuring instrument used in the present invention uses PG-3D (incident angle θ = 75 °) manufactured by Nippon Denshoku Industries Co., Ltd., and the standard surface uses black glass with a glossiness of 96.9. did.
A: 75 ° gloss average value 15.0 or more B: 75 ° gloss average value 10.0 or more and less than 15.0 C: 75 ° gloss average value 5.0 or more and less than 10.0 D: 75 ° gloss average value Less than 0

(3) Image fog Toner durability was evaluated by conducting a durability test using a non-magnetic one-component contact development system cartridge shown in FIGS. 2 and 3 and an image forming apparatus LBP5400 (manufactured by Canon Inc.). (Modified to process speed 200 mm / sec, sleeve peripheral speed 300 mm / sec).
The conditions of the durability test are a high temperature and high humidity environment (30 ° C., 80% RH [H / H]), a normal temperature and normal humidity environment (23 ° C., 50% RH [N / N]), a low temperature and low humidity environment (15 ° C., 10% % RH [L / L]), 20,000 original images with a printing ratio of 2% were output. The toner to be evaluated is packed in the cartridge shown in FIG. 2 and then mounted on the cyan station C unit of the apparatus shown in FIG. 3 to output a white image every 1,000 sheets. It was.
Using “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the white background portion of the standard paper and the printed image was measured, and the fog (reflectance:%) was calculated by the following formula. The filter was measured by attaching amber for cyan, blue for yellow, green filters for magenta and black.
Fog (reflectance;%) = (reflectance of standard paper;%) − (reflectance of sample;%)
In addition, the evaluation standard judged the worst value through an endurance test with the following standards.
A: Very good Less than 1.0% B: Good 1.0% or more to less than 2.0% C: No practical problem 2.0% or more to less than 3.0% D: Practical problem 3.0 %that's all

(4) Image density stability An original image in which nine 20 mm square solid black patches are arranged in the development area is output, and the maximum density difference of the image density during the durability test is compared with the initial image density of the nine-point average density. Thus, the concentration stability was evaluated.
The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
The durability test conditions and the sampling timing were performed in accordance with the evaluation of (3) image fog.
A: Very good Maximum density difference less than 0.15 B: Good Maximum density difference between 0.15 and less than 0.25 C: No practical problem Maximum density difference between 0.25 and less than 0.3 D: Somewhat difficult Maximum density difference 0.3 or more

(5) Halftone image reproducibility In order to confirm the presence or absence of halftone image quality deterioration due to member contamination or toner deterioration by visual evaluation based on the original halftone image, and earlier and strictly, A solid-tone potential image of a solid image was output, and the presence or absence of an image defect was evaluated by visual confirmation. The endurance test conditions and sampling timing were performed according to the above (3) evaluation of image fog.
A: Good reproducibility for both halftone images and solid halftone potential images.
B: Although the reproducibility of the original halftone image is good, the solid halftone potential image shows a streak along the image traveling direction and a rough feeling accompanying a decrease in transferability.
However, there is no problem with image quality.
C: Although the reproducibility is somewhat inferior in the original halftone image, there is no practical problem. In the halftone potential image, streaks along the image traveling direction and a decrease in transferability are recognized.
D: Even in the original halftone image, deterioration of quality such as defects and roughness is recognized.

It is a load-displacement curve in the micro compression test of toner. FIG. 4 is a cross-sectional explanatory diagram of a process cartridge suitable for performing image formation using the toner of the present invention. 1 is a schematic configuration diagram of an example of an image forming apparatus suitable for forming an image using the toner of the present invention. It is the binarized image of the image data in a flow type particle image measuring device.

Explanation of symbols

Pa, Pb, Pc, Pd Image forming station 1 (1a to 1d) Photosensitive drum (image carrier)
2 (2a to 2d) Charging means (charging roller)
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 Electrostatic transfer belt 12 (12a to 12d) ) Transfer roller 13 Belt drive rollers 14a, 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 Bonding hole 50 Cleaner unit 60 Cleaning blade 100 Image forming apparatus main body S Recording medium (recording material sheet)

Claims (16)

A toner having a binder resin, a colorant, a wax component, and toner particles containing a vinyl copolymer having a hydroxyl group , and an inorganic fine powder,
The hydroxyl value of the vinyl copolymer having the hydroxyl group contained in the toner particles is 3 to 70 mgKOH / g,
The toner has a glass transition temperature (TgA) measured by a differential scanning calorimeter of 40 to 60 ° C.,
The glass transition temperature (TgB) of the insoluble component of cyclohexane (CHX) in the tetrahydrofuran (THF) soluble component of the toner is 80 to 120 ° C., and the TgA and TgB are 25 ° C. ≦ (TgB−TgA) ≦ 70 ° C. Meet the relationship,
A toner characterized in that the inorganic fine powder is an inorganic fine powder whose surface is treated with a surface treatment agent. The toner in tetrahydrofuran (THF) cyclohexane in the soluble matter (CHX) insoluble matter The toner according to 請 Motomeko 1 you containing vinyl copolymer having a hydroxyl group. The toner according to claim 1, wherein the vinyl copolymer having a hydroxyl group is a vinyl copolymer having a repeating unit (I) represented by the following structural formula.

[In formula (I), R ₁ Is an alkylene group having 1 to 6 carbon atoms, and the repeating unit (I) may be of multiple types. ] The vinyl-based copolymer having a hydroxyl group has a repeating unit derived from hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, or hydroxyisobutyl methacrylate. The toner according to claim 3, which is a vinyl copolymer. The toner according to claim 4, wherein the vinyl copolymer having a hydroxyl group is a vinyl copolymer having a repeating unit derived from 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate. The toner content of the vinyl copolymer having particles a hydroxyl group contained in the said Ru 3-30% by mass with respect to all of the binder resin contained in the toner particles 請 Motomeko 1 The toner according to any one of 5 . The toner according to the the binder resin contained in the toner particles, 請 Motomeko 1-6 any one of you mainly containing vinyl polymer. In the micro compression test for the previous Quito toner at a measurement temperature 25 ° C., applying a maximum load of the one toner over particle children loading rate 9.8 × ¹⁰ -5 N / sec at 2.94 × ^{10 -4} N displacement obtained when finished ([mu] m) and the displacement amount X _2, wherein after finishing applying a maximum load, displacement amount obtained was left 0.1 seconds the maximum load ([mu] m) the maximum displacement X ₃ and then, after standing the 0.1 seconds, unloaded at an unloading rate 9.8 × ¹⁰ -5 N / sec, the amount of displacement obtained when the load becomes 0N ([mu] m) and the displacement amount _{X 4} the When the restoration rate Z (25) represented by (X ₃ −X ₄ ) / X ₃ × 100 satisfies the relationship of 40 ≦ Z (25) ≦ 80,
In the load-displacement curve in which the load and displacement amount in the micro-compression test for the toner are plotted, the slope of the load-displacement curve from the origin to the end of applying the maximum load is represented by R (25) [R (25) = 2. can to have a 94 × ¹⁰ -4 (N) / displacement _{X 2 (μm)],} wherein R (25) ^{is, 0.49 × 10 -3 ≦ R (} 25) ≦ 1.70 × 10 -3, the toner according to any one of 請 Motomeko 1-7 you satisfy the relation. The toner, the temperature of the maximum endothermic peak measured by differential scanning calorimetry (P1) is present in 70 ~ 120 ° C.,
The maximum endothermic peak temperature (P1), and the toner glass transition temperature measured by differential scanning calorimetry (TgA), but satisfying the 15 ℃ ≦ (P1-TgA) ≦ 80 ℃, the relationship
The toner according to any one of 請 Motomeko 1-8. The toner according to any one of viscosity at 100 ° C. as measured by a flow tester heating method of the toner, 5,000 ~ 32,000Pa · s der Ru請 Motomeko 1-9. The toner particles, a sulfonic acid group, the toner is sulfonate or polymer also having a sulfonic acid ester group according to any one of 請 Motomeko 1-10 you containing copolymer. The toner particles, the toner of the polymer also having a carboxylic acid group according to any one of 請 Motomeko 1 to 11 you containing copolymer. In the molecular weight distribution measured by the toner in tetrahydrofuran (THF) soluble matter of gel permeation chromatography (GPC), the molecular weight of the main peak (MpA) is Ru 10,000-40,000 der 請 Motomeko 1 13. The toner according to any one of items 12 . In the molecular weight distribution measured by gel permeation chromatography (GPC) of the cyclohexane (CHX) insoluble matter in the tetrahydrofuran (THF) soluble content of the toner, the molecular weight (MpB) of the main peak is 10,000 to 250,000. the toner according to any one of der Ru請 Motomeko 1-13. The toner is represented by the following structural formula (1) contains a compound represented by and at least one ether compound selected from the group consisting of compounds represented by the following structural formula (2) in 請 Motomeko 1-14 of The toner according to any one of the above.

[In the structural formulas (1) and (2), R ₁ to R ₁₁ are each independently an alkyl group having 1 to 6 carbon atoms. ] The toner particles are
And a shell layer in which the hydroxyl value containing a vinyl copolymer of 3 ~ 70mgKOH / g,
The toner according to any one of claims 1 to 15 having a core-shell structure having a core portion containing said coated with a shell layer, the wax component and the binder resin.

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