JP2002082481A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having excellent low temperature fixing property and high temperature offset resistance, excellent developing property for a long time, and excellent environmental stability. SOLUTION: In the toner containing at least a binder resin, coloring agent, wax and organic metal compound, the binder resin consists of a hybrid resin containing a vinyl polymer unit and a polyester unit. The organic metal compound is an azo iron compound produced from a monoazo compound having one or more alkyl groups and two hydroxyl groups which can be coupled with iron atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method.

[0002]

2. Description of the Related Art Conventionally, vinyl resins such as polyester resins and styrene resins have been mainly used as resins for toner. Polyester resins originally have excellent low-temperature fixability, but have the disadvantage that offset phenomena are likely to occur at high temperatures. Attempts to increase the viscosity by increasing the molecular weight of the polyester resin to compensate for this drawback not only impair the low-temperature fixability, but also worsen the pulverizability during toner production, making it unsuitable for toner micronization. It will be something.

[0003] Vinyl copolymers such as styrene resins are excellent in pulverizability at the time of toner production. If the molecular weight is reduced in order to improve the fixing property, blocking resistance and developability will be deteriorated.

[0004] In order to make effective use of the advantages of these two types of resins and to compensate for the drawbacks, there have been studied several methods of mixing and using these resins. For example, Japanese Unexamined Patent Publication No.
Japanese Patent No. 114245 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl copolymer. However, since the polyester resin and the vinyl copolymer are inherently poorly compatible, it is difficult to satisfy all of the low-temperature fixing property, the high-temperature offset resistance, and the blocking resistance unless the compounding ratio is appropriate. . In addition, the dispersibility of the coloring agent, wax and the like added during the production of the toner becomes insufficient, so that a problem is likely to occur in the developability. In particular, in recent years, this problem is remarkable in a toner in which fine particles are advanced.

[0005] JP-A-56-116043 and JP-A-58-159546 disclose toners characterized by containing a polymer obtained by polymerizing a monomer in the presence of a polyester resin. Have been. JP-A-58-1
JP-A-02246 and JP-A-1-156759 disclose toners characterized by containing a polymer obtained by polymerizing a vinyl copolymer in the presence of an unsaturated polyester resin. JP-A-2-881 discloses a toner containing a polymer obtained by esterifying an acid value-containing styrenic resin and a polyester resin. In these methods, although the compatibility between the polyester resin and the vinyl copolymer is improved, it is difficult to uniformly disperse the wax added during the production of the toner. There still remains a problem to be improved in developability.

JP-A-4-338973 discloses a toner using two kinds of polyester resins having different softening points, and JP-A-8-166688 discloses a toner using two kinds of polyester resins having different molecular weights. . However, in all cases, the high-temperature offset resistance is within the range of the polyester resin and is a problem to be improved.

Japanese Patent Application Laid-Open No. 8-54754 discloses that a polyester resin is mixed with a hybrid resin obtained by performing an addition polymerization reaction with a vinyl resin monomer and a polycondensation reaction with a polyester resin monomer in parallel. Discloses a toner using the obtained resin. In Japanese Patent Application Laid-Open No. 8-44108, two types of hybrid resins having different softening points obtained by performing an addition polymerization reaction with a vinyl resin monomer and a polycondensation reaction with a polyester resin monomer in parallel are described. The disclosed toner is disclosed. Also, with these methods,
The balance between the crosslinking on the low molecular weight side and the crosslinking on the high molecular weight side of the toner is not good, and there are still problems to be improved with respect to low-temperature fixability, wax dispersion and long-term developability.

Japanese Unexamined Patent Publication No. 7-128912 discloses a negatively chargeable toner containing a monoazo complex of chromium or cobalt atoms.

Japanese Patent Application Laid-Open No. 10-10785 discloses a toner containing a metal complex type monoazo compound and a metal complex of an aromatic hydroxycarboxylic acid as a charge control agent.

Japanese Patent Application Laid-Open No. 9-169919 discloses a monoazo metal compound having two hydroxyl groups capable of metallization.

Japanese Patent Application Laid-Open No. 11-7164 discloses a charge control agent comprising an amorphous metal salt having a monoazo compound as a ligand.

When such a monoazo metal complex is added to a toner as a charge control agent, excellent charge controllability is exhibited, but developability may be insufficient depending on the toner formulation. Further, although a polyester (hybrid) resin can provide good fixing properties, there is room for improvement in developability, and a better charge control agent is also required.

[0013]

SUMMARY OF THE INVENTION The present invention provides a toner which has solved the above-mentioned problems. That is, an object of the present invention is to provide a toner which is excellent in low-temperature fixability and high-temperature offset resistance, excellent in developability over a long period of time, and excellent in environmental stability.

[0014]

The present invention relates to a toner containing at least a binder resin, a colorant, a wax and an organometallic compound, wherein the binder resin is a hybrid resin having a vinyl polymer unit and a polyester unit. Wherein the organometallic compound comprises one or more alkyl groups,
The present invention relates to a toner, which is an azo iron compound that can be produced from a monoazo compound having two hydroxyl groups capable of binding to an iron atom, wherein the monoazo compound can be represented by the following formula (a).

[0015]

Embedded image (In the formula, R _{9 to} R ₁₈ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and at least one of R _{9 to} R ₁₈ is an alkyl group.)

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION

According to the present invention, in a toner containing at least a binder resin, a colorant, a wax and an organometallic compound, the binder resin comprises a hybrid resin having a vinyl polymer unit and a polyester unit, so that a low temperature By utilizing the properties of a polyester resin having good fixing properties and a vinyl resin having good high-temperature offset resistance, both low-temperature fixing property and high-temperature offset resistance can be achieved.

However, if the toner is left under the environment for a long time after endurance under high temperature and high humidity, the chargeability of the toner may be lowered and the density may be lowered. On the other hand, by having an azo iron compound that can be generated from a monoazo compound represented by the following formula (a) as an organometallic compound, sufficient triboelectric charge can be maintained even in a hybrid resin, and after leaving for a long time after durability, Can be avoided. In the present invention, by having an azo iron compound that can be formed from a monoazo compound having an alkyl group represented by the following formula (a), the rise of charge application is fast, and the chargeability of the toner is quickly recovered. An azo iron compound that can be produced from a monoazo compound having an alkyl group represented by the following formula (a) is kneaded in a hybrid resin having both an ester bond and a carbon-carbon bond. By increasing the affinity with the azo iron compound, the azo iron compound can be uniformly and finely dispersed. Therefore, it has been found that the concentration of the azo iron compound does not decrease even after the durability test. In addition, the charge release action of the hybrid resin prevents the azo iron compound from being excessively charged, makes the change over time in the chargeability of the toner uniform, and effectively prevents tailing of an image during development due to electrostatic aggregation of the toner. be able to.

[0019]

Embedded image (In the formula, R _{9 to} R ₁₈ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and at least one of R _{9 to} R ₁₈ is an alkyl group.)

That is, the monoazo compound forming the azo iron compound used in the present invention is a compound represented by the above formula (a), and obtains a good rise of toner charge and high chargeability. And development stability such as image density can be achieved. Further, the monoazo compound is characterized in that it has an alkyl group as a substituent, so that the affinity with the binder resin can be increased, and the chargeability and environmental stability of the toner can be obtained. From the viewpoint of further increasing the affinity with the binder resin, particularly, an ester bond and a carbon-
From the viewpoint of uniform fine dispersion in a hybrid binder resin having both carbon bonds, a monoazo compound having an alkyl group having 4 to 12, more preferably 6 to 10 carbon atoms as a substituent is preferred. Further, a monoazo compound having a tertiary alkyl group as a substituent, which can further stabilize charge by ion stabilization by superconjugation, is preferable.

In this structure, the position at which the alkyl group is formed is not particularly limited. However, the presence of the alkyl group at the positions R _{13 to} R ₁₈ gives a stable chargeability to the toner. Particularly preferred. In particular, R _{13 to} R
_It is preferable to introduce an alkyl group having 6 to 10 carbon atoms into ₁₆ in order to increase the bulk of the molecule and enhance the chargeability.

Such a monoazo compound can be obtained by a diazo coupling reaction.

The following are specific examples of the monoazo compound preferably used in the present invention, but the present invention is not limited to these monoazo compounds. -T-Oct represents _{-C (CH 3) 2 -CH 2} -C (CH 3) 3, -t-
Bu represents _{-C (CH 3) 3, -t} -C 5 H 11 is -C
(CH ₃ ) ₂ represents —CH ₂ —CH ₃ , and —Me represents —CH ₃ .

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

The azo iron compound used in the present invention is a reaction product of iron and a monoazo compound, and is an azo iron compound in which the above monoazo compound is coordinated to an iron atom. The azo iron compound is an iron complex, an iron complex salt or a mixture thereof, and is an azo iron compound selected from the azo iron compounds represented by the following general formulas (b), (c) and (d) or a mixture thereof. is there.

[0028]

Embedded image (In the formulas (b), (c) and (d), A and B each independently represent o-phenylene or 1,2-naphthylene, and at least one of A and B has one or more alkyl groups. A and B may each further have a halogen atom as a substituent, and M is a cation and represents a hydrogen ion, an alkali metal ion, an ammonium ion, or an organic ammonium ion.)

The azo iron compound used in the present invention can be obtained by reacting a monoazo compound capable of binding to an iron atom with an ironing agent in water and / or an organic solvent (preferably in an organic solvent). .

In general, the reaction product obtained in an organic solvent can be taken out by filtering and washing with water, or dispersing in an appropriate amount of water, collecting the precipitate by filtration, washing with water, and drying. . Examples of the organic solvent used in such an ironation reaction include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol dimethyl ether (monoglyme), and diethylene glycol dimethyl ether. (Diglyme), ethylene glycol diethyl ether, triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraclime),
Alcohol, ether and glycol organic solvents such as ethylene glycol and propylene glycol;
Water-soluble organic solvents such as aprotic polar solvents such as N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and dimethylsulfoxide can be mentioned. Preferred examples of the organic solvent include isopropanol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), and ethylene glycol.

The amount of the organic solvent to be used is not particularly limited, but is 2 to 5 times by mass the monoazo compound used as a ligand.

[0032] Examples of suitable ironing agents include ferric chloride, ferric sulfate, and ferric nitrate. The ironing agent is generally used in an amount of 1/3 to 2 equivalents, preferably 1/2 to 2/3 equivalents in terms of an iron atom equivalent per 1 mol of the monoazo compound serving as a ligand.

The above-mentioned monoazo iron compound as the organometallic compound of the present invention is used in an amount of 0.1 to 100 parts by mass of the binder resin.
By including 1 to 10 parts by mass, good charge controllability can be imparted to the toner. The monoazo iron compound and another organometallic compound may be used in combination.

In the THF-soluble component having a molecular weight of less than 10,000, the content of trivalent or more polycarboxylic acid or anhydride thereof is W1 (mol%), and the content of THF having a molecular weight of 10,000 or more is W1 (mol%).
When the content of the trivalent or higher polycarboxylic acid or its anhydride in the F-soluble component is W2 (mol%), 0 <W1 (mol%) <30 and 0 <W2 (mol%)
<50, more preferably 1 <W1 (mol%) <25 and 2 <W
2 (mol%) <30, more preferably 3 <W1, W2
By satisfying (mol%) <20, the low-temperature fixability and the high-temperature offset resistance can be further improved.

The component having a molecular weight of 10,000 or more in the toner is a component that affects the high-temperature offset resistance, and the restoring force of the toner at a high temperature is important. Therefore, it is preferable that the crosslink is sufficiently crosslinked with a trivalent or higher polycarboxylic acid or an anhydride thereof. For this purpose, 0 <W2 (mol%)
It is preferable to satisfy <50. If the molecular weight of the toner is less than 10,000, it is a component that affects the low-temperature fixability, and it is important that the toner melts well at low temperatures. Therefore, it is not necessary for the toner to be crosslinked as much as 10,000 or more components. However, if the toner is crosslinked to some extent, the blocking resistance can be improved. Therefore, 0 <W1 (mol%) <30
It is preferable to satisfy the following. When W1 is 30 or more, crosslinking on the low molecular weight side proceeds too much, and the low-temperature fixability deteriorates.
On the other hand, when W2 is 50 or more, the crosslinking on the high molecular weight side proceeds excessively, which may adversely affect the low-temperature fixability.

When W1 and W2 satisfy the above conditions, the charge relaxation of the azo iron compound is reduced, and the change in the charge amount is reduced, so that the change over time in the chargeability of the toner is reduced.
As a result, even if durability is performed for a long period of time, the density does not decrease. Also, when the values of W1 and W2 are both large and small, the degree of crosslinking of the resin is extremely biased,
The dispersibility of the azo iron compound tends to deteriorate.

More preferably, W1 (mol%) and W2
When the relationship of (mol%) is W2> W1, the high molecular weight side of the toner is crosslinked by a trivalent or higher polyvalent carboxylic acid or an anhydride thereof than the low molecular weight side, and the elastic force (restoring force) increases. As a result, the high-temperature offset resistance is improved, and the low-molecular-weight side is not crosslinked as much as the high-molecular-weight side, so that it is well melted even at a low temperature. As a result, both low-temperature fixability and high-temperature offset resistance can be achieved. Further, by satisfying the relationship of W1 and W2, the dispersion of the azo iron compound described above is improved, the charge control action can be exerted uniformly, and tailing can be further suppressed.

Further, the content of the THF-insoluble component in the toner is preferably 1 to 50% by mass. Preferably,
It is 2 to 40% by mass, more preferably 5 to 30% by mass. If the content of the THF-insoluble component is less than 1% by mass, the long-term storage stability may be deteriorated or the high-temperature offset resistance may be affected. If it exceeds 50% by mass, the fixability is poor. The trend comes out. G soluble in THF
In the molecular weight distribution of PC, the content (M1) of the component having a molecular weight of less than 10,000 is 40 to 70% by mass, the content (M2) of the component having a molecular weight of 10,000 to 50,000 is 25 to 50% by mass, and the molecular weight is 5%.
It is preferable that the content (M3) of the component exceeding 10,000 is 2 to 25% by mass and that M1 ≧ M2> M3 is satisfied in order to balance the fixing property, the offset resistance and the blocking resistance.

In the GPC molecular weight distribution of the THF-soluble component of the toner, when the content M3 of the component having a molecular weight exceeding 50,000 exceeds 25% by mass, the low-temperature fixability deteriorates. The content M1 of the component having a molecular weight of less than 10,000 exceeds 70% by mass,
When M1 ≧ M2> M3 is not satisfied, there is a problem in the storability of the toner under high temperature and high humidity and the high temperature offset resistance.
Further, the component having a molecular weight of less than 10,000 is a component that is well soluble at a low temperature. When the content (M1) having a molecular weight of less than 10,000 satisfies 40 to 70% by mass, sufficient low-temperature fixability can be obtained. The excess component is a component that plays a role of restoring force of the toner at a high temperature. When the content (M3) of the component having a molecular weight exceeding 50,000 satisfies 2 to 25% by mass, the high-temperature offset resistance is improved. . Further, in order to obtain sufficient developability, a component having a molecular weight of 10,000 to 50,000 is used in order to disperse materials such as a colorant, a charge control agent, and a magnetic substance in a binder resin to make the chargeability uniform. Is preferably 25 to 50% by mass.

The molecular weight of the THF-soluble component of the toner is measured by gel permeation chromatography (GPC). As a specific GPC measurement method, a sample obtained by previously extracting the toner with a THF (tetrohydrofuran) solvent for 10 hours using a Soxhlet extractor was used, and the column configuration was A-801, 802, 80 manufactured by Showa Denko.
3, 804, 805, 806 and 807 are connected, and the molecular weight distribution is measured using a standard polystyrene resin calibration curve.
The content (M1) of the component having a molecular weight of less than 10,000, the content (M2) of the component having a molecular weight of 10,000 to 50,000 (M2), and the content (M3) of the component having a molecular weight of more than 50,000 are expressed by mass% in terms of the area ratio of the GPC chromatogram. And The lower limit of the molecular weight region of the content (M1) of the component having a molecular weight of less than 10,000 is set to 800 in consideration of noise at the time of measuring the molecular weight.

The THF soluble component of the toner particles is determined by
It is possible to extract the THF-soluble component with a HF Soxhlet extractor, solidify the extract, and separate it.

The content of THF-insoluble matter in the toner particles was determined by weighing about 1 g of the toner (W3 g), placing it in a cylindrical filter paper (for example, No.-86R manufactured by Toyo Filter Paper), passing through a Soxhlet extractor, and using 200 ml of THF as a solvent. After extracting for a period of time and evaporating the soluble component extracted with the THF solvent, vacuum drying is performed at 100 ° C. for several hours, and the mass (W4 g) of the THF soluble resin component is weighed. The mass of components other than the binder resin component such as the colorant and the wax in the toner is measured in advance, and is set to W5 g. The THF-insoluble content is obtained from the following equation.

THF insoluble matter (% by mass) = 100 × (W3
− (W5 + W4)) / (W3-W5)

Further, THF having a molecular weight of less than 10,000 of the toner is used.
Content of the vinyl polymer unit in the soluble component Wa
(% By mass) and the content Wb (% by mass) of a vinyl polymer unit in 10,000 or more THF-soluble components preferably satisfy | Wa−Wb | <20.

By satisfying | Wa−Wb | <20,
The difference in the content of the vinyl polymer unit contained in the low molecular weight side and the high molecular weight side is not so large, and as a result, the compatibility between the low molecular weight side and the high molecular weight side is improved, and the kneading share is required when producing a toner. Is uniformly applied, the dispersibility of the azo iron compound in the toner is improved, and the developability is improved even in long-term durability.

The content Wa (% by mass) of the vinyl polymer unit in the THF-soluble component having a molecular weight of less than 10,000 of the toner and the content Wb (%) of the vinyl polymer unit in the THF-soluble component having a molecular weight of 10,000 or more were obtained. The mass% is 0 <Wa (mass%) <50 and 0 <Wb (mass%) <3
0 is preferably satisfied.

When the molecular weight of the toner is less than 10,000, the cross-linking component is small and the viscosity is low as described above. Dispersion of the toner additive material is likely to be poor. Therefore, the molecular weight of the toner is 1
Less than 10,000 vinyl polymer unit content Wa (% by mass)
Satisfying 0 <Wa (mass%) <50, the viscosity of the toner having a molecular weight of less than 10,000 is increased, and the dispersibility of the azo iron compound is further improved. Further, if the toner does not have a vinyl polymer unit having a molecular weight of 10,000 or more, the compatibility between the low molecular weight side and the high molecular weight side deteriorates. Therefore, in order to improve the compatibility between the low molecular weight side and the high molecular weight side, THF
Content Wb of vinyl polymer unit in soluble component
(% By mass) preferably satisfies 0 <Wb (% by mass) <30.

(Preparation of each molecular weight component)
The fractionation of each molecular weight component of the binder resin can be obtained by the following method.

"Apparatus configuration" LC-908 (manufactured by Nippon Kagaku Kogyo Co., Ltd.) JRS-86 (company: repeat injector) JAR-2 (company: autosampler) FC-201 (Gilson; hula cushion collector) "Column configuration" JAIGEL-1H to 5H (20mm x 600m in diameter)
m: Preparative column) “Measurement conditions” Temperature: 40 ° C. Solvent: THF Flow rate: 5 ml / min Detector: RI In the sample, additives other than the polymer component are previously separated. As a fractionation method, a solvent time at which the molecular weight reaches 10,000 is measured in advance, and a sample is fractionated before and after that. The solvent is removed from the fractionated sample to obtain a sample for composition analysis of a component having a trivalent or higher polycarboxylic acid.

"Composition Analysis of Binder Resin" The sample obtained by the above-mentioned preparative column was treated with 6 mol / liter of NaO
After hydrolyzing with H, adjusting the pH to 5 to 6, and extracting with ether, each sample is methylated, the polyvalent carboxylic acid is identified by GC / MS, and the content (mol%) is determined by the peak area value of GC. I asked.

(Measurement of Content Wa, Wb of Vinyl Polymer Unit in Toner) A component having a molecular weight of less than 10,000 and a component having a molecular weight of 10,000 or more are fractionated by the above method. 0.2 to 0.3 g of the sample is weighed, dissolved in 6 mol / liter of NaOH, and hydrolyzed at 180 ° C. for 6 hours. This is extracted with ether, the polyester-based monomer component soluble in the aqueous layer is removed, and the ether layer is collected. Next, methanol was added to the ether layer until the vinyl-based polymer component was precipitated, and the vinyl-based polymer component was collected by filtering the same, and the mass ratio of the vinyl-based polymer component in the hybrid resin was determined. .

The toner of the present invention preferably contains a wax so as to have at least one endothermic peak in the differential thermal analysis at 60 ° C. or more and 120 ° C. or less.

The wax used in the present invention has a weight average molecular weight (Mw) and a number average molecular weight (M
It is preferable that the ratio (Mw / Mn) to n) is 1.0 to 2.0 and the molecular weight distribution is extremely sharp.

In the present invention, by using a wax having an extremely sharp molecular weight distribution, the release effect is quickly exhibited, and even more excellent low-temperature offset resistance and high-temperature offset resistance are achieved, while the resistance is further improved. The blocking property does not deteriorate. Further, since the binder resin used in the toner is made of a hybrid resin, these waxes are uniformly dispersed, so that this effect is remarkably exhibited. The use of a sharply soluble wax exerts a mold release effect, and the use of a hybrid resin improves the wax dispersibility, so that both the wax dispersibility and the mold release effect can be achieved.

The molecular weight of the wax is measured under the following conditions. Apparatus: GPC-150C (Waters) Column: GMH-HT 30 cm, 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C Solvent: o-dichlorobenzene (0.1% by mass ionol added) Flow rate: 1.0 ml / min Sample: 0.45 ml of 0.15 mass% wax is injected. The measurement is performed under the above conditions, and the molecular weight of the wax is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Houwink
The molecular weight of the wax is calculated by converting to a polyethylene based on a conversion formula derived from the viscosity formula.

The wax has a number average molecular weight of 200 to 2
000 (more preferably 300 to 1500, still more preferably 350 to 1000), dispersibility in a binder resin, low-temperature offset resistance, high-temperature offset resistance,
It is more preferable in terms of blocking resistance and durability of many sheets.

Examples of the wax include a low-molecular-weight hydrocarbon wax composed of carbon and hydrogen, a long-chain alkyl alcohol wax having an OH group, a long-chain alkyl carboxylic acid wax having a COOH group, and an ester wax.

Examples of the low molecular weight hydrocarbon wax include petroleum waxes such as paraffin wax, microcrystalline wax and petrolactam and derivatives thereof; low molecular weight polyolefin wax such as low molecular weight polyethylene; and polymethylene wax such as Fischer-Tropsch wax. . Since the low molecular weight polyolefin wax usually has a Mw / Mn value of more than 2.0, the Mw / Mn becomes 1.0 to 2.0 and the DS
It is preferable to purify so that the C endothermic main peak is 60 to 120 ° C.

Examples of the long-chain alkyl alcohol wax include a mixture of long-chain alkyl alcohols having 20 to 200 carbon atoms.

As the ester wax, a wax obtained by purifying carnauba wax, a wax obtained by purifying candelilla wax, a long-chain alkyl alcohol having 15 to 45 carbon atoms, and a long-chain alkyl carboxylic acid having 15 to 45 carbon atoms. The toner of the present invention is preferably a low molecular weight hydrocarbon wax having a sharp molecular weight distribution in order to obtain good offset resistance.

The DSC endothermic peaks of the wax and the toner were measured with a differential thermal analyzer (DSC analyzer).
7 (manufactured by PerkinElmer) using ASTM D34
Measure according to 18-82. Measurement sample is 2-10m
Weigh accurately in g range. This was put in an aluminum pan, and an empty aluminum pan was used as a reference. The temperature was raised at a rate of 10 ° C./min between 30 and 160 ° C.
Then, the measurement is performed under normal temperature and normal humidity.

When the toner has at least one endothermic peak in the differential thermal analysis at 60 ° C. or more and 120 ° C. or less, the fixing property can be further improved, and the low-temperature fixing property can be improved.
Both high-temperature offset resistance and blocking resistance can be achieved. When the endothermic peak is below 60 ° C., the blocking resistance deteriorates, and when the endothermic peak exceeds 120 ° C., improvement in low-temperature fixability cannot be expected.

As the colorant used in the present invention, a black colorant that uses carbon black, a magnetic substance, and the following yellow / magenta / cyan colorants as a black colorant is used.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
A compound represented by an azo metal complex, a methine compound or an allylamide compound is used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 97, 109, 1
10, 111, 120, 127, 128, 129, 14
7, 168, 174, 176, 180, 181, 191
Etc. are preferably used.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacdrine compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
44, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254 are particularly preferred.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I.
I. Pigment Blue 1, 7, 15, 15: 1, 15:
2, 15: 3, 15: 4, 60, 62, 66 can be used particularly preferably.

When a magnetic material is used as a black colorant, unlike other colorants, 30 parts by mass with respect to 100 parts by mass of the resin.
Used in an amount of up to 200 parts by mass.

As the magnetic material, there is a metal oxide containing an element of iron, cobalt, nickel, copper, magnesium, manganese, aluminum or silicon. Among them, those containing iron oxide as a main component, such as triiron tetroxide and γ-iron oxide, are preferable. From the viewpoint of controlling the chargeability of the toner, another metal element such as a silicon element or an aluminum element may be contained. These magnetic particles are obtained by BE adsorption using a nitrogen adsorption method.
The T specific surface area is preferably from ² to 30 m ² / g, particularly preferably from ³ to 28 m ² / g, and more preferably the Mohs hardness is from 5 to 7.

The specific surface area was determined by adsorbing nitrogen gas on the sample surface according to the BET method and calculating the specific surface area using the BET multipoint method.

The shape of the magnetic material may be an octahedron, a hexahedron,
There are spherical, needle-like, scale-like, but octahedral, hexahedral, spherical,
An amorphous type having a small anisotropy is preferable for increasing the image density, and a spherical shape is particularly preferable. Further, in order to further increase the image density, a magnetic material containing silicon is particularly preferable.

The average particle size of the magnetic material is 0.05 to
1.0 μm is preferred, and more preferably 0.1 to 0.1 μm.
6 μm, more preferably 0.1 to 0.4 μm.

The average particle size of the magnetic material was measured by taking a transmission electron micrograph of the magnetic powder and arbitrarily selecting 250 particles having a particle size of 0.01 μm or more per 40,000-fold magnification. The Martin diameter (the length of a line segment that bisects the projected area in a fixed direction) in the projected diameter is measured, and is represented by the number average diameter.

The polyester-based monomers constituting the polyester unit contained in the hybrid resin used in the present invention include the following.

The alcohol component monomers include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, , 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
There are hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (A), and diols represented by the following formula (A).

[0075]

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Examples of the acid component monomer include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride or anhydrides or lower alkyl esters thereof; succinic acid, adipic acid, sebacic acid, azelaic acid, etc. Alkyl dicarboxylic acids or their anhydrides or lower alkyl esters thereof, and further having 6 to 18 carbon atoms
And unsaturated anhydrides thereof such as fumaric acid, maleic acid, citraconic acid, itaconic acid, and mesaconic acid, and anhydrides thereof. Examples of the acid component monomer include trivalent or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid.

Further, the acid component monomers include methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid half ester, citraconic acid butyl half ester, methyl itaconate half Half esters of unsaturated dicarboxylic acids such as esters, methyl alkenyl succinate half ester, methyl half fumarate and methyl half mesaconic acid; and unsaturated dicarboxylic acid diesters such as dimethyl maleate and dimethyl fumarate.

In the toner of the present invention, the binder resin is cross-linked by a trivalent or higher polycarboxylic acid. Preferred examples of the crosslinking component include trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and its anhydride, benzophenonetetracarboxylic acid, pentaerythritol, and oxyalkylene ether of novolak type phenol resin.

In the toner of the present invention, the binder resin may be crosslinked with a polyhydric alcohol in addition to the trivalent or higher polycarboxylic acid. Glycerin, pentaerythritol, sorbit, sorbitan,
Further, for example, polyhydric alcohols such as oxyalkylene ether of novolak type phenol resin and the like can be mentioned.

The vinyl monomers constituting the vinyl polymer unit contained in the hybrid resin used in the present invention include the following.

Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-butylstyrene, p-tert-tributylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxy Styrene, p-chlorostyrene, 3,4-dichlorostyrene,
Styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride, odor Vinyl halides such as vinyl chloride and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate and isobutyl methacrylate Α-methylene fats such as n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Monocarboxylic acid esters: methyl acrylate, ethyl acrylate, propyl acrylate / n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid Acrylic esters such as 2-chloroethyl and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl Pyrrole, N-vinylcarbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinyl naphthalenes; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

Further, α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic anhydride; An anhydride of a β-unsaturated acid and a lower fatty acid; monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxy group such as (hydroxy-1-methylhexyl) styrene are exemplified.

Further, methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinate Unsaturated dicarboxylic acid half esters such as methyl acid half ester, methyl fumarate half ester and methyl mesaconate half ester; unsaturated dicarboxylic acid diesters such as dimethyl maleate and dimethyl fumarate; maleic acid, citraconic acid, itaconic acid Unsaturated dicarboxylic acids such as alkenyl succinic acid, fumaric acid and mesaconic acid; unsaturated dicarboxylic acids such as maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydride Carboxylic acid anhydrides can also be used as a vinyl monomer, but when calculating the ratio of the polyester monomer component all Monomani ingredients used to prepare the binder resin in the present invention as a reference,
Only these are calculated as polyester monomer components.

Further, if necessary, the polymer may be crosslinked with a crosslinking monomer as exemplified below.

Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include:
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds In which acrylate is replaced with methacrylate;
Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and diethylene glycol diacrylate. Propylene glycol diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; diacrylate compounds linked by a chain containing an aromatic group and an ether bond include, for example, polyoxyethylene (2)-
2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate are listed. The polyester type diacrylates include, for example, MANDA (Nippon Kayaku).

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and those obtained by replacing the acrylate of the above compound with methacrylate; Triallyl cyanurate and triallyl trimellitate;

These crosslinking agents can be used in an amount of 0.01 to 10.0 parts by mass (more preferably 0.03 to 5 parts by mass) based on 100 parts by mass of the other vinyl monomer component.

In the present invention, the vinyl copolymer component and / or the polyester resin component preferably contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include, for example, phthalic acid, maleic acid,
Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid or anhydrides thereof are exemplified. Among the monomers constituting the vinyl copolymer component, those which can react with the polyester resin component include those having a carboxyl group or a hydroxy group, acrylic acid or methacrylic acid esters, and the like.

As a method for obtaining a reaction product of a vinyl resin and a polyester resin, either a polymer containing a monomer component capable of reacting with each of the above-mentioned vinyl resins and polyester resins is used. Alternatively, a method obtained by polymerizing both resins is preferable.

Examples of the polymerization initiator used for producing the vinyl copolymer of the present invention include, for example, 2,2′-
Azobisisobutyronitrile, 2,2′-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′azobisisobutyrate,
1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4 -Dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane); methyl ethyl ketone peroxide,
Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide; 2,2-
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α,
α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, otatanyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, di- Isopropyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3- Methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneo Canoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxy isophthalate, t- Butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxy hexahydroterephthalate, di-t-butyl peroxyazelate are exemplified.

As the initiator used for producing the vinyl polymer unit used in the present invention, a polyfunctional polymerization initiator exemplified below may be used alone or in combination with a monofunctional polymerization initiator. May be.

Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-
3,3,3-trimethylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene,
2,5-dimethyl-2,5- (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxydichlorohexane, 2-di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyase , Di-tert-butylperoxytrimethyl adipate, 2,2-bis- (4,4-di-tert-butylperoxycyclohexyl) propane and 2,2-t
A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as butyl peroxyoctane; and diallyl peroxy dicarbonate, tributyl peroxy maleic acid, t
Polyfunctional polymerization initiator having both a functional group having a polymerization initiation function such as a peroxide group and a polymerizable unsaturated group in one molecule, such as -butylperoxyallyl carbonate and t-butylperoxyisopropyl fumarate Is mentioned.

Of these, more preferred are 1,
1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-t-butylperoxydichlorohexane, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyase And 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.

In the present invention, the binder resin contains a hybrid resin component. The “hybrid resin” means a resin in which at least a part of the polyester resin component and at least a part of the vinyl polymer component are chemically bonded. The chemically bonded polyester resin component side is a polyester unit, and the chemically bonded vinyl polymer component is a vinyl polymer unit.

Specifically, the polymerization includes a vinyl monomer having a polyester unit and a carboxylic acid such as (meth) acrylic acid, or a vinyl monomer having a carboxylic ester group such as (meth) acrylic ester. And a vinyl polymer unit formed by an esterification reaction or a transesterification reaction. As a form of the copolymerization, it is preferable to form a graft copolymer or a block copolymer in which a vinyl polymer unit is used as a trunk polymer and a polyester unit is used as a branch polymer.

Accordingly, in the present invention, the hybrid resin component means that at least a part of the polyester unit and the vinyl-based polymer unit are

[0098]

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Are linked through the

In the present invention, examples of the method for producing a hybrid resin include the following production methods (1) to (7). (1) After separately producing a vinyl polymer and a polyester resin, they are dissolved / swelled in an organic solvent, and an esterification catalyst,
This is a method in which an alcohol is added as required, and an esterification reaction and / or a transesterification reaction is performed by heating, and then the organic solvent is distilled off to produce the compound. Also,
In this step, waxes may be added. (2) This is a method in which a polyester-based monomer is added in the presence of a vinyl-based polymer, and polymerization is carried out to perform an esterification reaction and / or a transesterification reaction with the vinyl-based polymer. At this time, if necessary, a vinyl-based monomer may be further added for polymerization. Also in this case, an organic solvent can be appropriately used. In this step, waxes may be added. (3) A method in which a vinyl-based monomer is added in the presence of a polyester resin to carry out polymerization and an esterification reaction or / and a transesterification reaction. At this time, if necessary, a polyester-based monomer may be added for polymerization. Also in this case, an organic solvent can be appropriately used. In this step, wax may be added. (4) In the presence of a vinyl polymer and a polyester resin,
There is a method in which a vinyl-based monomer and / or a polyester-based monomer are added, and a polymerization and an esterification reaction or / and a transesterification reaction are performed. Also in this case,
Organic solvents can be used. In this step, wax may be added. (5) This is a method in which a vinyl-based monomer and a polyester-based monomer are mixed and subjected to addition polymerization and polycondensation, and esterification and / or transesterification. Also in this case, an organic solvent can be appropriately used. In this step, wax may be added. (6) The resin containing the hybrid resin component produced in the above (1) to (5) is further mixed with a vinyl polymer and / or polyester resin by, for example, dissolving / swelling in an organic solvent. Then, the organic solvent is distilled off to produce. (7) In the presence of the resin containing the hybrid resin component produced in the above (1) to (5), a vinyl-based monomer and / or a polyester-based monomer is further added, and polymerization and esterification reaction and / or esterification are performed. This is a method of producing by an exchange reaction. Further, an organic solvent can be appropriately used. In this step, wax may be added.

In the above methods (1) to (4) and (6), the vinyl polymer and / or polyester resin may be a plurality of polymers having different molecular weights and different degrees of crosslinking.

Among the production methods (1) to (7),
In particular, the production method (3) is preferable in that the molecular weight can be easily controlled, the generation of the hybrid resin component can be controlled, and when a wax is added, the dispersion state can be controlled.

In the present invention, charge stability, developability,
In order to improve the storage stability, it is preferable to externally add an inorganic fine powder such as silica, alumina and titania, or a double oxide thereof. Further, it is preferably silica. For example, as the silica, both a so-called dry method produced by vapor-phase oxidation of a silicon halide and an alkoxide, and a so-called wet silica produced from dry glass and alkoxide called fumed silica and water glass can be used. However, dry silica having few silanol groups on the surface and inside the silica fine powder and having little production residue such as Na ₂ O and SO ₃ ^2- is preferred. In the case of fumed silica, for example, aluminum chloride,
By using another metal halide such as titanium chloride together with a silicon halide, it is possible to obtain a composite fine powder of silica and another metal oxide, and these are also included.

The inorganic fine powder used in the present invention is BET.
The specific surface area by measuring nitrogen adsorption 30 m ² / g or more by law, in particular 50 to 400 m ² / g give good results in the range of, inorganic fine powder with respect to 100 parts by weight of the toner particles 0.1-8 It is preferable to use it by mass, preferably 0.5 to 5 mass parts, more preferably more than 1.0 to 3.0 mass parts.

The inorganic fine powder used in the present invention may be a silicone varnish, if necessary, for the purpose of hydrophobicity and charge control.
Silicone oils, various modified silicone oils, silane coupling agents, silylating agents, other organosilicon compounds,
It is preferable that the treating agent such as an organic titanium compound is used alone or in combination.

The specific surface area was measured according to the BET method by using a specific surface area measuring apparatus, Autosorb 1 (manufactured by Yuasa Ionics) to adsorb nitrogen gas on the sample surface, and calculating the specific surface area by the BET multipoint method.

In order to maintain stable toner storability, the inorganic fine powder is preferably treated with at least silicone oil.

An external additive other than the inorganic fine powder may be added to the toner of the present invention, if necessary.

For example, resin fine particles function as a charge auxiliary agent, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent at the time of hot roll fixing, a lubricant, an abrasive, and the like.

As a method for producing the toner of the present invention,
After sufficiently mixing the above-mentioned toner constituent materials with a ball mill or other mixer, the mixture is kneaded well using a heat kneader such as a hot roll kneader or an extruder, and after cooling and solidifying, mechanically pulverized to obtain a pulverized powder. A method of obtaining a toner by classification is preferable. Another method is a polymerization method in which a predetermined material is mixed with a monomer to constitute a binder resin to form an emulsified suspension and then polymerized to obtain a toner. In the microcapsule toner, a method in which a predetermined material is contained in a core material or a shell material, or both of them; a method in which a constituent material is dispersed in a binder resin solution and then spray-dried to obtain a toner. Further, if necessary, the desired additive and the toner particles are sufficiently mixed by a mixer such as a Henschel mixer to produce the toner of the present invention.

For example, as a mixer, Henschel mixer (manufactured by Mitsui Mining); super mixer (manufactured by Kawata); ribocorn (manufactured by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Ledige mixer (manufactured by Matsubo), and kneading machines include KRC kneader (manufactured by Kurimoto Iron Works); bus co-kneader (manufactured by Buss); TEM Mold extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); knee Decks (manufactured by Mitsui Mining Co., Ltd.); MS-type pressurized kneader, Nidder Ruder (manufactured by Moriyama Seisakusho); And a pulverizer such as a counter jet mill, a micron jet, an inomaizer (manufactured by Hosokawa Micron); an IDS-type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic) and a cross jet mill (Kurimoto Iron Works) Ullmax (Nisso Engineering); SK Jet
O-Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); and Turbo Mill (manufactured by Turbo Kogyo Co., Ltd.). Classifiers include Crasheal, Micron Classifier, and Spedd Classifier (Seishin Enterprise). Turbo Classifier (manufactured by Nissin Engineering); Micron separator, Turboflex (ATP), TSP separator (manufactured by Hosokawa Micron); Elbow jet (manufactured by Nippon Steel Mining), dispersion separator (manufactured by Nippon Pneumatic) YM Microcut (manufactured by Yaskawa Shoji Co., Ltd.). Examples of the sieving apparatus used for sieving coarse particles and the like include Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona Sheep, Gyro Shifter (Tokuju Kosakusho Mori) ); Vibrasonic System (Dalton Ltd.); Soni clean (Sintokogio Co., Ltd.), manufactured by Turbo Screener (Turbo Kogyo Co., Ltd.), manufactured by micro-shifter (Makino Mfg. Co., Ltd.); circular vibration sieve, and the like.

[0112]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

(Production Example 1 of Azo Iron Compound) 4-Chloro-2
A monoazo compound synthesized by a general diazotization coupling reaction of -aminophenol and 6-t-octyl-2-naphthol was converted to N, N-dimethylformamide (D
MF) and stirred. Sodium carbonate was added to this solution, the temperature was raised to 70 ° C., iron (II) sulphate heptahydrate was added, and the mixture was reacted for 5 hours. This reaction solution was dispersed in water, purified, filtered, washed with water, and dried to obtain an azo iron compound (I) represented by the following formula.

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(Production example 2 of azo iron compound) 4-chloro-2
A monoazo compound synthesized by a general diazotization coupling reaction of -aminophenol and 6-t-octyl-2-naphthol was converted to N, N-dimethylformamide (D
MF) and stirred. Sodium carbonate was added to this solution, the temperature was raised to 70 ° C., iron (II) sulphate heptahydrate was added, and the mixture was reacted for 5 hours. The reaction solution was dispersed in water and made weakly acidic with dilute hydrochloric acid, and then purified, filtered, washed with water, and dried to obtain an azo iron compound (II) represented by the following formula.

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(Production Example 3 of Azo Iron Compound) An azo iron compound was prepared in the same manner as in Production Example 1 of azo iron compound except that 4-t-butyl-2-aminophenol and 6-t-octyl-2-naphthol were used as raw materials. Using the same method as in Production Example 1, an azo iron compound (III) represented by the following formula was obtained.

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(Production Example 4 of Azo Iron Compound) The same procedure as in Production Example 1 of an azo iron compound was conducted except that 4-t-butyl-2-aminophenol and 2-naphthol were used as raw materials. Using the method, an azo iron compound (IV) represented by the following formula was obtained.

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(Azo-iron compound production example 5) A method similar to the azo-iron compound production example 1 was used, except that 4-methyl-2-aminophenol and 2-naphthol were used as raw materials in the azo iron compound production example 1. As a result, an azo iron compound (V) represented by the following formula was obtained.

[0122]

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(Azo iron compound production example 6) In the azo iron compound production example 1, 2-aminophenol and 2
An azo iron compound (VI) represented by the following formula was obtained in the same manner as in Example 1 for producing an azo iron compound except that -naphthol was used.

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[Binder resin production example 1] BPA-PO (bisphenol A PO adduct (2 mol addition)) 25 mol% BPA-EO (bisphenol A EO adduct (2 mol addition) 25 mol% TPA ( (Terephthalic acid) 16 mol% ・ TMA (trimellitic acid) 24 mol% ・ FA (fumaric acid) 20 mol%
Charge the autoclave together with 0 mmol and equip it with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirrer, and carry out the polycondensation reaction while heating to 210 ° C. under a reduced pressure under a nitrogen atmosphere in a conventional manner. As a result, a polyester resin A was obtained.

Next, 85 parts by mass of the obtained polyester resin and 50 parts by mass of xylene, styrene / 2-ethylhexyl acrylate (mass% of each monomer: 84%)
/ 16) 15 parts by mass of a vinyl monomer mixture and 0.3 parts by mass of dibutyltin oxide as an esterification catalyst were charged into an autoclave, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device were provided. Attach and add under normal pressure while reducing pressure under nitrogen atmosphere.
It was heated to 0 ° C. to dissolve and swell. Under nitrogen atmosphere, t-
1 part by weight of butyl hydroperoxide in xylene 10
The radical initiator solution dissolved in parts by mass was added dropwise over about 30 minutes. The temperature was further maintained for 10 hours to complete the radical polymerization reaction. The pressure was further reduced while heating, and the solvent was removed to obtain a binder resin a containing a hybrid resin component. Table 1 shows the physical properties of the binder resin a.

[Binder Resin Production Example 2] BPA-PO 25 mol% BPA-EO 25 mol% TPA 14 mol% TMA 18 mol% FA 18 mol% The composition of the polyester monomer is as described above, and the binder resin is prepared. Polyester resin B was obtained in the same manner as in Production Example 1. A binder resin b containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 1, except that the polyester resin was 90 parts by mass and the vinyl monomer mixture was 10 parts by mass. Table 1 shows the physical properties of the binder resin b.

[Binder Resin Production Example 3] BPA-PO 29 mol% BPA-EO 23 mol% TPA 14 mol% TMA 12 mol% FA 16 mol% The composition of the polyester-based monomer is as described above, and the binder resin is prepared. Polyester resin C was obtained in the same manner as in Production Example 1. Binder resin c containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1, except that 95 parts by weight of polyester resin C and 5 parts by weight of a vinyl-based monomer mixture were used. Table 1 shows the physical properties of the binder resin c.

[Binder Resin Production Example 6] BPA-PO 31 mol% BPA-EO 19 mol% TPA 19 mol% TMA 6 mol% FA 25 mol% The composition of the polyester-based monomer was as described above, Polyester resin d was obtained in the same manner as in Production Example 1. A binder resin d containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 1, except that the polyester resin was 90 parts by mass and the vinyl monomer mixture was 10 parts by mass. Table 1 shows the physical properties of the binder resin d.

[Binder Resin Production Example 5] BPA-PO 25 mol% BPA-EO 25 mol% TPA 15 mol% FA 35 mol% Similarly, a polyester resin resin was obtained. A binder resin e containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 1, except that the polyester resin was 50 parts by mass and the vinyl monomer mixture was 50 parts by mass. Table 1 shows the physical properties of the binder resin e.

[Binder Resin Production Example 6] BPA-PO 15 mol% BPA-EO 35 mol% TPA 15 mol% TMA 0.1 mol% FA 34.9 mol% The composition of the polyester monomer was as described above. In the same manner as in Binder Resin Production Example 1, a polyester resin was obtained. Binder resin f containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1, except that 95 parts by mass of the polyester resin and 5 parts by mass of the vinyl-based monomer mixture were used. Table 1 shows the physical properties of the binder resin f.

[Binder Resin Production Example 7] BPA-PO 23 mol% BPA-EO 27 mol% TPA 4 mol% TMA 36 mol% FA 10 mol% The composition of the polyester-based monomer was as described above and the binder resin was used. A polyester resin was obtained in the same manner as in Production Example 1. A binder resin g containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 1, except that the polyester resin was 10 parts by mass and the vinyl monomer mixture was 90 parts by mass. Table 1 shows the physical properties of the binder resin g.

[Binder Resin Production Example 8] BPA-PO 28 mol% BPA-EO 22 mol% TPA 5 mol% TMA 30 mol% FA 15 mol% The composition of the polyester-based monomer was as described above, A polyester resin foil was obtained in the same manner as in Production Example 1. A binder resin h containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 1, except that 95 parts by mass of the polyester resin was used and 5 parts by mass of the vinyl monomer mixture. Table 1 shows the physical properties of the binder resin h.

[Binder Resin Production Example 9] BPA-PO 21 mol% BPA-EO 29 mol% TPA 3 mol% TMA 40 mol% FA 7 mol% The composition of the polyester monomer is as described above, and the binder resin is A polyester resin was obtained in the same manner as in Production Example 1. A binder resin i containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 1, except that the polyester resin was 95 parts by mass and the vinyl monomer mixture was 5 parts by mass. Table 1 shows the physical properties of the binder resin i.

<Example 1> Binder resin a 70 parts by mass Binder resin d 30 parts by mass Magnetic body (shape: spherical, average particle size: 0.20 μm) 100 parts by mass Azo iron compound (I) 2 parts by mass ・ Low molecular weight polyethylene (DSC endothermic peak 106.7 ° C., Mw / Mn = 1.08) 2 parts by mass After premixing the above materials with a Henschel mixer, 13
The mixture was melt-kneaded by a twin-screw extruder (PCM-30; Ikegai Iron Works) set at 0 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, then pulverized by a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified using a multi-part classifier utilizing the Coanda effect. Thus, a magnetic toner having a weight average particle size of 7.0 μm was obtained.

To the obtained magnetic toner, dry silica treated with silicone oil and hexamethyldisilazane was used.
2% by mass was added and mixed by a mixer to obtain toner 1.
Table 3 shows the physical properties of Toner 1 thus obtained.

Example 2 30 parts by mass of binder resin a 70 parts by mass of binder resin e 100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm) Azo iron compound (chemical formula II) 2 parts by mass Low-molecular-weight polyethylene (DSC endothermic peak: 106.7 ° C., Mw / Mn = 1.08) 2 parts by mass A toner 2 was obtained using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 2 thus obtained.

Example 3 Binder resin 60 parts by mass Binder resin d 40 parts by mass Magnetic material (shape: spherical, average particle size: 0.20 μm) 100 parts by mass Azo iron compound (chemical formula I) 2 parts by mass Higher alcohol (DSC endothermic peak 99 ° C., Mw / Mn = 1.84) 2 parts by mass Toner 3 was obtained using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 3 thus obtained.

Example 4 40 parts by mass of binder resin e 60 parts by mass of binder resin i 100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm) Azo iron compound (chemical formula III) 2 parts by mass Low-molecular-weight polyethylene wax (DSC endothermic peak: 106.7 ° C., Mw / Mn = 1.08) 4 parts by mass Toner 4 was obtained using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 4 thus obtained.

<Example 5> Binder resin f 50 parts by mass Binder resin g 50 parts by mass Magnetic body (shape: spherical, average particle size: 0.20 μm) 100 parts by mass Azo iron compound (chemical formula IV) 2 parts by mass Low-molecular-weight polypropylene wax (DSC endothermic peak 145 ° C., Mw / Mn = 8.8) 4 parts by mass Toner 5 was obtained using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 5 thus obtained.

Example 6 5 parts by mass of binder resin a 95 parts by mass of binder resin e 100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm) Azo iron compound (chemical formula V 2 parts by mass Low-molecular-weight polypropylene (DSC endothermic peak: 145 ° C., Mw / Mn = 8.8) 4 parts by mass Toner 6 was obtained using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 6 thus obtained.

Example 7 Binder resin f 20 parts by mass Binder resin i 80 parts by mass Magnetic material (shape: spherical, average particle size: 0.20 μm) 100 parts by mass Azo iron compound (chemical formula V) 2 parts by mass Low-molecular-weight polypropylene (DSC endothermic peak 145 ° C., Mw / Mn = 8.8) 4 parts by mass Toner 7 was obtained using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 7 thus obtained.

<Example 8> Binder resin a 60 parts by mass Binder resin f 40 parts by mass Magnetic material (shape: spherical, average particle size: 0.20 μm) 100 parts by mass Azo iron compound (chemical formula I) 2 parts by mass Low-molecular-weight polyethylene (DSC endothermic peak 106.7 ° C., Mw / Mn = 1.08) 2 parts by mass Toner 8 was obtained by using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 8 thus obtained.

Example 9 Binder resin d 100 parts by mass Carbon black 10 parts by mass Azo iron compound (chemical formula V) 2 parts by mass Low molecular weight polyethylene (DSC endothermic peak 126 ° C., Mw / Mn = 1. 5) 2 parts by mass A toner 9 was obtained using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 9 thus obtained.

Example 10 100 parts by mass of binder resin e 10 parts by mass of carbon black 2 parts by mass of azo iron compound (chemical formula V) Low-molecular-weight polypropylene (DSC endothermic peak 145 ° C., Mw / Mn = 8. 8) 4 parts by mass A toner 10 was obtained by using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 10 thus obtained.

<Example 11> Binder resin h 50 parts by mass Binder resin g 50 parts by mass Carbon black 10 parts by mass Azo iron compound (chemical formula V) 2 parts by mass Low molecular weight polypropylene (DSC endothermic peak 145) 4 ° C., Mw / Mn = 8.8) 4 parts by mass A toner 11 was obtained using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 11 thus obtained.

Comparative Example 1 Binder resin d 100 parts by mass Carbon black 10 parts by mass Azo iron compound (chemical formula VI) 2 parts by mass Low molecular weight polyethylene wax (DSC endothermic peak 126 ° C., Mw / Mn = 1) 5.5) 2 parts by mass Toner 12 was obtained using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 12 thus obtained.

Comparative Example 2 Binder resin e 100 parts by mass Carbon black 10 parts by mass Monoazochrome compound (1) (the following structural formula) 2 parts by mass Low molecular weight polypropylene (DSC endothermic peak 145 ° C., Mw / Mn = 8.8) 4 parts by mass A toner 13 was obtained using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 13 thus obtained.

Embedded image

Comparative Example 3 Binder resin h 50 parts by mass Binder resin g 50 parts by mass Carbon black 10 parts by mass Monoazochromium compound (2) (the following structural formula) 2 parts by mass Low-molecular-weight polypropylene ( (DSC endothermic peak: 145 ° C., Mw / Mn = 8.8) 4 parts by mass A toner 14 was obtained by using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 14 thus obtained.

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Embedded image

Table 2 summarizes the constitutions of the toners 1 to 14.

The evaluation method is described below.

[Low-Temperature Fixing Property]
ser Jet 8100 (Hewlett-Packard Company)
The fuser) and remove the toner on the paper
Is 0.6mg / cm ^TwoUnfixed solid black image
Was drawn. Laser Jet 810 removed
0 external fixing device and fixing device temperature control device
I attached. Set the temperature of this external fixing unit to 160 ° C,
Unfixed solid at a process speed of 235 mm / s
The black image is passed through and fixed, and a load of 4.9 kPa is applied.
Rate of concentration decrease when rubbing with Dasper (manufactured by Ozu Sangyo)
I asked.

Using the toners 9 to 14, Color La
ser Shot LBP 2160 (manufactured by Canon Inc.)
Was removed, and a halftone of one dot and two spaces was drawn such that the amount of toner on the paper was 0.2 mg / cm ² . Color L removed
An external driving device and a temperature control device of the fixing device were attached to the fixing device of the user Shot LBP 2160. 3. The temperature of the external fixing device is set to 160 ° C., the speed is set to 117 mm / s, and the unfixed solid black image is passed through to fix.
The density reduction rate when a 9 kPa load was applied and rubbed with a Dasper (manufactured by Ozu Sangyo) was determined.

[Offset Resistance] Using toners 1 to 8,
In the same manner as in the evaluation of the low-temperature fixing property, an unfixed solid black image is formed such that the amount of toner on the paper becomes 0.6 mg / cm ^2, and the temperature of the external fixing device is set to 240 ° C.
The speed was set to 235 mm / s, and the unfixed solid black image was passed through and fixed.

Using toners 9 to 14, the amount of applied toner on the paper was set to 0.
An unfixed solid black image of 4 mg / cm ² was drawn, the temperature of the external fixing device was set to 240 ° C., and the speed was set to 117.
mm / s, and an unfixed solid black image was passed through and fixed.

(Rank of Hot Offset) Rank 5: Not generated at all Rank 4: Very slight offset is generated, but practically acceptable Rank 3: Offset which can be easily discriminated visually is generated, but not practical Rank 2: Offset occurrence that is practically problematic Rank 1: Remarkable offset occurrence [Developability] Image evaluation was performed using toners 1 to 8 as Laser Jet 8100 (manufactured by Hewlett-Packard Company) as an image forming apparatus. ; A4 width, 32 sheets / minute)
At 2.5 ° C and 85% RH, images with a printing ratio of 4%
The solid black image density after forming 00 sheets was measured. still,
The image density was measured using "Macbeth reflection density type" (manufactured by Macbeth).

Using the toners 9 to 14, a Color Laser Shot LBP 216 is used as an image forming apparatus.
0 (manufactured by Canon; A4 width, 24 sheets / min)
At 2.5 ° C and 85% RH, images with a printing rate of 4%
The density of the solid black image after zero image formation was measured. The image density was measured using a "Macbeth reflection density type" (manufactured by Macbeth).

[Environmental stability] In the evaluation of developability, toner 1
-8 as an image forming apparatus using Laser Jet
8100 (manufactured by Hewlett-Packard Company; A4 horizontal, 3
(2 sheets / min.), 30000C, 85% RH, 20,000 images with a print rate of 4% were formed, and then allowed to stand for one week to measure the solid black image density at that time. The image density was measured using a "Macbeth reflection density type" (manufactured by Macbeth).

Using the toners 9 to 14, a Color Laser Shot LBP 216 as an image forming apparatus is used.
0 (manufactured by Canon; A4 width, 24 sheets / min)
At 2.5 ° C and 85% RH, images with a printing rate of 4%
After zero images were formed, the images were allowed to stand for one week, and the solid black image density at that time was measured. The image density was measured using a "Macbeth reflection density type" (manufactured by Macbeth).

[Evaluation of Tail] In the evaluation of the developing property, as an image forming apparatus, Laser Je
t 8100 (manufactured by Hewlett-Packard Company; A4 side)
32 sheets / min) at 32.5 ° C. and 85% RH.
After printing 20,000 images at a printing rate of 4%, one pattern was printed in which a 4-dot horizontal line was printed in a 20-dot space, and the number of trailing lines on the line was counted.

Using the toners 9 to 14 and a Color Laser Shot 2160 (manufactured by Canon Inc .; A4 width, 24 sheets / min) as an image forming apparatus, 32.5
After printing 6000 images at a printing rate of 4% at 85 ° C. and 85% RH, one pattern was printed in which a 4-dot horizontal line was printed in a 20-dot space, and the pattern was trailed on the line. Counted the number.

Table 4 shows the evaluation results.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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According to the present invention, a low-temperature fixing property and a high-temperature offset resistance can both be achieved by using a hybrid resin having a vinyl polymer unit and a polyester unit. Further, by using an azo iron compound for a hybrid resin having a vinyl polymer unit and a polyester unit, developability and environmental stability can be achieved.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Yusa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yoshihiro Ogawa 3- 30-2 Shimomaruko, Ota-ku, Tokyo Kia Inside Non-corporation (72) Inventor Hirohide Tanikawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H005 AA01 AA02 CA02 CA08 CA17 CA22 CA25 DA02 DA06 DA10 EA03 EA06 EA07 FA06

Claims (9)

[Claims] 1. A toner containing at least a binder resin, a colorant, a wax and an organometallic compound, wherein the binder resin comprises a hybrid resin having a vinyl polymer unit and a polyester unit, A toner which is an azo iron compound which can be produced from a monoazo compound having at least two alkyl groups and two hydroxyl groups capable of binding to an iron atom, wherein the monoazo compound can be represented by the following formula (a). Embedded image (In the formula, R _{9 to} R ₁₈ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and at least one of R _{9 to} R ₁₈ is an alkyl group.) 2. The azo iron compound according to the following formula (b):
The toner according to claim 1, wherein the toner is represented by (c) or (d). Embedded image (In the formulas (b), (c) and (d), A and B each independently represent o-phenylene or 1,2-naphthylene, and at least one of A and B has one or more alkyl groups. A and B may each further have a halogen atom as a substituent. M is a cation and represents a hydrogen ion, an alkali metal ion, an ammonium ion, or an organic ammonium ion.) 3. The content of trivalent or more polyvalent carboxylic acids or anhydrides thereof in a THF-soluble component having a molecular weight of less than 10,000 of the toner is W1 (mol%), and T is a molecular weight of 10,000 or more.
When the content of the trivalent or higher polycarboxylic acid or its anhydride in the HF-soluble component is W2 (mol%), 0 <W1 (mol%) <30, 0 <W2 (mol%) <
The toner according to claim 1 or 2, wherein 4. The toner according to claim 3, wherein the relationship between W1 and W2 satisfies W2> W1. 5. The toner has a THF insoluble content of 1
In the GPC molecular weight distribution of the THF-soluble component, the content (M1) of the component having a molecular weight of less than 10,000 is 40 to 70% by mass, and the content of the component having a molecular weight of 10,000 to 50,000 (M2). ) Is 25 to 50% by mass, the content of the component having a molecular weight exceeding 50,000 (M3) is 2 to 25% by mass, and M1 ≧
5. The method according to claim 1, wherein M2> M3 is satisfied.
The toner according to any one of the above. 6. The content Wa (% by mass) of a vinyl-based polymer unit having a molecular weight of less than 10,000 in the THF-soluble component of the toner and the content of 10,000 or more vinyl-based polymer units in the THF-soluble component. 6. The toner according to claim 1, wherein the relationship of Wb (% by mass) satisfies | Wa-Wb | <20. 7. The toner according to claim 1, wherein the toner has a DSC endothermic main peak at least at 60 to 120 ° C. 8. The GPC molecular weight distribution of the wax contained in the toner, wherein the ratio (Mw / Mn) of the number average molecular weight (Mn) to the weight average molecular weight (Mw) is 1.0 to 2.0. The toner according to any one of claims 1 to 7, wherein: 9. The toner according to claim 1, wherein the toner contains 30 to 200 parts by mass of a magnetic material as the colorant based on 100 parts by mass of the binder resin.