JP2000047428A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner showing satisfactory low-temperature fixability even in a middle-speed to high-speed machine using a heat roll fixing device or a middle-speed to low-speed machine using pressure heat fixing method by a fixed heater through a heat resisting film, and never causing the contamination of a heating member by offset extending from low temperature to high temperature. SOLUTION: In a toner containing a binder resin a coloring agent, a wax and an organic metal compound, the contact angle of the toner to water is 105 to 130 deg., the binder resin consists of a polyester resin having an acid number of 10 to 40 mgKOH/g, the organic metal compound consists of a complex or salt having aluminum as metal element and an aromatic diol or aromatic polycarboxylic acid coordinated therein the resin component of the toner contains 10 to 40 wt.% of THF insoluble component, and the wax has a main peak in the molecular weight of 300-5000 with a ratio of weight average molecular weight to number average molecular weight of 1.2 to 15.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method utilizing an electrophotographic method, an electrostatic recording method, an electrostatic printing method, a toner jet recording method, or the like.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
Numerous methods are known as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electrostatic charge image on a photoreceptor by various means,
Then, the electrostatic image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper, and then fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a toner image. is there.

Various methods and apparatuses have been developed for fixing the toner image onto a sheet such as paper, which is the above-mentioned final step. The most common method at present is a fixed heat generation through a heat roller or a heat-resistant film. This is a compression heating method using a heater.

In the pressure heating method using a heating roller, the toner image is fixed by passing the surface of the heat roller having a releasing property to the toner and the toner image surface of the sheet to be fixed while pressing the sheet under pressure. Is performed. In this method, since the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. Can be.

[0005] Since the surface of the heating roller and the toner image come into contact with each other in a molten state and under pressure, a part of the toner image adheres to the surface of the fixing roller and is transferred. The offset phenomenon, which stains the sheet, is greatly affected by the fixing speed and the fixing temperature. Generally, when the fixing speed is low, the surface temperature of the heating roller is set relatively low, and when the fixing speed is high, the surface temperature of the heating roller is set relatively high. This is because the amount of heat applied from the heating roller to the toner to fix the toner is made substantially constant regardless of the fixing speed.

Since the toner on the sheet to be fixed forms several toner layers, particularly in a system in which the fixing speed is high and the surface temperature of the heating roller is high, the toner layer in contact with the heating roller includes: When the surface temperature of the heating roller is high because the temperature difference between the lowermost toner layer in contact with the fixing sheet and the lowermost toner layer is large, the toner in the uppermost layer is likely to cause an offset phenomenon, and When the surface temperature is low, the toner in the lowermost layer is not sufficiently melted, so that the toner is not fixed on the sheet to be fixed and a phenomenon of low-temperature offset is likely to occur.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing and anchoring the toner to the sheet to be fixed is usually used. According to this method, the temperature of the heating roller can be reduced to some extent, and the high-temperature offset phenomenon of the uppermost toner layer can be prevented. However, since the shearing force applied to the toner becomes very large, the sheet to be fixed winds around the fixing roller, and a winding offset occurs, or after the separation claw for separating the sheet to be fixed from the fixing roller is separated. Easily appear in the fixed image. Furthermore, because of the high pressure, the line image is crushed or the toner is scattered at the time of fixing, and the image quality of the fixed image is likely to deteriorate.

Conventionally, vinyl resins such as polyester resins and styrene resins have been mainly used as toner resins. Polyester resin has excellent low-temperature fixability, but it is said that it has the disadvantage that offset phenomenon easily occurs at high temperature.To compensate for this defect, the molecular weight of the polyester resin is increased to increase the viscosity. Attempts have been made to improve the elastic properties, but in this case, there is a problem that the low-temperature fixability is impaired, and the pulverizability during the production of the toner is also deteriorated, which is not suitable for making the toner into fine particles. It becomes a binder resin.

Further, vinyl copolymers such as styrene resins are excellent in pulverizability at the time of toner production and high in high molecular weight, so they are excellent in high-temperature offset resistance, but in order to improve low-temperature fixability. However, when the molecular weight is lowered or the glass transition temperature is lowered, there is a problem that the blocking resistance and the developability deteriorate.

[0010] In order to make effective use of the advantages of these two types of resins and to compensate for the drawbacks, some methods of mixing and using these resins have been studied.

For example, Japanese Patent Application Laid-Open No. Sho 54-114245 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl copolymer. However, the compatibility between polyester resin and vinyl copolymer is poor due to the large difference in chemical structure, low-temperature fixability,
It is difficult to satisfy both high-temperature offset resistance and blocking resistance.

Further, it is difficult to uniformly disperse various additives, particularly wax, added during the production of the toner, so that not only the fixing performance of the toner, but also the developability tends to be problematic. This problem is significant for certain toners.

Further, Japanese Patent Application Laid-Open No. 56-116043,
JP-A-58-159546 discloses a toner containing a polymer obtained by polymerizing a monomer in the presence of a polyester resin.

JP-A-58-102246 and JP-A-1-156759 disclose a toner characterized by containing a polymer obtained by polymerizing a vinyl copolymer in the presence of an unsaturated polyester. It has been disclosed.

Japanese Patent Application Laid-Open No. 2-881 is characterized in that a styrene-based resin obtained by copolymerizing a monomer having an acid group and a polyester resin include a polymer in which an ester bond is formed via an acid group of the styrene-based resin. Is disclosed.

JP-A-9-146300 discloses a toner containing a polyester resin having a specific THF-insoluble content as a binder resin and containing a graft-modified polyethylene wax.

Japanese Patent Application Laid-Open No. 9-204071 discloses a toner containing a polyester resin having a specific acid value and a specific molecular weight distribution as a binder resin.

JP-A-9-319142 discloses a toner in which the binder resin is a polyester resin having a specific THF-insoluble content and contains a polyethylene wax having a specific penetration and melt viscosity.

Japanese Patent Application Laid-Open No. 9-146292 discloses a toner containing fine particles of polyalkylene having a specific dynamic friction coefficient, wherein the contact angle of the solid image surface fixed on the OHP sheet is within a specific range. I have.

JP-A-9-244294 discloses a toner containing fine particles of polyalkylene having a specific dynamic friction coefficient, wherein the contact angle of the toner and the dielectric loss tangent of the toner satisfy a specific relationship.

Although these toners improve the fixability to some extent, they are insufficient to prevent the toner from offsetting to a heating roller or a heat-resistant film as a heating member of a fixing device.

[0022]

SUMMARY OF THE INVENTION The present invention provides a toner which has solved the above-mentioned problems.

That is, the object of the present invention is good even for a medium-to-high-speed machine using a hot roll fixing device, or a medium-to-low-speed machine using a press-bonding heat fixing system using a fixed heating heater via a heat-resistant film. An object of the present invention is to provide a toner that exhibits excellent low-temperature fixability and does not cause contamination of a heating member due to offset from low to high temperatures.

An object of the present invention is to provide a low-temperature fixer which exhibits good fixability of a halftone portion even when used in a binder resin of a toner having a reduced particle diameter and an increased content of a colorant (particularly a magnetic substance). An object of the present invention is to provide a toner having excellent properties.

[0025]

According to the present invention, in a toner containing at least a binder resin, a colorant, a wax and an organometallic compound, (a) the toner has a contact angle of 105 to 130 degrees with water, b) the binder resin is a polyester resin having an acid value of 10 to 40 mgKOH / g, (c) the organometallic compound has aluminum as a metal element, and aromatic hydroxycarboxylic acids and aromatic diols as ligands Or a complex or salt coordinating an aromatic polycarboxylic acid, wherein (d) the resin component of the toner has a tetrahydrofuran (THF) insoluble content of 10 to 40;
(E) a wax having a main peak (Mp) at a molecular weight of 300 to 5000 in a chromatogram measured by gel permeation chromatography (GPC), and a ratio of a weight average molecular weight to a number average molecular weight. (Mw / Mn) is 1.2 to 15.

[0026]

According to the study of the present inventors, in order to prevent the fixing member from being contaminated by offset regardless of the heating method of the fixing device, the low-temperature fixing property and the high-temperature offset resistance of the toner are improved. Alone is not sufficient, and it has been found that it is important to improve the releasability of the toner from the fixing member.

Conventionally, improvement of the toner offset phenomenon and improvement of the fixability of the toner have been regarded as the same. However, the improvement of the fixability due to the improvement of the binder resin, the wax contained in the toner and the like is accompanied. Improving the offset in such a way is limited and inadequate.

In the case where the releasability of the fixing member and the cleaning member defined by the contact angle of water or toner is not sufficient, if the releasability of the toner is insufficient, sufficient offset prevention can be achieved at the initial stage of use. Even if the effect can be expected, if used for a long period of time, each member may deteriorate over time, and eventually an offset may occur.

Conventionally, it has been proposed that the binder resin of the toner has an insoluble component in an organic solvent such as THF from the viewpoint of improving the hot offset resistance of the toner. However, even such a toner has deteriorated over time. In some cases, a sufficient offset prevention effect is not exerted on the fixing member and the cleaning member. Further, the toner may contain wax for the purpose of imparting releasability, but aged fixing members,
A large amount of wax needs to be contained in the cleaning member in order to maintain a sufficient offset prevention effect. In this case, the developing property of the toner, that is, a problem such as a decrease in image density and an increase in fog density occurs. Further, it is difficult to control the dispersion state of the wax contained in the toner particles. It will contain a large amount of wax. As a result, the toner on the photoconductor may not be sufficiently cleaned and may remain, resulting in an image defect. When the binder resin is polyester, it is difficult to uniformly disperse the wax because of the high polarity of the polyester. In particular, the non-polar wax such as polyethylene and polypropylene is remarkable.

In order to maintain a sufficient offset prevention effect even for aged and deteriorated fixing members and cleaning members in a toner using polyester as a binder resin, release of the toner specified by a contact angle of the toner with water is required. Needs to be improved.

According to the study of the present inventors, in the toner having the above-mentioned contact angle, the binder resin has a specific acid value, contains a specific organometallic compound as a crosslinking agent, and has a specific peak molecular weight and a specific peak molecular weight. Achieved by containing a structured wax.

In the toner of the present invention, the contact angle of the toner with water may be 105 to 130 degrees, preferably 107 to 127 degrees, and more preferably 110 to 125 degrees. is there. if,
When the contact angle of the toner is less than 105 degrees, it is difficult to maintain a sufficient offset prevention effect on the fixing member and the cleaning member that have been deteriorated in durability, and when the contact angle of the toner exceeds 130 degrees. However, there is a possibility that a problem occurs in developing property of the toner and cleaning property of the toner remaining on the photoconductor, which is not preferable.

The polyester, which is a binder resin of the toner particles of the present invention, forms a complex with the metal element contained in the organometallic compound to form a complex, thereby controlling the dispersion state of the wax.
To 40 mgKOH / g, preferably 12 to 35 mgKOH / g, more preferably 15 to 30 mgKOH / g.
It is a case where it has an acid value of. If the acid value is 10mg KO
When it is less than H / g, the complex formation reaction is insufficient, and when it exceeds 40 mg KOH / g, an excessive complex formation reaction proceeds, and in both cases, it is difficult to control the dispersion state of the wax. Becomes

The polyester does not have to contain a THF-insoluble component before being formed into a toner, but preferably contains 10 to 40% by weight, more preferably 15 to 35% by weight. Things. if,
When the THF-insoluble content exceeds 40% by weight, the THF-insoluble content contained in the toner when the toner is formed may exceed 40% by weight, and the object of the present invention cannot be achieved.

The polyester which is a binder resin of the toner of the present invention has a THF content of less than 1% by weight.
A polyester containing no HF-insoluble component and a polyester containing 10 to 40% by weight of a THF-insoluble component are mixed in a weight ratio of 5/1 to 1/3, preferably in a weight ratio. 4/1 to 1/2, more preferably 3/1 by weight.
It is mixed at a ratio of 1 to 1/1. If the weight ratio of the polyester containing substantially no THF-insoluble component is more than 5/1, uniform dispersion of the wax becomes difficult, and the polyester containing substantially no THF-insoluble component is less than 1/3. In this case, the THF-insoluble content of the binder resin of the toner particles may exceed 40% by weight, which is not preferable.

The toner of the present invention is an organometallic compound which is a complex or salt having aluminum as a metal element and coordinating an aromatic hydroxycarboxylic acid, an aromatic diol or an aromatic polycarboxylic acid as a ligand. Is contained in an amount of 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin, preferably 1 to 8 parts by weight, more preferably 1.5 to 5 parts by weight. It is. If the content is less than 0.5 part by weight, the complex formation reaction with the binder resin is insufficient, and if it exceeds 10 parts by weight, the complex formation reaction becomes excessive. However, it is difficult to control the dispersion state, and this is not preferable.

In the toner of the present invention, the THF-insoluble content contained in the binder resin not only gives the toner a hot offset resistance, but also the melt viscosity of the binder resin in the kneading step at the time of toner production is determined by dispersing the wax. It is also important to control the content, and it is sufficient to contain 10 to 40% by weight.
The content is preferably 12 to 37% by weight, and more preferably 15 to 35% by weight.
If the content is less than 10% by weight, not only the hot offset resistance of the toner is deteriorated, but also the melt viscosity in the kneading step becomes too low, so that the wax is re-agglomerated and the dispersion state can be controlled. When the content is more than 40% by weight, not only low-temperature offset tends to occur, but also a component having a high melt viscosity in the kneading step and a component having a low melt viscosity are mixed, so that the dispersed particle size of the wax becomes wide. The dispersion state cannot be controlled, which is not preferable.

The wax contained in the toner of the present invention comprises:
Mp measured by GPC is 300-5000, ratio (M
(w / Mn) may be 1.2 to 15, preferably 350 to 4500, and the ratio (Mw / Mn) is 1.3 to 10, more preferably 400 to 40.
00, where the ratio (Mw / Mn) is between 1.4 and 8. If Mp is less than 500 and the ratio (Mw / Mn) is 1.
If it is less than 2, the dispersed particle size of the wax in the toner particles becomes too small, the Mp exceeds 5,000, and the ratio (Mw
When (/ Mn) is more than 15, the dispersed particle size becomes too large, and in either case, it is difficult to control the dispersed particle size of the wax, which is not preferable.

The toner of the present invention may contain two or more different waxes, in which case the GPC
Mp measured at 300 to 5000, ratio (Mw / M
n) may be 1.2 to 15, but preferably 35.
0 to 4500, and the ratio (Mw / Mn) is 1.5 to 12, more preferably 400 to 4000,
This is the case where the ratio (Mw / Mn) is 2 to 10. If Mp is less than 500 and the ratio (Mw / Mn) is less than 1.2, Mp is more than 5000 and the ratio (Mw / Mn) is 1
In both cases, when the value exceeds 5, the particle size distribution of the wax in the toner particles is widened, and it is difficult to control, which is not preferable.

The wax contained in the toner of the present invention comprises:
They are selected from hydrocarbon waxes, polyethylene waxes and polypropylene waxes.

The wax contained in the toner of the present invention is:
A wax such as a synthetic hydrocarbon obtained from the distillation residue of a hydrocarbon obtained by the Age method consisting of carbon monoxide and hydrogen or by hydrogenating them is preferred. Further, those obtained by performing separation of hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation, or a separation crystallization method are more preferably used.

The wax contained in the toner of the present invention is:
It has a structure represented by the formula (1).

[0043]

Embedded image In the formula, A represents a hydroxyl group or a carboxyl group;
It represents an integer of 0 to 60, preferably A represents a hydroxyl group, and a represents an integer of 30 to 50.

The wax contained in the toner of the present invention comprises:
In the case of acid-modified polyethylene, 1 to 20 mgK
It has an acid value of OH / g and is obtained by modifying polyethylene with an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride, preferably 2 to 15 mg KOH.
/ G of acid value.

The wax contained in the toner of the present invention is:
1-20 mg when acid-modified polypropylene
Having an acid value of KOH / g and polyethylene as maleic acid,
Modified with an acid monomer selected from at least one of maleic acid half ester and maleic anhydride, preferably 2 to 15 mg KO
H / g.

When two kinds of wax are contained in the toner of the present invention, it is preferable that at least one kind of wax uses the above-mentioned wax.

Preferred combinations of waxes when the toner of the present invention contains two types of waxes are shown in Table 1 below.

[0048]

[Table 1]

The wax contained in the toner of the present invention is
Differential scanning calorimeter (DSC) for toner containing wax
In the DSC curve measured at
° C, preferably has an endothermic main peak in the temperature range of 75 to 135 ° C, more preferably 80 to 13 ° C.
It has an endothermic main peak in the region of 0 ° C. and has an endothermic sub-peak or endothermic shoulder at the same time. If there is an endothermic main peak outside the above temperature range, it is difficult to satisfy all of the low-temperature fixing property, hot offset resistance and blocking resistance.

In the toner of the present invention, the wax is added and dispersed in the toner in the kneading step, but is preferably added in the step of producing the polyester which is the binder resin, and more preferably, the binder resin is insoluble in THF. When a mixture of a polyester containing substantially no component and a polyester containing 2 to 35% by weight of a THF-insoluble component is used,
In the process of producing a polyester containing 2 to 35% by weight of a THF-insoluble component, a wax is added. In this case, uniform dispersion of the wax is further facilitated.

When two or more different waxes are contained in the toner of the present invention, the wax added in the polyester production process is preferably a hydrocarbon wax, a polyethylene polymer, a polypropylene polymer, An acid-modified polypropylene having an acid value of 1 to 20 mgKOH / g and an acid-modified polyethylene having an acid value of 1 to 20 mgKOH / g.

In the toner of the present invention, the carboxylic acid and alcohol constituting the polyester are preferably a divalent carboxylic acid represented by the formulas (2) to (5), or a formula (6).
And at least one of a monovalent carboxylic acid represented by the formula (1) and a monohydric alcohol represented by the formula (7).

[0053]

Embedded image [In the formula, R ₁ represents a linear, branched or cyclic alkyl group or alkenyl group having 14 or more carbon atoms. R ₃ and R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group or alkenyl group having 3 or more carbon atoms, and may be the same substituent, but are not hydrogen atoms at the same time. R ₅ and R ₆ represent a hydrogen atom, a linear, branched or cyclic alkyl group or alkenyl group having 3 or more carbon atoms, and may be the same substituent, but are not hydrogen atoms at the same time. R ₇ and R _{8 each} represent a linear, branched or cyclic alkyl group having 12 or more carbon atoms;
Represents an alkenyl group. n represents an integer of 12 to 40. ]

As the compound represented by the formula (2), for example,

[0055]

Embedded image And the like.

As the compound represented by the formula (3), for example,

[0057]

Embedded image And the like.

As the compound represented by the formula (4), for example,

[0059]

Embedded image

As the compound represented by the formula (5), for example,

[0061]

Embedded image

As the compound represented by the formula (6), for example,

[0063]

Embedded image And the like.

As the compound represented by the formula (7), for example,

[0065]

Embedded image And the like.

Examples of the polyester resin monomer used in the present invention include the following.

Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and (8-
1) a bisphenol derivative represented by the formula:

[0068]

Embedded image

Diols represented by the formula (8-2);

[0070]

Embedded image And the like.

Examples of the acidic component include benzenedicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid and anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid and anhydrides thereof; Succinic acid or its anhydride substituted with an alkyl group of Formulas 6 to 12; fumaric acid, maleic acid, citraconic acid, or dicarboxylic acids such as anhydride, fumaric acid, maleic acid, and maleic anhydride.

In the toner of the present invention, the organometallic compound contained in the toner has aluminum as a metal element and coordinates an aromatic hydroxycarboxylic acid, aromatic diol or aromatic polycarboxylic acid as a ligand. Which are represented by the formulas (9) to (11).

[0073]

Embedded image

In the general formulas (9), (10) and (11), M is an aluminum element, R is hydrogen, an alkyl group,
Aryl group, aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group,
Represents an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a carboxyl group, a halogen, a nitro group, an amino group, or a carbamoyl group, and may be connected to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring. In this case, the ring may have a substituent R, and the substituents R may be the same or different, and C is a monovalent cation, hydrogen, an alkali metal, ammonium, alkyl, 1 represents 1 to 1
And n represents 2, 3 or 4, and m represents 0, 2, or 4. In each complex or salt, the aromatic carboxylic acids and aromatic diols serving as ligands are the same. Or different ones. Also, a mixture of complex compounds having different numbers of n and m may be used. The substituent R is preferably an alkyl group, an alkenyl group, a carboxyl group, or a hydroxyl group from the viewpoint of improving the dispersibility of the complex or the salt in the binder resin or improving the chargeability.

The organometallic compound containing aluminum preferably used in the toner of the present invention is represented by the formula (12)
Can be represented by

[0076]

Embedded image

The chemical structure of these compounds is FAB-
It can be confirmed by analysis means such as MS, NMR and thermobalance. Although those in which 2 to 4 water molecules are coordinated are included, the description of the water molecules is omitted here. In addition, a counter ion having a plurality of types is included, but the description is omitted here.

In the toner of the present invention, a charge control agent may be used if necessary in order to further stabilize the chargeability. The charge control agent is 0.1 to 100 parts by weight of the binder resin.
It is preferred to use 10 parts by weight, preferably 0.2 to 5 parts by weight.

Examples of the charge control agent include the following.

For example, an organic metal complex, a chelate compound and an organic metal salt can be mentioned. Specific examples include a monoazo metal complex; a metal complex or a metal salt of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid compound. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their anhydrides and esters, and phenol derivatives of bisphenol.

The charge controlling agent preferably used in the toner of the present invention is represented by the formula (13) or (14).
An organic compound containing an iron atom represented by

[0082]

Embedded image

[0083]

Embedded image

The compound represented by the formula (15) is preferred.

[0085]

Embedded image

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co, Ni Or a metal such as Al, Co, Cu,
Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like.

Specifically, examples of the magnetic material include iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide ( Y ₃ Fe ₅
O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuFe)
₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), and neodymium iron oxide (NdFe
₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like. The above-mentioned magnetic materials are used alone or in combination of two or more. Particularly preferred magnetic materials are fine powders of triiron tetroxide or gamma-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
μm (more preferably 0.1 to 0.5 μm) and 10K
The magnetic properties upon application of the Oersted are coercive force of 20 to 150 Oersted, saturation magnetization of 50 to 200 emu / g (preferably 50 to 100 emu / g), and residual magnetization of 2 to 20 em.
u / g is preferred.

The magnetic substance 1 was added to 100 parts by weight of the binder resin.
It is preferable to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

In addition to the magnetic substance, carbon black, titanium white and other pigments and / or dyes can be used as the coloring agent. For example, when using the toner of the present invention as a magnetic color toner, as the dye,
C. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I.
I. Acid Blue 9, C.I. I. Acid blue 15,
C. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I.
I. Basic Green 6 and the like. Pigments include mineral fast yellow, navel yellow, naphthol yellow S, Hanza yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange,
Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, First Sky Blue, Indanthrene Blue BC, Pigment Green B, Malachite Green Lake, Final Yellow Green G and the like.

When the toner of the present invention is used as a two-component full-color toner, the following colorants may be used. Examples of the magenta coloring pigment include C.I.
I. Pigment Red 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
17, 18, 19, 21, 22, 23, 30, 31, 3
2,37,38,39,40,41,48,49,5
0, 51, 52, 53, 54, 55, 57, 58, 6
0, 63, 64, 68, 81, 83, 87, 88, 8
9, 90, 112, 114, 122, 123, 163,
202, 206, 207, 209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,1
0, 13, 15, 23, 29, 35 and the like.

Although the above pigments may be used alone,
It is more preferable to improve the sharpness by using a dye and a pigment in combination from the viewpoint of the image quality of a full-color image. Magenta dyes include C.I. I. Solvent Red 1,3,8,2
3,24,25,27,30,49,81,82,8
3,84,100,109,121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8,1
3, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,
2, 9, 12, 13, 14, 15, 17, 18, 22,
23, 24, 27, 29, 32, 34, 35, 36, 3
7, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,
And basic dyes such as 27 and 28.

Examples of the coloring pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula.

[0094]

Embedded image

Examples of yellow color pigments include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, C.I. I. Bat Yellow 1,3,20
And the like.

The amount of the nonmagnetic coloring agent used is 100
0.1 to 60 parts by weight, preferably 0.5 part by weight,
５０50 parts by weight.

A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner to increase the fluidity before and after the addition. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet-process silica and dry-process silica, fine powder titanium oxide, fine powder alumina, a silane coupling agent thereof, There are treated silica, treated titanium oxide, and treated alumina that have been surface-treated with a titanium coupling agent and silicone oil.

Preferred fluidity improvers are fine powders produced by the vapor phase oxidation of silicon halides, and are so-called dry silica or fumed silica. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this production process, it is possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with the silicon halide. They are also included. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used. .

Commercially available silica fine powder produced by the vapor phase oxidation of a silicon halide is, for example, one commercially available under the following trade names.

AEROSIL (Aerosil Japan) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15WAC -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, a treated silica fine powder obtained by subjecting a silica fine powder produced by vapor-phase oxidation of the silicon halide compound to a hydrophobic treatment is more preferable. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The method for imparting hydrophobicity is provided by chemically treating with an organosilicon compound or the like which reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Bromomethyldimethylchlorosilane,
α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each having one to each of the terminal units. Examples include dimethylpolysiloxane containing a hydroxyl group bonded to Si. Further, a silicone oil such as dimethyl silicone oil may be used. These are used alone or as a mixture of two or more.

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. Toner 1
0.01 to 8 parts by weight of the fluidity improver based on 00 parts by weight,
Preferably, 0.1 to 4 parts by weight is used.

To produce the toner of the present invention, a binder resin,
A colorant and / or a magnetic substance, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and are melted, kneaded and kneaded using a hot kneader such as a kneader or an extruder. Then, the resins are mutually dissolved, and the melt-kneaded product is cooled and solidified, and then the solidified product is pulverized, and the pulverized product is classified to obtain the toner of the present invention.

The toner of the present invention preferably has a weight average particle diameter of 3 to 9 μm (more preferably, 3 to 8 μm) in terms of resolution and image density. And heat and pressure.

Further, in the present invention, when the volume average particle diameter (D _V ) of the toner is 2.5 μm or more, a decrease in image density hardly occurs and a sufficient image density is obtained.
When the particle size is 0 μm or less, the volume average particle diameter (D _V ) of the toner is preferably 2.5 to 6.0 μm since the gradation of a halftone image is particularly improved.

Further, the fluidity improver and the toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain a toner having a fluidity improver on the surface of toner particles.

The methods for quantifying the solvent-soluble components of the toner of the present invention and measuring other physical properties are described below.

(1) Tetrahydrofuran (TH) of toner
F) Quantification of Insoluble Components 2 g of the toner is precisely weighed (TW1), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha, Ltd.), and passed through a Soxhlet extractor, and 200 ml of THF is used. Reflux for 10 hours using an oil bath adjusted to about 120 ° C. TH
The component (W1) soluble in F can be quantified by concentrating and drying the THF, followed by vacuum drying at 60 ° C. for 24 hours.
When the THF-insoluble component (W2) of the toner is determined, the THF-insoluble component (T2) other than the binder resin such as a colorant (magnetic substance) is used.
W2) is calculated from the following equation.

[0113]

(Equation 1)

(2) Measurement of Acid Value of Toner The measurement is performed according to the measurement method described in JIS K0070. Measurement device: Automatic potentiometric titrator AT-400 (manufactured by Kyoto Electronics) Calibration of the device: 120 ml of toluene and 30 ml of ethanol
Is used. Measurement temperature: 25 ° C. Sample preparation: 0.5 g of toner (0.3 g for a component soluble in ethyl acetate) was added to 120 ml of toluene, and room temperature (about 2 g) was added.
(5 ° C.) for about 10 hours to dissolve. Further, 30 ml of ethanol is added to make a sample solution.

(3) Measurement of melting point of wax ASTM D3418-8 using a differential scanning calorimeter (DSC measuring apparatus) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In this heating process, an endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained.

The temperature of the endothermic main peak is defined as the melting point of the wax.

(4) Measurement of DSC Curve of Toner The DSC curve in the process of raising the temperature of the toner is measured in the same manner as the measurement of the melting point of the wax.

(5) Glass transition temperature (Tg) of binder resin
ASTM D3418-8 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The sample to be measured is 5 to 20 mg, preferably 10
Weigh the mg precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In the process of raising the temperature, an endothermic peak of a main peak in a temperature range of 40 to 100 ° C. is obtained.

At this time, the intersection between the line of the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg in the present invention.

(6) Measurement of molecular weight distribution of wax Gel permeation chromatography (GPC) measuring device: GPC-150C (Waters) Column: GMH-HT 30 cm 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample injected

Measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Hou
It is calculated by converting to polyethylene using a conversion formula derived from the wink viscosity formula.

(7) Measurement of Molecular Weight Distribution of Binder Resin Raw Material or Binder Resin of Toner The molecular weight of a chromatogram by GPC is measured under the following conditions.

The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) is passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute.
When the sample is a binder resin material, a material obtained by passing the binder resin material through a roll mill (130 ° C., 15 minutes) is used. If the sample is a toner, dissolve the toner in THF
m, and the filtrate is used as a sample.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. 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 count number. As standard polystyrene samples for creating calibration curves,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and at least about 10 standard polystyrene samples are suitable. An RI (refractive index) detector is used as the detector.

In order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ^6, a plurality of commercially available polystyrene gel columns may be used in combination.
rs Co., Ltd. μ-styragel 500, 10 ³ , 1
0 ⁴ 10 ⁵ of combinations and, shodex of Showa Denko Co., Ltd.
KA-801, 802, 803, 804, 805, 8
06,807 are preferred.

(8) Measurement of Contact Angle of Toner Measuring device: FACE contact angle measuring device (manufactured by Kyowa Interface Chemical Co., Ltd.) Measuring temperature: 23 to 25 ° C. Measuring humidity: 40 to 60% relative humidity Sample preparation: about 10 g of toner Is compression molded at a pressure of 200 kgf / cm ² for 2 minutes to have a diameter of 25 mm and a thickness of about 10 mm.
A disc-shaped sample of mm is prepared. This is about 27mm inside diameter
Glass sample bottle (for example, Snap Cup N
o. 30) and apply a pressure of 5 to 10 kgf / cm ² for about 5 to 10 minutes on a hot plate heated to 100 to 120 ° C. through a Teflon sheet. When the toner is softened and melted, it is cooled to room temperature, the glass sample bottle is broken, and the melted and molded product of the toner is taken out.
This is sequentially polished using an abrasive of # 280 → # 800 → # 1500 to obtain a disk-shaped sample having a diameter of 25 mm and a thickness of 5 mm. The surface for measuring the contact angle is finished so as not to be visually damaged. The contact angle was measured five times for each sample using ion-exchanged water or commercially available purified water, and the average value was taken as the toner contact angle.

The particle size distribution of the toner of the present invention is measured using a Coulter Counter TA-II or a Coulter Multisizer (manufactured by Coulter). The electrolyte is 1
A 1% NaCl aqueous solution is prepared using graded sodium chloride. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and a measurement sample is further added to 2-2.
Add 0 mg. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and the number of toner particles having a size of 2 μm or more were measured using the measuring device with a 100 μm aperture as the aperture. The distribution and number distribution were calculated.

Then, the weight-based weight average particle diameter (D ₄ ) determined from the volume distribution according to the present invention was determined.

[0134]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

Production of the polymer of the present invention: (Production Example 1)-5.0 mol of terephthalic acid-3.0 mol of succinic acid derivative represented by the formula (2-3)-2.0 mol of trimellitic anhydride-PO-BPA 7 3.0 mol-EO-BPA 3.0 mol The above polyester monomer was charged into an autoclave together with an esterification catalyst, and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device, and under a nitrogen gas atmosphere, in a conventional manner. The polycondensation reaction was carried out while heating to 210 ° C. in accordance with the above to obtain a low-crosslinked polyester resin composition (1) containing about 1% by weight of a THF-insoluble matter.

(Production Example 2)-2.0 mol of terephthalic acid-3.0 mol of succinic acid derivative represented by the formula (2-3)-4.0 mol of trimellitic anhydride-7.0 mol of PO-BPA-EO-BPA 0 mol The above-mentioned polyester monomer was charged into an autoclave together with an esterification catalyst, and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirrer. A condensation polymerization reaction was performed to obtain a highly crosslinked polyester resin composition (2) containing about 28% by weight of a THF-insoluble component.

(Production Example 3) In Production Example 1, the formula (1)
The same procedure was repeated except that 1 part by weight of an organometallic compound containing aluminum as a metal element represented by 2) was added.
A low crosslinked polyester resin composition (3) containing about 8% by weight of an HF insoluble content was obtained.

(Production Example 4) A low-crosslinked polyester resin composition containing about 6% by weight of a THF-insoluble component was prepared in the same manner as in Production Example 1 except that 5 parts by weight of the wax (3) shown in Table 2 was added. 4) was obtained.

(Production Example 5) A highly crosslinked polyester resin composition (5%) containing about 29% by weight of a THF-insoluble component was prepared in the same manner as in Production Example 2 except that 5 parts by weight of the wax (3) shown in Table 2 was added. ) Got.

(Production Example 6) A highly crosslinked polyester resin composition (6) containing about 32% by weight of a THF-insoluble component was prepared in the same manner as in Production Example 2 except that 5 parts by weight of the wax (4) shown in Table 2 was added. ) Got.

(Production Example 7) A highly crosslinked polyester resin composition (7) containing about 27% by weight of a THF-insoluble component was prepared in the same manner as in Production Example 2 except that 5 parts by weight of the wax (5) shown in Table 2 was added. ) Got.

(Production Example 8) A highly crosslinked polyester resin composition (8%) containing a THF-insoluble content of about 36% by weight was prepared in the same manner except that the following monomers constituting the polyester used in Production Example 2 were used. ) Got. -Terephthalic acid 2.0 mol-Dicarboxylic acid represented by formula (3-3) 1.0 mol-Trimellitic anhydride 5.0 mol-PO-BPA 7.0 mol-EO-BPA 3.0 mol

(Production Example 9) A highly crosslinked polyester resin composition (9) containing about 34% by weight of a THF-insoluble component was prepared in the same manner as in Production Example 8 except that 5 parts by weight of the wax (3) shown in Table 2 was added. ) Got.

(Comparative Production Example 1) A comparative polyester resin composition (1) was obtained in the same manner except that the monomers constituting the polyester used in Production Example 1 were as shown below. -4.0 mol of terephthalic acid-3.0 mol of fumaric acid-2.0 mol of trimellitic anhydride-7.0 mol of PO-BPA-3.0 mol of EO-BPA

(Comparative Production Example 2) The monomers constituting the polyester used in Production Example 2 were as shown below, except that 5 parts by weight of a comparative wax (2) shown in Table 2 was added. Thus, a comparative polyester resin composition (3) was obtained. -Terephthalic acid 2.0 mol-Fumaric acid 2.0 mol-Trimellitic anhydride 4.0 mol-PO-BPA 7.0 mol-EO-BPA 3.0 mol

Example 1 100 parts by weight of low crosslinked polyester resin composition (1) of the present invention 1 part by weight of organometallic compound represented by formula (12) Charge control containing iron represented by formula (15) 2 parts by weight ・ 7 parts by weight of wax (2) ・ 100 parts by weight of magnetic iron oxide (average particle size 0.18 μm, coercive force 10.7 KA / m, residual magnetization 11.2 Am ² / kg, saturation magnetization 81.5 Am ²⁾ / Kg)

The above mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., and the cooled mixture was roughly pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a jet mill, and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average diameter of 6.9 μm.

The THF insoluble content in the resin component of the toner was 19% by weight in terms of the resin composition excluding the amount of the mixed wax. The acid value of the binder resin calculated by excluding the magnetic iron oxide and wax contained in the toner is 29 mg.
KOH / g, and the contact angle of the toner was 107 degrees.

To 100 parts by weight of this magnetic toner, 1.0 part by weight of hydrophobic dry silica (BET = 200 m ² / g) was externally added using a Henschel mixer to obtain a toner. Using this toner, a Canon digital copier G
P-215 (process speed: 105 mm / sec, surf fixing) and Canon copier NP-6250 (process speed: 320 mm / sec, hot roll fixing). When the state of adhesion of the toner to the heating members (heat-resistant film, heating roller, pressure roller) of the container was evaluated, good results were obtained as shown in Table 4.

Further, the fixing devices of GP-215 and NP-6250 were removed, and an external drive device and a temperature control device of the fixing device were attached. When a fixing test was performed with the fixing speed set to be the same as each copying machine and the fixing temperature was changed, good results were obtained as shown in Table 4.

[Examples 2 to 9] In Example 1, Table 3
The toners (3) to (9) of the present invention were obtained by using the binder resin and wax shown in (1). The results of analysis and evaluation performed in the same manner as in Example 1 are shown in Tables 3 and 4.

Comparative Examples 1 and 2 Comparative toners (1) and (2) shown in Table 3 were produced using comparative resins (1) and (2). The results of the analysis and evaluation are shown in Tables 3 and 4.

[0153]

[Table 2]

[0154]

[Table 3]

[0155]

[Table 4]

(Decrease in concentration by GP-215) 150 ° C.
The density reduction rate when a solid black image having an image density of 1.3 to 1.4 is passed through a fixing device set at, and the image is fixed, and a load of 50 g / cm ² is applied and rubbed with a daspar (manufactured by Ozu Sangyo). I asked.

(Rank of low-temperature fixability according to NP-6550) GP-2 except that the set temperature of the fixing unit was set to 180 ° C.
15 was performed under the same conditions as in the fixing test.

(Rank of Hot Offset) Rank 5: Not generated at all Rank 4: Slight offset generated, but practically acceptable Rank 3: Offset generated easily discriminated visually Rank 2: Notable offset generated Rank 1: Paper wraps around rollers

(Rank of toner contamination of the heating member of the fixing device) Rank 5: No toner contamination was found. Rank 4: Slight contamination was found, but practically acceptable. Rank 3: Contamination that could be easily visually discriminated. Rank 2: Remarkable contamination is observed Rank 1: Contaminated toner adheres to the front and back surfaces of paper

[0160]

According to the present invention, the toner can be used for a long time regardless of the heating method of the fixing device because the toner has a sufficient low-temperature fixing property and high-temperature offset resistance and has an improved releasing property from the fixing member. Offset does not occur, and a high-quality image can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tadashi Michigami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yuichi Mizoo 3- 30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Yasuko Shibayama 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H005 AA01 AA06 AB02 CA08 CA13 CA14 CA25 DA01 DA02 DA06 EA03 EA06 EA07 EA10

Claims (27)

[Claims] 1. A toner containing at least a binder resin, a colorant, a wax and an organometallic compound, wherein (a)
The contact angle of the toner to water is 105 to 130 degrees, (b) the binder resin is a polyester resin having an acid value of 10 to 40 mgKOH / g, and (c) the organometallic compound contains aluminum as a metal element. And a complex or salt in which an aromatic hydroxycarboxylic acid, an aromatic diol or an aromatic polycarboxylic acid is coordinated as a ligand, and (d) the resin component of the toner has a tetrahydrofuran (THF) insoluble content of 10 to 40% by weight, (e)
The wax has a main peak (Mp) at a molecular weight of 300 to 5000 in a chromatogram measured by gel permeation chromatography (GPC),
A toner characterized in that the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight is from 1.2 to 15. 2. The toner according to claim 1, wherein the contact angle is 107 to 127 degrees. 3. The toner according to claim 1, wherein the contact angle is 110 to 125 degrees. 4. The binder resin having an acid value of 12 to 35 mg KO.
The toner according to claim 1, wherein the H / g is H / g. 5. The binder resin having an acid value of 15 to 30 mg KO.
The toner according to claim 1, wherein the H / g is H / g. 6. The binder resin has a THF insoluble content of 12 to 37.
The toner according to any one of claims 1 to 5, wherein the toner is contained by weight%. 7. The binder resin has a THF insoluble content of 15 to 35.
The toner according to any one of claims 1 to 5, wherein the toner is contained by weight%. 8. The wax has a main peak at a molecular weight of 350 to 4500 and a ratio (Mw / Mn) of 1.3 to 1
The toner according to claim 1, wherein the value is 0. 9. The wax has a main peak at a molecular weight of 400 to 4000, and has a ratio (Mw / Mn) of 1.4 to 8.
The toner according to any one of claims 1 to 7, wherein 10. The toner according to claim 1, wherein the wax is one of a hydrocarbon wax, a polyethylene polymer and a polypropylene polymer. 11. The toner according to claim 1, wherein the wax has a structure represented by Formula (1). Embedded image (In the formula, A represents a hydroxyl group or a carboxyl group, and a represents an integer of 20 to 60.) 12. Wax is 1 to 20 mgKOH / g
The toner according to any one of claims 1 to 9, wherein the toner is an acid-modified polypropylene having an acid value of: 13. A wax having a concentration of 1 to 20 mg KOH / g.
The toner according to any one of claims 1 to 9, wherein the toner is an acid-modified polyethylene having an acid value of: 14. The wax is a differential scanning calorimeter (DSC).
The toner according to any one of claims 1 to 13, wherein a melting point defined by an endothermic peak temperature at the time of temperature rise measured at 70 to 140 ° C. 15. The wax is a differential scanning calorimeter (DSC).
The toner according to any one of claims 1 to 13, wherein the melting point defined by the endothermic peak temperature at the time of temperature rise measured in (1) is 80 to 135 ° C. 16. The wax is a differential scanning calorimeter (DSC).
The toner according to any one of claims 1 to 13, wherein a melting point defined by an endothermic peak temperature at the time of temperature rise measured at 85 to 130 ° C. 17. A composition containing two different waxes, having a main peak at a molecular weight of 300 to 7000, and a ratio (Mw).
The toner according to claim 1, wherein (/ Mn) is from 1.2 to 15. 18. A wax containing two different waxes, having a main peak at a molecular weight of 350 to 6000, and having a ratio (Mw
The toner according to claim 1, wherein (Mn) is from 1.5 to 12. 19. It contains two different waxes, has a main peak at a molecular weight of 400 to 5000, and has a ratio (Mw
/ Mn) is 2 to 10.
The toner according to 1. 20. The method according to claim 1, wherein the at least one wax is one of a hydrocarbon wax, a polyethylene polymer and a polypropylene polymer.
Or the toner according to any one of 17 to 19. 21. The at least one wax of formula (1)
2. A structure having a structure represented by the following formula:
20. The toner according to any one of 7 to 19 above. Embedded image (In the formula, A represents a hydroxyl group or a carboxyl group, and a represents an integer of 20 to 60.) 22. The method according to claim 19, wherein the at least one wax comprises 1 to 2 waxes.
20. The toner according to claim 1, which is an acid-modified polypropylene having an acid value of 0 mgKOH / g. 23. The method according to claim 1, wherein the at least one wax comprises 1 to 2
20. The toner according to claim 1, which is an acid-modified polyethylene having an acid value of 0 mgKOH / g. 24. The THF-soluble component has a molecular weight of 4000 to 9.
The toner according to claim 1, having a peak at 000. 25. The THF-soluble component has a molecular weight of 4500 to 8
The toner according to claim 1, having a peak at 000. 26. The THF-soluble component has a molecular weight of 5,000 to 7,
The toner according to claim 1, having a peak at 500. 27. The toner according to claim 1, wherein at least one type of wax is added during the production of the binder resin.