JP2002055485A - Toner and method for forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which improves low temperature fixing property, transparency in an OHP image as well as high temperature offset resistance and which gives stable high quality images. SOLUTION: The toner contains toner particles having a binder resin, coloring agent, organic metal compound and wax, and external additives. The wax shows the maximum endothermic peak at 81 to 130 deg.C in the temperature range from 30 to 160 deg.C of the DSC endothermic curve with 2 to 15 deg.C harf-width of the maximum endothermic peak. The binder resin component essentially comprises polyester resin. The toner shows 100 to 100,000 dN/m2 dynamic elastic modulus at 140 deg.C and 0.05 to 50 ratio of the dynamic elastic modulus at 140 deg.C to that at 170 deg.C. In the Soxhlet extraction of the toner by using tetrahydrofuran(THF) as the solvent, the TFT insoluble content (A) of the binder resin in the period from the start of extraction to 8 hours after starting is 10 to 20 mass%, the TFT insoluble content (B) after 24 hours is 1 to 10 mass %, and the ratio of A to B ranges from 0.1 to 0.8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used for developing an electrostatic image formed in an image forming method such as an electrophotographic method, an electrostatic recording method, and an electrostatic printing method, and an image forming method.

[0002]

2. Description of the Related Art In a full-color copying machine proposed in recent years, an electrostatic charge image formed on each photoreceptor by using four photoreceptors and a belt-like transfer member is cyan toner,
After developing using magenta toner, yellow toner and black toner, the transfer material is transported between the photoreceptor and the belt transfer member and transferred between straight passes, and then a full-color image is formed, or the surface of the transfer member facing the photoreceptor Generally, a method is used in which a transfer material is wound around by a mechanical action such as an electrostatic force or a gripper, and a development-transfer process is performed four times to obtain a full-color image.

[0003] Toners loaded on these full-color copiers need to be sufficiently mixed in the heat and pressure fixing step without increasing color reproducibility and without impairing the transparency of overhead projector (OHP) images. It is.

[0004] A low-molecular weight binder resin having sharp melt properties is preferable for a black toner for a black-and-white copying machine and a toner for a full-color image. However, when a sharp-melting binder resin is usually used, when the toner is melted in the heating and pressurizing fixing step, the self-cohesive force of the binder resin is low, so that a problem tends to occur in the high-temperature offset resistance.

In general black toners for black-and-white copying machines, relatively high-crystalline waxes such as polyethylene waxes and polypropylene waxes are used as a release agent to improve the high-temperature offset resistance during fixing. For example, it is proposed in JP-B-52-3304, JP-B-52-3305, and JP-A-57-52574. However, in the case of full-color image toner, transparency is hindered when projected through OHP due to the high crystallinity of the release agent itself and the difference in refractive index from the material of the OHP sheet, and the projected image has a high saturation. And the brightness becomes lower.

[0006] In order to solve this problem, a method of lowering the crystallinity of wax by using a nucleating material in combination with wax is disclosed in JP-A-4-149559 and JP-A-4-107.
No. 467.

Further, a method using a wax having a low crystallinity is disclosed in JP-A-4-301853 and JP-A-5-6123.
No. 8 has been proposed. As a wax having a relatively high transparency and a low melting point, there is a montan-based wax. The use of a montan-based wax is described in JP-A-1-185660, JP-A-1-185661, and JP-A-1-185.
No. 662, Japanese Patent Application Laid-Open No. 1-185663, and Japanese Patent Application Laid-Open No. 1-238672.

However, these waxes are OH
All of the transparency in P, the low-temperature fixability at the time of heat and pressure fixing, and the high-temperature offset resistance are not sufficiently satisfied. For this reason, in a normal color toner, oil such as silicone oil or fluorine oil is applied to the heat fixing roller without adding a release agent as much as possible to improve the high-temperature offset resistance and O
The transparency in HP is aimed at.

However, in the fixed image obtained as described above, hot offset toner accumulates on the member to which the oil is applied to the fixing roller and the oil application becomes uneven, so that extra oil adheres to the surface of the fixed image. are doing.

In order not to generate oil streaks on the fixed image, it is necessary to supply oil uniformly and quantitatively on the surface of the fixing roller, and the size of the fixing device tends to increase.

[0011] Therefore, there is a long-awaited demand for a toner which suppresses the occurrence of offset in the heating and pressurizing fixing means using a small amount of oil, and which has excellent transparency of a fixed image.

Therefore, Japanese Patent Application Laid-Open No. 8-314300 discloses
Japanese Patent Application Laid-Open No. 8-50368 proposes a toner and an image forming method which do not use a fixing oil by encapsulating a wax by a polymerization suspension method.

However, in these toners, although oil streaks on a fixed image are suppressed, a large amount of wax must be included in the toner, and styrene-
Since a binder containing acrylic as a main component is used, unevenness on the surface of a fixed image is inevitable, and as a result, it is hard to say that the OHP permeability is satisfactory.

At the same time, the image recorded matter using these toners necessarily has a low gloss. Therefore, in a graphic image in which a graph and a character portion are mixed, there is an advantage that a good image without a sense of incongruity can be obtained. In a real image, since the toner after fixing is not sufficiently melted, there is a disadvantage that the color mixing property of the secondary colors is low and the color reproduction range is narrow.

Therefore, in the heat and pressure fixing means using a small amount of oil, a high gloss is achieved by using a polyester having high sharp melt properties as a main binder, the secondary color mixing property is excellent, and the color reproduction range is high. Is wide,
In addition, a toner excellent in OHP permeability has been desired.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner and an image forming method which solve the above-mentioned problems.

An object of the present invention is to provide a toner and an image forming method having a wide color reproduction range because of good transparency in OHP and good color mixing of secondary colors.

An object of the present invention is to provide a toner and an image forming method which are excellent in low-temperature fixing property and high-temperature offset resistance.

An object of the present invention is to provide a toner and an image forming method which have excellent blocking resistance when left in a high-temperature environment.

[0020]

Specifically, the present invention provides:
The toner is a toner having at least a binder resin, a colorant, an organometallic compound, and a wax, and a toner having an external additive.
The maximum endothermic peak in the range from 1 to 160 ° C is 81 to 130 ° C, and the half-value width of the maximum endothermic peak is 2 to 15 ° C.
A ° C., the binder resin component is a main component a polyester resin, the toner has a dynamic elastic modulus at a temperature of 140 ° C. is (G _'140), 100 to 100000dN / m ²
And the dynamic modulus at 140 ° C. (G ′ ₁₄₀ )
The ratio (G ′ ₁₄₀ / G ′ ₁₇₀ ) of the dynamic elastic modulus (G ′ ₁₇₀ ) at a temperature of 170 ° C. is 0.05 to 50, and in Soxhlet extraction of a toner using tetrahydrofuran (THF) as a solvent, The THF-insoluble content A of the binder resin component at 8 hours after the start of extraction is 10 to 20% by mass.
The THF-insoluble content B of the binder resin component at 24 hours from the start of the extraction is 1 to 10% by mass, and the THF is
The ratio (B / A) of the insoluble matter A to the THF insoluble matter B is 0.1
To 0.8.

Further, according to the present invention, an electrostatic image is formed on an electrostatic image holder, and the electrostatic image is developed with toner to form a toner image on the electrostatic image holder. In an image forming method in which a toner image is transferred to a transfer material via an intermediate transfer member or without an intermediate transfer member, and the toner image on the transfer material is heated and pressed, the toner includes a binder resin, A toner having at least a colorant, an organometallic compound and a wax, and a toner having an external additive. The wax has a maximum endothermic peak in a temperature range of 30 to 160 ° C. in a range of 30 to 160 ° C. in a DSC endothermic curve at 81 to 130 ° C. The half width of the maximum endothermic peak is 2 to 15 ° C., the binder resin component is mainly composed of a polyester resin, and the toner has a dynamic elastic modulus (G ′) at a temperature of 140 ° C.
₁₄₀ ) is 100 to 100000 dN / m ² , and the dynamic elastic modulus (G ′ ₁₄₀ ) at a temperature of 140 ° C. and the temperature of 17
The ratio to the dynamic elastic modulus (G ′ ₁₇₀ ) at 0 ° C. (G ′ ₁₄₀ /
G ′ ₁₇₀ ) is 0.05 to 50, and in the Soxhlet extraction of the toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content A of the binder resin component at 8 hours from the start of the extraction is 10 to 20 mass%. %, The THF-insoluble content B of the binder resin component at 24 hours from the start of the extraction is 1 to 10% by mass, and the ratio (B / A) of the THF-insoluble content A to the THF-insoluble content B is 0%. .1 to 0.8
And an image forming method.

The present inventors have proposed that when the constituents of the toner satisfy the above conditions, no oil is used, or
A toner and an image forming method satisfying high gloss, excellent in color mixing of secondary colors, having a wide color reproduction range, and excellent in OHP transparency can be provided in a heat and pressure fixing unit using a small amount of oil. The present invention has been achieved because the knowledge has been obtained.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a toner according to the present invention will be described.

In the present invention, the binder resin of the toner particles is a polyester resin having a carboxyl group,
A polyester resin having a carboxyl group and a molecular skeleton represented by the following formula (1) is preferable.

[0025]

Embedded image [In the formula, x and y are integers of 1 or more, and the average value of x + y is 2 to 4. ]

The polyester resin having a molecular skeleton represented by the formula (1) is liable to form a metal ion cross-linking structure when melt-kneaded with a metal salicylate compound which will be described in detail later. And a toner having a clear minimum value (G′min) can be satisfactorily generated.

For example, in the dynamic elastic modulus curve of the toner similar to the below-described embodiment shown in FIG. 1, the dynamic elastic modulus (G ′ ₁₇₀ ) in the region of 170 ° C. is different from that in the region of 140 ° C. Since the toner has high viscoelasticity at a temperature higher than the elastic modulus (G ' ₁₄₀ ), the toner has extremely high hot offset resistance.

[0028] The present inventors have found that the dynamic elastic modulus at a temperature ₁₄₀ ℃ (G '140) and dynamic elastic modulus at a temperature 170 ° C. (G' ratio of _{170) (G '140 / G} ' 170) However, those having a strong correlation with high-temperature offset resistance and having G ′ ₁₄₀ / G ′ _{170 in} the range of 0.05 to 50 have good transparency in OHP and good color mixing of secondary colors. Therefore, it has been found that a toner and an image forming method having a wide color reproduction range can be provided, and a toner and an image forming method having excellent low-temperature fixability and excellent high-temperature offset resistance can be provided.

When the value of G ′ ₁₄₀ / G ′ ₁₇₀ is less than 0.05, the transparency in OHP is insufficient, and the color mixing range of secondary colors is insufficient, so that the color reproduction range is narrow.

On the other hand, when the value of G ′ ₁₄₀ / G ′ ₁₇₀ exceeds 50, the dynamic elastic modulus of the toner is remarkably reduced as the temperature increases even on the side higher than 140 ° C.

Such a toner is inferior in high-temperature offset resistance and has a narrower fixing temperature range than the toner of the present invention.

Although it is not fully understood why the molecular skeleton represented by the formula (1) specifically interacts with the metal salicylate compound, the flexibility inherent in this molecular chain forms a conformation that is apt to interact. (Molecular configuration interaction) and p
It is considered that the electron donating property of the phenyl group having an electron donating property at the position and the π electron donating interaction of —CH ＝ CR— are closely related.

The crosslinked metal ion structure of the toner of the present invention appears in the Soxhlet extraction of the tetrahydrofuran (THF) -insoluble portion with the extraction time.

The THF-insoluble content A of the binder resin component at 8 hours after the start of extraction is 10 to 20% by mass, and the THF-insoluble content B of the binder resin component at 1 hour after the start of extraction is 1 to 10% by mass. And THF insolubles A and TH
The binder resin according to the present invention, which has a ratio (B / A) to the F-insoluble component B of 0.1 to 0.8, has a softness such that the crosslinked structure is loosened by the solvation energy of THF. It is important that a proper crosslinked structure is formed. The present inventors have determined that the T of the binder resin component at 24 hours from the start of the extraction.
It was found that the correlation between the HF insoluble matter B and the THF insoluble matter A at 8 hours was related to the fixing performance.

When the ratio (B / A) of the THF-insoluble component A to the THF-insoluble component B is in the range of 0.1 to 0.8, the high temperature offset resistance, the glossiness of the fixing surface, the low temperature fixing property, etc. When (B / A) is less than 0.1, the cross-linked structure is too weak and the high-temperature offset resistance is insufficient. The glossiness of the surface is low, and the translucency of OHP tends to deteriorate.

In order to construct such a metal ion crosslinking structure, it is necessary to prevent the wax according to the present invention from forming a strong and hard ion crosslinking structure, which will be described later.
The present inventors consider that a soft ion-crosslinked structure in the toner of the present invention could be formed.

According to the present invention, in the DSC endothermic curve, the maximum endothermic peak in the temperature range of 30 to 160 ° C. is 81.
A wax having a maximum endothermic peak half-width of 2 to 15 ° C as a release agent in the toner particles.

The following are examples of the wax used in the present invention.

Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; aliphatic hydrocarbon waxes such as oxidized polyethylene wax; blocks of aliphatic hydrocarbon waxes Polymers; waxes mainly containing fatty acid esters such as carnauba wax, sasol wax and montanic acid ester wax; and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax. Further, as a releasing agent, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and vinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, and carnaubyl alcohol Saturated alcohols such as glycerol, seryl alcohol and melisyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide;
Saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N'-dioleyl Unsaturated fatty acid amides such as adipic amide and N, N'-dioleylsebacic amide; aromatic bisamides such as m-xylene bisstearic amide and N, N'-distearyl isophthalic amide; calcium stearate and laurate Fatty acid metal salts such as calcium phosphate, zinc stearate, and magnesium stearate (commonly referred to as metal soaps); graft waxes obtained by grafting a vinyl monomer such as styrene or acrylic acid to an aliphatic hydrocarbon wax Partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable fats and oils; and purification of these by vacuum distillation or fractional crystallization. By making full use of the method, one having a maximum endothermic peak in a temperature range of 30 to 160 ° C. at 81 to 130 ° C. and a half-value width of the maximum endothermic peak of 2 to 15 ° C. is used.

Among these waxes, particularly preferred waxes include aliphatic hydrocarbon waxes such as paraffin wax, waxes mainly containing fatty acid esters such as ester waxes, and saturated fatty acid bisamides.

The wax used in the present invention has a maximum endothermic peak at 81 to 130 ° C. and a half width of the maximum endothermic peak at 2 to 15 ° C. When a wax having a maximum endothermic peak of less than 81 ° C. is used, it is unlikely to be familiar with the fixing oil (silicone oil), or the fixing oil aggregates on the fixed image, and is different from the above-described oil streak due to a defective oil application mechanism. Minute oil unevenness is likely to occur.

As the wax used in the present invention, a wax having a half width of an endothermic peak of 15 ° C. or less is used. 1
If the temperature exceeds 5 ° C., the toner cannot be transferred to the surface of the molten toner quickly at the time of fixing and melting. Particularly in a resin having a structure cross-linked with a metal compound, the transfer speed of the wax becomes slow, so that a sufficient releasing effect, The high-temperature offset resistance cannot be satisfied, and the above-mentioned soft metal ion crosslinking is not formed.

The amount of the wax is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 8 parts by mass, per 100 parts by mass of the binder resin. If the amount exceeds 10 parts by mass, the dispersibility of the colorant in the toner is impaired, and sufficient color reproducibility cannot be obtained. On the other hand, if the amount is less than 0.1 part by mass, it is insufficient to prevent a high-temperature offset that cannot be visually judged.

The wax is contained in the binder resin by dissolving the resin in a solvent, increasing the temperature of the resin solution, and adding and mixing while stirring, a method of internally adding the resin in advance at the time of resin synthesis, and a method of mixing at the time of kneading. .

Examples of the dihydric alcohol component for producing the polyester resin according to the present invention 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, bisphenol A hydroxide, and bisphenol derivative represented by formula (2)

[0046]

Embedded image [Wherein, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2
10 to 10. ].

The trihydric or higher alcohol component for forming the non-linear polyester resin includes, for example, sorbitol, 1,2,3,6-hexanetetrol,
1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,2
4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2
-Methyl-1,2,4-butanetriol, trimethylolethane, trimetrolpropane, 1,3,5-trihydroxybenzene. The amount of trihydric or higher polyhydric alcohol used is 0.1 to 20 m based on all monomers.
ol% is preferred.

The divalent acid component for producing the polyester resin includes, for example, fumaric acid, maleic acid, maleic anhydride, succinic acid, adipic acid, sebacic acid, malonic acid and those having 8 to 14 carbon atoms. Aliphatic acid component monomers substituted by 22 saturated or unsaturated hydrocarbon groups; and phthalic acid,
Examples include isophthalic acid, phthalic anhydride, terephthalic acid and ester derivatives thereof.

The trivalent or higher polyvalent carboxylic acid component for forming the non-linear polyester resin includes, for example, 1,2,4-benzenetricarboxylic acid, 1,2,5
-Benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof. The use amount of the trivalent or higher polyvalent carboxylic acid component is preferably 0.1 to 20 mol% based on all monomers.

In the present invention, the glass transition temperature of the polyester resin is preferably from 50 to 75 ° C., more preferably from 54 to 75 ° C.
The temperature is preferably 67 ° C. The glass transition temperature of the toner is 50 to 75 ° C., preferably 52 to 70 ° C.
It is good to be ° C.

The glass transition temperature of the polyester resin is 50
° C or the glass transition temperature of the toner is 50
When the temperature is lower than 0 ° C., although the fixing property is excellent, the offset resistance is reduced, and the fixing roller is contaminated and the winding around the fixing roller occurs, which is not preferable. Further, the gloss of the image surface after fixing becomes too high, and the image quality deteriorates, which is not preferable.

The glass transition temperature of the polyester resin is 75
When the glass transition temperature of the toner is higher than 75 ° C. or when the glass transition temperature of the toner is higher than 75 ° C., the fixing property is deteriorated, and the fixing temperature of the copier body must be increased, and the obtained image generally has low gloss. In addition, the color mixing for full-color toner is reduced.

In the present invention, the polyester resin TH
In GPC measurement of F-soluble component, number average molecular weight (Mn)
Is from 1300 to 9500, and the weight average molecular weight (Mw)
And the ratio (Mw / Mn) between the weight average molecular weight (Mw) and Mn of the THF-soluble component of the polyester resin is preferably 2 to 20.

In the GPC measurement of the THF-soluble component of the toner when the toner was converted to a toner, the number average molecular weight (Mn) was 1
Preferably, the weight average molecular weight (Mw) is 3,000 to 200,000, and the ratio of Mw to Mn (Mw / Mn) is 2 to 20.

Number average molecular weight (Mn) of polyester resin
Is less than 1300 or the weight average molecular weight (Mw) is 2
When the number average molecular weight (Mn) of the toner is less than 1500, or when the weight average molecular weight (Mw) is less than 30;
When the value is less than 00, the smoothness of the fixed image surface is high and the appearance of the image is vivid, but the high-temperature offset is liable to occur in the durability, and the long-term storage stability is reduced. There are also concerns about new problems such as fusion of the toner and occurrence of carrier spent due to toner components adhering to the carrier surface. Further, it is difficult to apply a shear during the melt-kneading of the toner raw material during the production of the color toner particles, the dispersibility of the colorant is easily reduced, and therefore, the coloring power of the toner is reduced and the charge amount of the toner is easily changed.

Number average molecular weight (Mn) of polyester resin
Exceeds 9500, the weight average molecular weight (Mw) exceeds 19,000, the number average molecular weight (Mn) of the toner exceeds 10,000, or the weight average molecular weight (Mw) exceeds 200,000. Although it has excellent properties, it is necessary to set the fixing temperature high, and even if the degree of dispersion of the pigment can be controlled, the surface smoothness in the image area is reduced and color reproducibility is likely to be reduced. turn into.

Mw of polyester resin or toner
When / Mn is less than 2, the generally obtained polyester resin has a small molecular weight itself. Therefore, similarly to the case where the molecular weight is small, high-temperature offset development due to durability, long-term storage stability is reduced, and Fusing of the toner and carrier spent tend to occur, and the charge amount of the toner tends to vary.

Mw of polyester resin or toner
When / Mn is more than 20, although the high-temperature offset resistance is excellent, the fixing temperature must be increased, and even if the degree of dispersion of the pigment can be controlled, the surface smoothness in the image area can be controlled. Is reduced, and the color mixing of the secondary colors is reduced, so that the color reproducibility tends to be reduced.

The organic metal compound used in the present invention is an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, and a metal compound of the aromatic carboxylic acid derivative. It is preferably a metal compound, and the metal is preferably a divalent or higher valent metal atom. As divalent metals, Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ ,
Ni ²⁺ , Zn ²⁺ , and Cu ²⁺ are mentioned. As the divalent metal, Zn ²⁺ , Ca ²⁺ , Mg ²⁺ , and Sr ²⁺ are preferable. 3
Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Ni ³⁺
Is raised. Preferred among these metals is A
l ³⁺ and Cr ³⁺ , and particularly preferred is Al ³⁺ .

In the present invention, as the organometallic compound, an aluminum compound of di-tert-butylsalicylic acid is particularly preferred.

For example, the salicylic acid metal compound is prepared by dissolving salicylic acid in an aqueous sodium hydroxide solution, dropping an aqueous solution in which divalent or higher-valent metal atoms are melted into the aqueous sodium hydroxide solution, stirring with heating, and then adjusting the pH of the aqueous solution. Adjust
After cooling to room temperature, a metal compound of aromatic salicylic acid can be synthesized by filtration and washing with water. However, the present invention is not limited to the above synthesis method.

When the organometallic compound is used in an amount of 0.1 to 10% by mass (more preferably 0.5 to 9% by mass) based on the mass of the toner, the initial fluctuation of the charge amount of the toner is small,
It is preferable that the absolute amount of charge required during development is easily obtained, and as a result, there is no decrease in image quality such as fogging or image density reduction.

When the content of the organometallic compound is less than 0.1% by mass (not added at all) on the basis of the mass of the toner, the charge amount at the time of durability becomes unstable, and as a result, the maintenance of the image density is deteriorated. It will be inferior. If the content of the organometallic compound exceeds 10% by mass on the basis of the mass of the toner, on the contrary, charge-up occurs at the time of endurance, resulting in a decrease in image density.

When the toner of the present invention is used as a magnetic toner, the magnetic toner particles include a magnetic substance. In that case, the magnetic material also has a function as a colorant. Examples of the magnetic material include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; Fe, Co, N
i, or these metals and Al, C
o, Cu, Pb, Mg, Ni, Sn, Zn, Sb, B
alloys with metals such as e, Bi, Cd, Ca, Mn, Se, Ti, W and V, and mixtures thereof.

For example, as the magnetic material, triiron tetroxide
(Fe_ThreeO_Four), Iron sesquioxide (γ-Fe _TwoO_Three), Iron oxide
Lead (ZnFe_TwoO_Four), Yttrium iron oxide (Y_ThreeFe_FiveO
₁₂), Cadmium iron oxide (CdFe_TwoO_Four), Iron oxide gado
Linium (Gd_ThreeFe_FiveO₁₂), Copper iron oxide (CuFe
_TwoO_Four), Lead iron oxide (PbFe₁₂O₁₉), Nickel iron oxide
(NiFe_TwoO_Four), Iron neodymium oxide (NdFe_TwoO_Three),
Barium oxide (BaFe)₁₂O₁₉), Iron oxide magnesium
(MgFe_TwoO_Four), Iron manganese oxide (MnFe)
_TwoO_Four), Iron oxide lanthanum (LaFeO)_Three), Iron powder (F
e), cobalt powder (Co), nickel powder (Ni), etc.
I can do it. Preferred magnetic materials are ferric oxide, magnetic ferrite
Or fine powder of γ-iron sesquioxide.

The magnetic material has an average particle size of 0.1 to 2 μm (preferably 0.1 to 0.5 μm) and 796 kA / m (10
k Oersted) and the coercive force is 1.6 to 12
kA / m (20-150 Oe), saturation magnetization 50
~200Am ² / kg (preferably 50~100Am ² /
kg), and those having a residual magnetization of ^{2 to 20} Am ² / kg are preferable.

When the magnetic material is used as a magnetic one-component developer that is carried on a developer carrying member containing a magnet with a magnetic binding force, the magnetic material is 5 parts by mass based on the toner mass.
Preferably, it is contained in an amount of about 120% by mass.

When used as a system non-magnetic one-component developer which is carried on a developer carrying member having no magnet without a magnetic restraining force, the magnetic material is used in an amount of 0.1% based on the mass of the toner. It is preferable to contain 1 to 5% by mass.

When the content is within this range, the toner scattering phenomenon (dirt in the machine) at the time of durability can be suppressed.

When the content of the magnetic substance is 5 based on the mass of the toner,
If the amount is more than 5% by mass, the surface of the regulating blade or the roller carrying the toner will be significantly damaged (cut), causing poor charging.

When used as a two-component developer by being mixed with magnetic carrier particles, the magnetic material preferably contains 0.1 to 5% by mass based on the mass of the toner.

When the content is within this range, the magnetic binding force with the roller carrying the developer is increased, so that the toner scattering phenomenon (dirt in the machine) at the time of durability can be suppressed.

When the content of the magnetic substance is 5 based on the mass of the toner,
If the amount is more than 10% by mass, the magnetic binding force with the roller carrying the developer is excessively increased, which causes a decrease in image density.

As the colorant used in the present invention, pigments and / or dyes can be used.

For example, dyes include C.I. 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. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. 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.

Examples of pigments include mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G,
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, chrome green, pigment green B, malachite green lake, final yellow green G and the like.

When used as a full-color image forming toner, the magenta coloring pigment may be 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, 144,
163, 184, 202, 206, 207, 209, 2
21, 238, 254, 269, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1, 2, 10,
13, 15, 23, 29, 35 and the like.

Although such a pigment 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,
23, 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; 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. Acid Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment obtained by substituting 1 to 5 phthalimidomethyl groups in a phthalocyanine skeleton.

The coloring pigments for yellow include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5,73,83,93,97,180, C.I. I. Bat Yellow 1, 3, 20 and the like.

The colorant is used in an amount of 1 to 15 parts by weight, preferably 3 to 12 parts by weight, more preferably 4 to 10 parts by weight, based on 100 parts by weight of the binder resin.

When the content of the coloring agent is more than 15 parts by mass, the transparency is lowered, and the reproducibility of an intermediate color typified by human skin color is also easily lowered. The stability of the properties is reduced, and it becomes difficult to obtain a desired charge amount.

When the content of the coloring agent is less than 1 part by mass, it is difficult to obtain a desired coloring power, and it is difficult to obtain a high quality image having a high image density.

It is preferable that a fluidity improver is externally added to the toner particles in order to improve the image quality.

As a fluidity improver, by externally adding to a toner particle, fluidity can be increased before and after addition. For example, fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder such as silica fine powder by a wet method, silica fine powder such as a silica fine powder by a dry method, and a silane coupling agent; Fine powder of treated silica which has been surface-treated with a treating agent such as a titanium coupling agent or silicone oil; fine powder of titanium oxide; fine powder of alumina, fine powder of treated titanium oxide, and fine powder of treated alumina oxide.

The fluidity improver has a specific surface area of 30 m ² / g or more, preferably 5 m ² / g or more, by nitrogen adsorption measured by the BET method.
Those with 0 m ² / g or more give good results. It is preferable to use 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass of the fluidity improver based on 100 parts by mass of the toner particles.

The toner particles are sufficiently mixed with a binder resin, a colorant, an organometallic compound and other optional additives by using a mixer such as a Henschel mixer or a ball mill, and using a heat kneader such as a kneader or an extruder. Melting,
After kneading and kneading, cooling and solidifying the melt-kneaded product, pulverizing the solidified product, and classifying the pulverized product, toner particles having a predetermined average particle size can be produced.

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

In the present invention, the weight average particle diameter (D ₄ ) of the toner is 3.0 to 15.0 μm, preferably 4.
It is preferably from 0 to 12.0 μm.

The weight average particle diameter (D ₄ ) of the toner is 3.0 μm.
If it is less than m, it becomes difficult to stabilize charging, and fog and toner scattering tend to occur in durability.

The weight average particle diameter (D ₄ ) of the toner is 15.0.
When the thickness exceeds μm, the reproducibility of the halftone portion is greatly reduced, and the obtained image becomes a rough image.

Next, a method of forming a full-color image by electrophotography using the toner of the present invention will be described with reference to FIG.

FIG. 3 is a schematic diagram showing an example of an image forming apparatus for forming a full-color image by electrophotography. The image forming apparatus shown in FIG. 3 is used as a full-color copying machine or a full-color printer. In the case of a full-color copying machine, as shown in FIG. 3, a digital color image reader section is provided at an upper portion, and a digital color image printer section is provided at a lower portion.

In the image reader section, the original 30 is placed on an original platen glass 31 and exposed and scanned by an exposure lamp 32 so that a reflected light image from the original 30 is condensed on a full-color sensor 34 by a lens 33, and a color image is formed. Obtain a decomposed image signal. The color-separated image signal is processed by a video processing unit (not shown) through an amplifier circuit (not shown) and sent to a digital image printer unit.

In the image printer section, the photosensitive drum 1, which is an image carrier, has a photosensitive layer having, for example, an organic photoconductor, and is rotatably carried in the direction of the arrow. Around the photosensitive drum 1, a pre-exposure lamp 11, a corona charger 2, a laser exposure optical system 3, a potential sensor 12, four developing devices 4Y, 4C, 4M, 4B of different colors, and a light amount detecting means 13 on the drum , A transfer device 5 and a cleaning device 6 are arranged.

In the laser exposure optical system, an image signal from the reader section is converted into an optical signal for image scan exposure by a laser output section (not shown), and the converted laser light is reflected by the polygon mirror 3a. The light is projected onto the surface of the photosensitive drum 1 via the lens 3b and the mirror 3c.

[0097] The printer unit includes a photosensitive drum 1 for forming an image.
Is rotated in the direction of the arrow, and after the charge is removed by the pre-exposure lamp 11, the photosensitive drum 1 is uniformly negatively charged by the charger 2 to irradiate a light image E for each of the separated colors, and the electrostatic charge is charged on the photosensitive drum 1. Form an image.

Next, a predetermined developing device is operated to develop the electrostatic charge image on the photosensitive drum 1 to form a toner image on the photosensitive drum 1 with toner. Developing units 4Y, 4C, 4M,
4B are eccentric cams 24Y, 24C, 24M,
By the operation of 24B, development is performed by selectively approaching the photosensitive drum 1 in accordance with each separation color.

The transfer device includes a transfer drum 5a, a transfer charger 5b, an attraction charger 5c for electrostatically attracting a transfer material as a recording material and an attraction roller 5g opposed thereto, an inner charger 5d, and an outer charger. It has a charger 5e and a separation charger 5h. The transfer drum 5a is rotatably supported so as to be rotatable, and a transfer sheet 5f, which is a transfer material carrier that supports a transfer material in an opening area of a peripheral surface thereof, is integrally adjusted on a cylinder. A resin film such as a polycarbonate film is used for the transfer sheet 5f.

The transfer material is conveyed from the cassette 7a, 7b or 7c through the transfer sheet conveying system to the transfer drum 5a, and is carried on the transfer drum 5a. The transfer material carried on the transfer drum 5a is repeatedly conveyed to the transfer position facing the photosensitive drum 1 as the transfer drum 5a rotates, and is transferred onto the transfer material by the action of the transfer charger 5b in the process of passing through the transfer position. Is transferred onto the photosensitive drum 1.

The toner image may be transferred directly from the photoreceptor to the transfer material. Alternatively, the toner image on the photoreceptor may be transferred to the intermediate transfer member, and the toner image may be transferred from the intermediate transfer member to the transfer material. good.

The above-described image forming process is performed by using yellow (Y),
By repeating the process for magenta (M), cyan (C), and black (B), a color image in which four color toner images are superimposed on the transfer material on the transfer drum 5 is obtained.

The transfer material on which the toner images of four colors have been transferred in this manner is separated from the transfer drum 5a by the action of the separating claw 8a, the separating push-up roller 8b and the separating charger 5h, and is heated and pressed by the fixing device. 9, where the toner is heated and pressurized and fixed, so that the toner is mixed, colored and fixed on the transfer material, and is fixed to a full-color image. Then, the image is discharged to the tray 10 and the formation of the full-color image is completed. I do.

At this time, the fixing operation speed of the heating / pressing fixing device 9 is set to the process speed of the main body (for example, 220 mm /
sec) later (for example, 55 mm / sec). This is because a sufficient amount of heating must be given to the toner when the unfixed image in which two to four layers of toner are stacked is melted and mixed. The amount is large.

In FIG. 4, a fixing roller 39 serving as a fixing means is, for example, a 2 mm thick RTV (room temperature vulcanization type, JIS-A hardness 2) on a 5 mm thick aluminum core bar 41.
0) A silicone rubber layer 42 and a 50 μm-thick polytetrafluoroethylene (PTFE) layer 43 on the outside thereof.

On the other hand, a pressing roller 40 as a pressing means
Is placed on an aluminum cored bar 44 having a thickness of, for example, 5 mm.
mm RTV silicone rubber layer 45 (rubber hardness JIS-
A hardness 40), 150 μm thick PTFE on the outside
Layers.

In FIG. 4, the outer diameter of both the fixing roller and the pressure roller is 60 mmφ. However, the hardness of the pressure roller is higher than that of the pressure roller. , The paper discharge direction is on the pressure roller side. It is extremely important that the paper ejection direction be on the pressure roller side to prevent the fixing roller from winding around the fixing support when fixing a copy image having a large image area. As a means for setting the paper discharging direction to the pressure roller side, a method of making the hardness difference described above, or a method of making the diameter of the pressure roller smaller than that of the fixing roller,
There is a method in which the set temperature of the pressure roller side is set higher than that of the fixing roller, and a small amount of paper dust is used by evaporating more water on the back side of the fixing paper, that is, the paper surface of the pressure roller side. .

The fixing roller 39 is provided with a halogen heater 46 which is a heat generating means.
At 0, a halogen heater 47 is disposed in the metal core to heat from both sides. Thermistors 48a and 48 in contact with the fixing roller 39 and the pressure roller 40
b, the temperatures of the fixing roller 39 and the pressure roller are detected, and based on the detected temperatures, the control devices 49a and 49b
Controls the halogen heaters 46 and 47, respectively, so that the temperature of the fixing roller 39 and the temperature of the pressure roller 40 are both controlled to be kept at a constant temperature (for example, 160 ° C. ± 10 ° C.). Roller 4
0 is a total pressure of about 390N (4
0 kgf).

In FIG. 4, C is a fixing roller cleaning device using an oil-impregnated paper web, and C1 is a cleaning blade for removing oil and dirt attached to the pressure roller. Oil for paper web impregnation is 5
The use of a silicone oil of 0 to 3000 cs (silicone oils such as dimethyl silicone oil and diphenyl silicone oil) makes it easy to supply a small amount of the applied oil and keeps the quality of the fixed image (particularly uniform). Glossiness, oil marks). When the oil is not applied, it is preferable to remove the cleaning device of C, use paper or a cloth web not impregnated with oil, or use a cleaning blade, a cleaning pad, or a cleaning roller.

The cleaning device C performs cleaning by pressing a nonwoven fabric web 56 made of Nomex (trade name) against the fixing roller 39 with a pressing roller 55.
The web 56 is appropriately wound by a winding device (not shown) so that toner and the like do not accumulate in the contact portion with the fixing roller 39.

Since the toner of the present invention is excellent in low-temperature fixability and high-temperature offset resistance, the amount of the release agent applied can be reduced, and the amount of dirt in the cleaning device is also small.

The toner image of the toner of the present invention is preferably fixed by heating and pressing under a temperature condition of a fixing roller surface temperature of 150 ° C. ± 30 ° C.

The color image formed on the recording sheet is obtained by fixing the color toner image having the toner of the present invention on the recording material sheet by the above image forming process.

The method for measuring the physical properties of the binder resin and the toner particles will be described below.

(1) 0.5 g of a measurement sample of a THF-insoluble component was weighed, and a cylindrical filter paper (eg, No. 86R ) was weighed.
(28 x 10 mm, manufactured by Toyo Roshi Kaisha, Ltd.) and run through a Soxhlet extractor. THF 200ml as solvent
Is extracted at 8 hours and 24 hours, and the insolubles A, B and B / A are calculated.

At this time, the THF extraction cycle is about 4 to 5
The extraction is performed at a reflux rate of once a minute. After completion of the extraction, the cylindrical filter paper is taken out and weighed to obtain an insoluble content of the sample.

FIG. 5 shows an example of a Soxhlet extraction apparatus.

The THF 92 contained in the container 91 is heated and vaporized by the heater 98, and the vaporized THF is led to the cooler 95 through the pipe 97. The cooler 95 includes a cooling water 96.
Is always cooled.

THF cooled and liquefied by the cooler 95
Accumulates in the storage unit having the cylindrical filter paper 93, and when the liquid level of THF becomes higher than the middle tube 94, the THF is discharged from the storage unit to the container 91.

The toner contained in the cylindrical filter paper is extracted by the circulating THF.

(2) Measurement of Dynamic Elastic Modulus of Toner Using a viscoelasticity measuring device (rheometer) RDA-II (manufactured by Rheometrics) under the following conditions, from 60 to 2
The dynamic elastic modulus G ′ is measured in a temperature range of 10 ° C.・ Measurement jig: 7.9m in diameter when elastic modulus is high
A flat circular plate having a diameter of 40 mm is used when the elastic modulus is low. A shallow cup corresponding to the circular plate is used on the actuator side. The gap between the bottom of the shallow cup and the circular plate is about 2 mm.・ Measurement sample: After heating and melting the toner, the diameter is about 8
mm, a cylindrical sample with a height of 2 mm, or a diameter of about 40 mm,
A disk-shaped sample having a height of about 2 mm is molded and used.・ Measurement frequency: 6.28 radians / second ・ Setting of measurement distortion: After setting the initial value to 0.1%, measure in the automatic measurement mode. -Sample extension correction: Adjust in the automatic measurement mode. Measurement temperature: The temperature is increased from 60 to 210 ° C at a rate of 2 ° C per minute.

(3) Measurement of Molecular Weight by GPC The molecular weight of a chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was passed through the column at this temperature at a flow rate of 1 ml per minute as a solvent.
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 mass. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the 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 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.
It is suitable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples. 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.
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, 80
6,807 combinations are preferred.

(4) Maximum heat absorption peak of wax and toner
Click and semi-width of the measured differential thermal analysis measuring apparatus (DSC measuring device), DSC-7
(Perkin Elmer).

The measurement sample 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 this heating process, an endothermic peak of a main peak in a temperature range of 30 to 160 ° C. is obtained.

The half-value width of the maximum endothermic peak is the temperature width at which the peak exists at a half or more of the height from the base line to the peak top of the maximum endothermic peak. The peak does not have to be continuous over half the height in all the half widths. 6 to 8 show specific examples of how to obtain the half width.

(5) Toner particle size or toner particle size distribution
As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.)
Is used. As the electrolyte, about 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON
(Registered trademark) -II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, a surfactant (preferably an alkylbenzene sulfonate) is used as a dispersant in 100 to 150 ml of the electrolytic aqueous solution.
, 0.1 to 5 ml, and the measurement sample is further
Add g. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the volume and the number of toner particles were measured for each channel by the measuring device using an aperture of 100 μm as an aperture. hand,
The volume distribution and the number distribution of the toner are calculated. then,
The weight average particle diameter (D ₄ ) and the volume average particle diameter (D _V ) of the mass-based toner particles or the toner determined from the volume distribution of the toner particles (the median value of each channel is a representative value for each channel) are determined. .

The channels are 2.00 to 2.52
μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm
m; 4.00 to 5.04 μm; 5.04 to 6.35 μm
m; 6.35 to 8.00 μm; 8.00 to 10.08 μm
m; 10.08 to 12.70 μm; 12.70 to 16.
00 μm; 16.00-20.20 μm; 20.20
25.40 μm; 25.40 to 32.00 μm;
13 channels of 40.30 μm are used.

Measurement of Friction Charge Amount FIG. 9 is an explanatory view of an apparatus for measuring the amount of friction charge. First, in a metal measuring container 92 having a 500-mesh screen 93 at the bottom, a mixture of a sample and a carrier whose frictional charge is to be measured, that is, in the case of toner, the mass ratio of toner to carrier is 1:19. , And in the case of an external additive, a mixture of 1:99 in 50 to 100 ml
Place in a polyethylene bottle of the container, shake by hand for about 10 to 40 seconds, and mix the mixture (developer) for about 0.5 to 1.5.
g and a metal lid 94 is formed. Measurement container 9 at this time
2 is referred to as W ₁ (g). Next, in the suction device 91 (at least a portion in contact with the measurement container 92 is an insulator), the pressure is suctioned from the suction port 97 and the air volume control valve 96 is adjusted to adjust the pressure of the vacuum gauge 95 to 250 mmAq. In this state, suction is sufficiently performed, preferably for 2 minutes, to remove the toner by suction. The potential of the electrometer 99 at this time is set to V (volt).
Here, 98 is a capacitor whose capacity is C (mF). In addition, the mass of the whole measurement container after suction is weighed and W
₂ (g). Triboelectric charge of this sample (mC / kg)
Is calculated as shown below.

Amount of triboelectric charge of sample (mC / kg) = C × V
/ (W ₁ -W ₂ ) (However, measurement conditions are 23 ° C. and 60% RH.)

The carrier used for the measurement is a carrier particle having a particle size of 70 to 90 with a 250 mesh pass and 350 mesh on.
A coated ferrite carrier having a mass% is used.

[0135]

EXAMPLES Examples of the toner and the image forming method of the present invention will be described below, but the present invention is not limited to these examples.

Production Example of Polyester Resin : Polyester Resin No. Polyester resin No. 1 as a binder resin The monomer composition ratio used in No. 1 is shown below.

[0137]

Embedded image 20 mol% of a diol component represented by (x + y = 2.0) in the above structure

[0138]

Embedded image In the above structure, the diol component represented by (x + y = 2.1) 31 mol% fumaric acid 20 mol% terephthalic acid 20 mol% trimellitic acid 9 mol% 1 means Tg is 6
0 ° C., GPC of a THF-soluble component, Mn was 3420, Mw was 34000, Mw / Mn
Was 9.9.

Polyester resin No. Polyester resin No. 2 as a binder resin The monomer composition ratio used in No. 1 is shown below.

[0140]

Embedded image 30 mol% of a diol component represented by (x + y = 2.1) in the above structure

[0141]

Embedded image In the above structure, the diol component represented by (x + y = 2.2) 20 mol% fumaric acid 15 mol% terephthalic acid 20 mol% trimellitic acid 15 mol% 2 means Tg is 6
2 ° C., GPC of a THF-soluble component, Mn was 4400, Mw was 74,000, and Mw / Mn
Was 16.8.

Polyester resin No. Polyester resin No. 3 as a binder resin The monomer composition ratio used in No. 1 is shown below.

[0143]

Embedded image 30 mol% of a diol component represented by (x + y = 2.0) in the above structure

[0144]

Embedded image In the above structure, the diol component represented by (x + y = 2.0) 20 mol% fumaric acid 35 mol% terephthalic acid 12 mol% trimellitic acid 3 mol% 3 means Tg is 5
7 ° C., GPC of a THF-soluble component, Mn was 5420, Mw was 18,000, Mw / Mn
Was 3.3.

Polyester resin No. Polyester resin No. 4 as a binder resin The monomer composition ratio used in No. 1 is shown below.

[0146]

Embedded image In the above structure, the diol component represented by (x + y = 2.1) 50 mol% terephthalic acid 40 mol% trimellitic acid 10 mol% 4 means Tg is 6
7.5 ° C., and the GPC
n is 4700, Mw is 198500, Mw
/ Mn was 42.2.

Examples of wax production Paraffin wax, Fischer-Tropsch wax,
The following waxes (shown in Table 1) were purified from polyethylene wax and polypropylene wax by a method such as vacuum distillation and fractional crystallization.

[0148]

[Table 1]

[Production of metal aromatic salicylic acid compound] Synthesis of aromatic aluminum salicylate compound (I) 75.0 g of 3,5-di-tert-butylsalicylic acid
(About 0.3 mol) in an aqueous sodium hydroxide solution (0.6
(mol / liter) and mixed by heating. An aluminum sulfate aqueous solution (0.25 mol
1 / liter) 400 ml was dropped at 10 ml / 10 seconds, and after the drop, the mixture was stirred at about 80 ° C. for 60 minutes to adjust the pH of the solution to pH
= 5.0 and collected by filtration.

The collected white precipitate was washed with water at almost pH =
After washing with water until the mixture became 7, an aromatic aluminum salicylate compound was obtained.

Synthesis of aromatic chromium salicylate compound (I)
A chromium aromatic oxycarboxylate compound was synthesized in a similar manner except that an aqueous solution of chromium sulfate was used in place of the aqueous solution of aluminum sulfate in the synthesis of the aluminum aromatic oxycarboxylate compound.

Aromatic zirconium salicylate compound
Synthesis of (I) An aromatic zirconium aromatic oxycarboxylate compound was synthesized in the same manner as in the synthesis of the aluminum aromatic oxycarboxylate compound, except that the aqueous solution of zirconium sulfate was replaced with an aqueous solution of calcium chloride.

Synthesis of Zinc Aromatic Salicylate Compound (I) A zinc aromatic oxycarboxylate compound was synthesized in the same manner as in the synthesis of an aluminum aromatic oxycarboxylate except that the aqueous solution of aluminum sulfate was replaced with an aqueous solution of zinc sulfate.

Example 1 Binder Resin: Polyester Resin No. 1 100 parts by mass Wax: WAX-A 3 parts by mass Charge control agent: Aromatic salicylic acid Al compound (I) 6 parts by mass Pigment: copper phthalocyanine 4 parts by mass The above materials are sufficiently premixed by a Henschel mixer and biaxially extruded. The mixture was melted and kneaded at an arbitrary barrel temperature using a mill, cooled, roughly crushed by about 1 to 2 mm using a hammer mill, and then finely crushed by a fine crusher by an air jet method. Fine powder and coarse powder were strictly removed from the obtained finely pulverized material at the same time by a multi-division classifier to obtain cyan color toner 1 having a weight average particle size of 7.8 μm as shown in Table 2.

On the other hand, 1.5 mass% of titanium oxide fine particles having a primary particle diameter of 50 nm and surface-treated with isobutyltrimethoxysilane were externally added to the toner particles and mixed.
Was manufactured. The type of binder resin used for cyan toner 1,
Table 2 shows a list of the types and endothermic peaks and half widths of the wax, the type and number of charge control agents, and the barrel setting temperature in the kneader. Table 3 shows the physical properties of the obtained toner.

Cyan toner 1 and magnetic ferrite carrier particles (average particle diameter 50 μm) coated on the surface with a silicone resin
m) was mixed so that the toner concentration became 6% by mass, to obtain a two-component cyan developer 1.

Regarding the evaluation of the fixable temperature range and the color reproduction range caused by the color mixing of the secondary colors, a commercially available plain paper full-color copier (color laser copier CLC700) with the above-described two-component cyan developer removed from the fixing unit is used. , Manufactured by Canon Inc.) and in a monochrome mode under normal temperature and normal humidity (2
(3 ° C., 60%), an unfixed image was output, the fixed image was output while changing the set temperature with a fixing tester having the configuration shown in FIG. 4, and the evaluation was performed by measuring the gloss (gloss).
To evaluate the feasible temperature range, apply 1.0 to
mg / cm ² and evaluated.

Regarding the gloss (gloss) measurement, VG-
Using a 10-type gloss meter (manufactured by Nippon Denshoku), measurement is performed using each solid image used for chromaticity measurement as a sample.

[0159] As a measurement, first, 6 V
Set to. Next, the light projection angle and the light reception angle are each set to 6
Adjust to 0 °.

Using the zero point adjustment and the standard plate, after setting the standard, place the sample image on the sample table,
Perform overlay measurement on the sheet, and read the numerical value shown in the marked part in%. At this time, the S, S / 10 switch SW is set to S, and the angle and sensitivity switch SW is set to 45-60.

A sample having an image density of 1.5 ± 0.1 is used.

The OHP transmittance was measured using a Shimadzu self-recording spectrophotometer UV2200 (manufactured by Shimadzu Corporation), the transmittance of the OHP film alone was taken as 100%, magenta toner: 650 nm, cyan toner: 500 nm yellow For toner: Measure the transmittance at the maximum absorption wavelength at 600 nm.

The blocking resistance of the sample toner was evaluated by leaving it in an oven at 50 ° C. for one week. As the evaluation, the level of cohesiveness was visually determined.

The evaluation criteria for toner cohesion are shown below. A: No aggregates are seen at all, and the flowability is very good. B: Aggregates are not seen at all. C: Some aggregates are seen, but are loosened immediately. E: Aggregates are not sufficiently loosened with the developer stirring device (somewhat bad)

Table 4 shows the results of the fixing test and the results of the OHP permeability and anti-blocking tests.

<Examples 2 and 3> Polyester resin no.
In the same manner as in Example 1 except for polyester resin N, polyester resin N
o. 2, polyester resin no. In place of Example 3, cyan toners 2 and 3 and developers 2 and 3 were prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 2 to 4.

<Examples 4, 5, and 6> Cyan toners 4, 5, and 6 and development were performed in the same manner as in Example 1 except that WAX-B, WAX-C, and WAX-D were used instead of WAX-A. Agents 4, 5, and 6 were prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 2 to 4.

<Examples 7 and 8> The cyan toners 7, 8 and 8 were manufactured in the same manner as in Example 1 except that the charge control agent was changed to 10 parts by mass and 2 parts by mass of the aromatic salicylic acid Al compound (I). Developers 7 and 8 were prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 2 to 4.

<Examples 9 and 10> The charge control agent was changed to the aromatic salicylic acid Al compound (I) by the aromatic oxycarboxylic acid C.
The cyan toners 9 and 10 and the developers 9 and 10 were prepared in the same manner as in Example 1 except that the compound (I) and the aromatic hydroxycarboxylic acid Zr compound (I) were used, and evaluated in the same manner as in Example 1. did. The results are shown in Tables 2 to 4.

<Comparative Example 1> WAX-A was used instead of WAX-A.
A cyan toner 11 and a developer 11 were prepared in the same manner as in Example 1 except that E was used, and evaluated in the same manner as in Example 1. The results are shown in Tables 2 to 4.

In the case of cyan toner 11, high-temperature offset resistance and blocking resistance deteriorate.

<Comparative Example 2> WAX-A was used instead of WAX-A.
A cyan toner 12 and a developer 12 were prepared in the same manner as in Example 1 except that F was used, and evaluated in the same manner as in Example 1. The results are shown in Tables 2 to 4.

In the case of the cyan toner 12, the high-temperature offset resistance and the anti-blocking performance were further deteriorated as compared with Comparative Example 1.

Further, in the case of the cyan toner 12, although the fixing performance is not so badly affected, the color mixture region is reduced due to the decrease in gloss, and as a result, the color reproduction range is also reduced. At the same time, the surface of the toner-fixed image becomes uneven, and the incident light is irregularly reflected.

<Comparative Example 3> Polyester resin no. In place of polyester resin No. 1 4 and use WAX-A
The cyan toner 13 and the developer 13 were prepared in the same manner as in Example 1 except that WAX-E was used in place of the above, and the Zn compound (I) of the aromatic oxycarboxylate was used instead of the Al compound (I) of the aromatic salicylate. Evaluation was performed in the same manner as in Example 1. The results are shown in Tables 2 to 4.

Although the blocking resistance is improved by the higher Tg of the resin, the molecular weight of the toner is increased, so that the gloss is reduced, the color mixture area is reduced, and as a result, the color reproduction range is narrowed.

At the same time, the unevenness of the surface of the toner-fixed image increases, and the incident light is irregularly reflected.
HP permeability also decreases.

<Comparative Example 4> A cyan toner 14 and a developer 14 were prepared in the same manner as in Example 1 except that the aromatic salicylate Al compound (I) added as a charge control agent was not used. Was evaluated. The results are shown in Tables 2 to 4.

Since there is no aromatic salicylic acid Al compound (I), a crosslinking reaction does not occur at the time of kneading, the high-temperature offset resistance is significantly reduced, and the blocking resistance is also deteriorated.

<Comparative Example 5> Polyester resin no. In place of polyester resin No. 1, 4 and WAX-
A cyan toner 15 and a developer 15 were prepared in the same manner as in Example 1 except that A was not used, and evaluated in the same manner as in Example 1. The results are shown in Tables 2 to 4. Since the crosslinking reaction at the time of kneading excessively proceeds and the fixing start temperature and the high temperature offset start temperature increase, the gloss decreases, and the color mixing region is also reduced. As a result, the color reproduction range is narrowed.

At the same time, the surface of the toner-fixed image becomes uneven, and the incident light is irregularly reflected.
HP permeability also decreases.

Comparative Example 6 A cyan toner 16 and a developer 16 were prepared in the same manner as in Example 1 except that the aromatic salicylic acid Al compound (I) and WAX-A added as charge control agents were not used. Evaluation was performed in the same manner as in Example 1. The results are shown in Tables 2 to 4.

When the Al compound of aromatic oxycarboxylic acid is not used, not only does ionic crosslinking not occur during kneading, but also there is no wax releasing effect, so a remarkable high-temperature offset occurs and the blocking resistance of the toner deteriorates. I do.

<Comparative Example 7> Polyester resin no. The TPC is 60 ° C. and the THF-soluble component is GPC.
In the above, Mn is 8000 and Mw is 240,000.
And a styrene-n-butyl acrylate-monobutyl maleate-divinylbenzene copolymer having a Mw / Mn of 30.0 (molar ratio: 75/25/5/1)
A cyan toner 17 and a developer 17 were prepared in the same manner as in Example 1 except that 0) was used, and evaluated in the same manner as in Example 1. The results are shown in Tables 2 to 4.

[0185] Since it is strongly crosslinked with the aromatic Al salicylic acid compound, the molecular weight of the toner becomes high, so that the gloss is reduced and the low-temperature fixability is impaired. The range is also reduced.

At the same time, the surface of the toner-fixed image becomes uneven, and the incident light is irregularly reflected.
HP permeability also decreases.

[0187]

[Table 2]

[0188]

[Table 3]

[0189]

[Table 4]

Example 11 The pigment was copper phthalocyanine;
Magenta Toner 1 and Developer 18 were prepared in the same manner as in Example 1 except that 5 parts by mass of quinacridone was used instead of 5 parts by mass. Copper phthalocyanine; Pigment Yellow 17; 5 was used instead of 5 parts by mass. Yellow toner 1 and developer 1 in the same manner as in Example 1 except that parts by mass were used.
9 was prepared, and a black toner 1 and a developer 20 were prepared in the same manner as in Example 1 except that 5 parts by mass of carbon phthalocyanine was used instead of 5 parts by mass of copper phthalocyanine.

Next, the cyan developer 1 obtained in Example 1
And magenta developer 18, yellow developer 19, and black developer 20 as shown in FIG.
4Y and 4B, and heated and fixed by the heat fixing unit 9 shown in FIG.
A full-color image fixed at 150 ° C. was obtained.

Since the image has a high gloss and a sufficiently wide color reproduction range, it is suitable especially when pictorial expression is required. Further, since the toner after fixing is sufficiently melted, the transparency of OHP is excellent.

Further, under low temperature and low humidity (15 ° C./10% RH)
As shown in Table 5, both the image density and the charge amount of the toner were stable, and the oil trace of the fixing oil and the dirt due to the offset toner of the oil application mechanism were completely observed as shown in Table 5. I couldn't.

Comparative Example 8 The pigment was copper phthalocyanine;
Magenta Toner 2 and Developer 2 in the same manner as in Comparative Example 7 except that quinacridone was used instead of 5 parts by mass.
And yellow toner 2 and developer 22 in the same manner as in Comparative Example 7 except that 5 parts by mass of pigment phthalocyanine were used instead of 5 parts by mass of copper phthalocyanine.
Was prepared, and a black toner 1 and a developer 23 were prepared in the same manner as in Comparative Example 7, except that 5 parts by mass of carbon phthalocyanine was used instead of 5 parts by mass of copper phthalocyanine.

Next, the cyan developer 1 obtained in Comparative Example 7
7, the magenta developer 21, the yellow developer 22,
Developing devices 4C and 4 shown in FIG.
M, 4Y, and 4B, and a full-color image fixed at 200 ° C. (at 150 ° C. because fixing failure occurs at 150 ° C.) was obtained by the heat fixing unit 9 shown in FIG.

Since the image has extremely low gloss and a considerably narrow color reproduction range, it is not suitable particularly when pictorial expression is required. Further, since the toner after fixing is not sufficiently melted, the transparency of OHP is also inferior.

As in Example 11, low temperature and low humidity (15 ° C. /
A continuous copy test of 30,000 sheets was performed at 10% RH). As a result, the image density decreased and the toner charge amount significantly increased. Further, toner scattering in the developing device was noticeable for each color, and fogging also occurred on a white background portion of the image. Oil marks were also remarkable, and there was a large amount of offset toner in the oil application mechanism.

[0198]

[Table 5]

[0199]

By using the toner of the present invention, in addition to improving low-temperature fixability and transparency of OHP images, high-temperature offset resistance is remarkably improved, and toner contamination in a fixing device due to long-term use is suppressed. A high-quality image free from oil unevenness and oil streaks can be stably provided.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a dynamic elastic modulus curve of the toner of the present invention.

FIG. 2 is a diagram illustrating an example of a dynamic elastic modulus curve of a conventional toner.

FIG. 3 is a schematic sectional view showing an example of an image forming apparatus using the toner of the present invention.

FIG. 4 is a schematic explanatory view showing an example of a heating and pressing fixing unit.

FIG. 5 is a schematic diagram showing an example of a Soxhlet extraction device.

FIG. 6 is a diagram showing an example of how to obtain a half width of an endothermic peak.

FIG. 7 is a diagram showing another example of how to obtain a half width of an endothermic peak.

FIG. 8 is a diagram showing another example of how to obtain a half width of an endothermic peak.

FIG. 9 is a schematic diagram of an apparatus for measuring a triboelectric charge amount of a toner.

[Explanation of symbols]

 Reference Signs List 1 photosensitive drum (image carrier) 4 developing device 9 heat-press fixing device

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoyoshi Sugawara 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yojiro Hotta 3-30-2 Shimomaruko 3-chome, Ota-ku, Tokyo Non-corporation F term (reference) 2H005 AA01 AA06 AA08 CA08 CA14 CB07 DA02 EA03 EA06 EA07 EA10

Claims (9)

[Claims] 1. A toner having at least a binder particle, a colorant, an organometallic compound and a wax, and a toner having an external additive, wherein the wax has a maximum at a temperature of 30 to 160 ° C. in a DSC endothermic curve. Endothermic peak 81 to 13
0 ° C., the half width of the maximum endothermic peak is 2 to 15 ° C., the binder resin component is mainly composed of a polyester resin, and the toner has a dynamic elastic modulus (G ′ ₁₄₀ ) at a temperature of 140 ° C. Is 100 to 100000 dN / m ² , and the ratio (G ′ ₁₄₀ / G ′ ₁₇₀ ) of the dynamic elastic modulus (G ′ ₁₄₀ ) at a temperature of ₁₄₀ ° C. to the dynamic elastic modulus (G ′ ₁₇₀ ) at a temperature of 170 ° C. In a Soxhlet extraction of a toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content A of the binder resin component at 8 hours from the start of the extraction is 10 to 20% by mass, The THF-insoluble content B of the binder resin component at 24 hours from the start of extraction is 1 to 10% by mass,
The ratio (B / A) of the F-insoluble component A to the THF-insoluble component B is 0.
1 to 0.8. 2. The toner according to claim 1, wherein the organometallic compound is a compound selected from the group consisting of an aromatic salicylic acid metal compound. 3. The toner has a glass transition temperature of 50 to 75 ° C., and has a number average molecular weight (Mn) of 150 based on gel permeation chromatography (GPC) of a tetrahydrofuran (THF) -soluble component.
3. The toner according to claim 1, wherein the toner has a weight average molecular weight (Mw) of 3,000 to 200,000 and a Mw / Mn of 2 to 20. 4. The toner according to claim 1, wherein the toner contains the organometallic compound in an amount of 0.1 to 10% by mass based on the mass of the toner. 5. An electrostatic image is formed on an electrostatic image holding member, and the electrostatic image is developed with toner to form a toner image on the electrostatic image holding member. Transfer to a transfer material via a transfer member or without an intermediate transfer member,
In an image forming method for fixing a toner image on a transfer material by heating and pressing, the toner is a toner having toner particles having at least a binder resin, a colorant, an organometallic compound and a wax, and a toner having an external additive. Indicates that the maximum endothermic peak in the temperature range of 30 to 160 ° C. is 81 to 13 in the DSC endothermic curve.
0 ° C., the half width of the maximum endothermic peak is 2 to 15 ° C., the binder resin component is mainly composed of a polyester resin, and the toner has a dynamic elastic modulus (G ′ ₁₄₀ ) at a temperature of 140 ° C. Is 100 to 100000 dN / m ² , and the ratio (G ′ ₁₄₀ / G ′ ₁₇₀ ) of the dynamic elastic modulus (G ′ ₁₄₀ ) at a temperature of ₁₄₀ ° C. to the dynamic elastic modulus (G ′ ₁₇₀ ) at a temperature of 170 ° C. In a Soxhlet extraction of a toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content A of the binder resin component at 8 hours from the start of the extraction is 10 to 20% by mass, The THF-insoluble content B of the binder resin component at 24 hours from the start of extraction is 1 to 10% by mass,
The ratio (B / A) of the F-insoluble component A to the THF-insoluble component B is 0.
An image forming method, which is 1 to 0.8. 6. The toner image on the transfer material is a cyan toner,
6. The image forming method according to claim 5, wherein the image forming method includes at least two kinds of toners selected from the group consisting of magenta toner, yellow toner, and black toner. 7. The image forming method according to claim 5, wherein said organometallic compound is a compound selected from the group consisting of aromatic salicylic acid metal compounds. 8. The toner has a glass transition temperature of 50 to 75 ° C., and has a number average molecular weight (Mn) of 150 in a molecular weight distribution by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) -soluble component.
The image forming method according to any one of claims 5 to 7, wherein the image forming method has 0 to 10000, a weight average molecular weight (Mw) of 3000 to 200000, and Mw / Mn of 2 to 20. 9. The image forming method according to claim 5, wherein the toner contains the organometallic compound in an amount of 0.1 to 10% by mass based on the mass of the toner.