JPH10198066A - Toner for developing electrostatic charge image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve low-temp. fixability and anti-hot-offsetting property, to ensure superior fixability and developing performance at a half tone part at the time of fine powdering, to prevent the contamination of an electrostatic charge imparting member and to improve environmental stability by incorporating polyester resin contg. specified repeating units as a bonding resin. SOLUTION: This toner contains at least polyester resin as a bonding resin and a colorant. When the mol.wt. distribution of the THF-soluble component of the polyester resin is measured by gel permeation chromatography, the peak mol.wt. is in the range of 4,000-8,000 and the amt. of a component whose mol.wt. is <=3,000 is 10 to <45wt.%. The component whose mol.wt. is <=3,000 contains repeating units represented by formulae I, II so that the ratio between carboxyl carbon *<1> C in the formula I and carboxyl carbon *<2> C in the formula II determined by<13> C-NMR is regulated to 99.5:0.5 to 85:15.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Numerous methods are known as described in Japanese Patent Application Laid-Open Publication No. Hei. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed using toner, and if necessary, a toner image is formed on a transfer material such as paper. Is transferred, and then fixed by heating, pressure, heating and pressurizing, or solvent vapor to obtain a toner image.

As a method for fixing a toner image on a sheet such as paper, which is the last step, a fixing method using a heating roller is the most common method at present.

In this method, a toner image is formed by allowing a toner image surface of a sheet to be fixed to pass through the sheet while the toner image is brought into contact with the surface of a heating roller having a surface formed of a material having a releasing property to the toner. Fixing.

According to this method, since the surface of the heating 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. Fixing can be performed quickly.

However, in this method, since the surface of the heating roller and the toner image come into contact with each other under pressure in a molten state, a part of the toner image adheres and transfers to the surface of the fixing roller, and is transferred to the next sheet to be fixed. This is re-transferred to cause a so-called offset phenomenon, which causes a problem that the sheet to be fixed is soiled. Therefore, it is necessary to have excellent low-temperature fixability and high-temperature offset resistance.

Until now, various toners have been proposed to achieve both low-temperature fixability and high-temperature offset resistance. For example, Japanese Patent Application Laid-Open Nos. Sho 63-225244-22
No. 5,246 discloses a toner containing two types of non-linear polyesters for the purpose of improving low-temperature fixing property, high-temperature offset resistance, and blocking resistance.
However, as a toner having a wide fixing temperature range applicable from low speed to high speed and excellent in anti-offset property, there still remains a problem to be improved in addition to image characteristics described later.

That is, in recent years, it has been desired to improve the quality of a copied image by making the toner finer. However, various problems occur even though the resolution and sharpness of an image can be increased by making the toner finer.

First, the fixability of the halftone portion deteriorates due to the fine particles of the toner. This is because the amount of toner applied to the halftone portion is small, the amount of heat transferred from the heating roller to the toner transferred to the concave portion of the fixing sheet is extremely small, and the fixing pressure is also suppressed by the convex portion of the fixing sheet. Because it gets worse. Further, since the toner transferred to the convex portion of the sheet to be fixed in the halftone portion has a small toner layer thickness, the shearing force applied per toner particle is much larger than that of a solid black portion having a large toner layer thickness. Therefore, an offset phenomenon occurs and a low-quality copy image is obtained.

[0010] Further, the conventional toner for the purpose of improving the fixability tends to contaminate (spent) a developer carrier or a carrier as a charging member, and there is a problem of fogging. By reducing the particle size of the toner, the surface area of the toner is increased, and the contamination of the charging member is remarkable. Therefore, the width of the distribution of the charging amount is increased, and fogging is likely to occur. Further, as the toner surface area increases, the charging characteristics of the toner are more likely to be affected by the environment.

At present, there is no toner that can solve the above various problems.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to achieve (1) good low-temperature fixability and high-temperature offset resistance, and (2) a halftone portion even when finely divided. An object of the present invention is to provide (3) a toner for developing an electrostatic image which exhibits excellent fixability and developability, does not cause contamination of the charging member, and has excellent environmental stability.

[0013]

According to the present invention, there is provided a toner for developing an electrostatic image containing at least a binder resin and a colorant, wherein the binder resin comprises a polyester resin, and the gel permeation of the toner. Solution chromatography (GP
In the measurement of the molecular weight distribution of the tetrahydrofuran (THF) soluble component in C), the peak molecular weight was 4000 to 80.
And the components having a molecular weight of 3,000 or less are in the range of 10% by weight to less than 45% by weight, and the components having a molecular weight of 3,000 or less are represented by the following structural formulas (I) and (I).
I)

[0014]

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[0015] The repeating units represented by the structural formula (I) carboxyl carbon ^{* 1} C and structural formula (II) Determination of the ratio by ¹³ C-NMR of the carboxyl carbon ^{* 2} C of ^* 1 C
/ ^{* 2} A toner for developing an electrostatic image, wherein C is contained in the range of 99.5 / 0.5 to 85/15.

The present inventors have found that a THF-soluble GPC of a toner having a polyester resin as a binder resin has a peak molecular weight of 4000 to 8000 and contains 10% by weight or more of a molecule having a molecular weight of 3000 or less. Although it was found that the fixing area could be expanded, it was found that the component having a molecular weight of 3000 or less easily contaminates the developer carrier, which is a toner charging member, and the carrier in two-component development. However, since a resin component having a molecular weight of 3000 or less shows a remarkable effect particularly on low-temperature fixability, if a polyester resin having a repeating unit described below is precisely controlled by a molecular structure, a component having a molecular weight of 3000 or less is used. Even if the toner is present in the toner in an amount of 10% by weight or more and less than 45% by weight, there is no contamination of the developer carrier and no contamination of the carrier. We have found a toner for developing a charge image.

[0017]

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The repeating unit of the above structural formula (II) is characterized in that although it has excellent low-temperature fixability, it has poor high-temperature offset resistance and poor toner storability. Further, the repeating unit of the structural formula (I) is excellent in offset resistance, but is insufficient in low-temperature fixability.

The present inventors have conducted intensive studies from the macroscopic viewpoint of the polymer having a molecular weight distribution and the microscopic viewpoint of the molecular skeleton. As a result, in the GPC, the carboxyl carbon ^{* 1} C and the structural formula The ratio of carboxyl carbon ^{* 2} C of (II) is ^{* 1} C / ^{* 2} C = 99.5 / 0.5
To 85/15, and the toner having the above-mentioned molecular weight distribution has (1) good low-temperature fixability and high-temperature offset resistance,
(2) Even if fine particles are formed, the fixability of halftone is good,
In addition, it has been found that the toner has excellent developability, and (3) there is no contamination of the toner by the charging member, and that the toner has a long life before development and is excellent in environmental stability.

[0020] The ^{* 1} C / * In ² C ^{* 1} C becomes insufficient low-temperature fixability than 99.5, also by so-called charge-up the charge amount of toner under low-humidity environment to accumulate easily, the image It was found that the concentration was easily reduced. Also ^{* 1}
When C is less than 85, the high-temperature offset resistance is insufficient and the toner adheres to the toner, that is, the toner adheres to the charging member, so-called spent becomes remarkable, and the toner charge leaks easily under high humidity due to the toner charging characteristics. Scattering and fogging from the carrier also tend to be noticeable. This is considered to indicate that the interaction between the structural formulas (I) and (II) is deeply related to the mechanism of transferring and receiving the toner charge.

The acid value of the toner of the present invention is preferably from 2 to 40. If the acid value is less than 2, the effect of suppressing charge-up in low humidity is small, and the image density tends to decrease with continuous paper passing. If it exceeds, it becomes easy to be scattered when left for a long time under high humidity.

The composition of the polyester resin used in the present invention is as follows.

In the polyester resin used in the present invention, the alcohol component accounts for 40 to 60 mol% of all components.
~ 40 mol% is the acid component.

As the alcohol component,

[0025]

Embedded image And the following formula (a)

[0026]

Embedded image (In the formula, R is ethylene, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

[0027]

Embedded image And the like.

As the alcohol component, 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, and 2-ethyl-1,3-hexanediol may be used.

As the acid component, it is preferable that 50 mol% or more of the total acid component be a divalent carboxylic acid. Specifically, unsaturated acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, etc. Examples include dicarboxylic acids or anhydrides thereof, phthalic acid, terephthalic acid, isophthalic acid, aromatic dicarboxylic acids such as phthalic anhydride, or adipic acid, sebacic acid, alkylenedicarboxylic acids such as azelaic acid or acid anhydrides thereof. You may use it.

Further, glycerin, pentaerythritol, sorbit, sorbitan, and polyhydric alcohols such as oxyalkylene ether of novolak type phenol resin; trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and anhydrides thereof May be used.

In the toner of the present invention, a charge control agent can be used if necessary in order to further stabilize the chargeability. The charge control agent is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the binder resin.

[0032] Charge control agents known in the art today include:

For example, organic metal complexes and chelate compounds are effective. Examples thereof include a monoazo metal complex, a metal complex of an aromatic hydroxycarboxylic acid, and a metal complex of an aromatic dicarboxylic acid. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides,
Examples include esters and phenol derivatives of bisphenol.

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, P
b, 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.

As the magnetic material, conventionally, triiron tetroxide (F
e 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 ), cadmium iron oxide (CdFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅ -O ₁₂ ), copper iron oxide (C
uFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), iron neodymium oxide (Nd
Fe ₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), lanthanum iron oxide (LaFeO)
₃ ), iron powder (Fe), cobalt powder (Co), nickel powder (Ni) and the like are known, but in the present invention, these can be used alone or in combination of two or more kinds. Particularly suitable magnetic materials for the purposes of the present invention are fine powders of triiron tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
At about μm, the magnetic properties when 795.8 kA / m is applied show a coercive force of 1.5 to 12 kA / m and a saturation magnetization of 50 to 200 Am
² / kg (preferably 50 to 100 Am ² / kg) and a residual magnetization of ^{2 to 20} Am ² / kg are desirable.

The magnetic material 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.

As the colorant irrespective of one component or two components, carbon black, titanium white, and any other pigments and / or dyes can be used. For example, when the toner of the present invention is used as a magnetic color toner, C.I. I. Direct Red 1,
C. 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. 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: graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red-mouthed graphite, 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, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue,
First Sky Blue, Indanthrene Blue BC,
Chrome green, chromium oxide, pigment green B,
Malachite Green Lake, Final Yellow Green G, etc.

When the toner of the present invention is used as a two-component full-color toner, the following may be mentioned. Examples of the magenta coloring pigment include C.I. I. Pigment Red 1-19, 21-23, 30-32, 37
~ 41,48 ~ 55,57,58,60,63,64,
68, 81, 83, 87-90, 112, 114, 12
2,123,163,202,206,207,20
9, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,10,13,15,23,29,3
5 and the like.

Although such a pigment may be used alone, it is more preferable to use a dye and a pigment in combination to improve the sharpness from the viewpoint of the image quality of a full-color image. Examples of such magenta dyes include C.I. I. Solvent Red 1,3,8,23-25,27,30,49,81-8
4,100,109,121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8,13,1
4, 21, 27, C.I. I. Disperse Violet 1
Oil-soluble dyes such as C.I. I. Basic Red 1,2,9,
12-15, 17, 18, 22-24, 27, 29, 3
2, 34 to 40, C.I. I. Basic Violet 1,
And basic dyes such as 3,7,10,14,15,21,25 to 28.

Other color pigments include cyan color pigments such as C.I. I. Pigment Blue 2, 3, 15 ~
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 represented by the following structural formula.

[0042]

Embedded image

Examples of yellow color pigments include C.I. I. Pigment Yellow 1-7,10-17,23,65,7
3,83, C.I. I. Bat Yellow 1, 3, 20 and the like.

The colorant is used in an amount of 0.1 to 60 parts by weight, preferably 0.5 to 60 parts by weight, based on 100 parts by weight of the binder resin.
50 parts by weight.

In the present invention, one or more release agents may be contained in the toner, if necessary.

The following are examples of the release agent used in the present invention. Aliphatic hydrocarbon-based waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax, and paraffin wax, and aliphatic hydrocarbon-based waxes such as oxidized polyethylene wax, or block copolymers thereof; Examples of the wax include waxes mainly containing a fatty acid ester such as wax, sasol wax and montanic acid ester wax, and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

Further, saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid, unsaturated fatty acids such as brandic acid, eleostearic acid and barinaric acid, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubivir Alcohols, saturated alcohols such as seryl alcohol and merisyl alcohol, polyhydric alcohols such as sorbitol, fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide, methylenebisstearic acid amide, ethylenebiscapramide Fatty acid bisamides, such as ethylene bis lauric amide, hexamethylene bis stearamide, ethylene bis oleamide, hexamethylene bis oleamide, N, N'-
Insoluble fatty acid amides such as dioleyl adipamide, N, N'-dioleyl sebacic amide, and aromatic bisamides such as m-xylene bisstearic acid amide and N, N'-distearyl isophthalic acid amide , Calcium stearate, calcium laurate, zinc stearate, magnesium stearate and other aliphatic metal salts (commonly referred to as metallic soaps),
Waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid, partially esterified fatty acids such as behenic acid monoglyceride and polyhydric alcohols, and hydrogenated vegetable oils and fats Examples include a methyl ester compound having a hydroxyl group obtained by addition or the like.

As the wax (release agent) particularly preferably used in the present invention, an aliphatic hydrocarbon wax is exemplified. For example, low-molecular-weight alkylene polymers obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst under low pressure, alkylene polymers obtained by thermally decomposing high-molecular weight alkylene polymers, carbon monoxide, and synthesis gas comprising hydrogen A wax such as a synthetic hydrocarbon obtained from the distillation residue of the hydrocarbon obtained by the method or by hydrogenating them is preferred.

The amount of the release agent used in the present invention is desirably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the binder resin.

These release agents are usually added to the binder resin by dissolving the resin in a solvent, increasing the temperature of the resin solution, and adding and mixing while stirring, or by mixing at the time of kneading.

As the negatively chargeable fluidizing agent used in the present invention, any material can be used as long as it can improve the fluidity by being added to the colorant-containing resin particles. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, fine powder silica such as wet-process silica, dry-process silica, etc .; these silicas as silane coupling agents, titanium coupling agents, silicone oils, etc. And the like, surface-treated silica.

Preferred fluidizing agents are fine powders produced by the above phase oxidation of silicon halide compounds.
It is what is called dry silica or fumed silica, and is manufactured by a conventionally known technique. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ O + O ₂ → SiO ₂ + 4HCl

In this production process, it is also 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 a silicon halide. Is also included. The particle diameter is desirably in the range of 0.001 to 2 μm as an average primary particle diameter, and it is particularly preferable to use silica fine powder in the range of 0.002 to 0.2 μm. .

Commercially available fine silica powder produced by vapor phase oxidation of a silicon halide used in the present invention includes, for example, those commercially available under the following trade names.

[0056]

[Table 1]

Further, it is more preferable to use a treated silica fine powder obtained by subjecting a silica fine powder generated by vapor-phase oxidation of the silicon halide compound to a hydrophobic treatment. 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 organic silicon compound or the like which reacts or physically adsorbs with silica fine powder. The preferred method is
The silica fine powder produced by the vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane, dimethylpolysiloxane having 2 to 12 siloxane units per molecule, and dimethylpolysiloxane containing hydroxyl groups bonded to Si, each of which is located at one of the terminal units. is there. These are used alone or as a mixture of two or more.

As the fluidizing agent used in the present invention, those obtained by treating the above-mentioned dry-processed silica with a coupling agent having an amino group or silicone oil as described below are necessary for achieving the object of the present invention. You may use it according to it.

[0061]

Embedded image

[0062]

Embedded image

As the silicone oil, an amino-modified silicone oil having a partial structure having an amino group in a side chain represented by the following formula is generally used.

[0064]

Embedded image

(Where R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, and R ₃ and R ₄ represent a hydrogen, an alkyl group or an aryl group. However, the alkyl group, the aryl group, the alkylene group, and the phenylene group may contain an amine, or may have a substituent such as halogen as long as the chargeability is not impaired. Indicates a positive integer.)

The following are examples of such silicone oils having an amino group.

[0067]

[Table 2]

The amine equivalent is a value obtained by dividing the molecular weight by the number of amines per molecule by the equivalent per amine (g / equiv).

Good results are obtained when the fluidizing agent used in the present invention has a specific surface area of 20 m ² / g or more, preferably 50 m ² / g or more measured by nitrogen adsorption by the BET method. Fluidizer 0.01 for 100 parts by weight of toner
To 8 parts by weight, preferably 0.1 to 4 parts by weight.

To prepare the toner for developing an electrostatic image 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. Then, using a hot kneader such as a kneader or extruder, melt, knead and knead to make the resins compatible with each other, and after cooling and solidifying the melt-kneaded material, pulverize the solidified material and classify the pulverized material. The toner of the present invention can be obtained.

Further, the fluidizing agent and the toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain a developer for developing an electrostatic image having an additive on the surface of the toner particles.

The molecular weight and molecular weight distribution of the THF-soluble component of the toner of the present invention, the acid value, the ratio of the THF-insoluble component, the glass transition temperature, ^* 1C of the structural formula (I) in the toner and the structural formula (II)
The method for measuring the ^* 2C ratio ( ^13C -NMR measurement) is as follows, and the examples described later are also based on this method. (1) Measurement of molecular weight The molecular weight of the chromatogram by GPC is as follows. Measured under conditions.

That is, the column is stabilized in a heat chamber at 40 ° C., and THF is passed through the column at this temperature at a flow rate of 1 ml per minute as a solvent. After dissolving the sample in THF and leaving it to stand overnight, it is filtered through a 0.2 μm filter, and the filtrate is used as a sample. A sample concentration of 0.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a sample prepared to a concentration of 0.5 to 0.6% by weight. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was 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 a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. (Pressure Chemical C)
o. ) Or Toyo Soda Kogyo Co., Ltd. with 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 , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and it is appropriate to use at least about 10 standard polystyrene samples. Also, the detector uses RI
A (refractive index) detector is used.

In addition, as the column, 10 ³ to 2 × 10 ⁶
In order to accurately measure the molecular weight region of a polystyrene gel column, a plurality of commercially available polystyrene gel columns may be used in combination, for example, μ-styragel manufactured by Waters.
Combinations of 500, 10 ³ , 10 ⁴ , 10 ⁵ , and Shodex KA-801, 802, 80 manufactured by Showa Denko KK
The combination of 3,804,805,806,807 is preferred.

(2) Acid value A sample is precisely weighed, dissolved in a mixed solvent and water is added. The solution is subjected to potentiometric titration with 0.1 N-NaOH using a glass electrode to determine an acid value (according to JIS K1557-1970).

(3) THF-insoluble matter The sample was weighed, and a cylindrical filter paper (for example, No. 86R size)
28 × 10 mm (manufactured by Toyo Roshi Kaisha, Ltd.). Extraction is performed for about 6 hours using 200 ml of THF as a solvent. At this time, extraction is performed at a reflux rate such that the THF extraction cycle is about once every 4 to 5 minutes. After completion of the extraction, the cylindrical filter paper is taken out and weighed to obtain an insoluble content of the sample.

FIG. 1 shows an example of a Soxhlet extraction apparatus. The THF 2 contained in the container 1 is heated and vaporized by the heater 8, and the vaporized THF is led to the cooler 5 through the pipe 7. The cooler 5 is constantly cooled by the cooling water 6.
The THF cooled and liquefied by the cooler 5 accumulates in the storage section having the cylindrical filter paper 3, and when the liquid level of THF becomes higher than the middle pipe 4, the THF is discharged from the storage section into the container 1. The toner contained in the cylindrical filter paper is extracted by the circulating THF.

(4) Glass transition temperature Tg Differential thermal analysis measuring device (DSC measuring device), DSC-7
(Perkin Elmer) ASTM D341
Measure according to 8-82.

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely. This is put in an aluminum pan, and the measurement is performed at a temperature rising rate of 10 ° C./min under normal temperature and normal humidity using an empty aluminum pan as a reference within a measurement temperature range of 30 to 200 ° C. During this heating process, the temperature
An endothermic peak of the main peak in the range of 100 ° C. is obtained. At this time, the intersection of the line of the midpoint between the baseline before the endothermic peak and after the data and the differential heat curve is defined as the glass transition temperature Tg in the present invention.

(5) ^{* 1} C / ^{* 2} C In the GPC measurement of the above (1), components having a molecular weight of 3000 or less were fractionated, and the THF solvent was removed.
And ¹³ C-NMR is measured. ^{* 1} C carboxyl carbon is detected at 164.14 PPM, ^{* 2} C carboxyl carbon is detected at 164.21 PPM, and calculated from the integrated values of these peaks.

[0081]

【Example】

 [Resin Production Example 1]

[0082]

Embedded image Fumaric acid 45 mol Terephthalic acid 4 mol

[0083] The above ingredients were charged into a four-necked 5-liter flask, reflux condenser, water separator, denoted N ₂ gas line, a thermometer and a stirrer, 230 while introducing N ₂ gas into the flask A polycondensation reaction was carried out at a temperature of, and the number average molecular weight (Mn) was 2,300 and the weight average molecular weight (Mw) was 630.
Thus, a polyester resin A having an acid value of 5.4 was obtained.

[Resin Production Example 2]

[0085]

Embedded image Fumaric acid 30 mol Terephthalic acid 20 mol

[0086] The above ingredients were charged into a four-necked 5-liter flask, reflux condenser, water separator, denoted N ₂ gas line, a thermometer and a stirrer, 230 while introducing N ₂ gas into the flask A polycondensation reaction was carried out at a temperature of, and the number average molecular weight (Mn) was 4,300 and the weight average molecular weight (Mw) was 120.
00, a polyester resin B having an acid value of 18.5 was obtained.

[Resin Production Example 3]

[0088]

Embedded image Fumaric acid 50mol

[0089] The above ingredients were charged into a four-necked 5-liter flask, reflux condenser, water separator, denoted N ₂ gas line, a thermometer and a stirrer, 230 while introducing N ₂ gas into the flask A polycondensation reaction was carried out at a temperature of, and the number average molecular weight (Mn) was 2,800 and the weight average molecular weight (Mw) was 930.
A polyester resin C having an acid value of 8.5 was obtained.

[Resin Production Example 4]

[0091]

Embedded image Fumaric acid 40 mol Terephthalic acid 10 mol

[0092] The above ingredients were charged into a four-necked 5-liter flask, reflux condenser, water separator, denoted N ₂ gas line, a thermometer and a stirrer, 230 while introducing N ₂ gas into the flask A polycondensation reaction was carried out at a temperature of, and the number average molecular weight (Mn) was 3,200 and the weight average molecular weight (Mw) was 735.
Thus, polyester resin D having an acid value of 15.0 was obtained.

[Resin Production Example 5]

[0094]

Embedded image Fumaric acid 20 mol Terephthalic acid 30 mol

[0095] The above ingredients were charged into a four-necked 5-liter flask, reflux condenser, water separator, denoted N ₂ gas line, a thermometer and a stirrer, 230 while introducing N ₂ gas into the flask A polycondensation reaction was carried out at a temperature of, and the number average molecular weight (Mn) was 2,200 and the weight average molecular weight (Mw) was 540.
Thus, a polyester resin E having an acid value of 0 and an acid value of 18.9 was obtained.

[Example 1] Polyester resin A 70 parts by weight Polyester resin B 30 parts by weight Chromium di-tert-butylsalicylate complex 4 parts by weight Copper phthalocyanine pigment 4 parts by weight

The above mixture was melt-kneaded with a twin-screw extruder heated to 100 ° C., and the cooled mixture was roughly pulverized by a hammer mill, and the coarsely pulverized substance was finely pulverized by a jet mill. Classification was performed with an air classifier to obtain a blue fine powder having a weight average diameter of 7.0 μm. This blue fine powder 10
0 parts by weight of hydrophobic fine particle titanium oxide (BET10
(0 m ² / g) 1.0 part by weight was externally added using a Henschel mixer to obtain a blue toner.

This blue toner was prepared with a fluorine / acryl-coated ferrite carrier (average particle size of 50 μm) and a toner concentration of 6% by weight, and was used as a developer at a high speed of 40 sheets per minute. CLC
At 1000, a continuous paper passing test was performed in a low humidity environment and a high humidity environment, and good results as shown in Table 3 could be obtained.

Further, GPC of the THF-soluble portion of the blue toner
Analysis and GPC fractionation and the ratio of carboxyl carbons having a molecular weight of 3000 or less by ¹³ C-NMR ^{* 1} C /
^{* 2} C is shown in Table 4.

Using this developer, the above-mentioned fixing machine of the copying machine was detached, an external drive and a temperature control function were attached, the fixing speed was increased to 250 mm / sec, and a fixing test was performed. Table 5 shows the results. As shown in Table 5, good results were also obtained in the fixing property.

[Example 2] Polyester resin A 50 parts by weight Polyester resin B 50 parts by weight Chromium di-tert-butylsalicylate complex 4 parts by weight Copper phthalocyanine pigment 4 parts by weight

The above mixture was converted into a toner and a developer in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 5. Table 4 shows the ratio of the THF-soluble component in the toner having a molecular weight of 3000 or less and the structure ratio of carboxyl carbon in ¹³ C-NMR.

Example 3 20 parts by weight of polyester resin A 80 parts by weight of polyester resin B 4 parts by weight of chromium di-tert-butylsalicylate complex 4 parts by weight of copper phthalocyanine pigment

The above mixture was converted into a toner and a developer in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 5. Table 4 shows the ratio of the THF-soluble component in the toner having a molecular weight of 3000 or less and the structure ratio of carboxyl carbon in ¹³ C-NMR.

Example 4 100 parts by weight of a polyester resin C 4 parts by weight of a chromium complex of di-tert-butylsalicylate 4 parts by weight of a copper phthalocyanine pigment

The above mixture was converted into a toner and a developer in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 5. Table 4 shows the ratio of the THF-soluble component in the toner having a molecular weight of 3000 or less and the structure ratio of carboxyl carbon in ¹³ C-NMR.

Example 5 100 parts by weight of a polyester resin D 4 parts by weight of a chromium complex of di-tert-butylsalicylate 4 parts by weight of a copper phthalocyanine pigment

The above mixture was converted into a toner and a developer in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 5. Table 4 shows the ratio of the THF-soluble component in the toner having a molecular weight of 3000 or less and the structure ratio of carboxyl carbon in ¹³ C-NMR.

Comparative Example 1 100 parts by weight of polyester resin E 4 parts by weight of chromium di-tert-butylsalicylate 4 parts by weight of copper phthalocyanine pigment

The above mixture was converted into a toner and a developer in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 5. Table 4 shows the ratio of the THF-soluble component in the toner having a molecular weight of 3000 or less and the structure ratio of carboxyl carbon in ¹³ C-NMR.

Comparative Example 2 100 parts by weight of polyester resin A 4 parts by weight of chromium di-tert-butylsalicylate complex 4 parts by weight of copper phthalocyanine pigment

The above mixture was converted into a toner and a developer in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 5. Table 4 shows the ratio of the THF-soluble component in the toner having a molecular weight of 3000 or less and the structure ratio of carboxyl carbon in ¹³ C-NMR.

Comparative Example 3 100 parts by weight of polyester resin B 4 parts by weight of chromium di-tert-butylsalicylate complex 4 parts by weight of copper phthalocyanine pigment

The above mixture was converted into a toner and a developer in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 5. Table 4 shows the ratio of the THF-soluble component in the toner having a molecular weight of 3000 or less and the structure ratio of carboxyl carbon in ¹³ C-NMR.

[0115]

[Table 3]

The image densities in Table 3 are Macbeth.
It was measured by RD918 (manufactured by Macbeth).

The fog was evaluated by calculating the fog density (%) from the difference between the whiteness of a white background portion of the printout image measured by a “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper. The fog was evaluated according to the following criteria.

Evaluation Criteria ：: Less than 1.2% △: 1.2% or more and less than 1.8% △: 1.8% or more and less than 2.5% △: 2.5% or more and less than 4.0% ×: 4.0% or more

The density gradation is good ← 〇, 〇 △, △, △ ×,
The evaluation was performed on a five-point scale of × → bad.

[0120]

[Table 4]

[0121]

[Table 5]

[0122]

According to the present invention, a polyester resin is used as a binder resin, and a toner having a specific molecular weight distribution and a specific carboxyl carbon structure is obtained.
A toner that has both good low-temperature fixability and high-temperature offset resistance, exhibits excellent fixability and developability even in the form of fine particles in the halftone portion, has a long life of the developer, and has excellent environmental stability. .

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an extraction device used for Soxhlet extraction.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Container 2 THF 3 Cylindrical filter paper 4 Middle tube 5 Cooler 6 Cooling water 7 Tube 8 Heater

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Iku Iku 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Ryoichi Fujita 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside the corporation

Claims (1)

[Claims] 1. A toner for developing an electrostatic image containing at least a binder resin and a colorant, wherein the binder resin has a polyester resin, and tetrahydrofuran of the toner is measured by gel permeation chromatography (GPC). (THF) In the molecular weight distribution measurement of the soluble component, the peak molecular weight is in the range of 4000 to 8000, and
10% to 45% by weight of components having a molecular weight of 3000 or less
And the component having a molecular weight of 3000 or less,
Structural formulas (I) and (II) shown below: Carboxyl carbon ^{* 2} C carboxyl carbon ^{* 1} C and structure of the structural formula of repeating units represented in (I) (II)
Ratio of ^{* 1} C / ^{* 2} C determined by ¹³ C-NMR of 99.5 was 99.5
/0.5 to 85/15. A toner for developing electrostatic images, characterized by being contained in the range of /0.5 to 85/15.