JPH0943906A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner which is excellent in offset resistance, blocking resistance, and fluidity, while exhibiting an excellent fixing property even if many coping are taken continuously. SOLUTION: In a toner containing a binder resin, colorant, and wax, the binder resin comprises the polyester resin containing a urethane denatured polyester resin as a reactional product of the polyester resin and an isocyanate compound. Also the wax comprises two types of waxes with different melting points, and the relation of the equations I and II is established with respect to the melting points of the two types of waxes. In the equation TMH-TML>=20, TMH and TML indicate the melting points of low and high melting point waxes, respectively.

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, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
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 photoconductor by various means, and then the latent image is developed with a toner, and a toner image is formed on a transfer material such as paper if necessary. After transfer, the toner is fixed by heating, pressure, heating and pressurizing, or solvent vapor to obtain a toner image.

Various methods and apparatuses have been developed for fixing the toner image to a sheet such as paper, which is the above-mentioned final step, but the most common method at present is a pressure heating method using a heat roller.

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

However, at present, different toners are used depending on the model of copying machine or printer. This is mainly due to the difference in fixing speed and fixing temperature. The heating roller surface and the toner image are in a molten state,
Due to the contact under pressure, a part of the toner image adheres to and transfers to the surface of the fixing roller and retransfers to the next sheet to be fixed, which stains the sheet to be fixed. Is to receive a large. In general, when the fixing speed is low, the heating roller surface temperature is low, and when the fixing speed is high, the heating roller surface temperature is high. This is because the amount of heat given to the toner by the heating roller for fixing the toner is made substantially constant regardless of the fixing speed.

However, since the toner on the sheet to be fixed forms several toner layers, the fixing speed is particularly high,
In a system with a high heating roller temperature, when the temperature of the heating roller is high, the temperature difference between the toner layer in contact with the heating roller and the lowermost toner layer in contact with the sheet to be fixed becomes extremely large. In addition, when the temperature of the heating roller is low, the toner in the uppermost layer causes an offset phenomenon, and the toner in the lowermost layer does not melt sufficiently, so that the toner is not fixed on the sheet to be fixed and a low temperature offset phenomenon occurs.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing to anchor the toner to the fixing target sheet is usually used. With this method, the temperature of the heating roller can be lowered to some extent, and the high temperature offset phenomenon of the uppermost layer toner can be prevented. However, since the shearing force applied to the toner becomes extremely large, the sheet to be fixed winds around the fixing roller, so-called winding offset, and after separation of the member separating the sheet to be fixed from the fixing roller appears in the image. In addition, since the pressure is high, the line image is crushed during fixing and the toner flies out, so that the image quality of the copy image is easily deteriorated.

Therefore, in high-speed fixing, generally, a toner having a lower melt viscosity than in the case of low-speed fixing is used, and the heating roller temperature and the fixing pressure are lowered to prevent high-temperature offset and winding offset, while fixing. I am letting you. However, when such a toner having a low melt viscosity is used for low-speed fixing, the offset phenomenon occurs at a high temperature because of the low viscosity.

That is, in the present situation, there is no toner having a wide fixing temperature range applicable to low speed to high speed and having excellent offset resistance.

Further, although the resolution of images and the sharpness of images can be improved by reducing the particle size of toner, various problems occur.

First of all, due to the small particle size of the root toner, the fixing property of the halftone portion is deteriorated. This phenomenon is particularly noticeable in high-speed fixing. This is because the toner amount in the halftone portion is small, the toner transferred to the concave portion of the fixing sheet has a very small amount of heat applied from the heating roller, and the fixing pressure is also suppressed by the convex portion of the fixing sheet. It will be worse because of 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 to each toner particle is much larger than that in the solid black portion having a large toner layer thickness. As a result, an offset phenomenon occurs or a copy image with low image quality is obtained.

Further, there is a problem of fog. By reducing the particle size of the toner, the surface area of the toner is increased, and therefore, the width of the charge amount distribution 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.

It is also clear that when the toner particle size is reduced, the dispersed state of the wax and the colorant has a great influence on the chargeability of the toner.

With such a small particle size toner, the wax is apt to be poorly dispersed, and when the toner is developed on the photosensitive drum, the wax is liable to adhere to the drum and cause cleaning failure. Further, the surface of the photosensitive drum may be scratched and filming may occur.

When such a toner having a small particle diameter is applied to a high speed copying machine, the toner may be fogged and the density may be lowered particularly under low humidity.

Further, in the multifunctionalization of a copying machine, for example, a part of an image is erased by exposure or the like, and then another image is inserted into the part to perform multiple multicolor copying or copy paper. With the function of removing the frame around the frame, fogging occurs in a portion to be whitened on the image.

That is, when an image is erased by applying a potential opposite to the latent image potential with respect to the development reference potential with strong light such as an LED or a fuse lamp, there is a problem that the fog tends to occur at that portion. .

JP-A-4-358159 discloses an electrophotography in which a vinyl polymer contains polyethylene wax and / or polypropylene wax having different softening points, one of which is added at the time of polymerization and the other of which is blended at the time of kneading. Although a developer for use is disclosed, the wax used has a high softening point of 100 ° C. or higher, and the temperature difference between the softening points of the two waxes is as small as 2 to 20 ° C., so that the offset resistance is high. However, the low temperature fixability is inferior and the dispersibility of the wax in the binder resin is insufficient.

Further, in Japanese Patent Laid-Open No. 4-362953, free fatty acid carnauba wax and acid value 10 to 30 are disclosed.
A toner containing the oxidized rice wax is disclosed. Although this toner is excellent in low-temperature fixability, it is insufficient in both offset resistance and blocking resistance, and the fluidity of the toner is not satisfactory.

Further, in JP-A-6-130714, a linear polyester is used as a fixing resin, a wax having a softening point at the same level as that of the linear polyester is used as a releasing agent, and a softening agent is used. A toner is disclosed which is used in combination with a wax having a high point. In the case of this toner, both blocking resistance and offset resistance are at practically acceptable levels, but the melting point of the wax used is high, and low temperature fixability is insufficient, and the wax is evenly distributed on the binder resin. Dispersion is also insufficient, and when it is used as a toner, wax is liberated, and problems such as adhesion to the photosensitive drum and deterioration of toner cleaning property and filming that accompany it have not been solved. .

Further, Japanese Patent Application Laid-Open No. 1-154068 discloses a toner containing urethane modified polyester as a binder resin and containing a polypropylene wax and a bisamide wax. In the case of this toner, the two types of wax used have a high melting point and the temperature difference between them is small, so that both blocking resistance and hot offset resistance are at practically acceptable levels, but low temperature fixability Is insufficient, and it is still insufficient as a toner from the viewpoint of uniform dispersion of wax, and the problems of compatibility between low temperature fixing property and offset resistance have not yet been solved.

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

[0023]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic charge image, which solves the above problems.

An object of the present invention is to provide a toner for developing an electrostatic charge image, which has good fixability from low speed to high speed copying machines and which is excellent in offset resistance, blocking resistance and fluidity. is there.

An object of the present invention is to provide an electrostatic charge image which shows excellent fixing property in the halftone portion even when the particle size is reduced from low speed to high speed copying machine and which can obtain a copy image of good quality. A developing toner is provided.

An object of the present invention is to provide a toner for developing an electrostatic charge image, which exhibits good dispersibility in a binder resin, does not release wax, does not damage the photosensitive drum, and has good cleaning properties. Is provided.

An object of the present invention is to provide an electrostatic charge image developing toner capable of obtaining a high density copy image without fog from low speed to high speed copying machines.

An object of the present invention is to provide an electrostatic charge image developing toner which gives good images even under low humidity and high humidity without being affected by environmental changes.

An object of the present invention is to provide an electrostatic charge image developing toner which gives a stable and good image even in a high-speed machine and has a wide range of applicable models.

An object of the present invention is to provide an electrostatic charge image developing toner which is excellent in durability, has a high image density even after continuous use for a long time, and is free from fog on a white background to obtain a copy image. .

An object of the present invention is to provide a toner for developing an electrostatic image in which a character of a copy image in a photographic image containing characters is clear and the photographic image has density gradation which is faithful to the original. is there.

[0032]

The present invention relates to a toner containing a binder resin, a colorant and a wax, wherein the binder resin contains a urethane-modified polyester resin which is a reaction product of a polyester resin and an isocyanate compound. An electrostatic charge image comprising a polyester resin, the wax comprising two kinds of waxes having different melting points, and the relationships of the following formulas (1) and (2) being established with respect to the melting points of the two kinds of waxes. The present invention relates to developing toner.

[0033]

[Equation 2] Formula (2) T _MH -T _ML ≧ 20 [In the formula, T _ML and T _MH represent the melting points of the low-melting wax and the high-melting wax, respectively. ]

[0034]

DETAILED DESCRIPTION OF THE INVENTION According to the study by the present inventors, in order to obtain a toner using a urethane-modified resin as a binder resin, which satisfies the contradictory characteristics of low-temperature fixing property, anti-offset property and anti-blocking property. For this, it is not enough to use the conventionally known wax.

That is, although it is possible to apparently improve the low temperature fixing property by using a wax having a low melting point, the offset resistance and blocking resistance are obviously inferior, and the wax having a high melting point is used. Although the offset property and the blocking resistance are not problematic, it is impossible to achieve the low temperature fixing property.

Further, if the wax having a low melting point and the wax having a high melting point are simply used in combination, the binder resin is plasticized by the low melting point wax, the dispersion of the high melting point wax is remarkably deteriorated, and the larger the difference between the melting points is. This tendency becomes strong, and dispersion failure tends to occur. As a result, not only the low-temperature fixability, offset resistance and blocking resistance cannot be satisfied, but also free wax adheres to the photosensitive drum due to poor wax dispersion, resulting in various adverse effects such as poor cleaning and filming. Cause

The toner of the present invention contains at least urethane-modified polyester resin as a binder resin, and
It contains waxes having different melting points, and these waxes have specific melting points as shown by the formulas (1) and (2).

[0038]

(Equation 3) Formula (2) T _MH -T _ML ≧ 20 [In the formula, T _ML and T _MH represent the melting points of the low-melting wax and the high-melting wax, respectively. ]

The formula (1) represents the average of the melting points of two kinds of wax, which may be 70 to 120 ° C, preferably 75 to 110 ° C, and more preferably 7 ° C.
This is the case of 5 to 100 ° C.

In the formula (1), the average melting point is 7
When the temperature is lower than 0 ° C., the low temperature fixability is good but the blocking resistance is significantly deteriorated. Also, 120
When the temperature exceeds ℃, the blocking resistance is good, but the low temperature fixability is obviously poor.

The formula (2) represents the melting point difference between the two types of wax, which may be 20 ° C. or higher, but is preferably 23-.
It becomes 75 degreeC, More preferably, it is 25-70 degreeC.
This is the case.

If the temperature is lower than 20 ° C. in the formula (2), the low temperature fixing property, blocking resistance and offset resistance cannot be satisfied at the same time. That is, when the melting point of the wax is relatively low, the low-temperature fixability is good, but the offset resistance is significantly impaired, and the blocking resistance may be poor. Further, when the melting point of the wax is relatively high, blocking resistance is good, but it is difficult to achieve low-temperature fixability, and offset resistance may be poor.

In the formula (2), the wax melting point difference is 75.
If the temperature is much higher than 0 ° C, the wax may be poorly dispersed in the binder resin when the magnetic toner is manufactured, and the wax is liable to be liberated, and the wax adheres to the photosensitive drum and Various adverse effects may occur, which is not preferable.

The wax preferably used in the toner of the present invention comprises a low melting point component having a relatively low melting point and a high melting point component having a relatively high melting point, and the low melting point component is 60.
The melting point may be from about 100 ° C, preferably from 62 to 95.
C., and more preferably 65 to 90.degree. The high melting point component may have a melting point of 80 to 140 ° C., preferably 82 to 135 ° C., and more preferably 85 to 130 ° C.

If the melting point of the low melting point component is less than 60 ° C., the blocking resistance becomes poor, and if the melting point of the high melting point component exceeds 140 ° C., it becomes difficult to achieve low temperature fixing.

In the wax used in the toner of the present invention, the ratio of the low melting point component and the high melting point component used is 1 by weight.
/ 19 to 9/1, but preferably 1/9 to 8
/ 1, and more preferably 1/7 to 7/1
This is the case. If the low melting point component is used at a ratio of 1 /
When it is less than 19, it becomes difficult to achieve low-temperature fixability, and when it is more than 9/1, both blocking resistance and offset resistance may be poor, which is not preferable. Generally, the ratio of the two waxes used is 1.
When it deviates from / 19 to 9/1, it becomes difficult to uniformly disperse the wax in the binder resin, and the wax is liberated, which is not preferable. Further, in addition to the low-melting wax and the high-melting wax, at least one other third wax component may be contained in order to finely adjust the low temperature fixing property, blocking resistance and offset resistance, and the content of the whole wax may be all. 20% by weight or less based on the amount, the melting point is 60 ~
It may be 140 ° C.

In the toner of the present invention, the wax may be contained in an amount of 1 to 20 parts by weight, preferably 2 to 17 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the binder resin. This is the case of including parts by weight. If the content is less than 1 part by weight, it is difficult to achieve low-temperature fixability, and if the content exceeds 20 parts by weight, both blocking resistance and offset resistance become poor, and wax is evenly dispersed. It becomes difficult and wax is liberated, which is not preferable.

The wax can be added to the toner of the present invention by various methods. Generally, each pulverized wax is added by stirring and mixing with a binder resin, a magnetic material and the like in a Henschel mixer, and then melt-kneading, but preferably, a low melting point component and a high melting point component of the wax If necessary, the third wax component is melt-mixed in advance and used as a uniform wax component. Further, as another preferable method for adding the wax, there is a method in which the binder resin is heated and dissolved in an organic solvent, and then the wax is added, and the solvent is evaporated to dryness, and the binder resin is added without using the organic solvent. There is a method of melting by heating and adding wax. When the wax is added to the binder resin by these methods, a wax having a low melting point component, a high melting point component and, if necessary, a third wax component melt-mixed can be used. Another preferable method for adding the wax is to add the wax in the step of synthesizing the binder resin, and in this case also, the wax whose melt-mixed components are adjusted in advance can be used. Another preferable method of adding the wax is to add only the low-melting wax to the binder resin in advance, specifically, a method of heating and melting only the binder resin and adding the binder resin to an organic solvent. Are dissolved in the solution by heating and added, and then the organic solvent is evaporated to dryness and the method is added in the step of synthesizing the binder resin. In this case, the high melting point wax is added to the toner by stirring and mixing with a binder resin, a magnetic material and the like containing the low melting point wax with a Henschel mixer or the like, and then melt-kneading.

The wax contained in the toner of the present invention is
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 those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax. Further, such as palmitic acid, stearic acid, montanic acid, or long-chain alkylcarboxylic acids having a longer-chain alkyl group,
Saturated straight chain fatty acids, unsaturated fatty acids such as blancinic acid, eleostearic acid, and valinaric acid, stearic alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol, melicyl alcohol, or a longer chain alkyl group. Saturated alcohols such as long-chain alkyl alcohols having
Polyhydric alcohols such as sorbitol, calcium stearate, calcium laurate, zinc stearate,
Fatty acid metal salts such as magnesium stearate (generally called metal soap), waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid, and behenin. Examples thereof include partial esterified products of fatty acids such as acid monoglyceride and polyhydric alcohols, and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

In the present invention, the low-melting wax component preferably used is a hydrocarbon having a long-chain alkyl group with few branches. Specifically, for example, alkylene is radically polymerized under high pressure or is polymerized with Ziegler catalyst under low pressure. Low molecular weight alkylene polymer, alkylene polymer obtained by pyrolyzing a high molecular weight alkylene polymer, carbon monoxide, from the distillation residue of hydrocarbons obtained by the Arge method from a synthesis gas consisting of hydrogen, or by hydrogenating these A wax such as a synthetic hydrocarbon obtained by the above is preferable. Further, those obtained by separating a hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation or a separation crystallization method are more preferably used. Hydrocarbons as a matrix are metal oxide catalysts (mostly two or more multi-component catalysts)
Synthesized by the reaction of carbon monoxide and hydrogen using, for example, the gintol method, the hydrocoal method (using a fluidized catalyst bed), or the Arge method (using a fixed catalyst bed) in which waxy hydrocarbons can be obtained in large quantities Is obtained by

The high-melting wax component preferably used in the present invention comprises a hydrocarbon having a long-chain alkyl group with few branches. Specifically, for example, alkylene is polymerized under a high pressure by radical polymerization or under a low pressure by a Ziegler catalyst. Low molecular weight alkylene polymer, alkylene polymer obtained by pyrolyzing a high molecular weight alkylene polymer, carbon monoxide, from the distillation residue of hydrocarbons obtained by the Arge method from a synthesis gas consisting of hydrogen, or by hydrogenating these A wax such as a synthetic hydrocarbon obtained by the above is preferable.

The wax preferably used in the toner of the present invention is a substituted alkyl wax having a chemical structure represented by the following formula (3).

Formula (3) RY [R: weight average molecular weight by gel permeation chromatography is 300
And represents a hydrocarbon group of 0 or less. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ]

Specific examples of the compounds include (A) CH ₃ (CH ₂ ) _n CH ₂ OH (n = about 20 to about 200) (B) CH ₃ (CH ₂ ) _n CH ₂ COOH (n = about 20
To about _{200) (C) CH 3 (} CH 2) n CH 2 O (CH 2 CH 2 O) m
CH ₃ (n = about 20 to about 200, m = 1 to about 100) (D) CH ₃ (CH ₂ ) _n CH ₂ COO (CH ₂ ) _m C
H ₃ (n = about 20 to about 200, m = 0 to about 100) (E) CH ₃ (CH ₂ ) _n CH ₂ OSO ₃ H (n = about 2
0 to about 200) and the like. These compounds are derivatives of the compound (A), and the main chain is a linear saturated hydrocarbon. Compounds other than those shown in the above examples can be used as long as they are compounds derived from the compound (A).

Examples of the combination of the low melting point wax and the high melting point wax which are preferably used in the present invention include the following combinations.

(1) Combination of low-melting hydrocarbon wax and high-melting hydrocarbon wax: The low-melting hydrocarbon wax is a long-chain alkyl group with few branches and has a melting point of 70 to 90 ° C.
Weight average molecular weight 400-700, Mw / Mn = 1.5-
It is around 2.

The high-melting hydrocarbon wax is a long-chain alkyl group with few branches, and has a melting point of 95 to 130 ° C., a weight average molecular weight of 800 to 2500, and Mw / Mn of about 2 to 2.5.

(2) Combination of low melting point hydrocarbon wax and high melting point substituted alkyl wax: The low melting point wax used is the same as the low melting point hydrocarbon wax shown in (1) above.

The high-melting-point substituted alkyl wax has a long-chain alkyl group with few branches, and the alkyl group having a substituent is contained in an amount of 50% by weight or more based on the whole wax. Melting point 95
~ 130 ° C, weight average molecular weight 800-5000, Mw /
Mn is about 1.5 to 2.5.

(3) Combination of low melting point substituted alkyl wax and high melting point hydrocarbon wax: The low melting point substituted alkyl wax has a long-chain alkyl group with few branches, and the alkyl group having a substituent is in all waxes. 40 wt% or more is contained. Melting point is 70 to 90 ° C, weight average molecular weight is 400
˜700, Mw / Mn = 2 or so.

As the high melting point hydrocarbon wax, the same high melting point hydrocarbon wax as described in (1) above can be used.

(4) Combination of low melting point substituted alkyl wax and high melting point substituted alkyl wax: The low melting point substituted alkyl wax may be the same as the low melting point alkyl wax shown in (3) above.

As the high melting point substituted alkyl wax, the same high melting point substituted alkyl wax as described in (2) above can be used.

In the present invention, the urethane-modified polyester resin may be contained in an amount of 3 to 70% by weight, preferably 5 to 60% by weight, more preferably 7 to 70% by weight, based on the total binder resin. This is the case when the content is 50% by weight.

When the content of the urethane-modified polyester resin is less than 3% by weight, the offset resistance may be remarkably deteriorated even when the wax according to the present invention is used in the toner, which is preferable. Absent. Further, when the content of the urethane-modified polyester resin exceeds 70% by weight, the low temperature fixing property may be impaired when it is used for a toner, and further, the image density is lowered when an image is formed. It may cause troubles, which is not preferable.

In the present invention, a polyester resin (hereinafter referred to as "polyester (R)") which is made into a urethane-modified polyester resin by reacting with an isocyanate compound.
Examples of the alcohol component used for ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and a bisphenol derivative represented by the formula (a);

[0067]

Embedded image

Further, diols represented by the formula (b):

[0069]

Embedded image And the like.

Further, trifunctional or higher functional alcohols such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbit, sorbitan, and oxyalkylene ether of novolac type phenol resin can be used.

As the bifunctional carboxylic acid, benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid. Or an anhydride thereof, and further having 6 to 1 carbon atoms
Examples include succinic acid substituted with an alkyl group of 8 or its anhydride; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid, and their anhydrides.

As the trifunctional or higher functional carboxylic acid,
Examples thereof include polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their anhydrides.

In the practice of the present invention, the alcohol component of the polyester (R) which is particularly preferable is the bisphenol derivative represented by the above formula (a), which is contained in an amount of 70 mol% or more of the total alcohol component. Examples of the acid component include phthalic acid or its acid anhydride, terephthalic acid, isophthalic acid, succinic acid, n-dodecersuccinic acid or its acid anhydride, and dicarboxylic acids such as fumaric acid, maleic acid and maleic anhydride.

In addition, an ethylene oxide adduct which is a bisphenol derivative represented by the above formula (a) (hereinafter referred to as "E
"O-BPA". ) And a propylene oxide adduct (hereinafter referred to as “PO-BPA”) are preferably used together, and the content ratio thereof is represented by a molar ratio.
EO-BPA / PO-BPA = 0.01 to 10 is preferable, but 0.05 to 5 is preferable, and 0.1 to 3 is more preferable.

When the molar ratio of EO-BPA / PO-BPA is less than 0.01, the glass transition temperature (hereinafter, referred to as "Tg") of the polyester (R) becomes too high, which is not preferable. On the other hand, when it exceeds 10, the Tg of the polyester produced is too low, which is not preferable.

As the trifunctional or higher functional carboxylic acid,
Examples thereof include trimellitic acid, its acid anhydride, and benzophenonetetracarboxylic acid.

Examples of trifunctional or higher functional alcohols include trimethylolethane, trimethylolpropane, glycerin and pentaerythritol.

In the polyester (R), the trifunctional or higher functional alcohol may be contained in an amount of 1 to 10 mol% of the total alcohol component, preferably 2 to 8 mol%, and more preferably 3 to 3. This is the case where 6 mol% is contained.

When the trifunctional or higher functional alcohol is less than 1 mol%, the hot offset resistance may be significantly deteriorated when used as a urethane-modified polyester resin in a toner, which is not preferable. If the trifunctional or higher-functional alcohol exceeds 10 mol%, the low-temperature fixability may be deteriorated in the same manner, which is not preferable.

The trifunctional or higher functional carboxylic acid may be contained in an amount of 0.5 to 10 mol%, preferably 1 to 7 mol%, based on the total carboxylic acid components.
More preferably, the content is 1.5 to 5 mol%.

The acid value of polyester (R) is 20 mgKO
H / g or less and hydroxyl value is 10-80 mg KOH /
The acid value is preferably 10 mgKOH / g
Hereinafter, it is the case where the hydroxyl value is 20 to 70 mgKOH / g, more preferably the acid value is 5 mgKOH / g or less, and the hydroxyl value is 30 to 60 mgKOH / g.

The acid value of polyester (R) is 20 mgKO
When it exceeds H / g, a side reaction between the isocyanate compound and the carboxyl group occurs when the urethane-modified polyester resin is used, which is not preferable. Further, when the hydroxyl value of the polyester (R) is less than 10 mgKOH / g, the reaction efficiency with the isocyanate compound is low and the hot offset resistance tends to be poor, which is not preferable. When the hydroxyl value of the polyester (R) exceeds 80 mgKOH / g, it is difficult to control the reaction with the isocyanate compound, which is not preferable.

Examples of the isocyanate compound capable of reacting with the polyester (R) include, for example, trellin diisocyanate (hereinafter referred to as "TDI"), hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate (hereinafter referred to as "M").
"DI". ), Xylylene diisocyanate, tetramethyl xylylene diisocyanate, and the like.

Tg of polyester (R) is 20 to 80 ° C.
The temperature is preferably 25 to 70 ° C., and more preferably 30 to 65 ° C.

When the Tg is less than 20 ° C., the blocking resistance is significantly deteriorated, and when the Tg is more than 80 ° C., the low temperature fixing property is deteriorated, which is not preferable.

The weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (hereinafter referred to as "GPC") measured using the THF-soluble content of polyester (R). .) Is 2000
The number average molecular weight (hereinafter referred to as “Mn”) of 100 to 100,000 may be 1,000 to 15,000, preferably Mw of 4,000 to 70,000 and Mn of 2,000 to 12,000, and more preferably. This is the case where Mw is 6000 to 50,000 and Mn is 2500 to 9000.

The above Mw is less than 2000 and Mn is 1
If it is less than 000, the hot offset resistance may be impaired when it is used as a urethane-modified polyester resin in a toner, which is not preferable. Also, Mw is 1
When it exceeds 0,000 and Mn exceeds 15,000, when it is used as a urethane-modified polyester resin in a toner,
The low temperature fixability may be significantly deteriorated, which is not preferable.

In the present invention, another resin that can be used in combination with the urethane-modified polyester resin without substantially reacting with the isocyanate compound is a polyester resin.

The alcohol component and acid component used in the above polyester resin (hereinafter referred to as "polyester (N)") may be the same as those used in polyester (R).

Particularly, as the alcohol component, it is preferable to use EO-BPA and PO-BPA which are bisphenol derivatives represented by the above formula (A) in combination.
The molar ratio of A / PO-BPA may be 0.01 to 10, preferably 0.05 to 5, and more preferably 0.1 to 3.

Further, the trifunctional or higher functional carboxylic acid may be contained in an amount of 0.5 to 10 mol%, preferably 1 to 7 mol% based on the total carboxylic acid component, as described above. And more preferably 1.5 to 5 mol%.

Tg of the polyester (N) is 45 to 9
It may be 0 ° C., preferably 47 to 80 ° C., and more preferably 52 to 70 ° C.

When the Tg is less than 45 ° C., the blocking resistance may be significantly deteriorated, which is not preferable. If the Tg exceeds 90 ° C., the low temperature fixability may be impaired, which is not preferable.

The Mw of polyester (N) is 300.
0 to 1,000,000, Mn may be 1000 to 50,000, preferably Mw is 5000 to 500,000 and Mn is 2000 to 3
In some cases, Mw of 7,000 to 7,000 is more preferable.
This is the case where the Mn is 300,000 and the Mn is 3000 to 10,000.

The above Mw is less than 3000 and Mn is 1
If it is less than 000, the hot offset resistance may deteriorate, which is not preferable. When Mw exceeds 1 million and Mn exceeds 50,000, low-temperature fixability is impaired, and at the same time, pulverizability is deteriorated, which is not preferable.

The acid value of polyester (N) is 100 mgK
OH / g or less and a hydroxyl value of 20 mgKOH / g or less, preferably an acid value of 10 to 70 mgKO.
H / g, the hydroxyl value is 10 mgKOH / g or less, and more preferably the acid value is 15 to 60 mgK.
OH / g and the hydroxyl value is 5 mgKOH / g or less.

The Tg of the urethane-modified polyester resin (hereinafter referred to as "modified polyester"), which is the reaction product of the polyester (R) and the isocyanate compound, is 30.
Up to 90 ° C., preferably 40 to 70 ° C., and more preferably 45 to 65 ° C.

If the Tg is less than 30 ° C., the blocking resistance tends to be poor, which is not preferable.
Is 90 ° C. or higher, the low-temperature fixability may be impaired, which is not preferable.

In the molecular weight distribution of the THF-soluble component of the modified polyester, the Z-average molecular weight (hereinafter referred to as "Mz") is 5.
10 to 50,000,000, Mw is 4000 to 2,000,000, Mn is 1000 to 100,000, and Mz / Mw is 5 to 5,000,000.
5,000, Mw / Mn should be 2.5 to 500, preferably Mz is 100,000 to 20,000,000, and M is
w is 5000 to 1.5 million, Mn is 2000 to 50,000, Mz / Mw is 15 to 4000, and Mw / M
The case where n is 3 to 400, and more preferably Mz is 2
It is 0,000,000-10,000,000, Mw is 10,000-1,200,000, Mn is 3000-30,000, and Mz / Mw is 20-.
2000, and the case where Mw / Mn is 5 to 300.

The Tg of the binder resin (hereinafter simply referred to as "binder resin") consisting of the modified polyester and the substantially unmodified polyester (N) may be 45 to 75 ° C, preferably 50. The temperature is up to 70 ° C, more preferably 52 to 68 ° C.

If the Tg is less than 45 ° C., the blocking resistance tends to be poor, and the Tg is 75 ° C.
If it exceeds, the low-temperature fixability may be impaired, which is not preferable.

The molecular weight distribution of the binder resin is such that Mz is 30,000 to 1 billion, Mw is 3000 to 3 million, and M is
n is 1000 to 80,000, Mz / Mw is 5 to 10,000, Mw / Mn is 2 to 2000, preferably Mz is 50,000 to 500 million, and Mw is 5000 to 2,000,000. And Mn is 1500 to 50,000 and Mz / Mw is 7
Is 5,000, and Mw / Mn is 3 to 100, more preferably Mz is 100,000 to 300 million, and
w is 5000 to 1,000,000, Mn is 2000 to 30,000, Mz / Mw is 10 to 3000, and Mw / M
This is the case where n is 10 to 800.

If the Mz is less than 30,000, the Mw is less than 3000, and the Mn is less than 1000, the hot offset resistance may be impaired when used in a toner, which is not preferable. In addition, Mz exceeds 1 billion, Mw is 30
If it exceeds 0,000 and Mn exceeds 80,000, the low-temperature fixability may be impaired when used in a toner, which is not preferable.

The above Mz / Mw is less than 5, Mw / M
When n is less than 2, the temperature range from the fixing start temperature to the temperature at which hot offset occurs is narrow, which may be a problem in practical use. Mz / Mw exceeds 1000 and Mw / Mn is 2000. If it exceeds the range, the dispersion of the wax or the colorant may be deteriorated, which is not preferable.

Further, the binder resin has a THF insoluble content of 2 to
70 wt% can be contained, but preferably 3 to 6
The content is 0% by weight, and more preferably 5 to 50.
This is the case where the content is wt%.

When the THF insoluble content is less than 2% by weight, the hot offset resistance may be deteriorated,
When the THF insoluble content exceeds 70% by weight, the dispersibility of the wax may be significantly deteriorated, which is not preferable.

In the toner produced by using the above binder resin, the content of the THF insoluble component in the toner may be 10% by weight or less based on the total binder resin.

Further, in the molecular weight distribution measured by GPC using THF-soluble matter, Mz may be 500,000 to 1 billion, preferably 800,000 to 700 million, and more preferably. This is the case where the number is 1 million to 500 million.
When the Mz is less than 500,000, the hot offset resistance is significantly deteriorated, and when the Mz is more than 1 billion, the pulverization efficiency in producing the toner may decrease, which is not preferable.

The Mw in the above molecular weight distribution is 50.
It may be from 0 to 10 million, but preferably from 10 to 7
It is a case of, 000,000, and more preferably 100,000 to 50.
This is the case when the number is 0,000. When the Mw is less than 5000, there is concern that the hot offset resistance may deteriorate, and the Mw
If it exceeds 10 million, the low temperature fixability may be impaired, which is not preferable.

Further, Mn in the above molecular weight distribution is 10
It may be from 00 to 200,000, preferably from 1500 to 1
In the case of 50,000, more preferably 2000 to 10
This is the case. When the Mn is less than 1000, there is a concern that the blocking resistance may be deteriorated, and Mn is 2
If it exceeds 0,000, there is a concern that the low temperature fixability may deteriorate.

In addition, Mz / Mw in the above molecular weight distribution
Is 100 or more, preferably 100 to 20
In the case of 00, more preferably 120 to 150
This is the case when it becomes zero. When the Mz / Mw is less than 100, there is concern that the hot offset resistance may deteriorate.
When Mz / Mw exceeds 2000, it is not preferable because the low temperature fixability is impaired or the efficiency of pulverization, fusion in the apparatus or the like is lowered in producing the toner.

In addition, Mw / Mn in the above molecular weight distribution
May be 5 to 1000, preferably 7 to 700
In this case, the case is 10 to 500, more preferably 10 to 500. When the above Mw / Mn is less than 5,
Hot offset resistance is impaired and Mw / Mn is 100.
If it exceeds 0, the low-temperature fixability may be impaired, which is not preferable.

In the molecular weight distribution measured by GPC, 5 to 30% of the molecular weight component of 100,000 or more is contained and 1 to 15% of the molecular weight component of 1 million or more.
It may be contained, but it is preferably 6 to 25% of the molecular weight component of 100,000 or more and 1.5 to 10% of the molecular weight component of 1,000,000 or more, and more preferably 1
It is a case where 8 to 20% of a molecular weight component of 0 or more is contained and 2 to 8% of a molecular weight component of 1,000,000 or more is contained.

When the above-mentioned molecular weight component of 100,000 or more is less than 5%, the hot offset resistance is significantly deteriorated, and the molecular weight component of 100,000 or more exceeds 30%, and 10 or more.
If the molecular weight component of 20,000 or more exceeds 15%, the low temperature fixability is impaired, which is not preferable.

Further, in the molecular weight distribution measured by GPC, it has a main peak in the molecular weight range of 2000 to 20,000 and a subpeak or shoulder in the molecular weight range of 100,000 or more, preferably 3000 to 1
It has a main peak at 5000 and a sub peak or shoulder in a molecular weight range of 150,000 or more,
More preferably, it has a main peak at 5000 to 10,000,
This is a case of having a subpeak or shoulder in the molecular weight range of 200,000 or more.

In the present invention, a vinyl resin is another resin that can be used in combination with the urethane-modified polyester resin.

Examples of the vinyl-based monomer for forming the vinyl-based resin include the following.

For example, styrene, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
styrene and its derivatives such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; ethylene; Ethylenically unsaturated monoolefins such as propylene, butylene and isobutylene; unsaturated polyenes such as butadiene;
Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid α-methylene aliphatic monomers such as n-butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Carboxylic esters;
Methyl acrylate, ethyl acrylate, acrylic acid n-
Butyl, isobutyl acrylate, propyl acrylate,
Acrylic esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; esters of the above-mentioned α, β-unsaturated acids and diesters of dibasic acids.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride Unsaturated dibasic acid anhydrides such as: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl ester Half ester of unsaturated dibasic acid such as half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated dibasic acid ester such as dimethyl maleic acid, dimethyl fumaric acid; Acid, methacrylic acid, crotonic acid, such as cinnamic acid alpha, beta-unsaturated acid; crotonic acid anhydride, such as alpha of cinnamic acid anhydride, beta-unsaturated acid anhydride, the alpha, beta
-Anhydrides of unsaturated acids and lower fatty acids; and monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Examples thereof include monomers having a hydroxyl group such as hydroxy-1-methylhexyl) styrene.

The glass transition temperature of this vinyl resin is 45.
To 80 ° C., preferably 55 to 70 ° C., the number average molecular weight (Mn) is 2,500 to 50,000, preferably 3,000 to 20,000, and the weight average molecular weight (M
It is preferred that w) is 10,000 to 1,500,000, preferably 25,000 to 1,250,000.

The binder resin containing the urethane-modified polyester resin can be produced by the following method.

Production method (1): A urethane-modified polyester resin is produced by reacting with an isocyanate compound in the presence of only the polyester (R).

The isocyanate compound may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyester (R), or may be added continuously in small amounts. The reaction temperature is 100 to 200 ° C., and the temperature can be changed stepwise as necessary. The reaction time is about 1 minute to 6 hours, although it varies depending on the reaction temperature. In the case where a relatively large amount of raw material is used for batch processing, and when a relatively small amount of raw material is continuously supplied using a single-screw or twin-screw extruder, continuous production can be performed. In addition, the wax according to the present invention can be included during production. By this manufacturing method, a binder resin containing a urethane-modified polyester resin as a main component is obtained.

Production method (2): A urethane-modified polyester resin is produced by reacting the polyester (R) with an isocyanate compound in the presence of the polyester (N).

Polyester (N) and polyester (R)
Can be produced using the same reaction apparatus under the same reaction conditions as in the above-mentioned production method (1), except that each is pulverized and thoroughly mixed. By this manufacturing method, a binder resin containing a urethane-modified polyester resin can be obtained.

Polyester (R) and polyester (N)
The mixing ratio can be 5:95 to 80:20 by weight.

Manufacturing method (3): The urethane-modified polyester resin manufactured by the manufacturing method (1) and / or the manufacturing method (2) and another resin are kneaded and mixed at the time of manufacturing the toner.

The urethane modified polyester resin and the resin mixed at the time of toner production can be used in a weight ratio of 5:95 to 95: 5. Specific resins that can be used include polyester resins including polyester (R) and polyester (N), and vinyl resins, and these resin compositions may contain the wax according to the present invention in advance. it can.

The electrostatic charge image developing toner of the present invention may optionally contain a charge control agent in order to further stabilize its chargeability. The charge control agent is a binder resin 100
0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight
It is preferred to use parts by weight.

Charge control agents known in the art today include the following.

For example, organic metal complexes and chelate compounds are effective. Examples thereof include a monoazo metal complex, an aromatic hydroxycarboxylic acid, a metal complex, and an aromatic dicarboxylic acid-based metal complex. 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 and Ni. Like metals, or these metals and 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.

Conventionally, as a magnetic material, ferrosoferric oxide (F) has been used.
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), etc. are known, but according to the present invention, the above-mentioned magnetic materials are selectively used alone or in combination of two or more. I do. 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
about 10 μm, the magnetic characteristics when a 10K Oersted is applied show a coercive force of 20 to 150 Oersted saturation magnetization of 50 to 200 e
mu / g (preferably 50 to 100 emu / g) and a residual magnetization of 2 to 20 emu / g 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.

Carbon black, titanium white and any other pigments and / or dyes can be used as the colorant regardless of whether it is a single component or a two component. 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 followings are listed. Examples of magenta color pigments include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,1
0, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1,52,53,54,55,57,58,60,6
3,64,68,81,83,87,88,89,9
0, 112, 114, 122, 123, 163, 20
2,206,207,209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,10,1
3, 15, 23, 29, 35 and the like.

Although such a pigment may be used alone, it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment in combination. Examples of such magenta dyes include C.I. I. Solvent Red 1,
3, 8, 23, 24, 25, 27, 30, 49, 81,
82, 83, 84, 100, 109, 121, C.I. I.
Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,18,
22, 23, 24, 27, 29, 32, 34, 35, 3
6, 37, 38, 39, 40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25
And basic dyes such as 26, 27 and 28.

Other color pigments include cyan pigments such as C.I. I. Pigment Blue 2, 3, 15,
16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by Chemical Formula 3.

[0141]

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As the coloring pigment for yellow, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, C.I. I. Bat Yellow 1,3,20
And the like.

The colorant is used in an amount of 0.1 to 60 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the binder resin.
0 parts by weight.

As the negatively chargeable fluidizing agent used in the present invention, any agent may be used as long as the fluidity can be increased by adding it to the colorant-containing resin particles as compared with before and after addition. It is possible. 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.

A preferable fluidizing agent is a fine powder produced by vapor phase oxidation of a silicon halogen compound,
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 an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this manufacturing process, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound. Also includes. The particle size is desirably in the range of 0.001 to 2 μm as an average primary particle size, and it is particularly preferable to use silica fine powder in the range of 0.002 to 0.2 μm. .

Examples of commercially available silica fine powders produced by vapor phase oxidation of a silicon halogen compound used in the present invention include those commercially available under the following trade names.

AEROSIL (Japan Aerosil Co.) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N 20 V15 (WACK) -CHEMIE GMBH) N20E T30 T40 D-C Fine Silica (Dow Corning Co.) Francol (Fransil)

Further, it is more preferable to use a treated silica fine powder obtained by subjecting the silica fine powder produced by vapor-phase oxidation of the silicon halogen 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.

As a method for hydrophobizing, it is imparted by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs on the fine silica powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl. Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule
For example, dimethylpolysiloxane having a hydroxyl group bonded to Si and having one siloxane unit as a terminal unit may be used. These are used alone or as a mixture of two or more.

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

[0154]

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[0155]

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

[0157]

[Chemical 6]

(Wherein 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 hydrogen, an alkyl group or an aryl group. However, the above-mentioned alkyl group, aryl group, alkylene group, and phenylene group may contain an amine, and may have a substituent such as halogen within a range not impairing the charging property. Indicates a positive integer.)

Examples of such silicone oil having an amino group are as follows.

Viscosity at 25 ° C. Amine equivalent Product name (cPs) SF8417 (Tore Silicone Co., Ltd.) 1200 3500 KF393 (Shin-Etsu Chemical Co., Ltd.) 60 360 KF857 (Shin-Etsu Chemical Co., Ltd.) 70 830 KF860 (Shin-Etsu Chemical Co., Ltd.) 250 7600 KF861 (Shin-Etsu Chemical Co., Ltd.) 3500 2000 KF862 (Shin-Etsu Chemical Co., Ltd.) 750 1900 KF864 (Shin-Etsu Chemical Co., Ltd.) 1700 3800 KF865 (Shin-Etsu Chemical Co., Ltd.) 90 4400 KF369 (Shin-Etsu Chemical Co., Ltd.) 20 320 KF383 (Shin-Etsu Chemical Co., Ltd.) 20 320 X-22-2680 (manufactured by Shin-Etsu Chemical Co., Ltd.) 90 8800 X-22-380D (manufactured by Shin-Etsu Chemical Co., Ltd.) 2300 3800 X-22-3801C (manufactured by Shin-Etsu Chemical Co., Ltd.) 3500 3800 X-22-2810B (manufactured by Shin-Etsu Chemical Co., Ltd.) Shin-Etsu Gakusha, Ltd.) 1300 1700

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

The fluidizing agent used in the present invention has a specific surface area by nitrogen adsorption of 30 m ² / g or more, preferably 50 m ² / g or more, which is measured by the BET method, and gives good results. 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 material, a charge control agent or other additives are sufficiently mixed with a mixer such as a Henschel mixer or a ball mill. Then, using a heat kneader such as a kneader or an extruder to melt, knead and knead the meat to make the resins compatible with each other. The toner of the present invention can be obtained.

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

The measuring method of the melting point and the molecular weight of the wax used in the toner of the present invention is as follows.

(1) Measurement of melting point of wax Differential thermal analysis analyzer (DSC analyzer), DSC-7
ASTM D341 using (manufactured by Perkin Elmer)
Measure according to 8-82.

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

This was placed in an aluminum pan, and an empty aluminum pan was used as a reference, and the measurement temperature range was 30 to 20.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

During this temperature rising process, the endothermic peak of the main peak in the temperature range of 40 to 100 ° C. is obtained.

The temperature of this endothermic peak is taken as the melting point of the wax. If it is difficult to determine the melting point of the wax, for example, if a sub-peak or shoulder is observed at a temperature near the main peak, the endothermic peak temperature is measured in the same manner as the wax using the toner containing this wax as a measurement sample. The temperature of the main peak is defined as the melting point of the wax.

(2) Measurement of glass transition temperature (Tg) of binder resin and toner Differential thermal analysis analyzer (DSC analyzer), DSC-7
ASTM D341 using (manufactured by Perkin Elmer)
Measure according to 8-82.

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, and the measurement temperature range was 30 to 20.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

During this temperature rising process, the endothermic peak of the main peak in the temperature range of 40 to 100 ° C. is obtained.

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

(3) Measurement of molecular weight distribution of wax (GPC measurement condition) Apparatus: GPC-150C (Waters Co.) Column: GMH-HT 30 cm 2 stations (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0. 1% ionol added) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample injected

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

(4) Measurement of molecular weight distribution of binder resin The molecular weight of the chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column is stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent is flown through the column at this temperature at a flow rate of 1 ml / min. When the sample is a resin, a resin that has been passed through a roll mill (130 ° C., 15 minutes) is used. When the sample is a developer, the developer is dissolved in THF and then 0.2 μm.
m-filter and use the filtrate as a sample.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for creating a calibration curve,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. with a molecular weight of 6 × 10
² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ ,
It is appropriate to use 8.6 × 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.

As the column, 10 ³ to 2 × 10
^In order to accurately measure the molecular weight region of ^6, a plurality of commercially available polystyrene gel columns are preferably combined.
μ-styragel 500, 10 manufactured by Aters
Combination of ³ , 10 ⁴ and 10 ⁵ and Showa Denko sho
dex KA-801, 802, 803, 804, 80
A combination of 5,806,807 is preferred.

(5) Measurement of toner charge amount (FIG. 1) Conductivity of 500 mesh (which can be appropriately changed to a size where magnetic particles do not pass) at the bottom after weighing the developer sampled from the developing device developing carrier The measurement sample is put in the metal measuring container 2 having the permeable screen 3 and the metal lid 4 is placed on the measuring sample. At this time, the weight of the entire measuring container 2 is weighed and W ₁ (g)
And Next, in the suction device 1 (at least the portion in contact with the measurement container 2 is an insulator), suction is performed from the suction port 7 and the air volume control valve 6 is adjusted to set the pressure of the vacuum gauge 5 to 250 mmAq. In this state, suction is sufficiently performed (for about 2 minutes) to remove the toner by suction. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a condenser, and the capacity is C
(ΜF). Further, the weight of the whole measurement container after suction is weighed to be W ₂ (g). This triboelectric charge amount T (μC / g)
Is calculated as follows.

T (μC / g) = (C × V) / (W ₁ −W ₂ ).

[0183]

Example Production of Polyester (R) Production Example 1 Alcohol components, acid components shown in Table 3 in a 5-liter separable flask equipped with a reflux pipe, a nitrogen gas introduction pipe, a degassing pipe, a thermometer and a stirrer. A small amount of tin compound was added as a reaction catalyst. The flask was heated to about 200 ° C. while aeration with nitrogen gas to start the esterification reaction.

About 1 hour after the reaction was started, the water generated was removed to the outside of the reaction system, and the inside of the reaction vessel was decompressed by using a vacuum pump connected to a trap device to further advance the reaction. Was maintained for 3 to 10 hours to complete the reaction.

The T of the polyester thus obtained was
When Tg, hydroxyl value and molecular weight were measured, Tg was about 46.
° C, hydroxyl value is 38 mgKOH / g, Mw is 12,10
It was 0. This polyester resin is designated as R-1.

Production Examples 2 to 8 Polyester resins R-2 to R were prepared in the same manner as in Production Example 1 except that the alcohol component and the acid component shown in Table 3 were used.
-8 was obtained.

Production of Polyester (N) Production Examples 9 to 16, except that the alcohol component and the acid component shown in Table 4 were used.
Polyester resins N-1 to N-8 in the same manner as in Production Example 1.
I got

Production of Comparative Polyester Comparative polyester resins were obtained in the same manner as in Production Example 1 except that the alcohol component and the acid component shown in Tables 3 and 4 were used.

Production of Urethane-Modified Polyester Production Example 17 Xylene was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing tube, a reflux tube and a dropping device for an isocyanate compound.
00 parts by weight and polyester resin R-1 (100 parts by weight) were added. The polyester resin was dissolved in xylene by heating with stirring. Under xylene reflux, a xylene solution containing 5 parts by weight of diphenylmethane-4,4′-diisocyanate was added dropwise over a period of 2 hours.
After completion of the dropping, stirring was continued for 1 hour to complete the reaction.
By removing xylene, urethane-modified resin M-
1 was obtained.

Production Example 18 Production Example 1 except that polyester resin N-3 was added to a xylene solution as a reaction solvent after completion of the urethane modification reaction to obtain a uniform mixed solution with the urethane modified polyester resin.
A urethane-modified polyester resin M-2 was obtained in the same manner as in 7.

Production Example 19 After completion of the urethane modification reaction, a polyester resin N-3 and a low melting point wax LM-3 were added to a xylene solution as a reaction solvent.
(See Table 1) and high melting point wax HM-2 (see Table 2)
Was added to prepare a urethane-modified polyester resin M-3 containing a low-melting wax and a high-melting wax in the same manner as in Production Example 17, except that a uniform mixed solution with the urethane-modified polyester resin was added.

Production Example 20 Polyester resin R-1 (100 parts by weight) and polyester resin N crushed so as to pass through a mesh having a diameter of 2 mm
-3 (200 parts by weight) is mixed by stirring with a Henschel mixer or the like.

Next, a twin-screw kneader equipped with a device capable of supplying 5 parts by weight of tolylene diisocyanate in fixed amounts in 1 hour is prepared. The temperature of the kneading machine is set to 140 ° C., and the rotation speed of the kneading shaft and the rotation speed of the resin supply device are adjusted so that the entire amount of the polyester resin mixture can be melted and kneaded in one hour.

Using the twin-screw kneader, the polyester resin was melt-kneaded and simultaneously reacted with an isocyanate compound to obtain a urethane-modified polyester resin M-4.

Production Examples 21 to 27 Urethane-modified polyester resins M-5 to M-11 were obtained by using the polyester resin, isocyanate compound and urethane modification method shown in Table 5.

Made of urethane-modified polyester resin for comparison
A urethane-modified polyester resin for comparison was obtained by using the polyester resin, isocyanate compound and urethane-modified method shown in Table 5.

[Example 1] Urethane-modified polyester resin M-4 100 parts by weight Magnetic material 100 parts by weight Monoazo metal complex 2 parts by weight LM-3 (see Table 1) About 71% by weight and HM-2 (see Table 2) 7 parts by weight About 29% by weight of a pulverized product of a wax melt mixture (The wax melt mixture is a mixture of a low-melting wax and a high-melting wax in a heated and melted state, which are homogenized. It is preferably used. An endothermic pattern by a typical DSC measurement is shown in FIG.

The above materials were premixed with a Henschel mixer, and then melt-kneaded at 130 ° C. with a twin-screw kneading extruder. After allowing the kneaded product to cool, it is roughly crushed with a cutter mill, then crushed with a fine crusher using a jet stream, and further classified with an air classifier to obtain a weight average particle size of 6.7 μm.
Magnetic toner of Hydrophobic dry silica (BET 200 m ^{2 /} g) 1.0 is added to 100 parts by weight of this magnetic toner.
Toner (1) of the present invention was obtained by externally adding parts by weight with a Henschel mixer.

In order to evaluate the dispersibility of the wax, the above magnetic toner was observed at a low magnification with a polarizing plate attached to an optical microscope. As a result, only 7 to 8 bright spots showing the presence of liberated wax were observed in the visual field. It was good.

Using this toner, a GP-55 digital copying machine (manufactured by Canon Inc.) was used for continuous image output durability of 100,000 sheets, and the image density was 1. When the endurance of 35,100,000 sheets was completed, there was almost no change to 1.36, and there was no change in image quality such as scattering of line images and thickening, which was good. Further, when the surface of the photosensitive drum was observed in detail at the end of the 100,000-sheet endurance, no adhered wax was observed and no conspicuous damage was observed on the surface of the photosensitive drum. There was no image defect presumably caused by damage on the surface of the photosensitive drum on the image.

Next, NP-6060 copying machine (manufactured by Canon)
The fixing device is removed, the nip is adjusted to about 3.5 mm, the external driving device is attached, the fixing roller is rotated at 150 mm / sec, the temperature control device is attached, and the temperature is 100 to 250.
It was modified so that the temperature of the fixing roller could be changed in the range of ° C. The fixing test was carried out in a constant temperature bath controlled at a temperature of 3 to 5 ° C., after confirming that the fixing roller was in agreement with the temperature inside the bath, the power was turned on and the upper roller (heating roller) was set to 12
Immediately after reaching 0 ° C., a fixing test was conducted. At this point, the temperature of the lower roller (pressure roller) was about 90 ° C. Next, set the fixing roller to 2 with the heater energized.
A fixing test was conducted by continuing rotation for 0 minutes. The temperature of the lower roller (pressure roller) was about 100 ° C.

Next, copy paper (75 g
/ M ² ) was passed through a fixing device of 150 sheets at a rate of 20 to 30 sheets / minute, and immediately after that, a fixing test was performed.

As a result of the fixing test as described above, 19% immediately after the power was turned on, 12% after 20 minutes, and the transfer paper was 150%.
Immediately after passing a single sheet, it was 25%, which was a practically acceptable level. Further, when a blocking resistance test was carried out by leaving it in a constant temperature bath whose temperature was controlled at 50 ° C. for 7 days, it was found that although slight aggregation was observed, it was easily loosened and the fluidity was recovered immediately.

When the glass transition temperature (Tg) of the binder resin of this developer and the melting point of the wax were observed using DSC, Tg did not decrease to 58.4 ° C. and low-melting wax and high-melting wax were It was confirmed that each had a melting point almost the same as the melting point measured with the wax alone.

Example 2 Urethane-modified polyester resin M-1 100 parts by weight Polyester resin N-3 200 parts by weight Magnetic material 300 parts by weight Monoazo metal complex 6 parts by weight Wax melt mixture 21 parts by weight (used in Example 1) The toner (2) of the present invention was obtained in the same manner as in Example 1 except that the same as the above). When evaluated in the same manner as in Example 1, good results were obtained as shown in Table 7.

[Example 3] Wax 3 used in Example 1
A mixture of 5 parts by weight and polyester resin N-3 (65 parts by weight) was heated with stirring and melt-mixed to prepare a mixture of polyester resin and wax having a uniform composition. This mixture was pulverized so as to pass through a mesh having an opening of 1 mm.

A mixture of the above polyester resin and wax 20 parts by weight Urethane-modified polyester resin M-4 80 parts by weight Magnetic material 100 parts by weight Monoazo metal complex 2 parts by weight In the same manner as in Example 1 except that the toner of the present invention ( 3) was obtained. When evaluated in the same manner as in Example 1, Table 7
Good results were obtained as shown in.

[Examples 4 to 10] Example 1 except that the urethane-modified polyester resin shown in Table 6 (see Table 5), the low melting point wax (see Table 1) and the high melting point wax (see Table 2) were used. In the same manner as in Toners (4) to (1) of the present invention
0) was obtained. When evaluated in the same manner as in Example 1, good results were obtained as shown in Table 7.

Comparative Example As shown in Table 6, a urethane-modified polyester resin for comparison (see Table 5), a low melting point wax for comparison (see Table 1) and a high melting point wax for comparison (see Table 2) were used. A comparative toner was obtained in the same manner as in Example 1 except for the above. When evaluated in the same manner as in Example 1, the results shown in Table 7 were obtained.

[0210]

[Table 1]

[0211]

[Table 2]

[0212]

[Table 3]

[0213]

[Table 4]

[0214]

[Table 5]

[0215]

[Table 6]

[0216]

[Table 7]

The evaluation ranks in Table 7 are as follows.

(Evaluation of anti-offset property) Rank 5 ... No occurrence Rank 4 ... Very slight Rank 3 ... Minor Rank 2 ... Clear Rank 1 ... Paper is spread

(Evaluation of Blocking Resistance) Rank 5 ... No change Rank 4 ... Aggregate, but loosen immediately Rank 3 ... Hard to loosen Rank 2 ... No fluidity Rank 1 ... Caking

(Evaluation of Wax Dispersibility) Rank 5 ... No bright spots through polarizing plate Rank 4 ... Several bright spots Rank 3 ... 10 Several bright spots Rank 2 ... Particles consisting of wax only Rank 1 ... Many There are wax particles

The notes in Tables 3 to 7 are as follows. 1) Propylene oxide adduct of bisphenol A 2) Ethylene oxide adduct of bisphenol A 3) Diphenylmethane-4,4'-diisocyanate 4) Tolylene diisocyanate

[0222]

[0223]

INDUSTRIAL APPLICABILITY The present invention is excellent in all of the fixing property, anti-offset property, anti-blocking property, and fluidity, and particularly when a large number of copies are continuously and once, the last one
It exhibits good fixability up to a sheet.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a device for measuring a triboelectric charge amount of toner.

FIG. 2 is a graph showing an example of a DSC endothermic pattern of a wax preferably used in the toner of the present invention.

FIG. 3 is a DSC of a comparative wax used for a comparative toner.
It is a graph which shows an example of an endothermic pattern.

Claims (3)

[Claims] 1. A toner containing a binder resin, a colorant and a wax, wherein the binder resin comprises a polyester resin containing a urethane modified polyester resin which is a reaction product of a polyester resin and an isocyanate compound,
Further, the wax is composed of two kinds of waxes having different melting points, and the melting point of the two kinds of wax is represented by the following formula (1).
And the toner of (2), wherein the electrostatic charge image developing toner is characterized. [Equation 1] Formula (2) T _MH -T _ML ≧ 20 [In the formula, T _ML and T _MH represent the melting points of the low-melting wax and the high-melting wax, respectively. ] 2. The following relational expression (2 ′) in the expression (2):
2. The toner for developing an electrostatic charge image according to claim 1, wherein Formula (2 ′) 20 ≦ T _MH −T _ML ≦ 75 3. At least one of the two waxes
The toner for developing an electrostatic charge image according to claim 1, wherein the type of wax has a chemical structure represented by the following general formula (3). Formula (3) RY [R: shows a hydrocarbon group having a weight average molecular weight of 3000 or less by gel permeation chromatography. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ]