JP3453482B2 - Toner for developing electrostatic images - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[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.
A number of methods are known as described in Japanese Patent Publication No. 43-24748 and Japanese Patent Publication No. 43-24748. 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 devices have been developed for the final step of fixing the toner image on a sheet such as paper, but the most general method at present is a pressure heating method using a heat roller.

In the pressure contact heating method using a heating roller, the surface of the heat roller having a releasability for the toner and the toner image surface of the sheet to be fixed are brought into contact with each other under pressure to pass the sheet to be fixed, thereby fixing the toner image. Is to do. 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 remarkable especially 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 toner particle size, the surface area of the toner is increased, so that the width of the charge amount distribution is increased and fogging is likely to occur. In addition, the increase in the toner surface area makes the charging characteristics of the toner more susceptible to 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. .

Japanese Patent Publication No. 2-48112 discloses a urethane-modified polyester resin obtained by reacting a saturated polyester resin having a specific number average molecular weight with an isocyanate compound. Although the average molecular weight is small and the molecular weight distribution is narrow, the fixability may be improved, but the hot offset resistance is not sufficient and improvement is required.

Further, in Japanese Patent Laid-Open No. 2-256066,
An electrophotographic toner using a urethane-modified polyester resin containing a gel content of 2 to 75% by weight as a binder resin is disclosed. In this case, the hot offset resistance is practically at a level at which there is no problem, but the low-temperature fixability is still insufficient, and improvement is required.

Further, Japanese Patent Application Laid-Open No. 1-154068 discloses a toner which uses urethane-modified polyester as a binder resin and contains polypropylene wax and 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.

[0021]

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 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 exhibits excellent fixability in the halftone portion even when the particle size is reduced from low speed to high speed copying machines, and which makes it possible to 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 a toner for developing an electrostatic charge image which gives a good image even under low humidity and high humidity without being affected by environmental changes.

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

[0030]

The present invention is a toner produced through a melt-kneading step and a pulverizing step, which is a toner containing a binder resin, a colorant and a wax.
The binder resin is a urethane-modified polyester resin which is a reaction product of a polyester resin and an isocyanate compound, and the polyester resin before modification is an ethylene oxide adduct of bisphenol A (EO-B) as an alcohol.
PA) and a propylene oxide adduct of bisphenol A (PO-BPA), which are used in a molar ratio of EO.
-BPA / PO-BPA = a polyester resin synthesized using a ratio of 0.01 to 10, wherein the toner contains 0.01 to 10 % by weight of tetrahydrofuran (THF) insoluble matter based on all binder resins. And toner of the toner
Soluble gel permeation chromatography (GP
In the molecular weight distribution measured by C), the molecular weight is 10
It has a main peak (Mp) in the region of 00 to 20,000 and a sub peak and / or a shoulder in the region of molecular weight of 100,000 or more, and the ratio of the Z average molecular weight (Mz) to the weight average molecular weight (Mw). And an Mz / Mw of 100 or more.

According to the study by the present inventor, in order to obtain a toner using a urethane-modified polyester resin as a binder resin, which satisfies the contradictory characteristics of low temperature fixing property, hot offset resistance and blocking resistance, However, it is not enough to control the gel content of the conventionally known binder resin.

That is, if the gel content in the binder resin is large, the hot offset resistance can be improved, but the low-temperature fixability is obviously inferior. Although the fixability may be improved, the hot offset resistance is obviously inferior.

Further, in order to obtain a toner satisfying both low temperature fixing property and hot offset resistance at the same time, it is not enough to define the gel content contained in the binder resin, because it is necessary to prepare a toner. This is because the binder resin is subjected to mechanical shearing force in the kneading step to break the polymer chains, which is also the case in the polymer chains constituting the gel component.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION The toner of the present invention contains at least a urethane-modified polyester resin as a binder resin,
Moreover, the toner contains 10% by weight or less of tetrahydrofuran (THF) insoluble matter with respect to the total binder resin, and the THF soluble matter of the toner has a molecular weight distribution measured by gel permeation chromatography (GPC). Main peak (M
pz), has a subpeak and / or a shoulder in the region of molecular weight of 100,000 or more, and is Mz / which is the ratio of the Z average molecular weight (Mz) and the weight average molecular weight (Mw).
The Mw is 100 or more.

The toner of the present invention has a THF insoluble content of 0.0
The content is 1 to 10% by weight, preferably 0.
The content is preferably 05 to 5% by weight, and more preferably 0.1 to 2% by weight. If the THF insoluble content of the toner exceeds 10% by weight, the hot offset resistance may be improved, but the low temperature fixing property cannot be satisfied, which is not preferable. Also, 0.0
If it is less than 1% by weight, the hot offset resistance is not improved, which is not preferable.

In addition, in the molecular weight distribution measured by GPC of the THF soluble component of the toner, the molecular weight is 1000-2.
It has a main peak in the region of 10,000 and a sub-peak and / or a shoulder in the region of molecular weight of 100,000 or more. The main peak may be in the molecular weight range of 1,000 to 20,000, preferably in the range of 3,000 to 15,000, and more preferably in the range of 5,000 to 10,000. The main peak molecular weight is 100
If it is less than 0, the hot offset resistance is impaired, and if it exceeds 20,000, the low-temperature fixability is impaired, which is not preferable.

The sub-peaks and / or shoulders may be in a region having a molecular weight of 100,000 or more, preferably in a region having a molecular weight of 150,000 or more, and more preferably in a region having a molecular weight of 200,000 or more. good. When it has no sub-peak and / or shoulder in the molecular weight range of 100,000 or more, the hot offset resistance is significantly impaired, which is not preferable.

Further, Mz / Mw of the THF-soluble component of the toner
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. If Mz / Mw is less than 100, hot offset resistance may be insufficient, and if it exceeds 2000, low-temperature fixability may be impaired, which is not preferable.

In the toner of the present invention, Mz is 500,000 to
It may be 1 billion, but it is preferably 800,000 to 700 million, and more preferably 1 million to 500 million. If the Mz is less than 500,000, the hot offset resistance is significantly deteriorated, and if the Mz is more than 1 billion, the pulverization efficiency in producing the toner may be decreased, which is not preferable.

The Mw may be 5,000 to 10,000,000, preferably 10,000 to 7,000,000, and more preferably 50,000 to 5,000,000.
If the Mw is less than 5,000, the hot offset resistance may be deteriorated, and if the Mw is more than 10 million, the low temperature fixability may be impaired, which is not preferable.

Although Mn may be 1,000 to 200,000,
The case is preferably 1500 to 150,000, and more preferably 2000 to 100,000. If M
If n is less than 1000, blocking resistance may be deteriorated, and if Mn is more than 200,000, low temperature fixability may be deteriorated.

The Mw / Mn may be 5 to 1000, preferably 7 to 700, and more preferably 10 to 500. If Mw / M
When n is less than 5, hot offset resistance may be impaired, and when Mw / Mn exceeds 1000, low-temperature fixability may be impaired, which is not preferable.

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

When the content of the component having a molecular weight of 100,000 or more is less than 5%, the hot offset resistance is significantly deteriorated, the content of the component having a molecular weight of 100,000 or more exceeds 30%, and the content of the component having a molecular weight of 1 million or more exceeds 15%. If it exceeds the range, low-temperature fixability is impaired, 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., 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
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 with respect to the amount, the melting point is 60 ~
It may be 140 ° C.

In the toner of the present invention, the wax can 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 waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, and oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; carnauba Examples thereof include waxes containing a fatty acid ester as a main component such as wax, sazol wax, and montanic acid ester wax, and those obtained by partially or entirely deoxidizing fatty acid ester 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 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. Further, the one in which the hydrocarbon wax is fractionated by the use of press sweating method, solvent method, vacuum distillation or fractional crystallization method is 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-point wax component preferably used in the present invention comprises a hydrocarbon having a long-chain alkyl group with a small number of 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 (1).

RY (1) [R: Shows a hydrocarbon group having a weight average molecular weight of 3000 or less by gel permeation chromatography. Y: Shows a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, and a sulfonyl group. ]

Specific compounds include (A) CH ₃ (CH ₂ ) _n CH ₂ OH (n = about 20 to about 20)
_{0) (B) CH 3 (} CH 2) n CH 2 COOH (n = about 20 to about _{200) (C) CH 3 (} CH 2) n CH 2 OCH 2 (CH 2) m CH
₃ (n = about 20 to about 200, m = 0 to about _{100) (D) CH 3 (} CH 2) n CH 2 COO (CH 2) m CH
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 20 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 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 having 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 contained 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 entire binder resin. This is the case when the content is 50% by weight.

If the content of the urethane-modified polyester resin is less than 3% by weight, the offset resistance may be significantly deteriorated when used in the toner even if the wax according to the present invention is used. Not preferable. Similarly, when the content of the urethane-modified polyester resin exceeds 70% by weight, the low-temperature fixability may be impaired when used in a toner, and further, when the image is formed, the image density It is not preferable because it may decrease.

In the present invention, the alcohol component used in the polyester resin (hereinafter referred to as polyester (R)) which is made into a urethane-modified polyester resin by reacting with an isocyanate compound is 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, a bisphenol derivative represented by the formula (a);

[0068]

[Chemical 1]

Further, diols represented by the formula (b):

[0070]

[Chemical 2] Is mentioned.

[0071] In addition, glycerin, trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, and further, can be used, for example novolak type phenolic resin oxyalkylene ether such trifunctional or higher alcohols Le.

[0072] In addition, phthalate as 2-carboxylic acid functionality, terephthalic acid, isophthalic acid, such <br/> benzene dicarboxylic acids or their anhydrides phthalic anhydride; succinic acid, adipic acid, sebacic acid, azelaic acid such alkyl dicarboxylic acids or anhydrides thereof, or even carbon number 6-1
Succinic acid substituted with an alkyl group of 8 or its anhydride
Products ; fumaric acid, maleic acid, citraconic acid, itaconic acid
Such unsaturated dicarboxylic acids or their anhydrides.

[0073] Further, trimellitic acid as the trifunctional or higher carboxylic acid, pyromellitic acid, polycarboxylic acid such such as benzophenonetetracarboxylic acid and anhydrides thereof.

The alcohol component of the polyester (R) which is particularly preferable in the practice of the present invention is a bisphenol derivative represented by the above formula (a), which is contained in an amount of 70 mol% or more of the total alcohol component. As the acid component, phthalic acid or its acid anhydride, terephthalic acid, isophthalic acid, succinic acid, n- dodecenylsuccinic acid or anhydrides thereof, fumaric acid, maleic acid, 如 maleic anhydride
It is mentioned come dicarboxylic acids.

Further, an ethylene oxide adduct which is a bisphenol derivative represented by the above formula (a) (hereinafter referred to as EO
-BPA) and a propylene oxide adduct (hereinafter referred to as PO-BPA) are preferably used in combination, and the content ratio thereof is EO-B if it is expressed by a molar ratio.
PA / PO-BPA may be 0.01 to 10, but
The case is preferably 0.05 to 5, and more preferably 0.1 to 3.

If the molar ratio of EO-BPA / PO-BPA is less than 0.01, the polyester (R) is used.
Is not preferable because the molecular weight of is not sufficiently large.
If it exceeds 0, it becomes difficult to control the growth reaction of the polyester produced, and Tg is too low at the same time, which is not preferable.

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 6 mol%. This is the case when the content is mol%. If it is less than 1 mol%, the hot offset resistance may be significantly deteriorated when used as a urethane-modified polyester in a toner, which is not preferable.
If it exceeds 10 mol%, the low-temperature fixability may be impaired in the same manner, which is not preferable.

In the trifunctional or higher functional carboxylic acid, the total carboxylic acid component may be similarly contained in an amount of 0.5 to 10 mol%, preferably 1 to 7 mol%, and further preferably. Is the case of containing 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.

If the acid value exceeds 20 mgKOH / g, a side reaction between the isocyanate compound and the carboxyl group is not preferable when the urethane-modified polyester resin is used. When the hydroxyl value 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 exceeds 80 mgKOH / g, it is difficult to control the reaction with the isocyanate compound, which is not preferable.

Examples of the isocyanate compound which can be reacted with the polyester (R) include, for example, trellin diisocyanate (hereinafter referred to as TDI), hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate (hereinafter referred to as MDI), xylylene diisocyanate, Tetramethyl xylylene diisocyanate etc. can be mentioned.

The glass transition temperature (hereinafter referred to as Tg) of the polyester (R) may be 20 to 80 ° C., preferably 25 to 70 ° C., more preferably 3
This is the case when the temperature is 0 to 65 ° C. If Tg is lower than 20 ° C, the blocking resistance is significantly deteriorated and
When it exceeds 80 ° C., the low temperature fixability 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), which is measured using the THF-soluble content of polyester (R), is 2,000 to 100,000. The number average molecular weight (hereinafter referred to as Mn) may be 1,000 to 50,000, and preferably Mw is 4,000 to 70,000.
Is 2000 to 12000, more preferably Mw is 6000 to 50,000 and Mn is 2500 to 9
000.

If the Mw is less than 2000 and the Mn is less than 1000, the hot offset resistance may be impaired when the urethane-modified polyester is used in the toner, which is not preferable. Also, Mw is 1
If the Mn exceeds 50,000 and the Mn exceeds 50,000, the low-temperature fixability may be significantly deteriorated when used as a urethane-modified polyester in a toner, which is not preferable.

In the present invention, another resin that can be used together with the urethane-modified polyester 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, EO which is a bisphenol derivative represented by the above formula (a)
-BPA and PO-BPA are preferably used in combination,
The molar ratio of EO-BPA / PO-BPA is 0.01-1.
It may be 0, preferably 0.05 to 5, and more preferably 0.1 to 3.

The tri- or higher functional carboxylic acid may be contained in an amount of 0.5 to 10 mol%, preferably 1 to 7 mol%, more preferably 1 This is the case where the content is 0.5 to 5 mol%.

The Tg of the above polyester may be 45 to 90 ° C., preferably 47 to 80 ° C., and more preferably 52 to 70 ° C. If Tg is less than 45 ° C., blocking resistance may be significantly deteriorated, which is not preferable. Also, Tg
If it 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, the Mw is more preferably 7,000 to 3
This is the case where the Mn is 30,000 and 10,000. if,
When Mw is less than 3000 and Mn is less than 1000, hot offset resistance may be deteriorated, which is not preferable. Further, 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 (hereinafter referred to as modified polyester), which is the reaction product of the polyester (R) and the isocyanate compound, may be 30 to 90 ° C, and preferably 40 to 70 ° C. Yes, 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, and if the Tg exceeds 90 ° C., the low-temperature fixability may be impaired, which is not preferable.

Regarding the molecular weight distribution of the THF-soluble component of the modified polyester, the Z-average molecular weight (hereinafter referred to as Mz) is 50,000 to 5
10 million, Mw is 4000-2 million, M
n is 1000 to 100,000 and Mz / Mw is 5 to 500
0, and Mw / Mn should be 2.5 to 500,
Preferably, Mz is 100,000 to 20,000,000 and Mw is 5
000 to 1.5 million, Mn is 2000 to 50,000, Mz / Mw is 15 to 4000, Mw / Mn is 3 to 400, and more preferably Mz is 200,000 to 10 million and Mw is 10,000 to 1.2 million, M
n is 3000 to 30,000 and Mz / Mw is 20 to 200
0, and Mw / Mn is 5 to 300.

The binder resin (hereinafter, simply referred to as the binder resin) composed of the modified polyester and the substantially unmodified polyester (N) may have a Tg of 45 to 75 ° C, preferably 50 to 70 ° C. And more preferably 5
This is the case of 2 to 68 ° C. If Tg is less than 45 ° C, blocking resistance tends to be poor,
If the Tg exceeds 75 ° C., the low temperature fixability may be impaired, which is not preferable.

The binder resin has a molecular weight distribution of Mz of 30,000 to
1 billion, Mw is 3000 to 3 million, Mn
Is 1000 to 80,000, Mz / Mw is 5 to 10,000, and Mw / Mn is 2 to 2000, preferably Mz is 50,000 to 500 million and Mw is 5000 to 20.
It is 0,000, Mn becomes 1500-50,000, and Mz / Mw
Is 7 to 5000, and Mw / Mn is 3 to 100, more preferably Mz is 100,000 to 300 million, Mw is 5000 to 1 million, and Mn is 2000.
~ 30,000, Mz / Mw becomes 10-3000, M
This is the case where w / Mn 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 the toner is used. When Mz exceeds 1 billion, Mw exceeds 3 million, and Mn exceeds 80,000, low-temperature fixability may be deteriorated, which is not preferable. Mz / Mw is less than 5, M
When w / Mn 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 practical problem. Also, Mz / Mw is 10
When it exceeds 00 and Mw / Mn exceeds 2000, the dispersion of the wax or the colorant may deteriorate, 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 when the weight percentage is reached. If the THF insoluble content is less than 2% by weight, the hot offset resistance may be deteriorated, and if the THF insoluble content exceeds 70% by weight, the dispersibility of the wax may be significantly deteriorated. Absent.

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 producing 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 and pn-dodecylstyrene; ethylene, Ethylenically unsaturated monoolefins such as propylene, butylene, 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 mono-monomers such as n-butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate. Carboxylic acid 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, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, 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; vinylnaphthalene compounds; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; esters of the above 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, alkenylsuccinic 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; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides thereof and monomers having a carboxyl group such as 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.

(1) A urethane-modified polyester resin is produced by reacting with an isocyanate compound in the presence of only the polyester (R). Polyester (R) 100
The isocyanate compound may be added in an amount of 0.1 to 10 parts by weight based on parts by weight, or may be continuously added in small amounts. The reaction temperature is 100 to 200 ° C., and the temperature can be changed stepwise as needed. The reaction time is about 1 minute to 6 hours, though it varies depending on the reaction temperature. When 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.

(2) Polyester (R) is reacted with an isocyanate compound in the presence of polyester (N) to produce a urethane-modified polyester resin. The polyester (N) and the polyester (R) can be produced using the same reaction apparatus under the same reaction conditions as in the above production method (1), except that a mixture of the pulverized and well mixed polyester is used. In addition, the wax according to the present invention can be included at the time of production. 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.

(3) The urethane-modified polyester resin produced by the production method (1) and / or the production method (2) and another resin are kneaded and mixed at the time of producing the toner. The urethane modified polyester resin and the resin mixed at the time of manufacturing the toner 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 can contain the wax according to the present invention in advance. .

In the toner for developing an electrostatic charge image of the present invention, a charge control agent can be used, if necessary, in order to further stabilize its chargeability. The charge control agent is the 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 monoazo metal complexes, aromatic hydroxycarboxylic acids, metal complexes, and aromatic dicarboxylic acid-based metal complexes. In addition, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides,
Examples thereof 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
Examples thereof include alloys with metals such as d, Ca, Mn, Se, Ti, W and V, and mixtures thereof.

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 ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuF)
e ₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), iron nickel oxide (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe)
₂ O ₃ ), iron oxide barium (BaFe ₁₂ O ₁₉ ), iron oxide magnesium (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known, but according to the present invention, the above magnetic materials are 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 ferric tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
The magnetic characteristics at the application of 10 K oersted are about 20 μm-150 oersted for coercive force and 50-200 for saturation magnetization at about μm.
Emu / g (preferably 50 to 100 emu / g) and 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 recommended 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, the dye may be 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. Mordant 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. Mordant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. There are Basic Green 6 etc. Examples of pigments include yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red lead yellow lead, 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, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue,
First Sky Blue, Indren Sren Blue BC,
Chrome Green, Chrome 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. Bat 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 to use it in combination with a dye and a pigment 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,
3,8,23,24,25,27,30,49,81,
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
Basic dyes such as 26, 27 and 28 can be mentioned.

Other color pigments include cyan color 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 in the phthalocyanine skeleton having the structure represented by the chemical formula 3 or the like.

[0119]

[Chemical 3]

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
Etc.

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

As the negatively chargeable fluidizing agent used in the present invention, any agent can be used as long as the fluidity can be increased by adding it to the colorant-containing resin particles before and after the addition. It is possible. For example, fine powder silica such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder and the like, fine powder silica such as wet process silica and dry process silica, and silane coupling agent, titanium coupling agent, silicone oil, etc. There is a treated silica which has been subjected to a surface treatment by.

A preferable fluidizing agent is a fine powder produced by vapor phase oxidation of a silicon halogen compound,
It is so-called dry process silica or fumed silica and is produced by a conventionally known technique. For example, the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame is utilized, 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 fine composite 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 preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, silica fine powder in the range of 0.002 to 0.2 μm is used. .

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.

[0127]   AEROSIL (Japan Aerosil Co., Ltd.) 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     (WACKER-CHEMIE GMBH company) N20E                                                       T30                                                       T40   D-C Fine Silica (Dow Corning Co.)   Francol (Fransil)

Furthermore, 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. Among the treated silica fine powders, those obtained by treating the silica fine powder so that the degree of hydrophobicity measured by the methanol titration test is in the range of 30 to 80 are particularly preferable.

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

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl. Dimethylchlorosilane, brommethyldimethylchlorosilane, 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, there is dimethylpolysiloxane having siloxane units and each terminal unit having a hydroxyl group bonded to Si. 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 the following amino group or silicone oil is necessary for achieving the purpose of the present invention. You may use according to it.

[0132]

[Chemical 4]

[0133]

[Chemical 5]

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.

[0135]

[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 alkyl group,
The 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. m and n represent positive integers. )

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

[0138]                                       Viscosity at 25 ° C Amine equivalent Product name (cPs) SF8417 (manufactured by Torre Silicone) 1200 3500 KF393 (Shin-Etsu Chemical Co., Ltd.) 60 360 KF857 (made by 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 (manufactured by Shin-Etsu Chemical Co., Ltd.) 90 4400 KF369 (Shin-Etsu Chemical Co., Ltd.) 20 320 KF383 (Shin-Etsu Chemical Co., Ltd.) 20 320 X-22-3680 (manufactured by Shin-Etsu Chemical Co., Ltd.) 90 8800 X-22-380D (manufactured by Shin-Etsu Chemical Co., Ltd.) 2300 3800 X-22-3801C (Shin-Etsu Chemical Co., Ltd.) 3500 3800 X-22-3810B (manufactured by Shin-Etsu Chemical Co., Ltd.) 1300 1700

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

The fluidizing agent used in the present invention has a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more by nitrogen adsorption measured by the BET method, which gives good results. Fluidizing agent 0.01 per 100 parts by weight of toner
-8 parts by weight, preferably 0.1-4 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, and after cooling and solidifying the melt-kneaded product, the solidified product is crushed and the crushed product is classified. The toner of the present invention can be obtained.

Further, the fluidizing agent and the toner are thoroughly mixed with a mixer such as a Henschel mixer to obtain the electrostatic image developing developer of the present invention having the additive on the surface of the 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) Melting point measurement of wax Differential thermal analysis measuring device (DSC measuring device), 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 between 0 ° C and normal temperature and normal humidity.

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, such as when sub-peaks or shoulders are observed at temperatures near the main peak, measure the endothermic peak temperature by the same method as the wax using the toner containing this wax as the measurement sample. The melting point of the wax is the temperature of the main peak.

(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
Precisely weigh mg.

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 between 0 ° C and normal temperature and normal humidity.

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 of 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 wax molecular weight distribution (GPC measurement conditions) Device: GPC-150C (Waters Co.) Column: GMH-HT 30 cm 2 stations (manufactured by Tosoh Corp.) 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 a 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 resin, the resin is passed through a roll mill (130 ° C., 15 minutes). If the sample is a developer, 0.2μ after dissolving the developer in THF
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.
Made or manufactured by Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
^It is suitable to use ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ standard polystyrene samples at least about 10 points. In addition, the detector is RI
A (refractive index) detector is used.

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

(5) Measurement of toner charge amount (FIG. 1) Conductor 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, weigh the entire measuring container 2 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 to adjust the air volume control valve 6 to adjust 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 V (volt). Here, 8 is a condenser, and the capacity is C
(ΜF). The weight of the entire measuring container after suction is weighed and is W ₂ (g). This triboelectric charge amount T (μC / g)
Is calculated as follows.

T (μC / g) = (C × V) / (W ₁ −W ₂ ) The THF insoluble matter in the present invention is insoluble in the THF solvent in the resin composition in the toner. It indicates the weight ratio of the polymer component (substantially crosslinked polymer) and can be used as a parameter indicating the degree of crosslinking of the resin composition containing the crosslinking component. The THF-insoluble matter is defined as a value measured as follows.

That is, 0.5 to 1.0 g of a toner sample is weighed (W ₁ g), and a cylindrical filter paper (for example, No.
86R) and applied to a Soxhlet extractor, and extracted with 100 to 200 ml of THF as a solvent for 6 hours to evaporate the soluble component extracted by the solvent,
After vacuum drying at 100 ° C. for several hours, the amount of the THF-soluble resin component is weighed (W ₂ g). The weight of a component other than the resin component such as the magnetic substance or pigment in the toner is (W ₃ g). T
The HF insoluble content is obtained from the following formula.

[0162]

[Equation 1]

[0163]

EXAMPLES The present invention will be described below with reference to examples.

Production of Polyester (R): (Production Example 1) In a 5 liter separable flask equipped with a reflux pipe, a nitrogen gas introduction pipe, a degassing pipe, a thermometer and a stirrer, the acid shown in Table 1 was used. A component, an alcohol component, and a small amount of a tin compound as a reaction catalyst were added. 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 produced water was removed to the outside of the reaction system, and the inside of the reaction vessel was decompressed 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 12
℃, hydroxyl value 28mgKOH / g, Mw 18700
Met. This polyester is designated as R-1.

(Production Examples 2 to 10) Polyesters R-2 to R-10 were obtained in the same manner as in Production Example 1 except that the acid component and alcohol component shown in Table 1 were used.

Production of Polyester (N): (Production Examples 11 to 20) Polyesters N-1 to N-10 were obtained in the same manner as in Production Example 1 except that the acid component and alcohol component shown in Table 2 were used.

Preparation of comparative polyesters: Tables 1 and 2
A polyester resin for comparison was obtained in the same manner as in Production Example 1 except that the alcohol component and the acid component shown in 1 were used.

Production of Urethane-Modified Polyester: (Production Example 21) 500 parts by weight of xylene and polyester resin R- were placed in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a reflux tube and an isocyanate compound dropping apparatus.
100 parts by weight of 1 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. Urethane-modified polyester resin M-1 was obtained by distilling off xylene. This is the urethane modification method A
And

Production Example 22 Same as Production Example 21 except that after the urethane modification reaction was completed, 300 parts by weight of polyester resin N-1 was added to a xylene solution as a reaction solvent to prepare a uniform mixed solution with the urethane modified polyester resin. Then, urethane-modified polyester resin M-2 was obtained. This is designated as urethane modification method B.

(Production Example 23) After completion of the urethane modification reaction, 300 parts by weight of the polyester resin N-1, 16 parts by weight of the low melting point wax LM-3 and 16 parts by weight of the high melting point wax HM-2 were added to a xylene solution as a reaction solvent.
Was added in the same manner as in Production Example 21 except that 12 parts by weight of was added to form a uniform mixed solution with the urethane-modified polyester resin.
A urethane-modified polyester resin M-3 containing a low melting point wax and a high melting point wax was obtained. This is designated as urethane modification method C.

(Production Example 24) 100 parts by weight of polyester resin R crushed so as to pass through a mesh having a diameter of 2 mm
-1 and 300 parts by weight of polyester resin N-1 were 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 a fixed amount in 1 hour was prepared. The temperature of the kneading machine was set to 140 ° C., and the rotation speed of the kneading shaft and the rotation speed of the resin supply device were adjusted so that the entire amount of the polyester resin mixture could be melted and kneaded in 1 hour.

Using this twin-screw kneader, the above polyester resin is melt-kneaded and at the same time reacts with an isocyanate compound to produce a urethane-modified polyester resin M.
-4 was obtained. This is designated as urethane modification method D.

(Production Examples 25 to 33) By using the polyester resin, isocyanate compound and urethane modification method shown in Table 3, urethane modified polyester resin M-
5 to M-13 were obtained.

Preparation of Comparative Urethane-Modified Polyester Resin: A urethane-modified polyester resin for comparison was obtained by using the polyester resin, isocyanate compound and urethane-modifying method shown in Table 3.

<Example 1>     Urethane modified polyester resin M-4 100 parts by weight     100 parts by weight of magnetic material     Monoazo metal complex 2 parts by weight     LM-3 (about 57% by weight) shown in Table 4 and HM-2 shown in Table 5     7 parts by weight of pulverized product of wax melt mixture (about 43% by weight)       (The wax melt mixture is a mixture of low-melting wax and high-melting wax.       The present invention is one in which the solution is heated and cultivated and mixed to make it uniform.       It is preferably used for the toner. Endotherm by typical DSC measurement       The pattern 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, when the above magnetic toner was observed at a low magnification with a polarizing plate attached to an optical microscope, 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 of 100,000 sheets, and the image density was 1. At the end of the 40,000,000-sheet endurance, there was almost no change to 1.42, 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, and after confirming that the fixing roller was in agreement with the temperature in the bath, the power was turned on and the upper roller (heating roller) was set to 12 ° C.
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, in this state, copying 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, 11.8% immediately after the power was turned on, 200 sheets of transfer paper were passed after 20 minutes, 1.3% for the first sheet, and 8.1 for the 200th sheet. %, 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. Similarly 45
A blocking resistance test was carried out by leaving it in a constant temperature bath controlled at a temperature of 30 ° C. for 30 days. As a result, it was found that although slight aggregation was observed, the loosening fluidity was immediately recovered and the fluidity was good.

Next, 1 g of the toner sample was precisely weighed to the mg unit, and cylindrical filter paper (No.
86R) and applied to a Soxhlet extractor, and extracted with an oil bath whose temperature was controlled at about 140 ° C. for 12 hours, using 200 ml of THF as a solvent. A THF-insoluble component was determined based on the weight of the component eluted in THF, and it was about 0.6% by weight.

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 was 58.8 ° C., which was almost the same as that of the low-melting wax and the high-melting wax. It was confirmed that each of the waxes had almost the same melting point as that measured with the wax alone.

Example 2 Urethane-modified polyester resin M-1 100 parts by weight Polyester resin N-1 300 parts by weight Magnetic material 400 parts by weight Monoazo metal complex 8 parts by weight Wax melt mixture 16 parts by weight (used in Example 1) The toner (2) of the present invention shown in Table 6 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 A mixture of 35 parts by weight of the wax mixture used in Example 1 and 100 parts by weight of the polyester resin N-1 is heated with stirring to be melt-mixed to obtain a uniform composition. A mixture of polyester resin and wax was prepared. Open this mixture 1m
It was crushed so as to pass through a m mesh.

Mixture of the above polyester resin and wax 27 parts by weight Urethane modified polyester resin M-4 80 parts by weight Magnetic material 100 parts by weight Monoazo metal complex 8 parts by weight except that the content is shown in Table 6 as in Example 1. Inventive toner (3) was obtained. When evaluated in the same manner as in Example 1, good results were obtained as shown in Table 7.

<Examples 4 to 14> Toners (4) to (14) of the present invention were prepared in the same manner as in Example 1 except that the urethane-modified polyester resin, low melting point wax and high melting point wax shown in Table 6 were used. Obtained. When evaluated in the same manner as in Example 1, good results were obtained as shown in Table 7.

Comparative Example The same as Example 1 except that the comparative urethane-modified polyester resin shown in Table 6 was used, and the comparative low melting point wax shown in Table 4 and the comparative high melting point wax shown in Table 5 were used. The evaluation results are shown in Table 7.

[0192]

[Table 1]

[0193]

[Table 2]

[0194]

[Table 3]

[0195]

[Table 4]

[0196]

[Table 5]

[0197]

[Table 6]

[0198]

[Table 7]

Evaluation of fixability

Blocking resistance evaluation

Offset resistance evaluation

Evaluation of wax dispersibility

Notes to Tables 1 to 3 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

[0205]

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.

Continuation of front page (56) Reference JP-A-63-56659 (JP, A) JP-A-7-168397 (JP, A) JP-A-4-361271 (JP, A) JP-A-4-318012 (JP , A) JP-A-4-226472 (JP, A) JP-A-4-211272 (JP, A) JP-A-4-36761 (JP, A) JP-A-2-256066 (JP, A) JP-A-2-25666 (JP, A) 2-87163 (JP, A) International publication 87/004811 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (2)

(57) [Claims] 1. A toner produced through a melt-kneading step and a pulverizing step, the toner containing a binder resin, a colorant, and a wax, wherein the binder resin is a reaction product of a polyester resin and an isocyanate compound. Which is a urethane-modified polyester resin, wherein the polyester resin before modification is an ethylene oxide adduct of bisphenol A as an alcohol (EO-BP).
A) and a propylene oxide adduct of bisphenol A (PO-BPA), which are used in a molar ratio of EO-
BPA / PO-BPA = a polyester resin synthesized using a ratio of 0.01 to 10, 0.01 to 10 wt% containing chromatic said toner respect tetrahydrofuran (THF) insoluble component of the total binder resin In addition, in the molecular weight distribution measured by gel permeation chromatography (GPC) of the THF soluble component of the toner, the main peak (M
p) and has a sub-peak and / or a shoulder in a region having a molecular weight of 100,000 or more, and Mz / Mw, which is a ratio of Z average molecular weight (Mz) and weight average molecular weight (Mw), is 100 or more. A toner for developing an electrostatic charge image, which is characterized in that 2. The THF-soluble matter Mz / Mw of the toner is 1
The toner for developing an electrostatic charge image according to claim 1, wherein the toner is from 00 to 2000.