KR20220120775A - Toner for high speed machinery and its effects - Google Patents

Abstract

A purpose of the present invention is to provide a toner for a high-speed machine in which an electrophotographic method has a high thermal roll speed or fixes at a low temperature in a toner for a copier or a printer, wherein the toner contains 0.05-1.0 equivalent of a glycidyl compound based on a vinyl resin with a wide molecular weight distribution (Mn = 1,000-20,000, Mw = 50,000-2,000,000, Tg = 40-75 ℃) and a low acid value (AV = 1-10) and 1 mole of a COOH group, shows a balance of fixation, offset, and blocking is excellent, and in particular, there is a remarkable effect in an offset property, and an excellent effect in grindability when producing the toner.

Description

Toner for high speed machinery and its effects

The present invention relates to an electrophotographic toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc.

did it More specifically, it can cope with high-speed aircraft, and the balance of fixation and offset properties is sufficient,

It also relates to an electrophotographic toner having excellent pulverization properties.

In general, electrophotographic usage in PPC copiers and printers forms an electrostatic latent image on the photoreceptor,

Then, the latent image is developed using toner, and the toner image is applied on a sheet to be fixed such as paper.

After transferring, a method of heat-compression bonding with a hot roll is carried out.

In the above method, fixing is carried out under heat and pressure.

Therefore, it is fast and the thermal efficiency is very desirable, and therefore the fixing efficiency is particularly preferable. However, the thermal roll room

While thermal efficiency is desirable in the formula, in order to bring the toner into molten contact with the surface of the hot roll, the toner

The problem that adhesion transfers to the surface of the thermal roll, and then it re-transfers to the adhesion site and becomes dirty (offset phenomenon)

there is a point

On the other hand, as the steady demand for high-speed copiers increases, the speed of the fixing rolls inevitably increases.

There is a demand for a toner that can be fixed by heating in a short time. In addition, in terms of energy saving or stability,

There is a great demand for a toner that can be fixed at a very low temperature. Possible for fixing at low temperature

It is necessary to melt at a very low temperature and to have excellent fluidity at the time of melting. Melting at low temperature as above

It is preferable to reduce the molecular weight of the resin used in order to obtain a toner with excellent fluidity.

As the molecular weight decreases, the cohesive force of the resin becomes insufficient, and the offset phenomenon easily occurs, which is undesirable.

not. Usually, fluidity is a property of some degree, but it is mixed with high molecular weight compounds, and high molecular weight compounds are used.

Performance is supplemented by this cohesive force. As an example of the above, Japanese Patent Application No. 55-6895, Japanese Patent Application

Related technologies have been proposed in Korean Patent Application Publication No. 63-32180, US Patent No. 4,921,771, and the like. However, speed

This is not enough so far, and in many cases, countermeasures for machine improvement, etc. are being devised.

That is, there is a method of preventing offset by applying silicone omil with fabric or paper to the surface of the thermal roll. Kyung Lee

It is desirable because the equipment of the machine becomes complicated, the maintenance and management of the machine becomes complicated, and the cost increase is linked.

don't Therefore, as a toner for high-speed machines, it is not necessary to use oil such as silicone oil.

There is a demand for development of a fixing toner for a fixing method that is not used.

In the development of toners for oil-free fixing methods, toners using cross-linked polymers are also available as an offset prevention method.

is being proposed For example, Japanese Patent Application No. 60-36582, etc. discloses a method using a crosslinked polymer prepared by an emulsion polymerization method. In this case, the crosslinked polymer used contains 50 to 90% of the gel.

And, if the gel ratio is large, the purpose of improving the offset resistance is to deteriorate the pulverization property. In addition

On the other hand, when the crosslinked polymer ratio is small, the pulverization property is preferable, but the offset resistance is not improved.

It is extremely difficult to satisfy both offset resistance and pulverization properties. In addition, the method includes a cross-linked polymer agent

It is necessary to use a dispersing agent or a dispersing auxiliary agent together in the roughing. Since the dispersant is easy to absorb moisture,

It is necessary to remove the cross-linked polymer as much as possible after the preparation of the cross-linked polymer, as it adversely affects the stability, in particular, the stability of the charged material.

However, it requires great effort to completely remove the dispersant by washing, and the amount of drainage is also very large.

It is also cumbersome to deal with. In addition, in US Patent No. 4,966,829 publication, the gel component is 0.1 to 60% by weight.

In the ratio of tetrahydrofuran used, the molecular weight of the peak is mainly 1,000 to 25,000, and the molecular weight is

Soil containing a vinyl polymer containing at least one subpeak or shoulder of 3,000 to 150,000

You are disclosing that you are desirable. However, the method for preparing it is a suspension method, and even in this case, during emulsification

Since a dispersing agent or a dispersing aid is used in combination during manufacturing as in the case of law, the above emulsion polymerization is also completely the same.

I have Due to these problems, the present inventors have developed a resin by solution polymerization method as a resin for toner having excellent fixability.

(U.S. Patent No. 4,963,456) previously provided.

The resin by the solution polymerization method removes the solvent after the polymerization is completed, and at this time, the unreacted residual monomer or initiator

All low volatile components such as decomposition products can be removed by distillation, so there are very few impurities and electrically stable homogeneity.

of resin can be obtained, and it is thought that the optimum resin for toner can be obtained. However, the solution polymerization method

The production of cross-linked polymer is not possible due to the Weissenberg effect (resin is wound around the stirring rod).

There was a problem. Therefore, the present inventors have a method of polymerizing as much as possible in bulk, etc. (U.S. Patent No. 5,084,368)

Ho), but there is a limit to polymerization, and it has not been able to completely overcome the offset properties.

In addition, Japanese Patent Application No. 60-38700 discloses a copolymer (A) containing 3 to 40% of a glycidyl group-containing monomer and crosslinkable.

A toner binder prepared by heating and mixing compound (B) is disclosed. In the toner, an epoxy group is

Because it remains in a high amount, the toner of the reverse-charged material is generated through a long-term test, resulting in a durability problem.

Lush toners have not been developed.

The present invention aims to satisfy the above requirements, and is prepared by a solution polymerization method

By using a compound having a dill group and crosslinking in a specific ratio, it is possible to cope with high-speed groups, and also

It was found that a toner having a favorable balance of offsetting and blocking properties and having favorable pulverization properties could be obtained.

and came to completion.

As shown in Table 1, it was found that offset properties could be more simply strengthened by the method of the present invention.

In addition, the balance of fixing and blocking properties is desirable, and pulverization and high-speed durability are also desirable to maintain excellent practical performance.

you are doing

That is, the invention relates to an electrophotographic toner comprising at least a colorant, a binder and a charge control agent, wherein the binder is

a number average molecular weight of 1,000 to 20,000, a weight average molecular weight of 50,000 to 1,000,000, and a Mw/Mn of 3.5 or greater, and an acid

Among the COOH group-containing vinyl resin (A) and the COOH group-containing vinyl resin (A) having a value of 1.0 to 10 and a Tg point of 40 to 75° C.

Characterized in that it is composed of a glycidyl compound (B) having 0.05 to 1.0 equivalents of glycidyl groups per equivalent of COOH group

It is an electrophotographic toner.

Furthermore, a colorant, a charge control agent, and a number average molecular weight of 1,000 to 20,000, and a weight average molecular weight

50,000 to 1,000,000, Mw/Mn of 3.5 or more, an acid value of 1.0 to 10, and a COOH group content ratio having a Tg point of 40 to 75°C

Having 0.05 to 1.0 equivalents of glycidyl groups per equivalent of COOH groups in the vinyl resin (A) and the COOH group-containing vinyl resin (A)

A composition composed of a binder composed of the glycidyl compound (B) is melt-kneaded, and the obtained kneaded material is finely pulverized.

It relates to a method for producing an electrophotographic toner, characterized in that

In the present invention, used for the production of the COOH group-containing vinyl resin (A) used as one component of the binder

is a vinyl monomer of acrylic acid, methacrylic acid, maleic anhydride, maleic acid, fumaric acid, cinnamic acid, and unsaturated diwaxacic acid.

Noesters such as methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, octyl fumarate, methyl maleate, malate

At least one selected from ethyl leate, propyl maleate, butyl maleate, octyl maleate, etc. is copolymerized with the vinyl monomer

The obtained resin is used.

Further, examples of the vinyl monomer copolymerizable with the COOH group-containing vinyl monomer include styrene, p-methylstyrene, and α-methyls.

styrene, such as tyrene and vinyltoluene; Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, jade acrylate

ethyl, cyclohexyl acrylate, stearyl acrylate, benzyl acrylate, furfuryl acrylate, hydroxyethyl acrylate,

acrylic acid esters such as hydroxybutyl acrylate, dimethylaminomethyl acrylate, and dimethylaminoethyl acrylate; mail

Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, cyclohexyl methacrylate

Thread, stearyl methacrylate, benzyl methacrylate, furfuryl methacrylate, hydroxyethyl methacrylate, methacrylic acid hydroxyethyl

methacrylic acid esters such as hydroxybutyl, dimethylaminomethyl methacrylate, and dimethylaminoethyl methacrylate; fumaric acid

Unsaturated 2 such as dimethyl, dibutyl fumarate, dioctyl fumarate, dimethyl maleate, dibutyl maleate, and dioctyl maleate

diesters of waxic acid; nitriles such as acrylonitrile and methacrylonitrile; of acrylic acid, methacrylic acid, and cinnamic acid

unsaturated carboxylic acids; Acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, etc.

mid; and acrylamide propanesulfonic acid, and at least one of these monomers is used. Among these, especially

Preferred vinyl monomers include styrene, acrylic acid esters, methacrylic acid esters, dialkyl fumarate,

acrylonitrile, acrylamide, methacrylamide, and the like.

The COOH group-containing vinyl resin (A) has a number average molecular weight of 1,000 to 20,000 and a weight average molecular weight of 50,000 to 1,000,000.

It is a resin with a wide molecular weight distribution of 3.5 or more, Mw/Mn, and a resin having a Tg point of 40 to 75°C is preferable. 1,000

At the number average molecular weight below, the Tg point becomes 40° C. or less and blocking is caused, which is undesirable, and 20,000 or more

At a number average molecular weight, fluidity deteriorates and fixability deteriorates. In addition, at a weight average molecular weight of 50,000 or less

In order to improve the offset, a large amount of crosslinking is required, and the overall molecular weight is increased by increasing the crosslinking.

Fixability deteriorates. Conversely, if it is more than 1,000,000, a small amount of crosslinking causes gelation and the accuracy deteriorates. special

If Mw/Mn is less than 3.5, it is difficult to obtain a balance between settling and offset.

sex gets worse In addition, when the Tg point is 75° C. or higher, the softening point increases and the fixability deteriorates, so that the present invention provides

toner can be obtained. The COOH group content in the COOH group-containing vinyl resin (A) is 1.0 to 10 KOHmg/g as an acid value.

is preferable At 1.0KOHmg/g or less, the effects of the present invention cannot be expressed, and on the contrary, at 10KOHmg/g or more,

A large amount of crosslinking causes gelation, and since it separates and precipitates in the resin, it is not centralized and the offset property is not improved.

In the present invention, as the glycidyl compound (B), the weight average molecular weight is 3,000 to 10,000, and the epoxy value is

A vinyl resin containing 0.01 to 0.2 equivalents/100 g of glycidyl ester is preferable. Vinyl water with glycidyl ester

vinyl monomers containing glycidyl groups, such as glycidyl acrylate, β-methyl glycidyl acrylate,

Co-mixing one or more vinyl monomers such as glycidyl taacrylate and β-methylglycidyl methacrylate and other vinyl monomers

It is a resin obtained by polymerization. If the weight average molecular weight is 3,000 or less, it hardly thickens even when crosslinked, and anti-off

You cannot improve set properties. Conversely, even at 10,000 or more, the compatibility of the cross-linked product does not deteriorate during cross-linking.

Since the cross-linked product is separated and precipitated on the surface, it is not thickened and the offset property is not improved. Also, the off-time value is

It is preferable to exist in the range of 0.01-0.2 equivalent/100g. In the case of 0.01 equivalent/100g or less, the thickening hardly occurs.

Improvement of high offset properties is not possible. At 0.2 equivalent/100g or more, the compatibility of the crosslinked product deteriorates, and

Since the cross-linked product is separated and precipitated, a gel is formed, but it is not thickened and the offset property is not improved.

In the present invention, the use ratio of the COOH group-containing vinyl resin (A); and the glycidyl compound (B) is the COOH group-containing vinyl resin.

so that 0.05 to 1.0 equivalents of glycidyl groups in the glycidyl compound are equivalent to 1 equivalent of COOH groups in the resin (A).

use. If the amount is less than 0.05 equivalent, the desired effect of the present invention is not expressed, and if it is greater than 1.0 equivalent, the effect of the present invention is not expressed.

It is undesirable because the charging material fluctuates during the durability test.

In addition, in the method for producing the COOH group-containing vinyl resin (A), solution polymerization is preferable, and furthermore, as described above,

In order to make a resin with a wide mass distribution, it is preferable to mix a low molecular weight compound and a high molecular weight compound.

An example will be described. That is, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, and cumene, Solves #100, #150

(trade name, Esso Chemical Co., Ltd.) at least one solvent, vinyl monomer and polymerization initiator

Continuously maintaining the temperature and internal pressure in a pressure-resistant container pre-filled with solvent

to carry out polymerization reaction. The steady state is stored in a tank and a low molecular weight polymerization solution is obtained.

Separately, a high molecular weight heavy liquid is obtained by bulk polymerization, and a low molecular weight and a high molecular weight one are sufficiently mixed and dissolved.

The solvent is distilled off by continuously brushing with a vacuum system of about 0 to 200 mmHg, and the vinyl resin and the solvent are separated.

A solid COOH group-containing vinyl resin (A) can be obtained.

In the case of using the binder, the COOH group-containing vinyl resin (A) and the glycidyl compound (B) characterized in the present invention

For this, various methods as presented below can be taken.

(1) After mixing the glycidyl compound (B) with the COOH group-containing vinyl resin (A) with a Henschel mixer, using a twin-screw kneader, etc.

After melt-kneading at a temperature of 160-220°C, reacting with a COOH group and a glycidyl group sufficiently, the colorant and

A method of making toners by adding fillers necessary for toners, such as charge control agents.

(2) COOH group-containing vinyl resin (A) and glycidyl compound (B) as they are in an unreacted state, with colorants and charge control agents

After sufficiently mixing with the filler required for the toner, melt and knead at a temperature of 160~220℃ using a twin-screw kneader, etc.

A method of banung during the tonerization process.

(3) COOH group-containing vinyl resin (A) and glycidyl compound (B) in an unreacted state

After sufficiently mixing with the filler you need, melt-knead at a temperature of 110~140℃ using a twin-screw kneader, etc.

In the case of melt-kneading, there is hardly any reaction, and when the copier is fixed, the temperature of the thermal roll is set to 160~220℃.

Although it is preferable to carry out by any method, such as a method of

It is most efficient to carry out simultaneously at the time of melt-kneading.

As a coloring agent used in this invention, the well-known dye pigment generally used can be used.

For example, black pigments such as carbon black, acetylene black, lamp black, magnetite, yellow lead, yellow iron oxide, Chinese characters

Yellow G. Quinoline Yellow Lake, Permanent Yellow NCG, Molybdenum Orange, Balkan Orange, Indanthrene, Brilliant

Orange GK, Red Iron Oxide, Brilliant Carmine 6B, Pleazarin Lake, Methyl Viloret Lake, Fast Bioret

B, Cobalt Blue, Alkali Blue Lake, Phthalocyanine Blue, Fast Sky Blue Permanent Green B, Malacca

magnetic powders such as yite green lake, titanium oxide, zinc white, magnetite and soft ferrite.

All. The amount used is within the range of 0.1 to 20 parts by weight generally used based on 100 parts by weight of the toner component before mixing.

In the present invention, within the range that does not impair the object of the present invention, other resins, such as polyester resins,

Polyamide resin, vinyl chloride resin, polyvinyl butyral resin, styrene-butadiene resin, coumarone-indene resin, mela

Min resin, polyolefin resin, etc. may be partially mixed and used. In addition, nigrosine, quaternary ammonium salt containing metal

A well-known charge control agent including azo dye can be appropriately selected and used, and the amount used depends on the toner properties before mixing.

It is within the range of 0.1 to 10 parts by weight commonly used based on 100 parts by weight per minute.

In the present invention, any conventionally known method can be used as a method for preparing the toner. for example resin

Coloring agent, charge control agent, wax, etc. are pre-mixed in advance, followed by heating and melting kneading with a twin-screw kneader, followed by cooling.

Grind and classify into fine particles of about 10 microns.

The number average molecular weight and weight molecular weight in the present invention are obtained by the GPC method, and monodisperse standard polystyrene

It is the reduced molecular weight for which the calibration curve was drawn. Measurement conditions are as follows.

GPC apparatus: Jasco Twinkle HPLC

Detector: Shodeck RI SE-31

Column: Shodex GPCA-80M×+Shodex KF-802

Solvent: tetrahydrofuran

Flow rate: 1.2ml/QNS

Example

The present invention will be described in detail by the following examples. In addition, the following "wealth" refers to the Chinese unless otherwise specified.

indicates quantity.

Preparation example of COOH group-containing vinyl resin (A)

Preparation Example 1

To a solution consisting of 69.3 parts of styrene, 0.7 parts of methacrylic acid and 30 parts of xylene solvent, 0.5 parts of di- per 100 parts of styrene

750cc/hour in a 5 liter banunggi that uniformly dissolves t-butyl peroxide at an internal temperature of 200°C and an internal pressure of 6kg/cm2

It was continuously fed and polymerized to obtain a low molecular weight polymer solution.

Separately, as vinyl monomers, 66 parts of styrene, 33 parts of n-butyl methacrylate, and 1 part of methacrylic acid were substituted with nitrogen.

It was placed in a container, and after raising the internal temperature to 120°C, the temperature was maintained at the same temperature, and bulk polymerization was carried out for 10 hours. At this time

The polymerization rate was 51%. Then, 50 parts of xylene was added, and 0.1 parts of dibutyl peroxide and

50 parts of silane solution was continuously added for 8 hours while maintaining at 130°C, and the remaining monomers were polymerized for another 2 hours.

The polymerization reaction was completed and a high molecular weight polymer solution was obtained. Then, 100 parts of the low molecular weight polymer solution and

After mixing 140 parts of polymer solution, flush it in a container at 160°C and 10 mmHg to distill the solvent, etc. 2

erred. The obtained vinyl resin had a number average molecular weight of 3,800, a weight average molecular weight of 210,000, and a Tg of 63

℃ and the acid value was 6.2.

Preparation Examples 2 and 3

In Preparation Example, when preparing the low molecular weight polymer solution, the polymerization temperature was 200 ° C., except that 180 ° C. and 220 ° C. were

A vinyl resin was obtained almost in the same manner as in Production Example 1. The physical properties of the obtained material are presented in Table 1.

Preparation 4

In Preparation Example 1, except that the polymerization temperature was 200 ° C. to 160 ° C. when preparing the low molecular weight polymer solution, Preparation Example

A vinyl resin was obtained almost in the same manner as in 1. The physical properties of the obtained material are presented in Table 1.

Preparation Examples 5, 6 and 12

In Preparation Example 1, the ratio of 100/140 between the low molecular weight polymer solution and the high molecular weight polymer solution was 100/70, 100/14 and

A vinyl resin was obtained in the same manner as in Production Example 1, except that it was set to 100/420. Table 1 shows the physical properties of each material.

presented.

Preparation 7

When preparing the low molecular weight polymerization solution in Preparation Example 1, 69.3 parts of styrene and 0.7 parts of methacrylic acid as vinyl monomers are skiren

Vinyl resin in the same manner as in Production Example 1, except that 65.1 parts, n-butyl acrylate 4.2 parts, and methacrylic acid 0.7 parts

was obtained. The physical properties of the obtained material are presented in Table 1.

Preparation 8

When preparing the high molecular weight polymer solution in Preparation Example 1, 66 parts of styrene, 33 parts of n-butyl methacrylate as a vinyl monomer

Parts and 1 part of methacrylic acid, except that 79 parts of styrene, 20 parts of octyl fumarate, and 1 part of methacrylic acid were used in Preparation Example 1 and

Similarly, a vinyl resin was obtained. The physical properties of the obtained material are presented in Table 1.

Preparation 9

When preparing the high molecular weight polymer solution in Preparation Example 1, 66 parts of styrene, 33 parts of n-butyl methacrylate as a vinyl monomer

parts, except that 1 part of methacrylic acid was used as 69 parts of styrene, 30 parts of n-butyl methacrylate, and 1 part of monobutyl maleate;

A vinyl resin was obtained in the same manner as in Production Example 1. The physical properties of the obtained material are presented in Table 1.

Preparation 10

When preparing the low molecular weight polymer solution in Preparation Example 1, 69.3 parts of styrene and 0.7 parts of methacrylic acid as a vinyl monomer

Completely the same as in Preparation Example 1, except that 60.9 parts of styrene, 6.3 parts of n-butyl acrylate, and 2.8 parts of methacrylic acid were used.

to obtain a vinyl resin. The physical properties of the obtained material are presented in Table 1.

Preparation 11

When preparing the low molecular weight polymerization solution in Preparation Example 1, except that methacrylic acid was substituted with styrene, it was completely prepared

A vinyl resin was obtained in the same manner as in Example 1. The physical properties of the obtained material are presented in Table 1.

Example 1

86 parts of the vinyl resin obtained in Preparation Example 1, PD6300 (Styrene-acrylic resin containing a glycidyl group, epoxy value

0.19 equivalent/100 g, weight average molecular weight = 98,000, Tg = 52 ° C., Mitsui Doatsu Chemical Co., Ltd.) 2.5 parts Henschel

After mixing with a mixer, it was kneaded and reacted at 200° C. with a twin-screw kneader (PCM-30 type, Ikegai Decco Co., Ltd.).

After cooling and grinding, carbon black MA 100 (Mitsubishi Kasei Corporation) 8 parts, polypropylene wax (Bischol 550P) 5

After adding 1 part of Eisen Spiron Black TRH as a part and charge control agent, and mixing again with a Henschel mixer, a twin-screw kneader

(PCM-30 type, Ikegai Decco Co., Ltd.) was kneaded at 150°C. Then, by cooling, pulverizing and classifying,

A toner of 10 microns was obtained. 3 parts of the toner and 97 parts of the carrier were mixed to make a developer, and a commercially available high-speed copier was used.

Reconstructed to make an image, evaluated, and the results are presented in Table 1.

Example 2

Except for replacing the vinyl resin obtained in Preparation Example 1 with the vinyl resin obtained in Preparation Example 2, Example 1 and

A toner was obtained exactly in the same manner, and image evaluation was performed exactly in the same manner as in Example 1, and the results are shown in Table 1.

Example 3

Except for replacing the vinyl resin obtained in Preparation Example 1 with the vinyl resin obtained in Preparation Example 3, Example 1 and

A toner was obtained exactly in the same manner, and image evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 4

Except for replacing the vinyl resin obtained in Preparation Example 1 with the vinyl resin obtained in Preparation Example 5, Example 1 and

A toner was obtained exactly in the same manner, and image evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 5

A toner was obtained in exactly the same manner as in Example 1, except that 2.5 parts of PD6300 was 1.25 parts in Example 1.

In the same manner as in Example 1, image evaluation was performed, and the results are presented in Table 1.

Example 6

In Example 1, PD6300 was replaced with PD6100 (styrenic-acrylic resin containing a glycidyl group (epoxy value 0.10 equivalent/100 g as a resin;

Weight average molecular weight = 8,000, Tg = 56 ° C., except that it was set as Mitsui Doatsu Chemical Co., Ltd.)

Toner was obtained exactly in the same manner as in 1, and image evaluation was performed in exactly the same manner as in Example 1, and the results are shown in Table 1.

All.

Example 7

Except for replacing the vinyl resin obtained in Preparation Example 1 with the vinyl resin obtained in Preparation Example 7, Example 1 and

A toner was obtained in the same manner as in Example 1, and image evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 8

The same as in Example 1, except that the vinyl resin obtained in Preparation Example 1 was replaced with the vinyl resin obtained in Preparation Example 8.

A toner was obtained, and image evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 9

Except for replacing the vinyl resin obtained in Preparation Example 1 with the vinyl resin obtained in Preparation Example 9, Example 1 and

A toner was obtained in the same manner as in Example 1, and image evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Examples 10 and 11

86 parts of the vinyl resin obtained in Preparation Example 1, PD6300 (Mitsui Doatsu Chemical Co., Ltd.) 2.5 parts, carbon black

MA100 (manufactured by Mitsubishi Kasei) 8 parts, polypropylene wax (Bischol 5650P) 5 parts, Eizenspiron as a charge control agent

After adding 1 part of black TRH, mixing with a Henschel mixer

de) at 130°C and 170°C. Except that, a toner was obtained in the same manner as in Example 1, and the same procedure as in Example 1 was used.

Table 1 shows the results of crab image evaluation.

Example 12

86 parts of the vinyl resin obtained in Preparation Example 1, 2.5 parts of PD6300, 8 parts of carbon black MA100 (manufactured by Mitsubishi Chemical), polypro

51 parts of fillene wax (Bischol 550P) and 2 parts of cetyltrimetalammonium bromide as a charge control agent were mixed with a Henschel mixer.

Then, it was kneaded at 150° C. with a twin-screw kneader (PCM-30 type, Ikegai Decco Co., Ltd.). Then, cooling,

A toner of about 10 microns was obtained by pulverization and classification. 3 parts of the toner and 97 parts of the carrier are mixed to form a developer.

+ An image was made by improving a commercial high-speed copier by using the charged material toner, and evaluated in the same manner as in Example 1.

The results are presented in Table 1 below.

How to evaluate toner

(1) Settling characteristics

Change the temperature of the fixing roll by 10℃ to make copies, and place a rubber paper between the all black part of the copy and the white background.

It is reciprocated 100 times with a constant force by a rain eraser (Plastic Rubber Eraser Mono).

The blackness of the all-black portion was measured with an ink densitometer, and the degree of toner drop-off was expressed as a density ratio. 80% or more

The lowest remaining temperature was shown.

(2) Offset resistance

When copied, the temperature at which the offset occurred is displayed as it is.

(3) Blocking resistance

Visually report the degree of agglomeration of the powder after curing the polymerized toner at a temperature of 50°C and a relative humidity of 50% for 1 week.

Measurements were made as follows.

(double-circle) : There is no aggregation at all.

○: It is slightly agglomerated, but it is loosened by shaking the container lightly.

(triangle|delta): There is an aggregate which does not loosen even if the container is shaken well.

x: It is completely lumped.

(4) High-speed durability

A commercial high-speed copier (copy speed of 72 sheets/min) is subjected to a continuous test of 10,000 sheets, and the pattern is copied to check the reproducibility.

was large. The difference in image quality was checked before and after the continuous test.

○: There is almost no difference between before and after

△: ID (phase density) significantly decreased after continuous testing

x: Blurring occurred and the image quality was greatly disturbed.

(5) Grinding Chamber

Partially collected and pulverized after biaxial kneading during toner manufacturing, particle size from 10 mesh to 16 mesh

It was pulverized with a jet mill in the range. Measure the particle size distribution with a Coulter counter and obtain a particle size ratio of 5-20μ.

do.

◎ : 85% or more

○ : 70~85%

△ : 50~70%

× : 50% or less

Claims (7)

An electrophotographic toner comprising at least a colorant, a binder and a charging composition, wherein the binder comprises a number average minute
A mass (Mn) is 1,000 to 20,000, a weight average molecular weight (Mw) is 50,000 to 1,000,000, Mw/Mn is 3.5 or more, and an acid
Glycylic acid per equivalent of COOH groups in vinyl resin (A) containing COOH groups having a value of 1.0 to 10 and a glass transition temperature (Tg) of 40 to 75° C.
a glycidyl compound (B) in an amount sufficient to provide 0.05 to 1.0 equivalents as diyl groups, wherein the glycidyl
The compound has a weight average molecular weight of 3,000 to 10,000 and contains a glycidyl-ester having an epoxy value of 0.01 to 0.3 equivalents/100 g
An electrophotographic toner, characterized in that it is a resin. The resin according to claim 1, wherein the binder is obtained by reacting a COOH group-containing vinyl resin (A) with a glycidyl compound (B).
A composition for electrophotographic toner. According to claim 1, wherein the binder is a COOH group-containing vinyl resin (A) acrylic acid, methacrylic acid, maleic anhydride,
At least one carboxyl selected from the group consisting of maleic acid, fumaric acid, cinnamic acid, and monoesters of unsaturated dibasic acids
Monomers comprising silic acid or carboxylic acid derivatives Co-polymerization of additional vinyl monomers copolymerizable with these monomers
An electrophotographic toner is obtained by polymerization. 4. The method of claim 3 wherein said additional vinyl monomer is selected from the group consisting of styrene, acrylate esters, methacrylate esters,
An electrophotographic toner selected from dialkyl fumarate, acrylonitrile, acrylamide and methacrylamide. A number average molecular weight (Mn) is 1,000 to 20,000, a weight average molecular weight (Mw) is 50,000 to 1,000,000, and Mw/Mn is 3.5 or more
and the COOH group-containing vinyl resin (A) and the COOH group having an acid value of 1.0 to 10 and a glass transition temperature (Tg) of 40 to 75 ° C.
A sufficient amount of glycidyl to provide 0.05 to 1.0 equivalents as glycidyl groups per equivalent of COOH groups in the euvinyl resin (A).
It includes a dill compound (B), wherein the glycidyl compound (B) has a weight average molecular weight of 3,000 to 10,000, and an epoxy value
A kneaded product obtained by melting and kneading a composition composed of this 0.01 to 0.3 equivalent/100 g of a binder, a colorant and a charge control agent.
A method for producing an electrophotographic toner, characterized in that the fine pulverization. The method according to claim 5, wherein at least one part of the COOH group-containing vinyl resin (A) is prepared by solution polymerization. The method according to claim 5, wherein the binder heats the COOH group-containing vinyl resin (A) and the glycidyl compound (B) at 160 to 220°C;
A method obtained by melting, kneading, or reacting.