JP3320319B2 - toner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in electrophotography, electrostatic recording, and the like.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
(U.S. Pat. No. 3,666,363) and Japanese Patent Publication No. 43-24748 (U.S. Pat.
As described in US Pat. No. 1,361), various methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. ,
Next, the latent image is developed with a toner to form a visible image, and if necessary, after transferring the toner image to a transfer material such as paper,
It is fixed by heating, pressure and the like to obtain a copy.

Various developing methods for visualizing an electrostatic latent image using toner have been known. For example, U.S. Pat.
No. 4,063, the magnetic brush method, the cascade developing method described in 2,618,552, and the powder described in 2,221,776. Cloud method, fur brush development method,
Many developing methods such as a liquid developing method are known.

Among these developing methods, a magnetic brush method, a cascade method, a liquid developing method, and the like using a developer mainly composed of toner and carrier have been widely put to practical use.
All of these methods are excellent methods in which good images can be obtained relatively stably.

On the other hand, various development methods using a one-component developer consisting of toner alone have been proposed, and one of the methods is a method using a developer consisting of magnetic toner particles.

Various methods and apparatuses have been developed for fixing the toner image to a sheet such as paper, which is the final step of the above-described electrophotographic method. One of the methods is a pressure heating method using a heat roller. is there.

In the pressure heating method using a heating roller, fixing is performed by allowing the toner image surface of the sheet to be fixed to pass through the surface of the heating roller, which has a surface having a releasability to the toner, while contacting the toner image surface under pressure. is there.

In this method, since the surface of the heat roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. And can be very effective in high speed electrophotographic copiers.

In particular, since copiers are moving toward higher speeds in the future, toners must meet the requirements of improved fixability to paper, good image density in high-speed development, and high durability. I have.

In such a heat roller fixing system,
In the prior art, a polyolefin wax is added to the toner to improve the offset resistance.

However, since the polyolefin wax has poor compatibility with the toner binder resin, poor dispersion of the polyolefin wax tends to occur during the production of the toner, and as a result, free polyolefin may be generated during pulverization.

Poor dispersion of the polyolefin wax in the toner not only leads to poor cleaning and deterioration of the offset resistance during running in a copying machine, but also increases the toner charging property. Image density reduction and the like are likely to occur.

In particular, further improvement in the dispersibility of the wax component is required since the particle size of the toner tends to be further reduced in the future.

As the particle size of the toner becomes smaller, charging up of the toner becomes a problem particularly in a low humidity environment, and the problem of a decrease in image density accompanying it is an unavoidable problem.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner capable of exhibiting good fixability and offset resistance even in a high-speed copying machine.

Still another object of the present invention is to provide a toner in which the amount of triboelectric charge between toner particles and between a toner and a toner carrier such as a sleeve is stable, and can be controlled to a charge amount suitable for a developing system to be used.

Still another object of the present invention is to provide a toner capable of increasing a density difference between dots for performing development faithful to a digital latent image, and in which a dot edge is sharply reproduced. is there.

Still another object is to provide a toner which maintains its initial performance even when the toner is used continuously for a long period of time.

It is still another object of the present invention to provide a toner having less fog and reversal fog even in an image forming process including post-charging.

Still another object is to provide a toner which reproduces a stable image which is not affected by changes in temperature and humidity.

It is still another object of the present invention to provide a toner having excellent storage stability that maintains initial characteristics even after long-term storage.

Still another object of the present invention is to provide a toner capable of preventing charge-up of a toner under low humidity, which is an adverse effect when the toner particle size is reduced, and providing a good image density.

[0023]

According to the present invention,

[0024]

Embedded image And a binder resin having an acid value of 2 mgKOH / g or more.

In the present invention, the substance represented by the above formula (1)

[0026]

Embedded image It is a toner containing a substance obtained by reacting the substance represented by the above formula (2).

Further, the present invention contains a substance obtained by reacting the substance represented by the above formula (1) with one substance selected from β-propiolactone, diketene, lactide, δ-valerolactone, and ε-caprolactone. The toner is characterized in that

By adopting the toner constitution of the present invention, even in a high-speed copying machine having a process speed of 380 mm / sec or more (a high-speed copying machine having an A4 copying speed of 60 sheets per minute or more), good fixability in a low-temperature environment can be obtained. And good image density in a low humidity environment.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention,

[0030]

Embedded image (Hereinafter referred to as substance a), n
Is preferably 30 or more, more preferably 40
That is all. Further, since the viscosity of the substance a increases as the number of n of the substance a represented by the above formula increases and affects the fixing property of the toner, the upper limit of the number of n of the substance a is 70 or less. It is preferred that

In the present invention, the substance a

[0032]

Embedded image (Hereinafter referred to as “substance A”) is obtained by reacting a substance (hereinafter referred to as “substance A”) with an alkyl chain length of the substance “a” and the substance “b”.

[0033]

Embedded image The viscosity and plasticity can be controlled by the amount of the reaction.

It is presumed that the structure of the substance A is as follows.

[0035]

Embedded image

Here, when the number n of the substance a is less than 20, the viscosity control tends to be insufficient even when the substance a is reacted with the substance b, and it is difficult to obtain the above action.

In the present invention, the number n of the substance a used for the substance A is 20 or more, preferably 30 or more, and more preferably 40 or more.

In the present invention, the substance a is a substance selected from the group consisting of β-propiolactone, diketene, lactide, δ-valerolactone, and ε-caprolactone.
The viscosity and plasticity of the substance (hereinafter, referred to as substance B) obtained by reacting with substance c) can be controlled by the amount of reaction between substance a and the alkyl chain length of substance a.

It is presumed that the structure of the substance B is as follows.

When an example of the substance c is ε-caprolactone

[0041]

Embedded image

In the present invention, when the number of n of the substance a is less than 20, even when the substance a is reacted with the substance c, the viscosity control is apt to be insufficient, and it is difficult to obtain the above-mentioned action.

In the present invention, the number n of the substance a used for the substance B is 20 or more, preferably 30 or more, and more preferably 40 or more.

In the present invention, the reason why the above effect is obtained is not clear, but it is speculated that the following phenomenon may occur.

When the toner containing the substance a and the binder resin having an acid value of 2 mg KOH / g or more or the substance A or the substance B is passed through the fixing roller and heated by the fixing roller, the substance a or the The substance A or the substance B exudes to the toner surface.

At this time, 1) the slipperiness of the toner with respect to the fixing roller is improved,
The toner on the unfixed image adheres preferentially to the paper instead of the fixing roller.

2) When the substance a, the substance A, or the substance B seeps out of the toner surface by heating the fixing roller, the substance a, the substance A, or the substance B covers the toner surface in a semi-molten or molten state. As a result, the heat transfer coefficient to the toner by the fixing roller is improved. It is considered that the occurrence of such a phenomenon improves the fixability and the anti-offset property.

In the present invention, the substance a and the acid value 2
The reason why good image density can be obtained in a low-humidity environment by using the binder resin or the substance A or the substance B at mgKOH / g or more is not clear, but it is presumed to be due to the following reason.

[0049]

Embedded image The substance B has a viscosity, depending on the reaction amount of the alkyl chain length of the substance a and the substance c (one substance selected from β-propiolactone, diketene, lactide, δ-valerolactone, ε-caprolactone). Plasticity can be controlled. Accordingly, the dispersibility of the substance A and the substance B can be improved in the binder resin. As a result, the chargeability and the environmental stability of the toner are improved, and the charge-up of the toner in a low humidity environment is prevented. However, it is considered that good image density can be obtained.

In the present invention, the substance a and the acid value 2 m
By using a binder resin of gKOH / g or more, the substance a
Is considered to be capable of forming and dispersing very small domains in a binder resin having an acid value of 2 mgKOH / g or more. For this reason, 1) the substance a is unlikely to be present on the surface of the pulverized particles even by pulverization, and the variation in the chargeability of the toner is reduced.

2) The dispersion state of the substance a in the binder resin can be easily controlled, and a more uniform dispersion state in the binder resin can be realized. For this reason, the variation in the chargeability of the toner is reduced. It is thought that as a result, the chargeability and environmental stability of the toner are improved, charge-up in a low humidity environment is prevented, and good image density can be obtained even in a low humidity environment. .

When the substance a and a binder resin having an acid value of less than 2 mgKOH / g are used, charge-up easily occurs in a low-humidity environment, and as a result, image density tends to decrease. This is because the dispersibility of the substance a in the binder resin becomes poor when the acid value of the binder resin is less than 2 mgKOH / g, and as a result, it becomes difficult to stabilize the toner charge amount. I believe.

In the present invention, in order to obtain the effect of the above-mentioned substance a, substance A or substance B, 1 to 20 parts by mass, preferably 2 parts by mass, per 100 parts by mass of the binder resin is used.
It is desirable to use up to 15 parts by mass.

In the present invention, the method of reacting the substance b with the substance a is not particularly limited. Examples of the method include sodium hydroxide, sodium ethoxide, potassium t-butoxide, metal sodium, and metal. Using a base catalyst such as potassium under pressure and at a temperature of 50
The reaction is carried out at a temperature of up to 300 ° C.

In the present invention, the method of reacting the substance c with the substance a is not particularly limited, but examples thereof include Al (C ₂ H ₅ ) ₃ and Zn (C ₂ H
₅ ) The reaction may be carried out in the presence of a catalyst such as ₂ or under heating.

In the present invention, the substance a is not particularly limited as long as n is 20 or more.

As an example, see US Pat. No. 2,892,85.
No. 8 obtained by modifying a wax alcohol produced by the production method described in No. 8.

The above-mentioned wax alcohol is produced in the stage of formation, polymerization, oxidation and hydrolysis of triethylaluminum.

The manufacturing process will be described below.

[0060]

Embedded image

Here, the substance in which R is H is

[0062]

Embedded image It is.

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image Can be cited.

In the present invention, the binder resin of the toner is not particularly limited, but polyester resin and styrene-acrylic resin are preferred.

The polyester resin is not particularly limited, and conventionally known polyester resins can be used. As the monomer constituting the polyester resin, the following known substances can be used, but the present invention is not limited thereto.

Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol,
Triethylene glycol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Pentaerythritol diallyl ether, trimethylene glycol, 2-ethyl-1,3-hexanediol,
Hydrogenated bisphenol A or a bisphenol derivative represented by the following formula;

[0069]

Embedded image

(Wherein R is an ethylene or propylene group, x and y are each an integer of 1 or more, and x +
The average value of y is 2-10. And the like.

Examples of the acid component include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid, or acid anhydrides thereof, succinic acid, adipic acid, and the like.
Examples thereof include dicarboxylic acids such as sebacic acid and azelaic acid, and anhydrides thereof, and aromatic dicarboxylic acids such as phthalic acid and terephthalic acid.

The trihydric or higher alcohol includes glycerin, sorbit, sorbitan and the like, and the trihydric or higher acid includes trimellitic acid, pyromellitic acid and the like, and acid anhydrides thereof.

The method for producing the polyester resin used in the present invention is not particularly limited, and a conventionally known production method is applied.

The styrene-acrylic resin is not particularly limited, and a conventionally known styrene-acrylic resin can be used. As the monomer constituting the styrene-acrylic resin, the following known substances can be used, but the present invention is not limited thereto.

For example, styrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p- n-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o -Nitrostyrene, p-
Styrene derivatives such as nitrostyrene; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate,
Α-methylene aliphatic monocarboxylic esters such as phenyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate,
Acrylic esters such as propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; acrylics such as acrylonitrile, methacrylonitrile, and acrylamide Acid or methacrylic acid derivatives; acroleins;
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Examples include carboxyl group-containing vinyl monomers such as maleic anhydride, fumaric acid, maleic acid and monoesters thereof such as methyl, ethyl, butyl and 2-ethylhexyl.

In the present invention, a combination of a styrene monomer, methacryl, or an acrylic monomer and a carboxyl group-containing monomer is preferred.

The method for measuring the acid value of the binder resin used in the present invention is described below.

Samples 2 to 10 g in 200 to 300 ml
Weighed in an Erlenmeyer flask, and methanol: toluene = 3
About 50 ml of a 0:70 mixed solvent is added to dissolve the resin.
If the solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% bromthymol blue and phenol red, a standardized N / 10
Titration is performed with a potassium hydroxide solution to an alcoholic solution, and an acid value is determined from the consumption of the potassium hydroxide solution by the following equation (1).

Acid value = KOH (ml) × N × 56.1 / sample mass (1) (where N is a factor of N / 10 KOH)

Examples of the binder resin for the toner include polyester resins, styrene-acrylic resins, styrene-vinyl methyl ether copolymers, styrene-butadiene copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile. -Styrene copolymer of styrene of indene copolymer and other vinyl monomers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid, phenol resin, aliphatic Alternatively, an alicyclic hydrocarbon resin, petroleum resin, chlorinated paraffin, or the like can be used.

In the present invention, a charge control agent can be used if necessary, and a conventionally known negative or positive charge control agent is used.

The following are examples of charge control agents known in the art today.

The following substances control the toner to be negatively charged.

For example, an organic metal complex or a chelate compound is effective, and examples thereof include a monoazo metal complex, an acetylacetone metal complex, an aromatic hydroxycarboxylic acid, and an aromatic dicarboxylic acid-based metal complex. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides and esters; and phenol derivatives such as bisphenol.

The following substances control the toner to be positively charged.

For example, denatured products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs thereof. Onium salts such as phosphonium salts and the like, and their lake pigments; triphenylmethane dyes and these lake pigments (as the lake-forming agent,
Phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide, etc. Diorganotin oxide; dibutyltin borate;
Examples thereof include diorganotin borates such as dioctyltin borate and dicyclohexyl tin borate. These can be used alone or in combination of two or more. Of these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

In the toner of the present invention, the charge stability,
In order to improve developability, fluidity and durability, it is preferable to add fine silica powder.

The silica fine powder used in the present invention is BE
The specific surface area by nitrogen adsorption measured by the T method is 30 m ² / g
Those within the above range (particularly 50 to 400 m ² / g) give good results. It is preferable to use 0.01 to 8 parts by mass, preferably 0.1 to 5 parts by mass of silica fine powder with respect to 100 parts by mass of the toner.

The silica fine powder used in the present invention may be, if necessary, a silicone varnish, various modified silicone varnishes for the purpose of hydrophobicity, charge control and the like.
It is also preferable to use a combination treatment with a treating agent such as silicone oil, various modified silicone oils, a silane coupling agent, a silane coupling agent having a functional group, and other organosilicon compounds.

As other additives, for example, Teflon,
Lubricants such as zinc stearate and polyvinylidene fluoride,
Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate, among which strontium titanate is preferred. Alternatively, for example, a fluidity-imparting agent such as titanium oxide and aluminum oxide, particularly a hydrophobic agent is preferable. A small amount of an anti-caking agent, or a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, and tin oxide, or white and black fine particles of opposite polarity can also be used as a developability improver.

For the purpose of further improving the offset resistance during hot roll fixing, a wax-like substance such as low molecular weight polyethylene, low molecular weight polypropylene, etc.
About 0.5 to 10 parts by mass with respect to 00 parts by mass may be added to the toner.

In the toner of the present invention, metals such as iron, cobalt and nickel or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium and manganese of these metals are included. Magnetic materials such as alloys of metals such as selenium, titanium, tungsten, and vanadium and mixtures thereof may be used in combination.

These ferromagnetic materials have an average particle of 0.1 to 2
μm, and preferably about 0.1 to 0.5 μm.
The amount is preferably about 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass, per 100 parts by mass of the resin component.

The magnetic properties when 7.95775 × 10 ² kA / m was applied showed a coercive force of 1.59155 to 11.936.
63 kA / m, saturation magnetization 6.2832 to 25.1328
μWb / g, residual magnetization 0.251328 to 2.5132
8 μWb / g is desirable.

The colorant that can be used in the toner of the present invention includes any suitable pigment or dye. Toner colorants are well known and include, for example, pigments such as carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengalara, phthalocyanine blue, and indanthrene blue. These are used in amounts necessary and sufficient to maintain the optical density of the fixed image.
0.1 to 20 parts by mass, preferably 2 to 10 parts by mass with respect to parts by mass
The addition amount of parts by mass is good. A dye is further used for the same purpose. Examples include azo dyes, anthraquinone dyes, xanthene dyes, methine dyes and the like.
The amount of addition is 0.1 to 20 parts by mass, preferably 0.3 to 3 parts by mass, per 100 parts by mass.

The toner of the present invention can be mixed with a carrier and used as a two-component developer composed of the toner and the carrier.

As the carrier, all known carriers can be used. For example, magnetic powders such as iron powder, ferrite powder and nickel powder, glass beads, etc. Alternatively, those treated with a silicone resin or the like may be used.

To prepare the toner according to the present invention, a binder resin, a metal salt or a metal complex, a pigment or dye as a colorant, a magnetic substance, a charge control agent, and other additives as necessary are mixed with a Henschel mixer. , Kneading and kneading using a hot kneading machine such as a heating roll, kneader, extruder, etc. ,
The toner according to the present invention can be obtained by dispersing or dissolving a dye or a magnetic substance, and solidifying by cooling, followed by pulverization and classification.

Further, if necessary, desired additives are sufficiently mixed by a mixer such as a Henschel mixer to obtain the toner according to the present invention.

In the present invention, the charge amount of the toner layer per unit area on the carrier was determined by using a so-called suction Faraday cage method. In this suction type Faraday cage method, the outer cylinder is pressed against the toner carrier to suck all the toner on a certain area on the carrier, and at the same time, the toner is accumulated in the inner cylinder electrostatically shielded from the outside. This is a method in which the amount of charge per unit area on the toner carrier can be determined by measuring the amount of charge.

In the present invention, particularly in the following examples, the evaluation of fixing property and anti-offset property was carried out according to the following procedures.

The fixing property was determined in a low temperature and low humidity environment (15 ° C., 10 ° C.).
%), The evaluation device was left overnight, and the evaluation device and the fixing device inside the evaluation device were completely adjusted to the low-temperature and low-humidity environment.
00 copy images were taken, and the 200th copy image was used for evaluation of fixability. For the evaluation of the fixing property, the image was rubbed with a silk-bon paper 10 times in a reciprocating manner at a load of about 100 g, and the peeling of the image was evaluated by the reduction rate (%) of the reflection density. Therefore,
As the value of the reflection density decrease rate (image density decrease rate) after rubbing is larger, the rate of peeling of the image due to rubbing is larger,
The fixability of the toner will be poor.

The offset resistance was evaluated based on whether or not the toner once taken in the cleaning wave during continuous copying was transferred to the upper fixing roller to contaminate the copy. As an evaluation method, a low-temperature and low-humidity environment (15
(10 ° C., 10%), after taking continuous 200 copy images, copy images were taken at 30 second intervals one by one for up to 3 minutes, and it was examined whether image contamination occurred.

[0104]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

First, substance a and substance b used in the present invention
An example of the production of a substance (substance A) reacted with

[0106]

Embedded image At a pressure of 2.0 × 10 ^{5 in} the presence of sodium ethoxide.
The reaction was carried out under the conditions of Pa and a temperature of 150 ° C. Reaction time 3
After 0 minutes, the reaction product was removed. This was designated as substance (1).

[0107]

Embedded image At a pressure of 2.0 × 10 ^{5 in} the presence of sodium ethoxide.
The reaction was carried out under the conditions of Pa and a temperature of 150 ° C. Reaction time 3
After 0 minutes, the reaction product was removed. This was designated as substance (2).

[0108]

Embedded image At a pressure of 2.0 × 10 ^{5 in} the presence of sodium ethoxide.
The reaction was carried out under the conditions of Pa and a temperature of 150 ° C. Reaction time 3
After 0 minutes, the reaction product was removed. This was designated as substance (3).

[0109]

Embedded image At a pressure of 1.7 × 10 ^{5 in} the presence of sodium ethoxide.
The reaction was carried out under the conditions of Pa and a temperature of 170 ° C. Reaction time 1
After 5 minutes, the reaction product was taken out. This was designated as substance (4).

[0110]

Embedded image In the presence of sodium hydroxide at a pressure of 3.0 × 10 ⁵ P
a, The reaction was carried out at a temperature of 160 ° C. Reaction time 60
After a minute, the reaction product was removed. This was designated as substance (5).

[0111]

Embedded image At a pressure of 1.9 × 10 ⁵ P in the presence of sodium hydroxide
a) The reaction was carried out at a temperature of 145 ° C. Reaction time 45
After a minute, the reaction product was removed. This was designated as substance (6).

[0112]

Embedded image In the presence of sodium hydroxide at a pressure of 1.8 × 10 ⁵ P
a, The reaction was carried out at a temperature of 160 ° C. Reaction time 30
After a minute, the reaction product was removed. This was designated as substance (7).

[0113]

Embedded image At a pressure of 2.1 × 10 ^{5 in} the presence of sodium ethoxide.
The reaction was performed under the conditions of Pa and a temperature of 175 ° C. Reaction time 3
After 0 minutes, the reaction product was removed. This was designated as substance (8).

Next, a production example of a substance (substance B) obtained by reacting substance a and substance c is shown below.

[0115]

Embedded image Was reacted in the presence of Al (C ₂ H ₅ ) ₃ to obtain a substance (9).

[0116]

Embedded image Is reacted in the presence of Al (C ₂ H ₅ ) ₃ to give the substance (10)
I got

[0117]

Embedded image Is reacted in the presence of Al (C ₂ H ₅ ) ₃ to give the substance (11)
I got

[0118]

Embedded image Is reacted in the presence of Al (C ₂ H ₅ ) ₃ to give the substance (12)
I got

[0119]

Embedded image Is reacted in the presence of Al (C ₂ H ₅ ) ₃ to give the substance (13)
I got

[0120]

Embedded image Is reacted in the presence of Al (C ₂ H ₅ ) ₃ to give the substance (14)
I got

[0121]

Embedded image

After mixing the above materials well in a blender,
The mixture was kneaded with a twin-screw kneading extruder set at 110 ° C. After cooling the obtained kneaded material and coarsely pulverizing with a cutter mill,
The powder was finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified to obtain a magnetic toner having a volume average particle size of 6.45 μm. Magnetic Toner 10 of Black Fine Powder Obtained
0 parts by mass of negatively charged hydrophobic dry colloidal silica (BE
0.6 parts by mass (T specific surface area: 300 m ² / g) were added and mixed with a Henschel mixer.

The magnetic toner was applied to a commercially available copying machine, NP-9800 manufactured by Canon Inc., and was subjected to normal temperature and low humidity (23.5 ° C., 5
%) Under the environmental conditions (%). Table 1 shows the results of the image formation test. As is clear from Table 1, the initial image,
The image density was high for all of the 30,000 sheet durability images, and the images were good. The charge amount on the sleeve was stable in the initial stage, even after the endurance of 30,000 sheets, and there was no occurrence of defective cleaning or fusing of the drum during the endurance of image formation. In addition, the fixability was a good level with the image density reduction rate of 7.9%, and the offset resistance was also good.

[0124]

Embedded image

As is clear from Table 1, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was a satisfactory level with the image density reduction rate of 13.7%, and the offset resistance was also good.

[0126]

Embedded image

As is clear from Table 1, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was a satisfactory level with the image density reduction rate of 14.5%, and the offset resistance was also good.

Example 4 Instead of a polyester resin, a styrene-acrylic resin (styrene-butyl acrylate-monobutyldivinylbenzene copolymer of maleic acid; acid value: 25.4 mg KO)
H / g; Mw of 163,000) was used, and a magnetic toner having a volume average particle size of 6.55 μm was obtained in the same manner as in Example 1 using the same material. 0.6 parts by mass of negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g) was added to 100 parts by mass of the magnetic toner of the obtained black fine powder, mixed with a Henschel mixer, and then commercially available copier Canon Example 1 applied to NP-9800
The same evaluation was performed.

As is clear from Table 1, both the initial image and the 30,000-sheet durability image had high image densities and were good images. Initial charge on sleeve is 3000
It was stable even after 0 sheets had been durable, and there was no occurrence of defective cleaning or fusing of the drum during the image formation durability. In addition, the fixability is a good level with the image density reduction rate of 9.3%.
The offset resistance was also good.

[0130]

Embedded image

A toner having a volume average particle size of 6.58 μm was obtained in the same manner as in Example 1 using the above materials. To 100 parts by mass of the obtained toner, 0.6 parts by mass of negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g) was added and mixed with a Henschel mixer. Then, it was mixed with a fluorine-coated carrier (300/350 mesh) to obtain a developer. This developer was applied to a commercially available copy machine Canon NP-5060, and the same evaluation as in Example 1 was performed.

As is clear from Table 1, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. Further, the fixing property was such that the image density reduction rate was a good level of 9.4%, and the offset resistance was also good.

[0133]

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A magnetic toner having a volume average particle size of 6.58 μm was obtained in the same manner as in Example 1 using the above materials.
100 parts by mass of the obtained black fine powder magnetic toner is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300
(m ^{2 /} g) 0.6 part by mass was added and mixed with a Henschel mixer, and the same evaluation as in Example 1 was performed. The initial image was good, and the image density was reduced as the image output durability was advanced. Since the image density was 1.10 at 3360 sheets, the durability was stopped at 3360 sheets. Further, the toner charge amount on the sleeve at the time of 3,360 sheets during the running is -2.
It was 1.9 mC / kg.

Further, during the image-printing durability, defective cleaning occurred around 3,300 sheets, and drum fusion occurred around 3,350 sheets.

The fixing property is such that the rate of decrease in image density is 20.
The level was as bad as 7%, and the offset resistance was such that image contamination due to wave contamination occurred.

[0137]

Embedded image

A magnetic toner having a volume average particle size of 6.51 μm was obtained in the same manner as in Example 1 using the above materials.
100 parts by mass of the obtained black fine powder magnetic toner is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300
(m ^{2 /} g) 0.6 part by mass was added and mixed with a Henschel mixer, and the same evaluation as in Example 1 was performed. The initial image was good, and the image density was reduced as the image output durability was advanced. The image density was 1.08 at 3340 sheets, so the durability was stopped at 3340 sheets. Further, the toner charge amount on the sleeve at the time of 3,340 sheets during the running is -2.
It was 2.1 mC / kg.

In addition, during the image output running, cleaning failure occurred around 3,270 sheets, and drum fusion occurred around 3,320 sheets.

As for the fixing property, the image density reduction rate was 21.
This was a bad level of 5%, and the offset resistance caused image contamination due to wave contamination.

[0141]

[Table 1]

Example 6 Polyester resin 100 parts by mass (polyester composed of bisphenol A-trimellitic acid-terephthalic acid-neopentyl glycol; acid value 30.5 mgKOH / g; Mw 43,000) Magnetic iron oxide 90 parts by mass Electric charge control agent 1 part by mass Substance (1) 3 parts by mass

After thoroughly mixing the above materials in a blender,
The mixture was kneaded with a twin-screw kneading extruder set at 110 ° C. After cooling the obtained kneaded material and coarsely pulverizing with a cutter mill,
The powder was finely pulverized using a pulverizer using a jet stream, and the obtained finely pulverized powder was classified to obtain a magnetic toner having a volume average particle size of 6.51 μm. Magnetic Toner 10 of Black Fine Powder Obtained
0 parts by mass of negatively charged hydrophobic dry colloidal silica (BE
After adding 0.6 parts by mass of T specific surface area 300 m ^{2 /} g) and mixing with a Henschel mixer, the mixture was applied to a commercially available copying machine NP-9800 manufactured by Canon Co., Ltd.
%) Under the environmental conditions (%). Table 2 shows the results of the image formation test.

As is clear from Table 2, the initial image, 30
The image density was high in both of the 000-sheet durability images, and the images were good. The charge amount on the sleeve is also stable at the initial stage and after the endurance of 30,000 sheets.
No drum fusion occurred. In addition, the fixability was as good as the image density reduction rate of 8.1%, and the offset resistance was also good.

Example 7 A magnetic toner having a volume average particle diameter of 6.31 μm was obtained in the same manner as in Example 6, except that the substance (2) was used in place of the substance (1). 100 parts by mass of the magnetic toner of the obtained black fine powder is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g).
After adding 6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 6 was performed by applying to a commercially available copying machine Canon NP-9800.

As can be seen from Table 2, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was a good level with the image density reduction rate of 13.5%, and the offset resistance was also good.

Example 8 A magnetic toner having a volume average particle diameter of 6.39 μm was obtained in the same manner as in Example 6, except that the substance (3) was used instead of the substance (1). 100 parts by mass of the magnetic toner of the obtained black fine powder is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g).
After adding 6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 6 was performed by applying to a commercially available copying machine Canon NP-9800.

As is clear from Table 2, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was a satisfactory level with an image density reduction rate of 14.4%, and the offset resistance was also good.

Example 9 A magnetic toner having a volume average particle size of 6.27 μm was obtained in the same manner as in Example 6, except that the substance (4) was used instead of the substance (1). 100 parts by mass of the magnetic toner of the obtained black fine powder is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g).
After adding 6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 6 was performed by applying to a commercially available copying machine Canon NP-6060.

As is clear from Table 2, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was a good level with the image density reduction rate of 7.7%, and the offset resistance was also good.

Example 10 A magnetic toner having a volume average particle size of 6.58 μm was obtained in the same manner as in Example 6, except that the substance (5) was used instead of the substance (1). 100 parts by mass of the magnetic toner of the obtained black fine powder is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g).
After adding 6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 6 was performed by applying to a commercially available copying machine Canon NP-9800.

As is clear from Table 2, both the initial image and the 30,000-sheet durability image had high image densities.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was as good as the image density reduction rate of 6.6%, and the offset resistance was also good.

Example 11 Styrene-acrylic resin 100 parts by mass (styrene-butyl acrylate-monobutyl maleate-divinylbenzene copolymer; acid value 25.4 mgKOH / g; Mw 163,000) Magnetic iron oxide 90 parts by mass Electric charge control agent 1 part by mass Substance (6) 3 parts by mass

A magnetic toner having a volume average particle size of 6.61 μm was obtained using the above materials and in the same manner as in Example 6.
100 parts by mass of the obtained black fine powder magnetic toner is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300
After adding 0.6 parts by mass of m ^{2 /} g) and mixing with a Henschel mixer, the same evaluation as in Example 6 was performed by applying to a commercially available copying machine Canon NP-9800.

As is apparent from Table 2, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was as good as the image density reduction rate of 10.4%, and the offset resistance was also good.

Example 12 Styrene-acrylic resin 100 parts by mass (Styrene-butyl acrylate-divinylbenzene copolymer; acid value 1.5 mg KOH / g; Mw 162,000) Magnetic iron oxide 90 parts by mass Charge control Agent 1 part by mass Substance (6) 3 parts by mass

A magnetic toner having a volume average particle size of 6.58 μm was obtained in the same manner as in Example 6 using the above materials.
100 parts by mass of the obtained black fine powder magnetic toner is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300
After adding 0.6 parts by mass of m ^{2 /} g) and mixing with a Henschel mixer, the same evaluation as in Example 6 was performed by applying to a commercially available copying machine Canon NP-9800.

As is clear from Table 2, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was as good as the image density reduction rate of 12.5%, and the offset resistance was also good.

Example 13 A magnetic toner having a volume average particle diameter of 6.37 μm was obtained in the same manner as in Example 11, except that the substance (7) was used instead of the substance (6). 100 parts by mass of the obtained black fine powder magnetic toner is added to negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g)
After adding 0.6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 6 was performed by applying to a commercially available copying machine Canon NP-9800.

As can be seen from Table 2, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was as good as the image density reduction rate of 10.6%, and the offset resistance was also good.

Example 14 A magnetic toner having a volume average particle size of 6.67 μm was obtained in the same manner as in Example 11, except that the substance (4) was used instead of the substance (6). 100 parts by mass of the obtained black fine powder magnetic toner is added to negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g)
After adding 0.6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 6 was performed by applying to a commercially available copying machine Canon NP-6060.

As a result, as is clear from Table 2, both the initial image and the 30,000-sheet durability image had high image densities and were good images. Initial charge on sleeve is 3000
It was stable even after 0 sheets had been durable, and there was no occurrence of defective cleaning or fusing of the drum during the image formation durability. In the fixing, the image density reduction rate was a favorable level of 11.4%, and the offset resistance was also good.

Example 15 100 parts by weight of polyester resin (polyester composed of bisphenol A-trimellitic acid-terephthalic acid-neopentyl glycol; acid value: 30.5 mgKOH / g; Mw: 43,000) Carbon black Mogar L (Cabot Corporation) 3 parts by mass Negative charge control agent 1 part by mass Substance (1) 3 parts by mass

A toner having a volume average particle size of 6.39 μm was obtained in the same manner as in Example 6 using the above materials. To 100 parts by mass of the obtained toner, 0.6 parts by mass of negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g) was added and mixed with a Henschel mixer. Then, it was mixed with a fluorine-coated carrier (300/350 mesh) to obtain a developer. This developer was applied to a commercially available copy machine Canon NP-5060, and the same evaluation as in Example 6 was performed.

As is clear from Table 2, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was as good as the image density reduction rate of 9.1%, and the offset resistance was also good.

Comparative Example 3 Polyester Resin 100 parts by mass (Polyester composed of bisphenol A-trimellitic acid-terephthalic acid-ethylene glycol: acid value 28.5 mgKOH / g; Mw 41,000) Magnetic iron oxide 90 parts by mass Charge control agent 1 part by weight Low molecular weight polypropylene 3 parts by weight

A magnetic toner having a volume average particle size of 6.56 μm was obtained using the above materials and in the same manner as in Example 6.
100 parts by mass of the obtained black fine powder magnetic toner is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300
(m ^{2 /} g) 0.6 part by mass was added and mixed with a Henschel mixer, and the same evaluation as in Example 6 was performed. Although the initial image was good, the image density was reduced as the image output durability was advanced.
Because of 1, the durability was stopped when 4150 sheets were printed. Further, the toner charge amount on the sleeve at the time of 4150 sheets during the durability is
It was -22.4 mC / kg.

Further, during image output durability, poor cleaning occurred around 3,800 sheets, and drum fusion occurred around 4000 sheets.

As for the fixability, the image density reduction rate was 21.
This was a bad level of 4%, and the offset resistance was such that image contamination due to wave contamination occurred.

Comparative Example 4 Comparative Example 3 was repeated except that the low molecular weight polypropylene was used as the substance (8).
A magnetic toner having a volume average particle size of 6.41 μm was obtained in the same manner as in Example 6 except that the following conditions were used. To 100 parts by mass of the magnetic toner of the obtained black fine powder, 0.6 parts by mass of negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g) was added, and mixed with a Henschel mixer. Was evaluated. Although the initial image was good, the image density decreased as the image output durability increased, and the image density became 1.08 at 4500 sheets, so the durability was stopped at 4500 sheets. The toner charge amount on the sleeve at the time of 4,500 sheets during running was -20.8 mC / kg.

In addition, during the image output durability, poor cleaning occurred around 4450 sheets, and drum fusion occurred around 4350 sheets.

As for the fixing property, the image density reduction rate was 20.
This was a bad level of 8%, and the offset resistance was such that image contamination due to wave contamination occurred.

Comparative Example 5 Styrene-acrylic resin 100 parts by mass (styrene-butyl acrylate-monobutyl maleate maleate copolymer; acid value 25.4 mg KOH / g; Mw 163,000) Magnetic iron oxide 90 parts by mass Charge control agent 1 part by weight Low molecular weight polypropylene 3 parts by weight

A magnetic toner having a volume average particle size of 6.27 μm was obtained in the same manner as in Example 6 using the above materials.
100 parts by mass of the obtained black fine powder magnetic toner is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300
(m ^{2 /} g) 0.6 part by mass was added and mixed with a Henschel mixer, and the same evaluation as in Example 6 was performed. The initial image was good, and the image density was reduced as the image output durability was advanced. The image density was 1.09 at 3100 sheets, so the durability was stopped at 3100 sheets. Further, the toner charge amount on the sleeve at the time of 3,100 sheets during the running is -2.
It was 1.8 mC / kg.

In addition, cleaning failure occurred around 2,900 sheets during image printing durability, and drum fusion occurred around 2,800 sheets.

As for the fixing property, the rate of decrease in image density was 22.0%.
This was a bad level of 3%, and the offset resistance was such that image contamination due to wave contamination occurred.

Comparative Example 6 In Comparative Example 5, the low molecular weight polypropylene was replaced with the substance (8)
A magnetic toner having a volume average particle size of 6.47 μm was obtained in the same manner as in Example 6 except for using the same material as in Comparative Example 5. To 100 parts by mass of the magnetic toner of the obtained black fine powder, 0.6 parts by mass of negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g) was added, and mixed with a Henschel mixer. Was evaluated. Although the initial image was good, the image density decreased as the image output durability increased, and the image density became 1.09 at 3350 sheets. Therefore, the durability was stopped at 3350 sheets. The charge amount of the toner on the sleeve at the time of 3,350 sheets during the running was -21.4 mC / kg.

In addition, during the image output durability, defective cleaning occurred around 3,200 sheets, and drum fusion occurred around 3,300 sheets.

The fixing property is such that the image density reduction rate is 20.
The level was as bad as 6%, and the offset resistance was such that image contamination due to wave contamination occurred.

[0180]

[Table 2]

Example 16 100 parts by weight of a polyester resin (polyester composed of bisphenol A-trimellitic acid-terephthalic acid; acid value: 31.5 mgKOH / g; Mw: 41,000) Magnetic iron oxide: 90 parts by weight Negative charge control agent 1 part by mass Substance (9) 3 parts by mass

After thoroughly mixing the above materials with a blender,
The mixture was kneaded with a twin-screw kneading extruder set at 110 ° C. After cooling the obtained kneaded material and coarsely pulverizing with a cutter mill,
The resulting finely pulverized powder was classified by using a fine pulverizer using a jet stream to obtain a magnetic toner having a volume average particle diameter of 6.31 μm. Magnetic Toner 10 of Black Fine Powder Obtained
0 parts by mass of negatively charged hydrophobic dry colloidal silica (BE
0.6 parts by mass (T specific surface area: 300 m ² / g) were added and mixed with a Henschel mixer.

The magnetic toner was applied to a commercially available copying machine, NP-9800 manufactured by Canon Inc., and was subjected to normal temperature and low humidity (23.5 ° C., 5
%) Under the environmental conditions (%). Table 3 shows the image formation test results. As is clear from Table 3, the initial image,
The image density was high for all of the 30,000 sheet durability images, and the images were good. The charge amount on the sleeve was stable in the initial stage, even after the endurance of 30,000 sheets, and there was no occurrence of defective cleaning or fusing of the drum during the endurance of image formation. In addition, the fixability was a satisfactory level with the image density reduction rate of 8.7%, and the offset resistance was also good.

Example 17 A magnetic toner having a volume average particle diameter of 6.47 μm was obtained in the same manner as in Example 16, except that the substance (10) was used instead of the substance (9). 100 parts by mass of the obtained black fine powder magnetic toner is added to negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g)
After adding 0.6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 16 was performed by applying to a commercially available copying machine Canon NP-9800.

As is clear from Table 3, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was a good level with the image density reduction rate of 13.4%, and the offset resistance was also good.

Example 18 A magnetic toner having a volume average particle diameter of 6.35 μm was obtained in the same manner as in Example 16, except that the substance (11) was used instead of the substance (9). 100 parts by mass of the obtained black fine powder magnetic toner is added to negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g)
After adding 0.6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 16 was performed by applying to a commercially available copying machine Canon NP-9800.

As can be seen from Table 3, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was a satisfactory level with the image density reduction rate of 14.6%, and the offset resistance was also good.

Example 19 A magnetic toner having a volume average particle diameter of 6.22 μm was obtained in the same manner as in Example 16, except that the substance (12) was used in place of the substance (9). 100 parts by mass of the obtained black fine powder magnetic toner is added to negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g)
After adding 0.6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 16 was performed by applying to a commercially available copying machine Canon NP-6060.

As can be seen from Table 3, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was a satisfactory level with an image density reduction rate of 7.5%, and the offset resistance was also good.

Example 20 A magnetic toner having a volume average particle diameter of 6.64 μm was obtained in the same manner as in Example 16, except that the substance (13) was used in place of the substance (9). 100 parts by mass of the obtained black fine powder magnetic toner is added to negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g)
After adding 0.6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 16 was performed by applying to a commercially available copying machine Canon NP-9800.

As can be seen from Table 3, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was as good as the image density reduction rate of 6.4%, and the offset resistance was also good.

Example 21 Styrene-acrylic resin 100 parts by mass (styrene-2ethylhexyl acrylate-monobutyl maleate-divinylbenzene copolymer; acid value 24.3 mgKOH / g; Mw 165,000) Magnetic iron oxide 90 parts by mass Part Negative charge control agent 1 part by mass Substance (9) 3 parts by mass

A magnetic toner having a volume average particle size of 6.46 μm was obtained in the same manner as in Example 16 using the above materials. 100 parts by mass of the magnetic toner of the obtained black fine powder was added to negatively charged hydrophobic dry colloidal silica (BET specific surface area 3
00m ² /g)0.6 parts by mass was added and mixed in a Henschel mixer, a commercially available copying machine manufactured by Canon Inc. NP-980
0, and the same evaluation as in Example 16 was performed.

As can be seen from Table 3, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. Further, the fixability was a satisfactory level with the image density reduction rate of 11.4%, and the anti-offset property was also good.

Example 22 Styrene-acrylic resin 100 parts by mass (styrene-2 ethylhexyl acrylate-divinylbenzene copolymer; acid value 1.4 mg KOH / g; Mw 166,000) Magnetic iron oxide 90 parts by mass Negatively charged Control agent 1 part by mass Substance (9) 3 parts by mass

A magnetic toner having a volume average particle size of 6.44 μm was obtained in the same manner as in Example 16 using the above materials. 100 parts by mass of the magnetic toner of the obtained black fine powder was added to negatively charged hydrophobic dry colloidal silica (BET specific surface area 3
00m ² /g)0.6 parts by mass was added and mixed in a Henschel mixer, a commercially available copying machine manufactured by Canon Inc. NP-980
0, and the same evaluation as in Example 16 was performed.

As is clear from Table 3, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was as good as the image density reduction rate of 12.6%, and the offset resistance was also good.

Example 23 A magnetic toner having a volume average particle diameter of 6.71 μm was obtained in the same manner as in Example 21, except that the substance (12) was used instead of the substance (9). 100 parts by mass of the obtained black fine powder magnetic toner is added to negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g)
After adding 0.6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 16 was performed by applying to a commercially available copying machine Canon NP-6060.

As can be seen from Table 3, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was a satisfactory level with an image density reduction rate of 10.7%, and the offset resistance was also good.

Example 24 A magnetic toner having a volume average particle size of 6.58 μm was obtained in the same manner as in Example 21, except that the substance (13) was used in place of the substance (9). 100 parts by mass of the obtained black fine powder magnetic toner is added to negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g)
After adding 0.6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 16 was performed by applying to a commercially available copying machine Canon NP-9800.

As is apparent from Table 3, the image density was high for both the initial image and the 30,000-sheet durability image.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was as good as the image density reduction rate was 10.2%, and the offset resistance was also good.

Example 25 100 parts by weight of a polyester resin (polyester comprising bisphenol A-trimellitic acid-terephthalic acid-neopentyl glycol; acid value: 30.5 mgKOH / g; Mw: 43,000) Carbon black Mogar L (Cabot Corporation) 3 parts by mass Negative charge control agent 1 part by mass Substance (9) 3 parts by mass

A toner having a volume average particle size of 6.48 μm was obtained in the same manner as in Example 16 using the above materials. To 100 parts by mass of the obtained toner, 0.6 parts by mass of negatively charged hydrophobic dry colloidal silica (BET specific surface area: 300 m ² / g) was added and mixed with a Henschel mixer. afterwards,
A developer was mixed with a fluorine-coated carrier (300/350 mesh). The same evaluation as in Example 16 was performed by applying this developer to a commercially available copying machine, NP-5060 manufactured by Canon Inc.

As is clear from Table 3, both the initial image and the 30,000-sheet durability image have high image densities.
The image was good. Initial charge on sleeve is 300
The sheet was stable even after the endurance of 00 sheets, and there was no occurrence of defective cleaning or fusion of the drum during the endurance of image formation. In addition, the fixability was as good as the image density reduction rate of 9.1%, and the offset resistance was also good.

Comparative Example 7 100 parts by mass of polyester resin (polyester composed of bisphenol A-trimellitic acid-terephthalic acid; acid value: 31.5 mgKOH / g; Mw: 41,000) Magnetic iron oxide: 90 parts by mass Negative charge control 1 part by weight Low molecular weight polyethylene 3 parts by weight

A magnetic toner having a volume average particle size of 6.29 μm was obtained in the same manner as in Example 16 using the above materials. 100 parts by mass of the magnetic toner of the obtained black fine powder was added to negatively charged hydrophobic dry colloidal silica (BET specific surface area 3
(00 m ^{2 /} g), and 0.6 parts by mass were added, mixed with a Henschel mixer, and evaluated in the same manner as in Example 16.
Although the initial image was good, the image density was reduced as the image output durability was advanced, and the image density was 1.11 at 3,800 sheets. Therefore, the durability was stopped at 3,800 sheets. Further, the toner charge amount on the sleeve at 3,800 sheets during the running was -21.7 mC / kg.

In addition, during the image printing durability, defective cleaning occurred around 3650 sheets, and drum fusion occurred around 3750 sheets.

As for the fixing property, the image density reduction rate was 21.
The level was as bad as 7%, and the offset resistance was such that image contamination due to wave contamination occurred.

Comparative Example 8 In Comparative Example 7, low-molecular-weight polyethylene was replaced with substance (14).
A magnetic toner having a volume average particle size of 6.36 μm was obtained in the same manner as in Comparative Example 7, except that 100 parts by mass of the magnetic toner of the obtained black fine powder is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g).
After adding 6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 16 was performed. Although the initial image was good, the image density decreased as the image output durability increased, and the image density reached 1.07 at 4050 sheets. Therefore, the durability was stopped at 4050 sheets. In addition, 40
The toner charge amount on the sleeve at the time of 50 sheets is -22.1 mC
/ Kg.

In addition, cleaning failure occurred around 3,900 sheets during image output durability, and drum fusion occurred around 3,850 sheets.

As for the fixability, the rate of decrease in image density was 22.0%.
This was a bad level of 4%, and the offset resistance was such that image contamination due to wave contamination occurred.

Comparative Example 9 Styrene-acrylic resin 100 parts by mass (styrene-2ethylhexyl acrylate-monobutyl maleate-divinylbenzene copolymer; acid value 24.3 mgKOH / g; Mw 16.5 million) Magnetic iron oxide 90 parts by mass Negative charge control agent 1 part by weight Low molecular weight polyethylene 3 parts by weight

A magnetic toner having a volume average particle size of 6.44 μm was obtained in the same manner as in Example 16 using the above materials. 100 parts by mass of the magnetic toner of the obtained black fine powder was added to negatively charged hydrophobic dry colloidal silica (BET specific surface area 3
(00 m ^{2 /} g), and 0.6 parts by mass were added, mixed with a Henschel mixer, and evaluated in the same manner as in Example 16.
Although the initial image was good, the image density decreased as the image output durability increased, and the image density became 1.11 at 2700 sheets, so the durability was stopped at 2700 sheets. The charge amount of toner on the sleeve at the time of 2,700 sheets during the running was -20.9 mC / kg.

In addition, cleaning failure occurred at about 2,650 sheets during image output durability, and drum fusion occurred at about 2,600 sheets.

As for the fixability, the image density reduction rate was 21.
This was a bad level of 1%, and the offset resistance was such that image contamination due to wave contamination occurred.

Comparative Example 10 In Comparative Example 9, low-molecular-weight polyethylene was replaced with substance (14).
A magnetic toner having a volume average particle size of 6.53 μm was obtained in the same manner as in Comparative Example 9 except that the above conditions were satisfied. 100 parts by mass of the magnetic toner of the obtained black fine powder is loaded with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g).
After adding 6 parts by mass and mixing with a Henschel mixer, the same evaluation as in Example 16 was performed. Although the initial image was good, the image density decreased as the image output durability was advanced, and the image density was 1.11 at 2900 sheets. Therefore, the durability was stopped at 2900 sheets. Also, 29
The toner charge amount on the sleeve at the time of sheet number 00 is -21.5 mC
/ Kg.

In addition, during the image output durability, poor cleaning occurred around 2,750 sheets, and drum fusion occurred around 2,800 sheets.

The fixing property was such that the image density reduction rate was 22.4.
%, Which is a bad level, and the offset resistance was such that image contamination due to wave contamination occurred.

[0219]

[Table 3]

[0220]

【The invention's effect】

[0221]

Embedded image According to the present invention, there is provided a toner containing a substance obtained by reacting a substance represented by the following formula (1) with β-propiolactone, diketene, lactide, δ-valerolactone, and ε-caprolactone. Since the toner contains a substance obtained by reacting with one selected substance, the toner has excellent fixability and offset resistance, and can stably provide an image having a good image density even in a low humidity environment.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yuji Mikituri 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-7-199521 (JP, A) JP-A-2 -1990867 (JP, A) JP-A-55-93159 (JP, A) JP-A-8-160658 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08 365 CA (STN) REGISTRY (STN)

Claims (19)

(57) [Claims] [Claim 1] And a binder resin having an acid value of 2 mgKOH / g or more. 2. The toner according to claim 1, wherein the number of n in the formula (1) is 30 or more. 3. The toner according to claim 1, wherein the number of n in the formula (1) is 40 or more. 4. The toner according to claim 1, further comprising a magnetic material as a colorant. 5. The toner according to claim 1, further comprising a pigment or a dye as a colorant. 6. The toner according to claim 1, which is used as a two-component developer composed of a toner and a carrier. (7) And a substance represented by A toner comprising a substance obtained by reacting a substance represented by the following formula: 8. The toner according to claim 7, wherein the number of n in the formula (1) is 30 or more. 9. The toner according to claim 7, wherein the number of n in the formula (1) is 40 or more. 10. The toner according to claim 7, further comprising a magnetic material as a coloring agent. 11. The toner according to claim 7, wherein the colorant contains a pigment or a dye. 12. The toner according to claim 7, wherein the toner is used as a two-component developer composed of a toner and a carrier. (13) A toner comprising a substance obtained by reacting a substance represented by the following formula with a lactone. 14. The toner according to claim 13, wherein the number of n in the formula (1) is 30 or more. 15. The toner according to claim 13, wherein the number n in the formula (1) is 40 or more. 16. The toner according to claim 13, wherein as the lactone, one selected from β-propiolactone, diketene, lactide, δ-valerolactone, and ε-caprolactone is used. 17. The toner according to claim 13, further comprising a magnetic material as a coloring agent. 18. The toner according to claim 13, further comprising a pigment or a dye as a colorant. 19. The method according to claim 1, wherein the developer is used as a two-component developer composed of a toner and a carrier.
19. The toner according to any one of items 3 to 18.