JPH08234480A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE: To obtain a toner capable of attaining satisfactory fixability in any environment or any service conditions and having satisfactory anti-offsetting property and blocking resistance. CONSTITUTION: This toner contains a bonding resin, a colorant and wax. The modulus (G'100 ) of storage elasticity of this toner at 100 deg.C is 1×10<4> -5×10<4> Pa and the ratio (G'60 /G'70 ) of the modulus (G'60 ) of storage elasticity at 60 deg.C to the modulus (G'70 ) of storage elasticity at 70 deg.C is >=30.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art US Pat.
A large number of methods are known as described in JP-A-7,691 and JP-B-42-23910 and JP-B-43-24748. Generally, a photoconductive substance is used to form an electrostatic charge image on a photoreceptor by various means,
Then, the electrostatic charge image is developed with toner, and the toner image is transferred to a transfer material such as paper, if necessary, and then fixed by heat, pressure, heat and pressure, or solvent vapor to obtain a toner image. is there.

Various methods and devices have been developed for the final step of fixing the toner image on a sheet such as paper, but the most general method at present is fixed heat generation through a heat roller or a heat resistant film. It is a pressure heating method with a heater.

In the pressure contact heating method using a heating roller, the surface of the heat roller having a releasability for the toner and the toner image surface of the sheet to be fixed are brought into contact with each other under pressure to pass the sheet to be fixed, thereby fixing the toner image. Is to do. In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so that the thermal efficiency at the time of fusing the toner image on the sheet to be fixed is extremely good, and quick fixing is required. You can

Since the surface of the heating roller and the toner image are in contact with each other in a molten state and under pressure, a part of the toner image adheres to the surface of the fixing roller and is transferred, and this is retransferred to the next sheet to be fixed and fixed. The offset phenomenon that stains the sheet is greatly affected by the fixing speed and fixing temperature. Generally, when the fixing speed is low, the surface temperature of the heating roller is set relatively low, and when the fixing speed is high, the surface temperature of the heating roller is set relatively high. This is because the amount of heat given to the toner from the heating roller to fix the toner is made substantially constant regardless of the fixing speed.

Since the toner on the sheet to be fixed forms several toner layers, in a system in which the fixing speed is particularly high and the surface temperature of the heating roller is high, the toner layer which comes into contact with the heating roller, When the surface temperature of the heating roller is high because the temperature difference between the lowermost toner layer that is in contact with the sheet to be fixed is large, the uppermost toner is likely to cause an offset phenomenon. When the surface temperature is low, the toner in the lowermost layer is not sufficiently melted, so that the toner is not fixed on the sheet to be fixed and a phenomenon of low temperature offset is likely to occur.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing and anchoring the toner to the sheet to be fixed is usually used. With this method, the temperature of the heating roller can be lowered to some extent, and the high temperature offset phenomenon of the uppermost toner layer can be prevented. However, since the shearing force applied to the toner becomes extremely large, the sheet to be fixed winds around the fixing roller, and a winding offset occurs, or after separation of the separation claw for separating the sheet to be fixed from the fixing roller. Tend to appear in fixed images. Further, since the pressure is high, the line image is crushed during the fixing and the toner flies off, so that the image quality of the fixed image is easily deteriorated.

In high-speed fixing, generally, a toner having a lower melt viscosity than that in low-speed fixing is used, and by lowering the surface temperature of the heating roller and lowering the fixing pressure, high-temperature offset and winding offset are prevented, The toner image is fixed. However, when such a toner having a low melt viscosity is used for low-speed fixing, an offset phenomenon easily occurs at high temperature.

In fixing, a toner having a wide fixing temperature range applicable from low speed to high speed and excellent in offset resistance is desired.

By reducing the particle size of the toner, the resolution and the sharpness of the image are increased, while the fixing property of the halftone portion formed by the toner having the small particle size is deteriorated. This phenomenon is remarkable especially in high-speed fixing. This is because the toner amount in the halftone portion is small, the toner transferred to the concave portion of the sheet to be fixed has a small amount of heat given from the heating roller, and the fixing pressure is also small due to the convex portion of the sheet to be fixed. This is because the pressure is suppressed and it becomes worse. Since the toner transferred to the convex portion of the fixing sheet in the halftone portion has a small toner layer thickness, the shearing force applied to each toner particle is larger than that in the solid black portion having a large toner layer thickness, and the offset The phenomenon is likely to occur, and a fixed image of low image quality is likely to occur.

Japanese Unexamined Patent Publication (Kokai) No. 1-128071 discloses a toner for electrophotographic development which uses polyester resin as a binder resin and has a specific storage viscosity at 95 ° C.
It is still necessary to improve fixability and offset resistance.

According to Japanese Patent Laid-Open No. 4-353866, the temperature at which the storage elastic modulus starts to fall is in the range of 100 to 110 ° C., the specific storage elastic modulus is at 150 ° C., and the peak temperature of the loss elastic modulus is An electrophotographic toner having a rheological property of 125 ° C. or higher is disclosed. However, since both the storage elastic modulus and the loss elastic modulus are too small and the peak temperature of the loss elastic modulus is too high, the low temperature fixability is not improved, and both the storage elastic modulus and the loss elastic modulus are too low, so that the heat resistance is low. .

JP-A-6-59504 discloses that a polyester resin having a specific structure is used as a binder resin,
The toner has a specific storage elastic modulus at 70 to 120 ° C., and 1
A toner for developing an electrostatic image having a specific loss elastic modulus at 30 to 180 ° C. is disclosed. However, 70-1
Since the storage elastic modulus at 20 ° C. is large and the loss elastic modulus at 130 to 180 ° C. is small, it is difficult to fix the magnetic toner having a small particle diameter at a low temperature, and the offset resistance is also desired to be improved.

When the content of the magnetic substance in the magnetic toner having a small particle size is large, the problem of fixing property becomes remarkable. From the viewpoint of rheology, an increase in the colorant contained in the toner tends to increase the storage elastic modulus and the loss elastic modulus, and the fixing property is remarkably fixed in a copy taken immediately after the copying machine is turned on in cold weather. May deteriorate, and improvement is required.

Japanese Patent Laid-Open No. 4-358159 discloses a vinyl polymer, two polyethylene waxes having different softening points and / or two polypropylene waxes having different softening points, one of which is added at the time of polymerization. , The other is a developer for electrophotography, which is compounded at the time of kneading. The wax used has a high softening point of 100 ° C or higher, and the temperature difference between the softening points of the two waxes is 2 to 20 ° C.
Since it is small, the offset resistance is excellent, but the low temperature fixability is poor.

Japanese Unexamined Patent Publication (Kokai) No. 4-362953 discloses a toner containing free fatty acid carnauba wax and oxidized rice wax having an acid value of 10 to 30. Although this toner has excellent low-temperature fixability, it has low offset resistance and blocking resistance, and has low toner fluidity.

In Japanese Unexamined Patent Publication No. 6-130714, a linear polyester is used as a fixing resin, a wax having a softening point similar to that of the linear polyester is used as a releasing agent, and a wax having a softening point higher than that of the linear polyester is used. Toners have been disclosed for use with high wax. In the case of this toner, the blocking resistance and the offset resistance are at a level at which there is no practical problem, but the melting point of the wax used is high and the low-temperature fixability is poor.

[0018]

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

An object of the present invention is to provide a toner for developing an electrostatic charge image, which exhibits a good fixing property even if the toner has a small particle size and the content of a coloring agent (particularly a magnetic material) associated therewith is increased. Is.

An object of the present invention is to provide an electrostatic charge image developing toner which can be satisfactorily fixed immediately after power is turned on in cold weather.

The object of the present invention is to develop an electrostatic image which can cope well with low-speed to high-speed copying machines, has a good fixing property, and is excellent in offset resistance, blocking resistance and fluidity. To provide toner.

An object of the present invention is to provide a toner for developing an electrostatic charge image, which exhibits excellent fixability even in a halftone portion and can obtain a fixed image of good quality.

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

[0024]

The present invention provides a toner for developing an electrostatic charge image containing a binder resin, a colorant and a wax, the toner comprising: (a) a storage elastic modulus (G) at a temperature of 100 ° C. ' ₁₀₀ ) is 1 × 10 ⁴ Pa to 5 × 10 ⁴ P
a, and (b) the storage elastic modulus (G ′ at a temperature of 60 ° C.).
₆₀₎ a toner relating for developing an electrostatic image, wherein the storage modulus ( 'ratio of _{70) (G' G 60 /} G '70) is 30 or more at a temperature 70 ° C..

[0025]

DETAILED DESCRIPTION OF THE INVENTION According to the study by the present inventor, the content of a colorant (particularly a magnetic material) is increased, and a toner having a small particle diameter is used to obtain a good fixing property and a good fixing property. To obtain a toner having both good blocking property and good fixability immediately after power-on of the copying machine even in cold weather,
It is important to use a binder resin or toner that has specific rheological properties.

In the conventionally known rheological characteristics, the power is turned on and a certain amount of time has passed (in other words, the standby state), and the upper roller (heating roller) and the lower roller (pressure roller) are The present invention relates to fixability in a sufficiently heated state, and there is a demand for improvement in fixability in a state in which a lower roller (pressure roller) immediately after power is turned on is not sufficiently heated.

The toner of the present invention has a storage elastic modulus at 100 ° C. (hereinafter referred to as G ′ ₁₀₀ ) of 1 × 10 ^{4 to} 5 ×.
And 10 ⁴ Pa, the ratio of storage modulus at 60 ° C. and 70 ° C. _{(hereinafter, G '60 / G' 70} ) is 30 or more.

According to the study by the present inventors, G _'100 is dependent polymer constituting the binder resin contained in the toner, especially entanglement between between the high molecular weight component with each other and / or low molecular weight component and a high molecular chain This is 1 × 10 ⁴
To 5 × 10 ⁴ Pa, but more preferably 1
× 10 ^{4 to} 4.5 × 10 ⁴ Pa, and more preferably 1.5 × 10 ^{4 to} 4 × 10 ⁴ Pa.

[0029] When the G _'100 is more than 5 × 10 ⁴ Pa, the entanglement between the polymer chains show that often, the toner during melting is hardly deformed. When G ′ ₁₀₀ is less than 1 × 10 ⁴ Pa, there is little entanglement between polymer chains,
The toner tends to change during melting, and the offset resistance tends to decrease.

[0030] G _'60 and G' ₇₀ is the process of transition to a state in which the binder resin in a not easily deformable glass state or glass transition initiation state even subjected to any force tending to deform from the outside can be deformed by an external force It can be understood that the storage elastic modulus of is shown. Generally, in the case of a toner containing a large amount of a colorant, especially in the case of a magnetic toner in which the colorant is a magnetic substance, there is a correspondence relationship between the content of the magnetic substance and the fixability. Tends to decline. The lowering of the fixing property of the toner becomes apparent when the fixing temperature is low, or when the fixing temperature is high but the entire fixing device is not uniformly heated. Specifically, when the fixing roller is in a state where the lower roller is not sufficiently heated immediately after the power of the copying machine is turned on in cold weather, the toner fixing property is remarkably deteriorated. This can be explained by the fact that the storage elastic modulus of the toner containing the colorant is higher than that of the binder resin alone.

[0031] Therefore, the value of G _'60 / G' ₇₀ is important in determining the toner fixability of the fixing device immediately after turning on the power at the time of fixing at low temperatures, especially cold.

[0032] In the present invention, G _'60 / G' value of ₇₀ is 3
It may be 0 or more, preferably 35 to 120,
More preferably, it is 40-110. G when the value of _'60 / G' ₇₀ is less than 30 reduces the fixing property of the toner in the fixing device immediately after power on fixability and when refrigeration at low temperature, G _'60 / G' ₇₀ of the When the value exceeds 120, only the uppermost toner (toner in contact with the upper roller) is excessively melted and deformed when the toner on the transfer paper passes through the fixing device, and offset is likely to occur, which is not preferable.

[0033] G _'60 of toner is preferably at 7 × 10 ⁶ Pa or more, more preferably 1 × 10 ⁷ ~5 × 1
0 ⁸ a case where the Pa, more preferably 2 × 10 ⁷ ~
This is the case where the pressure is 4 × 10 ⁸ Pa. Toner _G'60 is 7
When it is less than × 10 ⁶ Pa, it is advantageous for fixing at low temperature, but blocking resistance and offset resistance are deteriorated.
If G _'60 of toner exceeds 5 × 10 ⁸ Pa, although it is advantageous for blocking resistance and offset resistance in some cases problems with fixing of toner at low temperatures may occur.

Similarly, the toner _G'70 is 7 × 10 ^6.
It is preferably Pa or less, more preferably 6 × 1.
It is a case where it becomes 0 ^{5 to} 6 × 10 ⁶ Pa, and more preferably a case where it becomes 8 × 10 ^{5 to} 5 × 10 ⁶ Pa. When the toner of G _'70 is more than 7 × 10 ⁶ Pa is lowered fixability at low temperatures, in the case of less than 6 × 10 ⁵ Pa offset resistance decreases.

In the present invention, the loss modulus (hereinafter referred to as G ") of the toner is preferably a toner having a maximum value in the range of 48 to 65 ° C., more preferably a maximum value in the range of 49 to 63 ° C. Toner, more preferably 50
The toner has a maximum value in the range of -60 ° C. When the maximum value of G ″ is less than 48 ° C., the blocking resistance is lowered, and when the maximum value of G ″ is more than 65 ° C., the blocking resistance is good but the fixing property is lowered.

The toner G ″ is 8 × 1 at the above maximum value.
It preferably has a value of 0 ^{7 to} 5 × 10 ⁸ Pa, more preferably 9 × 10 ⁷ to 4 × 10 ⁸ Pa, further preferably 1 × 10 ^{8 to} 3 × 10 ⁸ Pa. When G "is less than 8 × 10 ⁷ Pa at the maximum value, fluidity may decrease or aggregates may be formed when the toner is stored for a long time. 5 × 10 ⁸ P
If it exceeds a, a large amount of force is required to melt and deform the toner during fixing.

In the toner of the present invention, the loss tangent (hereinafter, t), which is the ratio (G "/ G ') of the loss elastic modulus to the storage elastic modulus.
It is preferably 0.5 or more at a temperature of 60 to 100 ° C. and has a maximum value of 1.5 or more at a temperature of 63 to 78 ° C. More preferably, the toner has a maximum value at 64 to 75 ° C., and further preferably 65 to 73.
The toner has a maximum value at ° C. When the temperature at which the maximum value of tan δ is less than 63 ° C, both the blocking resistance and the offset resistance are lowered, and when it exceeds 78 ° C, the fixability is lowered.

[0038] G _'100 of the binder resin contained in the toner of the present invention is preferably from ^{5 × 10 3 ~1 × 10 5} Pa, more preferably be ^{7 × 10 3 ~9 × 10 4} Pa And more preferably 1 × 10 ⁴ to 8 × 10 ⁴ Pa.
G binder resin _{'when 100} is 5 × 10 ³ less than Pa decreases offset resistance of the toner, G' ₁₀₀ is 1 × 10 ⁵
When it exceeds Pa, the fixing property of the toner is deteriorated.

The binder resin preferably used in the toner of the present invention has a high elastic modulus resin component having a G ′ ₁₀₀ of 1 × 10 ⁴ to 1 × 10 ⁶ Pa and a G ′ ₁₀₀ of less than 1 × 10 ⁴ Pa. It is preferably composed of a resin composition having a low elastic modulus resin component. High modulus resin component of G _'100 is 1 × 1
It is preferably 0 ⁴ to 1 × 10 ⁶ Pa, more preferably 1.5 × 10 ⁴ to 8 × 10 ⁵ Pa, and further preferably 2 × 10 ^{4 to} 6 × 10 ⁵ Pa. If the G ′ ₁₀₀ of the high elastic modulus resin component is less than 1 × 10 ⁴ Pa, the offset resistance of the toner is lowered. When the G ′ ₁₀₀ of the high elastic modulus resin component exceeds 1 × 10 ⁶ Pa, the fixability of the toner is deteriorated, and it becomes difficult to uniformly mix the high elastic modulus resin component and the low elastic modulus resin component. There is also.

The low modulus resin component G ′ ₁₀₀ is 1 × 10 ⁴ P
It is preferably less than a, more preferably 1 x 10
^{2 to} 9 × 10 ³ Pa, more preferably 5 × 10 ² to
It is 8 × 10 ³ Pa. Low modulus resin component _G'100 is 1
When it is more than × 10 ⁴ Pa, the fixing property of the toner is lowered,
When the G ′ ₁₀₀ of the low elastic modulus resin component is less than 1 × 10 ² Pa, the offset resistance of the toner decreases, and it becomes difficult to uniformly mix the low elastic modulus resin component and the high elastic modulus resin component. There is also.

When the binder resin is formed of the high elastic modulus resin component and the low elastic modulus resin component, the mixing ratio is preferably 90:10 to 10:90 by weight, and more preferably, It is preferably 80:20 to 15:85, more preferably 70:30 to 20:80. If the content of the high elastic modulus resin component in the binder resin is less than 10% by weight, the offset resistance of the toner is lowered, and 90% by weight is obtained.
When it exceeds, the fixing property of the toner is deteriorated, which is not preferable.

As the binder resin in the toner of the present invention,
A polyester resin, a vinyl resin or a mixture thereof is preferably used.

The composition of the polyester resin used in the present invention will be described below.

The polyester resin is 45 to 55 in all the components.
mol% is alcohol component, 55-45 mol%
Is preferably an acid component.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and a bisphenol derivative represented by the formula (A);

[0046]

Embedded image

Diols represented by the formula (B);

[0048]

Embedded image And other diols.

Examples of the divalent carboxylic acid containing 50 mol% or more in the total acid components include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides; succinic acid, adipic acid, sebacic acid, Alkyl dicarboxylic acids such as azelaic acid or their anhydrides, and succinic acid substituted with an alkyl group or an alkenyl group having 6 to 18 carbon atoms or their anhydrides; fumaric acid, maleic acid, citraconic acid, itaconic acid Saturated dicarboxylic acid or its anhydride etc. are mentioned.

Further, as alcohol components, glycerin, pentaerythritol, sorbit, sorbitan,
Examples thereof include polyhydric alcohols such as oxyalkylene ether of novolac type phenolic resin, and examples of the acid component include polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and its anhydride.

The alcohol component of the polyester resin particularly preferred in the practice of the present invention is the bisphenol derivative represented by the above formula (A), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, and succinic acid. , N-dodecenylsuccinic acid or its anhydride, and dicarboxylic acids such as fumaric acid, maleic acid and maleic anhydride. Preferred examples of the crosslinking component include trimellitic anhydride, benzophenonetetracarboxylic acid, pentaerythritol, and oxyalkylene ether of novolac type phenol resin.

The glass transition temperature of polyester resin is 40
To 90 ° C is preferable, and 45 to 85 ° C is more preferable. The number average molecular weight (Mn) of the polyester resin is 1,0
It is preferably from 00 to 50,000, more preferably from 1,500 to 20,000, still more preferably from 2,500 to 10,000. The weight average molecular weight (Mw) of the polyester resin is 3,000 to 3,000,
It is preferably 000, more preferably 10.0
It is from 00 to 2,500,000, more preferably 4
It is 20,000 to 2,000,000.

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

Styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,
4-dichlorostyrene, p-ethylstyrene, 2,4-
Dimethyl styrene, pn-butyl styrene, p-te
rt-butyl styrene, pn-hexyl styrene, p
-N-octyl styrene, pn-nonyl styrene, p
Styrene and its derivatives such as -n-decyl styrene and pn-dodecyl styrene; Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Unsaturated polyenes such as butadiene; Vinyl chloride, vinylidene chloride, odor Vinyl halides such as vinyl chloride and vinyl fluoride; vinyl acetate, vinyl propionate,
Vinyl ester acids such as vinyl benzoate; 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 acid esters such as phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, Acrylic esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; Methyl ether, vinyl ethyl ether, such as vinyl ethers vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, such as vinyl ketones of methyl isopropenyl ketone; N- vinyl pyrrole, N- vinyl carbazole, N
-N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinyl naphthalenes; acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide;
-Unsaturated acid esters, dibasic acid diesters.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride. Unsaturated dibasic acid anhydrides such as: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl ester Half ester of unsaturated dibasic acid such as half ester, methyl alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated dibasic acid ester such as dimethyl maleic acid, dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic acid anhydride,
An anhydride of β-unsaturated acid and lower fatty acid; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Mention may be made of monomers having a hydroxyl group such as hydroxy-1-methylhexyl) styrene.

The glass transition temperature of vinyl resin is 45 to 8
The temperature is preferably 0 ° C., more preferably 55 to 70.
° C. The number average molecular weight (Mn) of vinyl resin is 2,
It is preferably 500 to 50,000, and more preferably 3,000 to 20,000. The weight average molecular weight (Mw) of the vinyl resin is 10,000 to 1,50
It is preferably 10,000, more preferably 2
It is 5,000 to 1,250,000.

When the toner is dissolved in a solvent (for example, tetrahydrofuran) and the filtrate is subjected to gel permeation chromatography (GPC) to measure the molecular weight distribution,
Molecular weight 2,000-40,000, preferably 3,000
0-30,000, more preferably 3,500-20,
000 low molecular weight region, and molecular weight 50,000-1,
200,000, preferably 80,000 to 1,10
10,000, more preferably 100,000 to 1,000
It is preferable that each has a peak in the high molecular weight region of 10,000.

More preferably, in the measurement of the molecular weight distribution of the filtrate by GPC, the area ratio of the low molecular weight region having a molecular weight of 45,000 or less to the high molecular weight region having a higher molecular weight is 1: 9 to 9.5: 0. .5, preferably 2: 8
It is preferably in the range of ˜9: 1, more preferably 3: 7 to 8.5: 1.5.

The wax contained in the toner includes low molecular weight polyethylene, low molecular weight polypropylene, aliphatic hydrocarbon wax such as microcrystalline wax and paraffin wax, oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax, or , Those block copolymers; waxes having fatty acid ester as a main component such as carnauba wax, sazol wax, montanic acid ester wax, and deoxidized part or all of fatty acid ester such as deoxidized carnauba wax There are things. Further, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkylcarboxylic acids having a longer-chain alkyl group,
Unsaturated fatty acids such as blancinic acid, eleostearic acid, and valinaric acid, stearic alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol, melysyl alcohol, or a long-chain alkyl alcohol having a longer-chain alkyl group. Alcohols such as bisphenol, polyhydric alcohols such as sorbitol, linoleic acid amide, oleic acid amide,
Fatty acid amides such as lauric acid amide, methylenebisstearic acid amide, ethylenebiscapric acid amide,
Saturated fatty acid bisamides such as ethylene bislauric acid amide and hexamethylene bisstearic acid amide, ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipic acid amide,
Unsaturated fatty acid amides such as N, N'-dioleyl sebacic acid amide, m-xylene bisstearic acid amide,
Aromatic bisamides such as N, N'-distearylisophthalic acid amide, fatty acid metal salts (generally called metal soap) such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, and fat Waxes made by grafting aromatic vinyl waxes with vinyl monomers such as styrene and acrylic acid, partial esterification products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride, and hydrogenation of vegetable oils and fats And a methyl ester compound having a hydroxyl group.

The wax preferably used in the toner of the present invention more clearly expresses the characteristic viscoelastic properties of the toner of the present invention. The wax-containing toner preferably has an endothermic main peak in the temperature range of 60 to 135 ° C. in the DSC curve measured by a differential scanning calorimeter from the viewpoint of low-temperature fixability and offset resistance of the toner. More preferably, the wax-containing toner preferably has an endothermic main peak in a temperature range of 60 to 100 ° C. in a DSC curve measured by a differential scanning calorimeter. More preferably, the wax containing toner has a D as measured by a differential scanning calorimeter.
In the SC curve, it is preferable to have an endothermic main peak, an endothermic subpeak, or an endothermic shoulder in the temperature range of 60 to 135 ° C. from the viewpoint of low temperature fixing, offset resistance and blocking resistance.

In order to form a clear endothermic peak in the temperature range of 60 to 135 ° C. in the toner DSC curve, the wax used is limited. When the temperature corresponding to the maximum endothermic peak is defined as the melting point of the wax in the DSC curve of the wax in the temperature range of 30 to 200 ° C. by a differential scanning calorimeter described below, the wax having a melting point of 60 to 135 ° C. Preferably used.
Since it is preferable that the wax is also functionally separated in order to improve the low temperature fixing property and the high temperature offset resistance of the toner, the wax has a low melting point wax component having a relatively low melting point and a relatively melting point wax. It is preferably formed of at least two types of high-melting-point wax components. More specifically, the low melting point wax component preferably has a melting point of 60 to 94 ° C, more preferably 70 to 90 ° C. The high melting point wax component preferably has a melting point of 95 to 135 ° C., more preferably 95 to 130 ° C., and further preferably 100 to 130 ° C.

When the melting point of the low melting point wax component is less than 60 ° C., the G ′ ₁₀₀ of the toner may be less than 1 × 10 ⁴ Pa, and the blocking resistance of the toner is deteriorated. If the melting point of the high melting point wax component exceeds 135 ° C., the G ′ ₆₀ / G ′ ₇₀ of the toner may be less than 30, and the low temperature fixability of the toner will deteriorate.

By using the low melting point wax component and the high melting point wax component in combination, a predetermined endothermic main peak and endothermic subpeak or shoulder can be suitably formed on the DSC curve of the toner.

More preferably, the wax comprises a low melting point wax component and a high melting point wax component, and the low melting point wax component and the high melting point wax component satisfy the following conditions.

[0066]

[Equation 2]

[In the formula, T _ML represents the melting point of the low melting point wax component, and T _MH represents the melting point of the high melting point wax component. ] Is good to be satisfied.

Further, the difference between the melting point (T _ML ) of the low melting point wax component and the melting point (T _MH ) of the high melting point wax component is preferably 20 to 75 ° C.

In the wax used in the toner of the present invention, the weight ratio of the low-melting wax component and the high-melting wax component is preferably 1/19 to 9/1, and more preferably 1/9 to 8 / 1, and more preferably 1/7 to 7/1. When the above blending ratio is satisfied, the low-melting wax component and the high-melting wax component contribute to the low-temperature fixability, blocking resistance, and
It is possible to further improve the offset resistance.

In addition to the low-melting point wax component and the high-melting point wax component, another third wax component within the range that does not impair the effects of the present invention is used for fine adjustment of low-temperature fixability, blocking resistance or offset resistance. More than one species can be contained. The content of other wax components is preferably 20% by weight or less based on the total amount of wax, and the melting point is preferably 60 to 140 ° C.

In the toner of the present invention, the wax is preferably contained in an amount of 1 to 20 parts by weight, more preferably 2 to 17 parts by weight, based on 100 parts by weight of the binder resin.
It is more preferably 3 to 15 parts by weight. When the toner contains the wax in the above content, it is possible to improve the low-temperature fixing property, blocking resistance and offset resistance of the toner, and further to reduce the amount of free wax particles from the toner particles.

In the present invention, examples of the low melting point wax component preferably used include a hydrocarbon wax having a long-chain alkyl group with few branches. Specifically, a low molecular weight alkylene polymer wax obtained by radically polymerizing alkylene under high pressure or a Ziegler catalyst under low pressure; an alkylene polymer wax obtained by thermally decomposing a high molecular weight alkylene polymer; consisting of carbon monoxide and hydrogen A wax of synthetic hydrocarbon obtained from a distillation residue of polymethylene hydrocarbon obtained from synthetic gas by an Arge process or obtained by hydrogenating these is preferable. Further, the one in which the hydrocarbon wax is fractionated by the use of press sweating method, solvent method, vacuum distillation or fractional crystallization method is more preferably used. Examples of the hydrocarbon as a matrix include polymethylene wax synthesized by a reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often two or more multi-component type). Furthermore, for example, the Jintor method,
Waxes obtained by the Hydrocoal method (using a fluidized catalyst bed) or the Arge method (using a fixed catalyst bed) where a large amount of waxy hydrocarbons can be obtained.

A part of the terminal of the long-chain alkyl group may be substituted with a hydroxyl group and a functional group derived from the hydroxyl group (eg, carboxyl group, ester group, ethoxy group, sulfonyl group, etc.). Long chain alkyl alcohols are, for example:
It is obtained by the following production method. Ethylene is polymerized using a Ziegler catalyst, and after the polymerization is completed, it is oxidized to form an alkoxide of a catalyst metal and polyethylene. Then, hydrolysis is performed to obtain a long-chain alkyl alcohol. The long-chain alkyl alcohol thus obtained has few branches, is small, and has a sharp molecular weight distribution, which is in accordance with the object of the present invention.

The high melting point wax component preferably used in the present invention includes a hydrocarbon wax having a longer chain alkyl group with less branching. Specifically, for example, a low molecular weight alkylene polymer wax obtained by radically polymerizing alkylene under high pressure or a Ziegler catalyst under low pressure; an alkylene polymer wax obtained by thermally decomposing a high molecular weight alkylene polymer; carbon monoxide and hydrogen A synthetic hydrocarbon wax obtained from the distillation residue of the polymethylene hydrocarbon obtained by the Arge process from the synthetic gas consisting of or obtained by hydrogenating these is preferable.

A part of the terminal of the long-chain alkyl group may be substituted with a hydroxyl group or a functional group derived from the hydroxyl group (eg, carboxyl group, ester group, ethoxy group, sulfonyl group, etc.).

The low melting point wax component preferably used in the present invention preferably has a weight average molecular weight of 300 to 1,000, more preferably 350 to 900.
Is. The Mw / Mn of the low melting point wax component should be 2.8 or less, preferably 2.3 or less. The high melting point wax component has a weight average molecular weight of 500 to 15,000, preferably 650 to 10,000, and more preferably 1,500 to 90,000. The high-melting-point wax component has Mw / Mn of 3.0 or less, preferably 2.
It should be 5 or less. A wax satisfying these conditions can further improve the low temperature fixing property, blocking resistance and offset resistance of the toner.

The combination of the low melting point wax component and the high melting point wax component preferably used in the present invention is as follows:
For example, there are the following combinations.

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

The high melting point hydrocarbon wax component has a long-chain alkyl group with few branches, has a melting point of 95 to 130 ° C., a weight average molecular weight of 800 to 2,500, and Mw / Mn.
Is preferably 2 to 2.5.

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

The high-melting-point substituted alkyl wax component has a long-chain alkyl group with few branches, has a substituent other than a hydrogen atom at a terminal or a part of the molecule, and the substituent is a hydroxyl group and / or a carboxyl group. It is preferable that the alkyl component having a substituent is contained in an amount of 50% by weight or more based on the total wax. Further, the high melting point substituted alkyl wax component has a melting point of 95 to 130 ° C., a weight average molecular weight of 800 to 5000, and an Mw / Mn of 1.5 to 2.
Those of 5 are preferred.

(3) Combination of low melting point substituted alkyl wax component and high melting point hydrocarbon wax component: The low melting point substituted alkyl wax has a long chain alkyl group with few branches,
It has a substituent other than a hydrogen atom at the terminal or in a part of the molecule, the substituent is a hydroxyl group and / or a carboxyl group, and the alkyl component having the substituent is 40% in all waxes.
Those containing more than wt% are preferable. The low melting point substituted alkyl wax has a melting point of 70 to 90 ° C., a weight average molecular weight of 400 to 700, and an Mw / Mn of 1.5.
A value of ~ 2.5 is preferable.

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

(4) Combination of low melting point substituted alkyl wax and high melting point substituted alkyl wax: As the low melting point substituted alkyl wax, the same low melting point alkyl wax as described in (3) above can be used.

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

In the toner of the present invention, the binder resins preferably used are, for example, the following combinations.

(1) Combination of vinyl low elastic modulus resin and vinyl high elastic modulus resin: The vinyl low elastic modulus resin has a weight average molecular weight of 5,000 to 50,000 and Mw / Mn of 1.5 to 20. And G ′ ₁₀₀ is 1 × 10 ² or more to 1 ×
It is preferably less than 10 ⁴ Pa.

The vinyl-based high elastic modulus resin has a weight average molecular weight of 300,000 to 1,500,000 and Mw / Mn of 1.5 to.
Is 20, one G _'100 is ^{1 × 10 4 ~1 × 10 6} Pa are preferred.

(2) Combination of polyester low elastic modulus resin and polyester high elastic modulus resin: The weight average molecular weight of the polyester low elastic modulus resin is 2000 to 30,000, and Mw / Mn is 1.5 to 20. And _G'100 is 1 ×
It is preferably 10 ² or more and less than 1 × 10 ⁴ Pa.

The polyester high elastic modulus resin has a weight average molecular weight of 40,000 to 1,000,000 and Mw / Mn of 1.
5 to 20 and G ′ ₁₀₀ is 1 × 10 ⁴ to 1 × 10 ⁶ Pa
It is preferred that

(3) Combination of vinyl low elastic modulus resin and polyester high elastic modulus resin: The vinyl low elastic modulus resin of (1) above and the polyester high elastic modulus resin of (2) above are used in combination. .

(4) Combination of polyester low elastic modulus resin and vinyl high elastic modulus resin: The polyester low elastic modulus resin of (3) above and the vinyl low elastic modulus resin of (1) above are used in combination. .

In the combination of the binder resins (1) to (4), the third resin component may be added within the range that does not impair the effects of the present invention. This may be a vinyl-based binder resin, a polyester-based binder resin, or another polycondensation method, and the addition amount thereof is 30 with respect to the total binder resin.
It is preferably not more than weight%.

In the toner of the present invention, the selection and combination of the binder resin and the wax are important, and the proper mixing of the binder resin and the wax is important in order to exhibit the predetermined rheological properties. . That is, even if the binder resin and the wax are properly selected, the original good rheological properties cannot be exhibited if the mixing of these is performed by an inappropriate method.

A method for mixing the binder resin and the wax preferably used in the toner of the present invention will be described below.

In order to develop the viscoelastic characteristics of the toner of the present invention, a low elastic modulus binder resin component, a high elastic modulus binder resin component, a high melting point wax component and a low melting point wax component are combined. Are used as a mixture and mixed by various methods.

Generally, the crushed individual waxes are mixed with the binder resin, the colorant (magnetic substance) and the like by stirring and mixing with a mixer such as a Henschel mixer, and then melt-kneading. The low melting point component, the high melting point component of the wax and, if necessary, the third wax component may be melt mixed in advance. As another method of adding the wax, there is a method in which the binder resin is heated and dissolved in an organic solvent, and then the wax is added and the solvent is evaporated to dryness. In addition, there is a method in which a binder resin is heated and melted without using an organic solvent and a wax is added. When the wax is added to the binder resin by these methods, the wax to be used may be a mixture of the low-melting wax component, the high-melting wax component and, if necessary, the third wax component, which are melt-mixed. . Another method of adding wax is a method of adding wax in the step of synthesizing the binder resin. Even in this case, the wax may be melt-mixed in advance and the components thereof may be adjusted. Another method of adding the wax is a method of previously adding only the low melting point wax component to the binder resin. Specifically, a method of heating and melting only the binder resin and adding the low melting point wax component, a method of heating and dissolving the binder resin in an organic solvent and adding the low melting point wax component, and then evaporating the organic solvent to dryness and binding. In this method, a low melting point wax component is added in the resin synthesis process. In this case, the high melting point wax component is added to the toner by stirring and mixing with a binder resin, a colorant (magnetic material) and the like containing the low melting point wax component with a Henschel mixer or the like and then melt-kneading.

The electrostatic image developing toner of the present invention may contain a charge control agent, if necessary, in order to further stabilize the chargeability thereof. The charge control agent is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin.

Examples of the charge control agent include the following.

Examples thereof include organic metal complexes, chelate compounds and organic metal salts. Specific examples thereof include a monoazo metal complex; a metal complex or a metal salt of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid compound. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and anhydrides thereof, esters thereof; and phenol derivatives of bisphenol.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co and Ni. Or a metal such as Al, Co, Cu,
Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Examples thereof include alloys with metals such as d, Ca, Mn, Se, Ti, W and V, and mixtures thereof.

Specifically, as the magnetic material, iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide ( Y ₃ Fe ₅
O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuFe)
₂ O ₄ ), iron oxide lead (PbFe ₁₂ —O ₁₉ ), iron oxide nickel (NiFe ₂ O ₄ ), iron oxide neodymium (NdFe)
₂ O ₃ ), iron oxide barium (BaFe ₁₂ O ₁₉ ), iron oxide magnesium (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like. The above magnetic materials are used alone or in combination of two or more. A particularly preferred magnetic material is a fine powder of ferric tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
μm (more preferably 0.1 to 0.5 μm), 10K
The magnetic characteristics under application of Oersted are coercive force of 20 to 150 Oersted, saturation magnetization of 50 to 200 emu / g (preferably 50 to 100 emu / g), and residual magnetization of 2 to 20 em.
u / g is preferable.

For 100 parts by weight of the binder resin, the magnetic material 1
It is recommended to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

In addition to the magnetic material, carbon black, titanium white and other pigments and / or dyes can be used as the colorant. For example, when the toner of the present invention is used as a magnetic color toner, the dye is
C. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Mordant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I.
I. Acid Blue 9, C.I. I. Acid Blue 15,
C. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Mordant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I.
I. There are Basic Green 6 etc. Pigments include mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange,
Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkaline Blue Lake, Victoria Blue rake, phthalocyanine blue, fast sky blue, indanthrene blue BC, pigment green B, malachite green rake, final yellow green G, etc. are available.

When the toner of the present invention is used as a two-component full-color toner, the following coloring agents can be mentioned. Examples of magenta color pigments include C.I.
I. Pigment Red 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
17,18,19,21,22,23,30,31,3
2,37,38,39,40,41,48,49,5
0,51,52,53,54,55,57,58,6
0,63,64,68,81,83,87,88,8
9, 90, 112, 114, 122, 123, 163
202, 206, 207, 209, C.I. I. Pigment violet 19, C.I. I. Bat red 1,2,1
0, 13, 15, 23, 29, 35 and the like.

The above pigments may be used alone,
From the viewpoint of the image quality of a full-color image, it is more preferable to use a dye and a pigment together to improve the sharpness. Examples of magenta dyes include C.I. I. Solvent Red 1,3,8,2
3,24,25,27,30,49,81,82,8
3,84,100,109,121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8,1
3, 14, 21, 27, C.I. I. Oil soluble dyes such as Disperse Violet 1, C.I. I. Basic red 1,
2, 9, 12, 13, 14, 15, 17, 18, 22,
23, 24, 27, 29, 32, 34, 35, 36, 3
7, 38, 39, 40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25,26,
And basic dyes such as 27 and 28.

As the color pigment for cyan, C.I. I. Pigment Blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Copper 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted in a phthalocyanine skeleton having a structure represented by the following formula.

[0109]

Embedded image

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

The amount of non-magnetic coloring agent used is 100
0.1 to 60 parts by weight, preferably 0.5 to parts by weight
˜50 parts by weight.

A fluidity improver may be added to the toner of the present invention. When the fluidity improver is added to the toner, the fluidity can be increased by comparing before and after the addition. For example, vinylidene fluoride fine powder, fluororesin powder such as polytetrafluoroethylene fine powder; fine silica powder such as wet process silica, dry process silica, fine powder titanium oxide, fine powder alumina, silane coupling agents thereof, There are titanium coupling agents, treated silica surface-treated with silicone oil, treated titanium oxide, and treated alumina.

The preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is so-called dry process silica or fumed silica. For example, the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame is utilized, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HC
l

In this manufacturing process, it is possible to obtain a composite fine powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound. They are also included. The average particle size of the particles is preferably in the range of 0.001 to 2 μm, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used. .

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

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

Further, treated silica fine powder obtained by subjecting silica fine powder produced by vapor-phase oxidation of the silicon halogen compound to a hydrophobic treatment is more preferable. Among the treated silica fine powders, those obtained by treating the silica fine powder so that the degree of hydrophobicity measured by the methanol titration test is in the range of 30 to 80 are particularly preferable.

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

As the organic silicon compound, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Brommethyldimethylchlorosilane,
α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, one for each terminally located unit. Examples include dimethylpolysiloxane containing a hydroxyl group bonded to Si. Further, a silicone oil such as dimethyl silicone oil may be mentioned. These are used alone or as a mixture of two or more.

As the fluidity-improving agent, the above-mentioned dry process silica may be used the following coupling agent having an amino group or positively charged hydrophobic silica treated with silicone oil having an amino group.

[0122]

[Chemical 4]

[0123]

Embedded image

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

[0125]

[Chemical 6]

(In the formula, R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, and R ₃ and R ₄ represent hydrogen, an alkyl group or an aryl group. However, the above alkyl group,
The aryl group, alkylene group and phenylene group may contain an amine, and may have a substituent such as halogen within a range not impairing the charging property. m and n represent positive integers. )

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

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

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

The fluidity improver has a specific surface area by nitrogen adsorption of 30 m ² / g or more, preferably 5 by BET method.
Those of 0 m ² / g or more give good results. Toner 1
0.01 to 8 parts by weight of a fluidity improver relative to 00 parts by weight,
It is preferable to use 0.1 to 4 parts by weight.

To prepare the electrostatic image developing toner of the present invention, a binder resin, a colorant and / or a magnetic material, a charge control agent or other additives are sufficiently mixed with a mixer such as a Henschel mixer or a ball mill. Then, using a heat kneader such as a kneader or an extruder to melt, knead and knead the meat to make the resins compatible with each other, and after cooling and solidifying the melt-kneaded product, the solidified product is crushed and the crushed product is classified. The toner of the present invention can be obtained.

The toner of the present invention has a weight average particle diameter of 3 to 9
It is preferable that the toner has a particle size of .mu.m (more preferably 3 to 8 .mu.m) from the viewpoint of resolution and image density, and even a toner having a small particle size can be satisfactorily heated and pressed and fixed.

Further, the fluidity improver and the toner can be sufficiently mixed with a mixer such as a Henschel mixer to obtain a toner having the fluidity improver on the surface of the toner particles.

The methods of measuring the rheological properties and other physical properties of the toner of the present invention are shown below.

(1) Measurement of Rheological Properties of Toner and Binder Resin The measurement is performed using a viscoelasticity measuring device (rheometer) RDA-II type (manufactured by Rheometrics).

Measuring jig: A parallel plate having a diameter of 7.9 mm is used when the elastic modulus is high, and a parallel plate having a diameter of 25 mm is used when the elastic modulus is low.

Measurement sample: Toner or binder resin is heated and melted, and then molded into a cylindrical sample having a diameter of about 8 mm and a height of 2 to 5 mm or a disk-shaped sample having a diameter of about 25 mm and a thickness of 2 to 3 mm and used.

Measurement frequency: 6.28 rad / sec Measurement distortion setting: The initial value is set to 0.1%, and measurement is performed in the automatic measurement mode.

Elongation correction of sample: Adjusted in the automatic measurement mode.

Measurement temperature: The temperature is raised from 25 ° C. to 150 ° C. at a rate of 1 ° C./min.

An example of the measurement result is shown in FIG.

(2) Melting point measurement of wax Using a differential scanning calorimeter (DSC measuring device), DSC-7 (manufactured by Perkin Elmer), ASTM D3418-8
Measure according to 2.

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

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

During this temperature rising process, the endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained.

The temperature of this endothermic main peak is taken as the melting point of the wax.

(3) Measurement of Toner DSC Curve The DSC curve during the temperature rising process of the toner is measured in the same manner as the measurement of the melting point of the wax.

(4) Glass transition temperature (Tg) of binder resin
Measurement of ASTM D3418-8 using a differential scanning calorimeter (DSC measuring device), DSC-7 (manufactured by Perkin Elmer)
Measure according to 2.

A measurement sample is 5 to 20 mg, preferably 10
Precisely weigh mg.

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

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

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

(5) Measurement of molecular weight distribution of wax Gel permeation chromatography (GPC) measuring apparatus: GPC-150C (Waters Co.) Column: GMH-HT 30 cm 2 series (Tosoh Corp.) Temperature: 135 ° C. Solvent: o-dichlorobenzene (Addition of 0.1% ionol) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample injected

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

(6) Measurement of Molecular Weight Distribution of Binder Resin Raw Material or Binder Resin of Toner The molecular weight of the chromatogram by GPC is measured under the following conditions.

The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is passed through the column at this temperature at a flow rate of 1 ml / min.
When the sample is a binder resin raw material, the binder resin raw material is passed through a roll mill (130 ° C., 15 minutes). If the sample is toner, 0.2μ after dissolving the toner in THF
m-filter and use the filtrate as a sample.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for creating a calibration curve,
For example, Pressure Chemical Co.
Made or manufactured by Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
^It is suitable to use ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ standard polystyrene samples at least about 10 points. An RI (refractive index) detector is used as the detector.

As the column, a plurality of commercially available polystyrene gel columns may be combined in order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ^6.
rs Inc. of μ-styragel 500,10 ^3, 1
Combination of 0 ⁴ , 10 ⁵ and shodex manufactured by Showa Denko KK
KA-801, 802, 803, 804, 805, 8
A combination of 06,807 is preferred.

An example of an image forming apparatus to which the toner of the present invention can be applied will be described with reference to FIGS.
The surface of the electrostatic charge image bearing member (photoreceptor) 1 is negatively or positively charged by the primary charger 2 and an electrostatic charge image (for example, a digital latent image by image scanning) is formed by analog exposure or laser light exposure 5. The magnetic blade 11
And an electrostatic charge image is developed by reversal development or regular development with the magnetic toner 13 of the developing device 9 including the developing sleeve 4 containing the magnet 23 having the magnetic poles N ₁ , N ₂ , S ₁ and S _2. . Alternate bias, pulse bias and / or DC bias are applied by the bias applying means 12 between the conductive substrate 16 of the photoconductor 1 and the developing sleeve 4 in the developing section. The magnetic toner image is transferred via the intermediate transfer member.
Alternatively, it is transferred to the transfer material without intervention. When the transfer paper P is conveyed and reaches the transfer portion, the transfer charger 3 charges the positive or negative polarity from the back surface (the surface opposite to the photoconductor side) of the transfer paper P, thereby negatively charging the surface of the photoconductor. Magnetic toner image or positively charged magnetic toner image is electrostatically transferred onto the transfer paper P. After the charge is removed by the charge removing unit 22, the transfer paper P separated from the photoconductor 1 is heated and pressure-fixed on the transfer paper P by the heating and pressure roller fixing device 7 including the heater 21.

The magnetic toner remaining on the photoconductor 1 after the transfer step is removed by the cleaning means having the cleaning blade 8. The photoconductor 1 after cleaning is erased by erase exposure 6 and the process starting from the charging process is repeated by the primary charger 2.

The electrostatic image carrier (photosensitive drum, for example) 1 has a photosensitive layer 15 and a conductive substrate 16 and moves in the direction of the arrow. Non-magnetic cylindrical developing sleeve 4 which is the developing sleeve 4.
Rotates so as to proceed in the same direction as the surface of the electrostatic image carrier 1 in the developing section. Inside the non-magnetic cylindrical developing sleeve 4, a multi-pole permanent magnet (magnet roll) 23, which is a magnetic field generating means, is arranged so as not to rotate. The magnetic toner 13 in the developing device 9 is applied to the developing sleeve 4,
Further, due to friction between the surface of the developing sleeve 4 and the magnetic toner particles, the magnetic toner particles are given a triboelectric charge. Further, a magnetic doctor blade 17 made of iron is placed close to the surface of the cylindrical developing sleeve 4 (interval 50 μm to 500 μm).
m), the magnetic toner layer is made thin (30 μm to
(300 μm) and regulated uniformly to form a magnetic toner layer which is equal to or thinner than the gap between the photoconductor 1 and the developing sleeve 4 in the developing section. By adjusting the rotation speed of the developing sleeve 4, the surface speed of the developing sleeve is adjusted to the photoconductor 1.
The speed should be substantially equal to or close to the speed of the surface of. Instead of iron as the magnetic doctor blade 17, a permanent magnet may be used to form the opposing magnetic poles. An AC bias or a pulse bias may be applied to the developing sleeve 4 in the developing section by the bias means 12. This AC bias has f of 200 to 4,000H
z, V _pp may if 500~3,000V.

During the transfer of the magnetic toner particles in the developing section, the magnetic toner particles are transferred to the electrostatic image side by the action of the electrostatic force on the photoconductor surface and the AC bias or the pulse bias.

Instead of the magnetic blade 11, an elastic blade made of an elastic material such as silicone rubber may be used to regulate the layer thickness of the magnetic toner layer by pressing and apply the magnetic toner onto the developing sleeve.

[0163]

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

Example 1 A toner was prepared using the materials shown below.

Regarding the low melting point wax, a high purity wax obtained by further refining petroleum wax produced by the press sweating method was used as the low melting point hydrocarbon wax. Regarding the high melting point wax, a synthetic wax produced by the Fischer-Tropsch method was used as the high melting point hydrocarbon wax.

(A) Low elastic modulus binder resin: styrene-butyl acrylate copolymer produced by solution polymerization method [glass transition temperature 62.1 ° C., weight average molecular weight 12,300, Mw / Mn = 2 , 4, G ′ ₁₀₀ = 2.3 × 10 ³ Pa] 70 parts by weight (b) High elastic modulus binder resin: Styrene / butyl acrylate copolymer produced by suspension polymerization [weight average molecular weight 793 , 600, Mw / Mn = 2.1, glass transition temperature 60.7 ° C., G ′ ₁₀₀ = 1.7 × 10 ⁵ Pa] 30 parts by weight (c) Magnetic substance: (average particle size 0.2 μm) 90 parts by weight (d) Monoazo metal complex: (negative charge control agent) 2 parts by weight (e) Low melting point wax: low melting point hydrocarbon wax [melting point 75 ° C., weight average molecular weight 520, Mw / Mn = 1.8] 4 parts by weight (f) High melting point wax: High melting point carbonization Motokei wax mp 108 ° C., a weight average molecular weight 1080, Mw / Mn = 2.0] ... 3 parts by weight

The above materials were premixed with a Henschel mixer, and then melt-kneaded at 130 ° C. with a twin-screw kneading extruder. After the kneaded product is allowed to cool, it is roughly crushed by a cutter mill, then crushed by a fine crusher using a jet stream, and further classified by an air classifier to obtain a weight average particle diameter of 6.4 μm.
To obtain a negatively chargeable insulating magnetic toner. This magnetic toner 1
Negatively charged hydrophobic dry silica (BET)
1.0 part by weight of a specific surface area of 300 m ² / g) was externally added by a Henschel mixer to obtain a magnetic toner (1).

To measure the rheological properties of this magnetic toner, the toner was heated and melted, and the diameter was about 8 mm and the height was 3 mm.
A cylindrical sample having a diameter of 7 mm was prepared, and a diameter of 7.9 m
The sample was fixed on a m parallel serrated type parallel plate and the temperature dependence of the storage elastic modulus and the loss elastic modulus was measured. The measurement result of the temperature dependence of the elastic modulus is shown in FIG.

In order to evaluate the dispersibility of the wax, the above magnetic toner was attached to a polarizing plate on an optical microscope and about 300 toner particles in one visual field were observed at a low magnification (about 60 times). There were only 7 to 8 bright spots indicating the presence of the above, which was good.

Using this magnetic toner, continuous copying of 100,000 sheets was carried out using a digital copying machine (GP-55 manufactured by Canon Inc.).

In a digital copying machine, the diameter is 30 m.
A photosensitive drum having an OPC photosensitive layer on a cylinder made of aluminum of m is charged to -700 V by a primary charger, a digital latent image is formed by image scanning with laser light, and four magnetic poles (developing magnetic pole is 950 gauss). Reverse development was carried out with a negatively charging insulating magnetic toner frictionally charged by a developing sleeve containing a fixed magnet containing

DC bias -600 was applied to the developing sleeve.
V and AC bias V _pp 800 V (1800 Hz) were applied. The magnetic toner image on the photosensitive drum is electrostatically transferred to the plain paper by the transfer means, the plain paper is discharged to separate the plain paper from the photosensitive drum, and the magnetic toner image on the plain paper has a heating roller and a pressure roller. It was fixed by means of heat and pressure.

The image density was 1.33 at the initial stage of durability (1st to 10th sheets) and remained unchanged at 1.35 at the end of durability of 100,000 sheets, and there was no change in image quality such as scattering of line images and thickening. there were. When the OPC photosensitive drum was observed in detail at the end of the 100,000-sheet endurance, no adhered wax was observed and no noticeable damage was observed on the surface of the OPC photosensitive drum. There was no image defect presumably caused by damage on the surface of the OPC photosensitive drum on the image.

Next, the fixing device of the digital copying machine was removed, the external driving device was attached, the fixing roller was rotated at 100 mm / sec, the temperature control device was attached, and
Modification was made so that the temperature of the fixing roller could be changed in the range of 250 ° C. The fixing test was carried out in a constant temperature bath controlled at a temperature of 3 to 5 ° C, and after confirming that the fixing roller was in agreement with the temperature inside the bath, the power was turned on and the upper roller (heating roller)
Immediately after the temperature reached 110 ° C., a fixing test was conducted. At this point, the temperature of the lower roller (pressure roller) is about 70 ° C.
Met. Next, a fixing test was conducted by continuously rotating the fixing roller for 20 minutes with the heater energized. The temperature of the lower roller (pressure roller) was about 90 ° C.

As a result of the above fixing test, the density decrease rate was 18% immediately after the power was turned on, and the density decrease rate was 13 after 20 minutes.
%, Which was a practically acceptable level. A blocking resistance test was carried out by leaving it in a constant temperature bath controlled at 50 ° C. for 7 days. As a result, although slight aggregation was observed, it was easy to loosen and the fluidity was recovered immediately.

The glass transition temperature (T
As a result of observing g), Tg was 62 ° C., which was hardly lowered. Further, in the DSC curve of the toner, the low melting point wax and the high melting point wax each showed an endothermic peak corresponding to the melting point measured with the wax alone.

Example 2 A binder resin prepared by dissolving the low elastic modulus binder resin and the high elastic modulus binder resin used in Example 1 in an organic solvent and uniformly mixing them, and then distilling off the organic solvent. A magnetic toner (2) was obtained in the same manner as in Example 1 except that was used. Image density, fixability and rheological properties were evaluated in the same manner as in Example 1.
The results are shown in Table 1.

Example 3 The binder resin used in Example 2 was prepared by using a homogeneous mixture of the low-melting wax and the high-melting wax prepared by melt-mixing the low-melting wax and the high-melting wax used in Example 1. A magnetic toner (3) was obtained in the same manner as in Example 1 except that the mixture was used. Table 1 shows the evaluation results including rheological properties.
Shown in

Example 4 A magnetic toner (4) was prepared in the same manner as in Example 1 except that the melt-mixed wax used in Example 3 was added at the same time when the binder resin used in Example 2 was prepared. Obtained. Table 1 shows the evaluation results.

Example 5 A high elastic modulus binder resin, a low melting point wax and a high melting point wax similar to those in Example 4 were prepared in the same manner as in Example 4 except that the following low elastic modulus binding resin was used. Thus, a magnetic toner (5) was obtained.

Low elastic modulus binder resin: Styrene / acrylic acid copolymer produced by solution polymerization method [glass transition temperature 5
9.3 ° C., weight average molecular weight 8,800, Mw / Mn =
2.3, G ′ ₁₀₀ = 9.2 × 10 ² Pa] Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 6 A low elastic modulus binder resin, a low melting point wax and a high melting point wax similar to those of Example 5 were used, except that the following high elastic modulus binder resin was used. Thus, a magnetic toner (6) was obtained.

High modulus binder resin: Styrene / acrylic acid copolymer produced by suspension polymerization method [glass transition temperature 5
9.4 ° C, weight average molecular weight 573,000, Mw / Mn
= 1.9, G ′ ₁₀₀ = 8.8 × 10 ⁴ Pa] Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 7 A magnetic toner (7) was obtained in the same manner as in Example 1 except that the polyester resin and wax shown below were used.

Low elastic modulus binder resin: Fumaric acid, propoxy adduct of bisphenol, polyester composed of trimellitic anhydride [glass transition temperature 63. 3 ° C., weight average molecular weight 6,700, Mw / Mn = 2.3, G ′ ₁₀₀ = 1.7 × 10 ² Pa] ... 40 parts by weight High elastic modulus binder resin: terephthalic acid, fumaric acid, trimellitic anhydride acid, propoxy adduct of bisphenol, polyesters [glass transition temperature of 61.2 ° C. consisting ethoxy with adducts of bisphenol, weight average molecular weight 43,200, Mw / Mn = 5.1, G '100 = 3.6 × 10 ⁴ Pa] 60 parts by weight Low melting point wax: Low melting point hydrocarbon wax [melting point 69 ° C., weight average molecular weight 410, Mw / Mn = 1.6] 3 parts by weight High melting point wax: high melting point long chain alkyl alcohol System wax [melting point 103 ° C., weight average molecular weight 980, Mw / Mn = 1.8] 4 parts by weight Table 1 shows the evaluation results.

Example 8 In Example 7, the low elastic modulus binder resin was heated and melted, and the low melting point wax and the high melting point wax were added thereto to prepare and use a uniform mixture of the binder resin and the wax. A magnetic toner (8) was obtained in the same manner as in Example 7 except for the above. Table 1 shows the evaluation results.

Example 9 A magnetic toner (9) was obtained in the same manner as in Example 7 except that the low melting point wax and the high melting point wax were melt mixed to form a uniform composition. Table 1 shows the evaluation results.

Example 10 A magnetic toner (10) was obtained in the same manner as in Example 9 except that the following resins were used as the high elastic modulus binder resin.
Table 1 shows the evaluation results.

High elastic modulus binder resin: Polyester consisting of terephthalic acid, fumaric acid, trimellitic anhydride, propoxy adduct of bisphenol, and ethoxy addition of bisphenol [glass transition temperature 58.7 ° C., weight average molecular weight 39 , 800, Mw / Mn = 3.4, G ′ ₁₀₀ = 2.5 × 10 ⁴ Pa] 60 parts by weight of Example 11 In Example 4, the high elastic modulus binder resin was used in Example 10. Except that the rate is changed to polyester binder resin
Magnetic toner (11) was obtained in the same manner. Table 1 shows the evaluation results
Shown in

Example 12 A magnetic toner (12) was obtained in the same manner as in Example 10, except that the low elastic modulus binder resin used in Example 1 was changed to the low elastic modulus binder resin. Table 1 shows the evaluation results.

Example 13 A magnetic toner (13) was obtained in the same manner as in Example 3 except that the amount of the magnetic material was 100 parts by weight. When evaluated in the same manner as in Example 1, the fixability and other evaluation items were almost the same, and a good result was obtained, although the amount of the magnetic substance was increased as compared with the magnetic toner (3). It was

Comparative Example 1 In Example 3, as the wax, an ethylene / propylene copolymer (melting point: 146 ° C., weight average molecular weight: 17,70) was used.
Comparative magnetic toner (1) was obtained in the same manner as in Example 3 except that 7 parts by weight of 0, Mw / Mn = 3.1) was used. The obtained comparative magnetic toner (1) was used and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 Styrene-butyl acrylate copolymer (weight average molecular weight 27
8,300, Mw / Mn = 2.3, G ′ ₁₀₀ = 4.1 ×
10 ³ Pa, a glass transition temperature of 57.8 ° C.), without the use of high melting point waxes, the exception of using only 7 parts by weight low melting wax, compared in the same manner as in Example 3 Magnetic toner (2) Obtained.

When a fixing test was carried out using the comparative magnetic toner (2), a good fixing property was shown immediately after the heater power of the fixing device was turned on, but the heater power was turned on 20.
When the fixing property was carried out again after a lapse of minutes, an offset considered to be a high temperature offset occurred.

Comparative Example 3 A comparative magnetic toner (3) was obtained in the same manner as in Comparative Example 1, except that the amount of the magnetic material was 100 parts by weight.

When evaluated in the same manner as in Example 1, as compared with the comparative magnetic toner (2), the fixability was further deteriorated, and both the offset resistance and blocking resistance were deteriorated.

Comparative Example 4 A comparative magnetic toner (4) was prepared in the same manner as in Example 1 except that 7 parts by weight of a low molecular weight polypropylene wax [Viscole 550P manufactured by Sanyo Chemical Industry Co., Ltd.] was used as the wax. did. The obtained comparative magnetic toner (4)
Was evaluated in the same manner as in Example 1. The results are shown in Table 1.

The evaluation method will be described below.

Low temperature fixing property The toner image is fixed on plain paper at the surface temperature of the heating roller of 110 ° C., and the fixing property is determined by applying a load of 50 g / cm ² to the sillbon paper [lenz cleaning pa].
per “dasper (R)” (Ozu Paper
r Co. , Ltd. )] Was rubbed 10 times, and the density reduction rate after rubbing was measured.

Rank 5 ... Density reduction rate 0 to 5% Rank 4 ... Density reduction rate 5 to 10% Rank 3 ... Density reduction rate 11 to 20% Rank 2 ... Density reduction rate 21 to 40% Rank 1 ... Density reduction rate 41 %that's all

Offset resistance The toner image is fixed on the plain paper at the heating roller surface temperature of 210 ° C., and then the plain paper is passed through a fixing device to check whether the toner is transferred from the heating roller surface to the plain paper surface. evaluated.

Rank 5 ... Toner does not migrate Rank 4 ... Very small amount of toner migrates Rank 3 ... Minor amount of toner migrates Rank 2 ... Toner migration is clear Rank 1 ... Paper clings to heating roller

Blocking resistance test About 20 g of magnetic toner was put in a 100 cc poly cup,
After leaving it at 50 ° C. for 10 days, it was visually evaluated.

Rank 5 ... No change Rank 4 ... Agglomerate but loosen immediately Rank 3 ... Difficult to loosen Rank 2 ... No fluidity Rank 1 ... Clear caking occurs

Image Density The maximum image density of a solid black portion (maximum image density of a portion having no edge effect) was measured with Macbeth RD918 (manufactured by Macbeth Co.).

Evaluation of Wax Dispersibility in Toner The toner was observed with a polarizing plate attached to an optical microscope at a low magnification (for example, 50 to 100 times), and the presence of wax particles free from the toner particles per 300 toner particles was observed. The number of bright spots shown was measured.

Rank 5 ... No bright spot through polarizing plate Rank 4 ... 1-10 bright spots Rank 3 ... 11-20 bright spots Rank 2 ... 21-50 bright spots Rank 1 ... 51 bright or more There is a point

[0208]

[Table 1]

Example 14 Low melting point wax (1) shown in Table 2 as low melting point wax
And the high melting point wax (1) shown in Table 3 was used. The constituent materials of the toner are shown below.

Binder resin Styrene / butyl acrylate / divinylbenzene copolymer produced by solution polymerization method [weight average molecular weight 387,500, main peak at molecular weight 5,400, subpeak at molecular weight 127,500, glass transition temperature 62. 4 ° C.] 100 parts by weight Magnetic substance (average particle size 0.2 μm) 90 parts by weight Monoazo metal complex (negative charge controlling agent) 2 parts by weight Low melting point wax (1) 3 parts by weight High melting point wax (1) 3 parts by weight

The above materials were premixed with a Henschel mixer, and then melt-kneaded at 130 ° C. with a twin-screw kneading extruder. After the kneaded product is allowed to cool, it is roughly crushed by a cutter mill, then crushed by a fine crusher using a jet stream, and further classified by an air classifier to obtain a weight average particle diameter of 6.4 μm.
To obtain a negatively chargeable insulating magnetic toner. This magnetic toner 1
Hydrophobic dry silica (BET 300m
1.0 part by weight of ² / g) was externally added with a Henschel mixer to obtain a magnetic toner (14).

When the above magnetic toner (14) was observed at a low magnification with a polarizing plate attached to an optical microscope, only a few bright spots showing the presence of liberated wax were observed in the visual field, which was good.

Using a magnetic toner (14) and a digital copying machine (GP-55 manufactured by Canon Inc.) for continuous image output of 100,000 sheets, the image density was
(1st to 10th sheets) 1.35 at the end of the 100,000th sheet durability.
There was almost no change to 37, and there was no scattering of the line image and no change in image quality due to fatness, which was good. When the surface of the photosensitive drum was observed in detail at the end of the 100,000-sheet endurance test, no loose wax was observed to adhere to the photosensitive drum surface and no noticeable damage was observed. There was no image defect presumably caused by damage on the surface of the photosensitive drum on the image.

Next, the fixing device of GP-55 was detached, the external driving device was attached, the device was rotated at 100 mm / sec, the temperature control device was attached, and the fixing temperature was changed in the range of 100 ° C. to 200 ° C. to perform the fixing test. However, at 120 ° C., the rate of reduction of the rubbing density was as good as about 8%, and no occurrence of high temperature offset was observed even at 200 ° C. Magnetic toner (14)
A blocking resistance test was carried out by leaving about 10 g in a constant temperature bath whose temperature was controlled at 50 ° C. for 7 days. As a result, although slight aggregation was observed, it was easy to unravel and recover the fluidity, which was good.

When the glass transition temperature (Tg) of the magnetic toner (14) was measured using DSC, Tg was 62 ° C., which was almost the same as the glass transition point of the binder resin. It was confirmed that there was an endothermic peak in the DSC curve of the toner at a temperature approximately the same as the melting points of the low melting wax and the high melting wax. Table 4 shows the evaluation results.

Example 15 A magnetic toner (1) was prepared in the same manner as in Example 14 except that the low melting point wax (1) and the high melting point wax (1) used in Example 14 were prepared by melt mixing in advance.
5) was obtained. The magnetic toner (15) thus obtained was used in Example 14
It evaluated similarly to. The results are shown in Table 4.

Example 16 To the binder resin produced by the solution polymerization method used in Example 14, low-melting wax (1) and high-melting wax (1) were added at the end of the polymerization reaction, and the solvent was added while heating and stirring. A magnetic toner (16) was obtained in the same manner as in Example 14 except that the wax and the binder resin composition produced by distilling off was removed. Table 4 shows the evaluation results of the obtained magnetic toner (16).

Example 17 A magnetic toner (17) was obtained in the same manner as in Example 16 except that the wax prepared in advance by melt-mixing used in Example 15 was used. The evaluation results of the obtained magnetic toner (17) are shown in Table 4.

Examples 18 to 20 Magnetic toners (18) to (20) were obtained in the same manner as in Example 15 except that the low melting point wax shown in Table 2 and the high melting point wax shown in Table 3 were used. Table 4 shows the evaluation results of the obtained magnetic toner.

Example 21 Terephthalic acid 15 mol% Fumaric acid 18 mol% Trimellitic anhydride 16 mol% Bisphenol A propoxy adduct 28 mol% Bisphenol A ethoxy adduct 20 mol%

A non-linear polyester resin having a weight average molecular weight of 496,500, Mw / Mn = 93.1 and a glass transition temperature of 61 ° C. was prepared by polycondensation of these.

On the other hand, the following monomers were polycondensed to prepare a linear polyester resin having a weight average molecular weight of 3,000 and Mw / Mn = 2.3.

Terephthalic acid 31 mol% Fumaric acid 18 mol% Bisphenol A propoxy adduct 28 mol% Bisphenol A ethoxy adduct 20 mol%

70 parts by weight of a linear polyester resin and 30 parts by weight of a non-linear polyester resin are used as a binder resin,
A magnetic toner (2) was prepared in the same manner as in Example 14 except that the low melting point wax shown in Table 2 and the high melting point wax shown in Table 3 were used to prepare the wax in the same manner as in Example 15.
1) was obtained. Table 4 shows the evaluation results of the obtained magnetic toner.

Example 22 In the same manner as in Example 21 except that the binder resin of Example 21 was heated and melted and the wax was added and mixed therein to prepare a mixture of the binder resin and the wax, the magnetic toner ( 22) was obtained. The evaluation results of the obtained magnetic toner (22) are shown in Table 4.

Examples 23 to 25 The same as Example 21 except that the wax was prepared by the same wax preparation method as in Example 15 except that the low melting point wax shown in Table 2 and the high melting point wax shown in Table 3 were used. Magnetic toners (23) to (25) were thus obtained. Table 4 shows the evaluation results of the obtained magnetic toner.

Comparative Example 5 Example 14 except that the low melting wax (1) was used alone.
Comparative magnetic toner (5) was obtained in the same manner as in. The comparative magnetic toner (5) thus obtained was evaluated in the same manner as in Example (14). The evaluation results are shown in Table 5.

Comparative Example 6 Example 14 except that the high melting point wax (2) was used alone.
Comparative magnetic toner (6) was obtained in the same manner as in. Table 5 shows the evaluation results of the comparative magnetic toner (6).

Comparative Example 7 Example 14 was repeated except that the low melting point wax (6) and the high melting point wax (9) (ethylene / propylene copolymer) were used.
Comparative magnetic toner (7) was obtained in the same manner as in. Table 5 shows the evaluation results of the comparative magnetic toner (7).

The image density was as low as 1.1, and it was observed that a large amount of free wax was present between the magnetic toner particles. The wax liberated at the time of continuous continuous image formation of 20,000 sheets adhered to the photosensitive drum, partly damaged the surface of the photosensitive drum, and the scar thereof appeared on the image. Fog was also observed.

When a fixing test was conducted, the fixing temperature was 12
At 0 ° C., the density reduction rate of the fixed image was about 35%. When the fixing temperature was raised to 200 ° C., although fixing was performed, some offset was observed.

Next, the glass transition temperature (Tg) of this comparative magnetic toner (7) was measured using DSC.
g had dropped to 59 ° C. In the DSC curve of the toner, almost no endothermic peak corresponding to the melting point of the high melting point wax component was observed. The results are shown in Table 5.

Comparative Example 8 A comparative magnetic toner (8) was obtained in the same manner as in Comparative Example 7 except that the low melting point wax (9) shown in Table 2 and the high melting point wax (9) shown in Table 3 were used. When evaluated in the same manner as in Example 14, the low-temperature fixability was good, but the offset resistance and blocking resistance were poor. The results are shown in Table 5.

Comparative Example 9 Low-melting wax (10) shown in Table 2 and high-melting wax (10) shown in Table 3 (ethylene / propylene copolymer)
Comparative magnetic toner (9) in the same manner as in Comparative Example 7 except that
Was obtained and evaluated in the same manner as in Example 14. The results are shown in Table 5.

Evaluation of low-temperature fixability (heating roller surface temperature 120 ° C.) Rank 5 ... Density reduction rate 0 to 5% Rank 4 ... Density reduction rate 5 to 10% Rank 3 ... Density reduction rate 11 to 20% Rank 2 ... Density reduction Rate 21 to 40% Rank 1 Concentration reduction rate 41% or more

Offset resistance evaluation (heating roller surface temperature: 200 ° C.) Rank 5: Toner does not migrate Rank 4: Very small amount of toner migrates Rank 3: Minor amount of toner migrates Rank 2… Toner migration Clear Rank 1 ... Paper clings to the heating roller

Evaluation of Blocking Resistance (Temperature: 50 ° C., 7 days) Rank 5: No change Rank 4: Agglomerate but loosen immediately Rank 3… Hard to loosen Rank 2… No fluidity Rank 1… Caking

Image Density and Wax Dispersibility Evaluation was conducted in the same manner as above.

[0239]

[Table 2]

[0240]

[Table 3]

[0241]

[Table 4]

[0242]

[Table 5]

[0243]

The toner for developing an electrostatic image of the present invention is excellent in low-temperature fixing property, anti-offset property, anti-blocking property, durability of many sheets, and the like.

[Brief description of drawings]

FIG. 1 is a graph showing the rheological properties of the toner of the present invention.

FIG. 2 is an explanatory diagram showing an example of an image forming apparatus to which the toner of the present invention can be applied.

3 is an enlarged view of a developing unit of the image forming apparatus shown in FIG.

Claims (48)

[Claims] 1. A toner for developing an electrostatic charge image containing a binder resin, a colorant and a wax, wherein the toner has (a) a storage elastic modulus (G ′ ₁₀₀ ) at a temperature of 100 ° C. of 1 × 10 ^4. Pa to 5 × 10 ⁴ Pa, and (b) the ratio (G ′ ₆₀ / of the storage elastic modulus (G ′ ₆₀ ) at a temperature of ₆₀ ° C. to the storage elastic modulus (G ′ ₇₀ ) at a temperature of 70 ° C.
_G'70 ) is 30 or more, a toner for developing an electrostatic charge image. 2. The toner has a ratio (G ′ ₆₀ / G ′ ₇₀ ) of 35.
The toner according to claim 1, which is about 120. 3. The toner according to claim 1, wherein the binder resin contains a low elastic modulus binder resin component and a high elastic modulus binder resin component. 4. The low elastic modulus binder resin component has a storage elastic modulus (G ′ ₁₀₀ ) at 100 ° C. of 1 × 10 ² to 1 × 10 ^2.
The toner according to claim 1, wherein the toner has a pressure of less than ⁴ Pa. 5. The high elastic modulus binder resin component has a storage elastic modulus (G ′ ₁₀₀ ) at 100 ° C. of 1 × 10 ⁴ to 1 × 10 ⁶ Pa.
The toner according to any one of claims 1 to 4, which is 6. The low elastic modulus binder resin component has a storage elastic modulus (G ′ ₁₀₀ ) at 100 ° C. of 1 × 10 ^{2 to} 1 × 10.
It is less than ⁴ Pa, and the high elastic modulus binder resin component has a storage elastic modulus (G ′ ₁₀₀ ) at 100 ° C. of 1 × 10 ⁴ to 1 × 10 ^6.
The toner according to claim 1, which has Pa. 7. The toner according to claim 1, wherein the toner has an endothermic main peak in a temperature range of 60 to 135 ° C. in a DSC curve measured by a differential scanning calorimeter. 8. The toner according to claim 7, wherein the toner has an endothermic main peak in a temperature range of 60 to 100 ° C. in a DSC curve measured by a differential scanning calorimeter. 9. The toner according to claim 1, wherein the toner has an endothermic main peak and an endothermic subpeak in a temperature range of 60 to 135 ° C. in a DSC curve measured by a differential scanning calorimeter. 10. The toner according to claim 9, wherein the toner has an endothermic main peak in a temperature range of 60 to 100 ° C. in a DSC curve measured by a differential scanning calorimeter. 11. The toner according to claim 1, wherein the toner has an endothermic main peak and an endothermic shoulder in a temperature range of 60 to 135 ° C. in a DSC curve measured by a differential scanning calorimeter. 12. The toner according to claim 11, wherein the toner has an endothermic main peak in a temperature range of 60 to 100 ° C. in a DSC curve measured by a differential scanning calorimeter. 13. The toner according to claim 1, wherein the wax has an endothermic main peak in a temperature range of 60 to 135 ° C. in a DSC curve measured by a differential scanning calorimeter. 14. The toner according to claim 1, wherein the wax has an endothermic main peak in a temperature range of 60 to 100 ° C. in a DSC curve measured by a differential scanning calorimeter. 15. The wax has an endothermic main peak and an endothermic subpeak in a temperature range of 60 to 135 ° C. in a DSC curve measured by a differential scanning calorimeter.
15. The toner according to any one of 14 to 14. 16. The toner according to claim 15, wherein the wax has an endothermic main peak in a temperature range of 60 to 100 ° C. in a DSC curve measured by a differential scanning calorimeter. 17. The toner according to claim 1, wherein the wax has an endothermic main peak and an endothermic shoulder in a temperature range of 60 to 135 ° C. in a DSC curve measured by a differential scanning calorimeter. 18. The toner according to claim 17, wherein the wax has an endothermic main peak in a temperature range of 60 to 100 ° C. in a DSC curve measured by a differential scanning calorimeter. 19. The toner according to claim 1, wherein the wax comprises a low melting point wax component having a melting point of 60 to 94 ° C. and a high melting point wax component having a melting point of 95 to 135 ° C. 20. The toner according to claim 19, wherein the wax comprises a low melting point wax component having a melting point of 70 to 90 ° C. and a high melting point wax component having a melting point of 95 to 130 ° C. 21. The toner according to claim 20, wherein the wax comprises a low melting point wax component having a melting point of 70 to 90 ° C. and a high melting point wax component having a melting point of 100 to 130 ° C. 22. The wax comprises a low melting point wax component and a high melting point wax component, and the low melting point wax component and the high melting point wax component satisfy the following conditions: [In the formula, T _ML represents the melting point of the low melting point wax component, and T _MH
Indicates the melting point of the high melting point wax component. The toner according to any one of claims 1 to 21, which satisfies the following condition. 23. The difference between the melting point (T _ML ) of the low melting point wax component and the melting point (T _MH ) of the high melting point wax component is 20 to 7.
The toner according to any one of claims 1 to 22, which has a temperature of 5 ° C. 24. The toner according to claim 1, wherein G ′ _{100 of the} toner is 1 × 10 ^{4 to} 4.5 × 10 ⁴ Pa. 25. The toner according to claim 1, wherein G ′ _{100 of the} toner is 1.5 × 10 ^{4 to} 4 × 10 ⁴ Pa. 26. The toner has a ratio (G ′ ₆₀ / G ′ ₇₀ ) of 3
26. The toner according to claim 1, which is 5 to 120. 27. The toner has a ratio (G ′ ₆₀ / G ′ ₇₀ ) of 4
27. The toner according to claim 1, which is 0 to 110. 28. The toner according to claim 1, wherein G ′ _{60 of the} toner is 7 × 10 ⁶ Pa or more. 29. The toner has a G ′ ₆₀ of 1 × 10 ^{7 to} 5
The toner according to any one of claims 1 to 28, which has a viscosity of × 10 ⁸ Pa. 30. The toner has a G ′ ₆₀ of 2 × 10 ^{7 to} 4
30. The toner according to claim 1, which has a pressure of × 10 ⁸ Pa. 31. The toner according to claim 1, wherein G ′ _{70 of the} toner is 7 × 10 ⁶ Pa or less. 32. The toner has a G ′ ₇₀ of 6 × 10 ^{5 to} 6
The toner according to claim 1, which has a viscosity of × 10 ⁶ Pa. 33. The toner has a G ′ ₇₀ of 8 × 10 ^{5 to} 5
The toner according to any one of claims 1 to 32, which has a pressure of × 10 ⁶ Pa. 34. The toner has a maximum loss elastic modulus (G ″) in a temperature range of 48 to 65 ° C. and a G ″ at the maximum value of 8 × 10 ^{7 to} 5 × 10 ⁸ Pa. 34. The toner according to any one of 1 to 33. 35. In the toner, G ″ has a maximum value in the temperature range of 49 to 63 ° C., and G ″ at the maximum value is 9 × 10 ^7.
The toner according to any one of claims 1 to 34, which has a viscosity of 4 to 10 ⁸ Pa. 36. In the toner, G ″ has a maximum value in a temperature range of 50 to 60 ° C., and G ″ at the maximum value is 1 × 10 ^8.
The toner according to any one of claims 1 to 35, having a viscosity of 3 to 10 ⁸ Pa. 37. The toner has a ratio (G ″ / G ′ = tan δ) of loss elastic modulus (G ″) to storage elastic modulus (G ′) of 60.
37. The temperature is 0.5 to 100 ° C. and is 0.5 or more.
The toner according to any one of 1. 38. The toner has a ratio (G ″ / G ′ = tan).
The toner according to any one of claims 1 to 37, wherein δ) has a maximum value of 1.5 or more at a temperature of 63 to 78 ° C. 39. The toner has a ratio (G ″ / G ′ = tan
The toner according to any one of claims 1 to 38, wherein δ) has a maximum value at a temperature of 64 to 75 ° C. 40. The toner has a ratio (G ″ / G ′ = tan).
The toner according to any one of claims 1 to 39, wherein δ) has a maximum value at a temperature of 65 to 73 ° C. 41. The coloring agent according to claim 1, which is a magnetic material.
0. The toner according to any one of 0. 42. The toner according to claim 41, wherein the magnetic substance is contained in an amount of 10 to 200 parts by weight based on 100 parts by weight of the binder resin. 43. The toner according to claim 42, wherein the magnetic substance is contained in an amount of 20 to 150 parts by weight based on 100 parts by weight of the binder resin. 44. The toner according to claim 1, wherein the colorant is a non-magnetic colorant. 45. The toner according to claim 44, wherein the non-magnetic colorant is contained in an amount of 0.1 to 60 parts by weight based on 100 parts by weight of the binder resin. 46. The toner according to claim 45, wherein the non-magnetic colorant is contained in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the binder resin. 47. The toner has a weight average particle diameter of 3 to 9 μm.
47. The toner according to claim 1, which comprises: 48. The toner has a weight average particle diameter of 3 to 8 μm.
The toner according to claim 46, which comprises: