JPH08278662A - Resin composition for toner and toner for developing electrostatic image - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a resin composition for a toner, which is capable of producing a toner excellent in offset resistance, blocking resistance, and fluidity, exhibiting good fixing property even after continuously copying a large amount of copies. To provide. In a resin composition for a toner having a high-molecular-weight resin composition and a low-molecular-weight resin composition, the loss elasticity of each of the high-molecular-weight resin composition and the low-molecular-weight resin composition constituting the resin composition for a toner The loss tangent, which is the ratio of the elastic modulus to the storage elastic modulus, has at least one maximum temperature and at least one minimum temperature in the range of 50 to 150 ° C., and the relationship represented by the following formulas (1) and (2) It is characterized by being established. [Equation 1] [ _Wherein T _PH , T _PL , and T _PB represent temperatures at which the loss tangents of the high-molecular weight resin composition, the low-molecular weight resin composition, and the resin composition for toner having these are maximum, respectively, and T _VH , T
_VL and _TVB represent temperatures at which the loss tangents of the high-molecular weight resin composition, the low-molecular weight resin composition and the toner resin composition containing them are minimized, respectively. ]

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for a toner for developing an electrostatic charge image used in an image forming method such as an electrophotographic method, an electrostatic recording method and an electrostatic printing method, and a resin composition thereof. The present invention relates to a toner for developing an electrostatic charge image, which is contained as a binder resin composition.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
A number of methods are known as described in Japanese Patent Publication No. 43-24748 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoconductor by various means, and then the latent image is developed with a toner, and a toner image is formed on a transfer material such as paper if necessary. After transfer, the toner is fixed by heating, pressure, heating and pressurizing, or solvent vapor to obtain a toner image.

Various methods and devices have been developed for the final step of fixing the toner image on a sheet such as paper, but the most general method at present is a pressure heating method using a heat roller.

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

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

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

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

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

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

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

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

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.
Both fixability and offset resistance are insufficient.

In 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 at 150 ° C., and the peak of the loss elastic modulus. An electrophotographic toner that exhibits rheological properties at a temperature of 125 ° C. or higher and has two peaks on the high molecular weight side and the low molecular weight side on the gel permeation chromatogram and has two peaks is disclosed. Since both the modulus and the loss modulus are too small and the peak temperature of the loss modulus is too high, the low temperature fixability is not improved, and both the storage modulus and the loss modulus are too low, so that the heat resistance is expected to be remarkably poor. It is not practical.

Further, Japanese Patent Laid-Open No. 6-59504 discloses that
A toner composition using a polyester resin having a specific structure as a binder resin has a specific storage elastic modulus at 70 to 120 ° C, and a specific loss elastic modulus at 130 to 180 ° C. It has been 70 to 1
Since the storage elastic modulus at 20 ° C. is too large and the loss elastic modulus at 130 to 180 ° C. is too small, when used for a magnetic toner, particularly a small particle size magnetic toner in which the content of a magnetic material is relatively increased. In addition to the low temperature fixability not being achieved, the offset resistance is also insufficient and improvements are required.

Further, JP-A-5-173363 discloses a binder resin for toner having two or more peaks having different molecular weights in a molecular weight distribution measured by gel permeation chromatography and having specific rheological properties. Although disclosed, although there may be some improvement effect on the offset resistance, the fixing property is not improved, and especially when used for toner having a reduced particle size, the fixing property at low temperature is improved. There is a marked shortage and demand for improvement.

It is already known that a toner contains a wax as a releasing agent, for example, JP-A-52.
-3304, JP-A-52-3305, JP-A-57-52574 and the like are disclosed.

These waxes are used in order to improve the performance at the time of fixing the toner, especially the offset resistance. However, on the other hand, these properties are improved, but on the other hand, the blocking resistance is deteriorated, and there is a problem in matching with the image forming means, which impairs developability and the like.

Further, a technique is disclosed in which two or more kinds of waxes are added to the toner in order to exert the effect of further adding wax from the low temperature region to the high temperature region during fixing. For example, Japanese Examined Patent Publication No. Sho 52-3305 and Japanese Unexamined Patent Publication No. Sho 5
8-215656, JP-A-62-10075, JP-A-4-124676, JP-A-299357, JP-A-362953, and JP-A-5-197192.
Techniques such as Japanese Patent Publication are disclosed.

However, none of these toners can satisfy all the toner performances, and some problems occur. For example, there are problems such as excellent high-temperature offset resistance and developability but poor low-temperature fixability, poor low-temperature offset resistance but poor blocking resistance, and further deterioration of developability. Also, if multiple wax components are used, the dispersion in the toner becomes uneven, which may cause toner charging failure, transport failure on the developing device / developing sleeve or uneven coating, and may cause fogging or blotch on the image. Image defects occurred.

This is because the content of the colorant contained in the toner tends to increase for various reasons as the toner has a smaller particle size, and particularly in a magnetic toner containing a magnetic material as the colorant. It is remarkable. From the viewpoint of rheology, an increase in the colorant contained in the toner means an increase in the storage elastic modulus and the loss elastic modulus, and from the viewpoint of the performance of the toner, a continuous copying machine having a copying speed of a medium speed or higher is used. Therefore, the fixing property may be significantly deteriorated when several hundreds of copies or more are taken, and improvement is required.

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

[0022]

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

The object of the present invention is suitable for a toner for developing an electrostatic charge image, which exhibits good fixing property even when the content of a colorant, especially a magnetic material, accompanying the reduction of the particle diameter of the toner is increased, and the toner. Another resin composition is provided.

The object of the present invention is suitable for an electrostatic charge image developing toner and a toner for developing such an electrostatic charge image, which shows a good fixing property from the initial to the last one even if a large number of copies of several hundreds or more are continuously transferred at one time. A resin composition is provided.

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

An object of the present invention is to provide an electrostatic charge image which exhibits excellent fixability in the halftone portion even when the particle size is reduced from low speed to high speed copying machines and which makes it possible to obtain a copy image of good quality. The present invention provides a developing toner and a resin composition suitable for this toner.

An object of the present invention is to provide a toner for developing an electrostatic charge image which can obtain a high-density copy image without fog from low speed to high speed copying machines, and a resin composition suitable for this toner. is there.

[0028]

The present invention relates to a toner resin composition having a high molecular weight resin composition and a low molecular weight resin composition, the toner resin composition and the high molecular weight resin composition constituting the same. The loss tangent, which is the ratio of the loss elastic modulus and the storage elastic modulus of the low molecular weight resin composition and the low molecular weight resin composition, is 50.
It is characterized in that there is at least one maximum temperature and at least one minimum temperature in the range of up to 150 ° C., and the relationships expressed by the following formulas (1) and (2) are established.

[0029]

(Equation 3)

[In the formula, T _PH , T _PL , and T _PB represent the temperatures at which the loss tangents of the high-molecular weight resin composition, the low-molecular weight resin composition and the resin composition for toner having these are maximum, respectively, _VH, T _VL, T _VB each shows the temperature of the high molecular weight resin composition, the loss tangent of the low molecular weight resin composition and resin composition for toner having these is minimized. ]

Furthermore, the present invention relates to a toner for developing an electrostatic charge image, which contains the above resin composition for toner as a binder resin composition.

According to the study by the present inventor, good fixing property and blocking resistance are made compatible by using a heat roll fixing device with a toner having a small particle size in which the content of a colorant, particularly a magnetic material is increased, In order to obtain a toner that exhibits good fixability immediately after power-on of the copying machine even in cold weather, and shows good fixability to the end even after continuous copying of several hundred sheets or more, it has been conventionally known. It is not enough to use the binder resin or toner having the rheological characteristics.

That is, what is expected to be improved by using conventionally known rheological characteristics as an index is a state in which a certain amount of time has passed since the power was turned on, in other words, a standby state, It relates to the fixing property when the upper roller (heating roller) and the lower roller (pressure roller) are sufficiently heated, and the state where the lower roller (pressure roller) is not sufficiently heated immediately after the power is turned on. However, there is little improvement in the fixability when the temperature of the lower roller is lowered after continuous copying.

According to the present invention, the loss tangent (hereinafter referred to as "the ratio of loss elastic modulus (G") to storage elastic modulus (G ') (G "/ G'))
(hereinafter referred to as tan δ) has a maximum value and a minimum value in the temperature range of 50 to 150 ° C., and a high molecular weight resin composition, a low molecular weight resin composition, and a toner having these resin compositions A resin composition for use in which the maximum temperature and the minimum temperature of tan δ satisfy the specific relationships represented by the formulas (1) and (2).

[0035]

[Equation 4]

[In the formula, T _PH , T _PL and T _PB respectively represent the temperatures at which the loss tangents of the high molecular weight resin composition, the low molecular weight resin composition and the resin composition for toner having these are maximum, and _VH, T _VL, T _VB each shows the temperature of the high molecular weight resin composition, the loss tangent of the low molecular weight resin composition and resin composition for toner having these is minimized. ]

The formula (1) shows the relationship of the temperature at which the tan δ of the high molecular weight resin composition, the low molecular weight resin composition and the resin composition for toner having these resin compositions becomes maximum. The temperature may be lower than or equal to 0 ° C, preferably lower than or equal to 15 ° C, and more preferably lower than or equal to 10 ° C.

If the formula (1) exceeds 20 ° C., the low temperature fixing property, which is one of the objects of the present invention, may not be achieved, or the hot offset resistance may be significantly deteriorated, which is not preferable. .

Formula (2) shows the relationship of the temperature at which the tan δ of the high molecular weight resin composition, the low molecular weight resin composition and the resin composition for toner having these resin compositions becomes the minimum, which is 65. The temperature may be up to 150 ° C., preferably 71 to 146 ° C., and more preferably 76 to 143 ° C.

If the formula (2) is less than 65 ° C., the hot offset resistance may be significantly deteriorated.
Further, when the formula (2) is 150 ° C. or higher, the hot offset resistance becomes good, but at the same time, the minimum fixing temperature rises and the object of the present invention cannot be achieved.

According to the study of the present inventors, the temperature at which tan δ becomes maximum corresponds to the temperature at which the resin composition transitions from the glass state to the heat-deformable state. It is different from the glass transition temperature measured by (DSC measuring device). It is also different from the heat distortion temperature specified by JIS or the like. The temperature at which tan δ reaches a maximum indicates that the micro-Brownian motion of the polymer chains constituting the resin composition is activated at that temperature. Specifically, when it is used as a binder resin for toner, it is closely related to the minimum fixing temperature of the toner and serves as a measure for evaluation of low-temperature fixability.

The temperature at which tan δ of the high molecular weight resin composition becomes maximum (hereinafter referred to as T _PH ) may be 60 to 80 ° C., preferably 62 to 78 ° C., more preferably 63 to 78 ° C. This is the case when the temperature is 77 ° C. If T _PH is less than 60 ° C, the hot offset resistance of the toner becomes extremely poor when it is included in the resin composition for toner, and if T _PH exceeds 80 ° C, the low temperature fixability of the toner is low. May not be achieved.

The temperature at which tan δ of the low molecular weight resin composition becomes maximum (hereinafter referred to as T _PL ) may be 65 to 85 ° C., preferably 67 to 83 ° C., more preferably 69 to 85 ° C. This is the case when the temperature is 82 ° C. If T _PL is less than 65 ° C., the hot offset resistance of the toner becomes extremely poor when it is included in the resin composition for toner, and if T _PL exceeds 95 ° C., the low temperature fixability of the toner is deteriorated. It may not be achieved.

Further, ta of the resin composition for toner of the present invention having the above high molecular weight resin composition and low molecular weight resin composition is ta.
The temperature at which nδ becomes maximum (hereinafter referred to as T _PB ) is 63 to 8
It may be 3 ° C., preferably 65 to 80 ° C., and more preferably 68 to 78 ° C. If T _PB is less than 63 ° C., the hot offset resistance of the toner becomes poor, and if T _PB exceeds 83 ° C., the low temperature fixability of the toner cannot be achieved.

Further, at a temperature at which tan δ becomes a minimum, it is shown that the resin composition is in a state of being easily flowed and deformed without applying external force. Dependent. Specifically, when it is used as a binder resin for toner, it is closely related to the maximum fixing temperature of toner, that is, hot offset.

Therefore, the temperature at which tan δ becomes maximum is ta
nδ is lower than the minimum temperature, and the temperature difference between the two may be 4 to 20 ° C in the low molecular weight resin composition, preferably 5 to 17 ° C, and more preferably 6 to 15 ° C. Is the case. If the temperature difference between the two is 4 ℃
When the amount is less than or less than the definite maximum and / or minimum, the low temperature fixability of the toner may be slightly good regardless of the high molecular weight resin composition used together with the resin composition for toner containing the same. However, the hot offset resistance is significantly deteriorated, which is not preferable. Further, if the temperature difference between the two exceeds 20 ° C., the low temperature fixability of the toner is significantly impaired, which is not preferable.

Similarly, in the high molecular weight resin composition, 3
It may be 0 to 60 ° C., preferably 32 to 57 ° C., and more preferably 35 to 55 ° C. If the temperature is lower than 30 ° C., the hot offset resistance of the toner is significantly deteriorated, and if the temperature is higher than 60 ° C., the low temperature fixing property of the toner is impaired, which is not preferable.

In the resin composition for toner having the above high molecular weight resin composition and low molecular weight resin composition, the temperature may be 35 to 67 ° C., and preferably 40 to 66 ° C.
More preferably, it is 42 to 65 ° C. if,
When the temperature is lower than 35 ° C., the low temperature fixability of the toner is slightly improved, but the hot offset resistance is significantly deteriorated.
If it exceeds 67 ° C, the hot offset resistance is slightly improved, but the low temperature fixability cannot be achieved.

In the resin composition for toner of the present invention,
A wax can be contained, and in this case, the wax is composed of two kinds of waxes having different melting points, and the wax has a relatively low melting point between the melting point and the temperature at which the loss tangent of the resin composition is maximized. The relationship of the following formula (3) is established,
Further, the relationship of the following formula (4) is established between the melting point of the wax having a relatively high melting point and the temperature at which the loss tangent of the resin composition is minimized.

Formula (3) | T _WL −T _PB | ≦ 10 Formula (4) | T _WH −T _VB | ≦ 10

[In the formula, T _WL and T _WH represent the melting point of the wax having a relatively low melting point and the melting point of the wax having a relatively high melting point, respectively. ]

According to the studies by the present inventors, in order to realize the low temperature fixing property which is one of the purposes of the resin composition for toner of the present invention, the melting points are different, and the melting points of these waxes are represented by the formula ( It has been found that it is most effectively exerted when the relationship expressed by 3) and the equation (4) is satisfied.

The melting point (hereinafter referred to as T _WL ) of the wax having a relatively low melting point (hereinafter referred to as low melting point wax) is 55.
Up to 90 ° C., preferably 60 to 87 ° C., and more preferably 62 to 85 ° C. If T _WL is less than 55 ° C., the hot offset resistance of the toner becomes extremely poor, and if it exceeds 90 ° C., low temperature fixing cannot be achieved.

The melting point of wax having a relatively high melting point (hereinafter referred to as high melting point wax) (hereinafter referred to as T _WH ) may be 95 to 155 ° C., preferably 97 to 155 ° C.
It may be 145 ° C., more preferably 100 to 1
This is the case when the temperature is 40 ° C. If T _WH is less than 95 ° C, the hot offset resistance of the toner may be poor, and if T _WH is more than 155 ° C, the low temperature fixability of the toner may be impaired. Not preferable.

The formula (3) shows the relationship between the melting point of the low melting point wax and the temperature at which the tan δ of the resin composition for toner containing no wax becomes maximum, which may be 10 ° C. or lower, and is preferable. Is the case below 8 ° C,
More preferably, it is 6 ° C. or less. If the formula (3) exceeds 10 ° C., the hot offset resistance of the toner becomes extremely poor, or the low temperature fixing property is significantly impaired, and the object of the present invention cannot be achieved.

The formula (4) shows the relationship between the melting point of the high melting point wax and the temperature at which tan δ of the resin composition for toner containing no wax becomes a minimum, which may be 10 ° C. or lower, and is preferable. Is a temperature of 25 ° C. or lower, more preferably 8 ° C. or lower. if,
If the expression (4) exceeds 10 ° C., the low temperature fixing property of the toner may be impaired, which is not preferable.

Using the resin composition for a toner of the present invention, the temperature at which the tan δ of the toner containing the high melting point wax and the low melting point wax preferably used for the toner of the present invention becomes maximum (hereinafter referred to as T _PT ). T _PB and toner tan
The following equations (5) and (6) are established between the temperature at which δ is a minimum (hereinafter referred to as T _VT ) and T _VB .

Formula (5) | _TPB - _TPT | ≤10 Formula (6) _0≤TVB - _TVT≤20

If the temperature exceeds 10 ° C., the formula (5) is not preferable because the blocking resistance of the toner may be remarkably deteriorated or the low temperature fixing property may be remarkably deteriorated. The formula (5) may be 10 ° C. or lower, preferably 8 ° C. or lower, and more preferably 6 ° C. or lower.

If the temperature exceeds 20 ° C., the formula (6) is not preferable because the hot offset resistance of the toner may be significantly deteriorated. The formula (6) may be 20 ° C. or lower, preferably 18 ° C. or lower, and more preferably 1
This is the case when the temperature is 5 ° C. or lower.

In the toner resin composition of the present invention, the high molecular weight resin composition contained therein may be produced by emulsion polymerization or suspension polymerization.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is performed using a water-soluble polymerization initiator. . In this method, it is easy to control the heat of reaction, and the phase in which the polymerization takes place (oil phase consisting of polymer and monomer)
And the aqueous phase are different, the termination reaction rate is low, and as a result, the polymerization rate is high and the polymerization degree is high. Further, in the production of toner, due to the relatively simple polymerization process and the fine particles of the polymerization product,
It is advantageous as a method for producing a binder resin for a toner because it can be easily mixed with a colorant, a charge control agent and other additives.

However, the resulting polymer is apt to become impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer, and suspension polymerization is convenient in order to avoid this inconvenience.

In the suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
0 to 90 parts by weight) is preferable. As the dispersant that can be used, a copolymer of methyl methacrylate and 3-sodium sulfopropylmethacrylic acid, polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, etc. are used, and there is an appropriate amount such as the amount of monomer in the aqueous solvent. Is generally used in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the aqueous solvent. Polymerization temperature is 50-9
Although 5 ° C. is suitable, it should be appropriately selected depending on the initiator used and the target polymer.

In the present invention, as the polymerization initiator used in the production of the resin composition for toner, all those usable as a radical polymerization initiator can be used,
The amount is 0.05 to 20 parts by weight based on 100 parts by weight of the monomer.

For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-)
Dimethylvaleronitrile), 2,2'-azobis (-
2,4-dimethylvaleronitrile), 2,2'-azobis (-2 methylbutyronitrile), dimethyl-2,2 '
-Azobisisobutyrate, 1,1'-azobis (1-
Cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,
Ketone peroxides such as 2,2′-azobis (2-methyl-propane), methylethylketone peroxide, acetylacetone peroxide, and cyclohexanone peroxide, 1,1-bis (t-butylperoxy) -3,3,5 -Trimethylcyclohexane, 1,
1-bis (butylperoxy) cyclohexane, 2,2
-Bis (t-butylperoxy) butane, 1,1-di-
t-butyl peroxycyclohexane, t-butyl hydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α′-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl per Oxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide,
m-trioyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxycarbonate, di-methoxyisopropylperoxide Oxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t
-Butyl peroxyisobutyrate, t-butyl peroxy neodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate,
t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t- Butyl peroxy hexahydroterephthalate, di-t-butyl peroxyazelate and the like can be mentioned.

In the present invention, the polymerization initiator preferably used for producing the high molecular weight resin composition is, for example, benzoylperoxyside, 2,2'-azobisisobutyronitrile, lauroyl peroxide, t-amylper. Oxy-2-ethylhexanoate, dicumyl peroxide, monofunctional polymerization initiators such as t-butylperoxycumene, and 1,1-di-t-butylperoxy-3,
3,5-trimethylcyclohexane, 1,1-di-t-
Butyl peroxycyclohexane, di-t-butyl peroxy hexahydroterephthalate, di-t-butyl peroxyazelate, 2,2-bis- (4,4-di-
t-butylperoxycyclohexyl) propane, t-
Examples thereof include polyfunctional polymerization initiators such as butyl peroxyallyl carbonate.

These polyfunctional polymerization initiators can be used alone or in combination, but in order to satisfy various performances required as a binder for a toner, half of the polyfunctional polymerization initiator is required. It is preferable to use in combination with a polymerization initiator having a decomposition temperature lower than that for obtaining 10 hours.

Specifically, benzoyl peroxide,
1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t
-Butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t
Organic peroxides such as -butyl peroxide, azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene can be used.

These polymerization initiators can be used in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the monomer.

In the present invention, a chain transfer agent may be used to adjust the molecular weight of the high molecular weight resin composition. Examples of the chain transfer agent include α-methylstyrene dimer, n-dodecyl mercaptan, 2-ethylhexyl thioglycolate, n-octyl mercaptan, and the like, preferably α-methylstyrene dimer, n-
It is dodecyl mercaptan.

In the present invention, a known method can be used as a method for producing the low molecular weight resin composition. However, in the bulk polymerization method, a low molecular weight polymer can be obtained by polymerizing at a high temperature to accelerate the termination reaction rate, but there is a problem that the reaction is difficult to control. In that respect, in the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature. It is preferable to obtain a low molecular weight product in the resin composition used in the present invention. In particular, the solution polymerization method under pressure is also effective in that the amount of the initiator used is minimized and the influence of the initiator residue is minimized.

As the polymerization initiator, the same ones as those used for producing the high molecular weight resin composition can be used.

In the present invention, examples of the monomer used in the high molecular weight resin composition and the low molecular weight resin composition include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene and p-
Phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p Styrene and its derivatives such as -n-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene; ethylene, propylene, butylene,
Ethylenically unsaturated monoolefins such as isobutylene;
Unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, methacrylic acid Ethyl, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate. Α-methylene aliphatic monocarboxylic acid esters such as; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-acrylate
Acrylic esters such as octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether,
Vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone And vinyl naphthalene; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; esters of the above α, β-unsaturated acids and diesters of dibasic acids.

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

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

In the present invention, the glass transition temperature (hereinafter referred to as Tg) of the high molecular weight resin composition may be 48 to 75 ° C., preferably 50 to 73 ° C.
More preferably, the temperature is 52 to 68 ° C. if,
If the Tg is less than 48 ° C., the blocking resistance of the toner tends to be poor, which is not preferable. Also, Tg is 7
If it exceeds 5 ° C., the low-temperature fixability of the toner becomes poor, which is not preferable.

The weight average molecular weight (hereinafter referred to as Mw) may be 400,000 to 3,000,000, preferably 55.
It is the case where it is 10,000 to 2,000,000, and more preferably 650,000 to 1.7 million. Number average molecular weight (hereinafter M
n) may be 20,000 to 2,000,000, preferably 30,000 to 1.3 million, and more preferably 3.
This is the case of 50,000 to 1,000,000. Mw / Mn is strongly influenced by the polymerization initiator used. For example, when a monofunctional polymerization initiator is used as a main component, a small amount of another monofunctional polymerization initiator or a polyfunctional polymerization initiator is used in combination. Including 1.5 to 1.5-10, preferably 2.0-
It is 7.0, and more preferably 2.3 to 5.
This is the case when it becomes zero.

When a polyfunctional polymerization initiator is used as a main component, Mw / Mn is 2.0 to 2.0 including a case where a small amount of a monofunctional polymerization initiator or another polyfunctional polymerization initiator is used in combination. It may be 20, preferably 2.5 to 15, and more preferably 3 to 10.

In the present invention, T of the low molecular weight resin composition is
g may be 50 to 80 ° C., preferably 53 to 75
C., and more preferably 55 to 72.degree. If the Tg is less than 50 ° C., the blocking resistance of the toner tends to be poor, which is not preferable. If the Tg exceeds 80 ° C., the low temperature fixability of the toner will be poor, which is not preferable.

The Mw may be 3000 to 50,000, preferably 5000 to 40,000, and more preferably 6000 to 28000. M
n may be from 1000 to 35000, preferably 2
000 to 22,000, and more preferably 3300 to 15,000. The Mw / Mn may be 1.5 to 40, preferably 1.7 to 20, and more preferably 1.8 to 8.

In the present invention, the resin composition for toner can be prepared by mixing the high molecular weight resin composition and the low molecular weight resin composition in an arbitrary ratio, and the weight ratio of each is 10:90.
If it is ˜50: 50, the object of the present invention can be achieved, but it is preferably 15:85 to 45:55, and more preferably 20:80 to 43:57.

The Tg of the resin composition for toner is 50 to 50.
It may be 77 ° C, preferably 52 ° C to 70 ° C, and more preferably 55 to 68 ° C.

The Mw of the resin composition for toner may be 150,000 to 600,000, preferably 160,000 to 550,000, and more preferably 170,000 to 500,000. Mn may be 2000 to 20000,
The case is preferably 2500 to 15000, and more preferably 3000 to 11000.
Mw / Mn may be 4 to 200, preferably 15
It becomes the case of -150, More preferably, it is 17-10.
This is the case when it becomes zero.

Examples of the wax that can be contained in the toner resin composition of the present invention include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax, and oxidized polyethylene. Oxides of aliphatic hydrocarbon waxes such as waxes, or block copolymers thereof; waxes containing fatty acid ester as a main component such as carnauba wax, sazol wax, montanic acid ester wax, and deoxidized carnauba wax Examples thereof include those obtained by partially or entirely deoxidizing fatty acid esters. Further, saturated straight-chain 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 blancic acid, eleostearic acid, and valinaric acid. , Stearin alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, melysyl alcohol,
Alternatively, saturated alcohols such as long-chain alkyl alcohols having a long-chain alkyl group, polyhydric alcohols such as sorbitol, fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide, methylenebisstearic acid amide Saturated bisamides such as ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide, ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipamide, Unsaturated fatty acid amides such as N, N′-dioleyl sebacic acid amide, aromatic bisamides such as m-xylene bisstearic acid amide, N, N′-distearyl isophthalic acid amide, calcium stearate, calcium laurate Fatty acid metal salts such as zinc stearate and magnesium stearate (generally called metallic soap), and waxes obtained by grafting aliphatic hydrocarbon wax with vinyl monomers such as styrene and acrylic acid. Further, a partial esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol, a methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable oils and the like can be mentioned.

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

Further, the long-chain alkyl group may be partially substituted at its terminal with a hydroxyl group or a sensitive group derived from a hydroxyl group, for example, a carboxyl group, an ester group, an ethoxy group, a sulfonyl group or the like. The long chain alkyl alcohol is obtained, for example, by the following production method. That is, 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 comprises a hydrocarbon having a long-chain alkyl group with few branches. Specifically, for example, alkylene is polymerized under a high pressure by radical polymerization or under a low pressure by a Ziegler catalyst. Low molecular weight alkylene polymer, alkylene polymer obtained by pyrolyzing a high molecular weight alkylene polymer, carbon monoxide, from the distillation residue of hydrocarbons obtained by the Arge method from a synthesis gas consisting of hydrogen, or by hydrogenating these A wax such as a synthetic hydrocarbon obtained by the above is preferable.

Further, the long-chain alkyl group may be partially substituted with a hydroxyl group or a functional group derived from a hydroxyl group, for example, a carboxyl group, an ester group, an ethoxy group, a sulfonyl group or the like. The long chain alkyl alcohol is obtained, for example, by the following production method. That is, 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 low melting point wax preferably used in the present invention has a molecular weight of 300 to 1000, preferably 350 to 900, and Mw /
In this case, Mn is 2.8 or less, preferably 2.3 or less, and most preferably 1.5 or less. Further, the high-melting-point wax has a molecular weight of 500 to 15000, preferably 650 to 10000.
/ Mn is 3.0 or less, preferably 2.5 or less, and most preferably 1.5 or less. By specifying the molecular weight distribution of each wax component, the interaction between the wax components is rapidly developed, and the above-mentioned various properties required for the toner are significantly improved.

In the present invention, the low-melting-point wax component and the high-melting-point wax component, and the molecular weight distribution of the wax composition of the present invention are measured by gel permeation chromatography (GPC). ).

If desired, an antioxidant may be added to the wax composition of the present invention. As the antioxidant, known compounds such as phenol compounds, amine compounds, sulfur compounds and phosphorus compounds can be used. These compounds are used at 0.5% by weight or less. If it is used in excess of 0.5% by weight, it may cause problems in the offset resistance and blocking resistance of the toner, and may cause troubles in the charging characteristics of the toner and in matching with the image forming apparatus. Further, it may cause an offensive odor during heat fixing, which is not preferable.

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

(1) Combination of low-melting hydrocarbon wax and high-melting hydrocarbon wax: The low-melting hydrocarbon wax is a long-chain alkyl group with few branches and has a melting point of 70 to 90 ° C.
Mw = 400 to 700 and Mw / Mn = 2.0 or less.

The high-melting hydrocarbon wax is a long-chain alkyl group with few branches and has a melting point of 95 to 130 ° C. and Mw = 80.
0 to 2500 and Mw / Mn = 5.0 or less.

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

The high-melting-point substituted alkyl wax has a long-chain alkyl group with few branches and has a substituent other than a hydrogen atom at the terminal or a part of the molecule, and the substituent is a hydroxyl group and / or a carboxyl group. And the alkyl group having a substituent is contained in an amount of 50% by weight or more based on the total wax.
Melting point 95-130 ° C, Mw = 800-5000, Mw /
Mn = 2.0 or less.

(3) Combination of low melting point substituted alkyl wax and high melting point hydrocarbon wax: The low melting point substituted alkyl wax has a long-chain alkyl group with few branches and has a hydrogen atom other than a hydrogen atom at a terminal or part of the molecule. And the substituent is a hydroxyl group and / or a carboxyl group, and the alkyl group having a substituent is contained in an amount of 40% by weight or more based on the whole wax. Melting point is 70 to 90 ° C., Mw = 400 to 70
0, Mw / Mn = 2.0 or less.

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

(4) Combination of low melting point substituted alkyl wax and high melting point substituted alkyl wax: 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.

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

For example, organic metal complexes and chelate compounds are effective. Examples thereof include monoazo metal complexes, aromatic hydroxycarboxylic acids, metal complexes, and aromatic dicarboxylic acid-based metal complexes. In addition, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides,
Examples thereof include esters and phenol derivatives of bisphenol. Further, an imidazole compound is also effective.

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, Ni. Like metals, or these metals and Al, Co, Cu, P
b, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Examples thereof include alloys with metals such as d, Ca, Mn, Se, Ti, W and V, and mixtures thereof.

Conventionally, as a magnetic material, triiron tetraoxide (F) has been used.
e ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe)
₅ O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuF)
e ₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), iron nickel oxide (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe)
₂ O ₃ ), iron oxide barium (BaFe ₁₂ O ₁₉ ), iron oxide magnesium (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known, but according to the present invention, the above magnetic materials are used alone or in combination of two or more kinds. Particularly suitable magnetic materials for the purposes of the present invention are fine powders of ferric tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
The magnetic characteristics under the application of 10 K oersted are about 20 μm to 20 oersted coercive force and 50 to 200 eersted saturation magnetization at about μm.
Those having a mu / g (preferably 50 to 100 emu / g) and a residual magnetization of 2 to 20 emu / g are desirable.

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.

Carbon black, titanium white, and any other pigments and / or dyes can be used as the colorant regardless of whether it is a single component or a two component. For example, when the toner of the present invention is used as a magnetic color toner, the dye may be C.I. I. Direct Red 1,
C. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Mordant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I.
I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Mordant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. There are Basic Green 6 etc. Examples of pigments include yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red lead yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G. , Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue,
First Sky Blue, Indren Sren Blue BC,
Chrome Green, Chrome Oxide, Pigment Green B,
Malachite Green Lake, Final Yellow Green G, etc.

When the toner of the present invention is used as a two-component full-color toner, the followings are listed. Examples of magenta color pigments include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,1
0,11,12,13,14,15,16,17,1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1, 52, 53, 54, 55, 57, 58, 60, 6
3,64,68,81,83,87,88,89,9
0,112,114,122,123,163,20
2,206,207,209, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 1
3, 15, 23, 29, 35 and the like.

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

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

[0112]

Embedded image

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

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

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

A preferred fluidizing agent is a fine powder produced by vapor phase oxidation of a silicon halogen compound,
It is so-called dry process silica or fumed silica and is produced by a conventionally known technique. For example, the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame is utilized, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

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

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

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

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

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

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

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

[0125]

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[0126]

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

[0128]

[Chemical 4]

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

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

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

The fluidizing agent used in the present invention has a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more by nitrogen adsorption measured by the BET method, which gives good results. Fluidizing agent 0.01 per 100 parts by weight of toner
-8 parts by weight, preferably 0.1-4 parts by weight.

To prepare the 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. The toner of the present invention can be obtained.

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

Measuring 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.

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

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

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

During this temperature rising process, the endothermic peak of the main peak in the temperature range of 40 to 170 ° C. is obtained.

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

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

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

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

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

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

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

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

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

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

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

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

T (μC / g) = (C × V) / (W ₁ −
W ₂ )

[0161]

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

Production of High Molecular Weight Resin Composition (Production Example 1) 200 parts by weight of deionized water containing 0.1% by weight of polyvinyl alcohol was placed in a reaction vessel equipped with a reflux tube, a stirrer and a thermometer. Then, a monomer mixture liquid consisting of 68 parts by weight of styrene, 27 parts by weight of n-butyl acrylate, 5 parts by weight of monobutyl maleate and 0.2 parts by weight of t-amylperoxy 2-ethylhexanoate is reacted under stirring. It was put into a container to prepare a suspension. In that state, nitrogen gas was introduced for about 30 minutes to degas, and then gradually heated with stirring to raise the temperature of the reaction vessel to about 75 ° C. and the reaction was carried out at that temperature for 20 hours. Next, the temperature of the reaction vessel was raised to 95 ° C., the reaction was continued for 1 hour, and the reaction was terminated by cooling to room temperature. The obtained suspended resin particles were separated by filtration, washed with water and dried.

This is designated as Polymer Resin Composition H-1 of the present invention.

To measure the tan δ of H-1, first put H-1 in a vacuum dryer whose temperature was adjusted to 150 ° C., and dry under reduced pressure for about 15 hours. The reaction monomer was completely removed. Next, this vacuum-dried H-1 was heated and melted to prepare a cylindrical sample having a diameter of about 8 mm and a height of 3 mm, which was fixed on a serrated parallel plate having a diameter of 7.9 mm according to a conventional method, and a storage elastic modulus was obtained. And the temperature at which the loss tangent (tan δ) becomes maximum and minimum by determining the temperature dependence of the loss elastic modulus. The maximum temperature (T _PH ) was 67.7 ° C, and the minimum temperature (T _VH ) was 114.2 ° C. tan δ
The measurement result of is shown in FIG.

Further, H-1 was determined by GPC to have a weight average molecular weight (Mw) = 763,000 and a number average molecular weight (Mn) = 3.
It was 55,000, Mw / Mn = 2.5, and Tg = 54.9 ° C. by DSC measurement.

(Production Example 2) Monomer composition was changed to styrene 8
High-molecular-weight resin composition of the present invention in the same manner as in Example 1 except that 0 part by weight and 20 parts by weight of n-butyl acrylate were used, the polymerization initiator was 0.2 parts by weight, and the reaction temperature was 78 ° C. The product H-2 was obtained. T _PH is 76.
The temperature was 5 ° C and T _VH was 123.5 ° C.

(Production Example 3) Monomer composition was changed to styrene 7
0 parts by weight and 30 parts by weight of n-butyl acrylate, and the polymerization initiator was 2,2'-azobisisobutyronitrile.
A high molecular weight resin composition H-3 of the present invention was obtained in the same manner as in Example 2 except that the reaction temperature was changed to 4 parts by weight and the reaction temperature was changed to 85 ° C.
T _PH was 70.5 ° C and T _VH was 116.6 ° C.

Production Example 4 The high molecular weight resin composition H of the present invention was produced in the same manner as in Production Example 1 except that 0.3 part by weight of n-dodecyl mercaptan was added to the monomer as a chain transfer agent.
-4 was obtained. T _PH was 73.2 ° C and T _VH was 127.3 ° C.

Production Example 5 Production Example except that the polymerization initiator was 0.1 part by weight of 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane and the reaction temperature was 87 ° C. A high molecular weight resin composition H-5 of the present invention was obtained in the same manner as in 1. T _PH is 71.0 ° C, T _VH is 11
It was 7.6 ° C. In addition, Mw = 14.3 million, Mn = 21
It was 8,000 and Mw / Mn = 6.6.

(Production Example 6) Production Example except that the polymerization initiator was 0.1 part by weight of 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane and the reaction temperature was 87 ° C. High molecular weight resin composition H-6 of the present invention was obtained in the same manner as in 2. T _PH is 74.8 ° C, T _VH is 11
It was 8.4 ° C.

(Production Example 7) Low melting point wax W shown in Table 1
A wax-containing high molecular weight resin composition H-7 of the present invention was obtained in the same manner as in Production Example 1 except that 9 parts by weight of L-2 were finely pulverized and added to the monomer composition to be in a dispersed state. .

(Production Example 8) Low melting point wax W shown in Table 1
6 parts by weight of L-2 and high melting point wax WH- shown in Table 2
A wax-containing high molecular weight resin composition H-8 of the present invention was obtained in the same manner as in Production Example 1 except that 6 parts by weight of 1 were finely pulverized and the monomer composition was added to obtain a dispersed state.

(Production Example 9) High melting point wax W shown in Table 2
A high molecular weight resin composition H-9 of the present invention containing a wax was obtained in the same manner as in Production Example 1 except that 9 parts by weight of H-1 were finely pulverized and added to the monomer composition to be in a dispersed state. .

Production Example of Low Molecular Weight Resin Composition (Production Example 10) 200 parts by weight of xylene is put into a reaction vessel equipped with a reflux tube, a stirrer, a thermometer and a dropping device, and then heated to reflux xylene.

Under reflux, a monomer mixture consisting of 85 parts by weight of styrene, 15 parts by weight of n-butyl acrylate, 5 parts by weight of di-tert-butyl peroxide and 100 parts by weight of xylene was continuously added in a constant amount over 6 hours. Was added dropwise. After completion of the dropping, the polymerization reaction was completed by refluxing for 2 hours to obtain a xylene solution of the low molecular weight resin composition L-1 of the present invention.

By removing xylene under reduced pressure, L
-1 solid was taken out. Tan similar to Production Example 1
When the temperature at which δ is maximum (T _PL ) and the temperature at which δ is minimum (T _VL ) are measured, T _PL = 76.8 ° C., T _VL =
It was 87.0 ° C.

L-1 has Mw = 12000 and Mn =
7300, Mw / Mn = 1.6, Tg = 64.3
° C.

Production Example 11 The low molecular weight resin composition L-2 of the present invention was produced in the same manner as in Production 7 except that styrene, n-butyl acrylate and monobutyl maleate were used as the monomers.
I got T _PL was 75.8 ° C. and T _VL was 88.1 ° C.

(Production Example 12) 200 parts by weight of xylene was put into an autoclave, and nitrogen gas was introduced to sufficiently degas. Next, the container was closed and heated to 190 to 200 ° C., and while maintaining the temperature, a monomer mixture consisting of 80 parts by weight of styrene, 20 parts by weight of n-butyl acrylate and 1.5 parts by weight of di-tert-butyl peroxide. 6 solution
A constant amount was continuously added dropwise over time. After the dropping is completed,
The temperature was maintained for another 2 hours to complete the polymerization reaction.
This is designated as the low molecular weight resin composition L-3 of the present invention. T _PL
Was 74.4 ° C and T _VL was 85.6 ° C. The measurement result of tan δ is shown in FIG.

Production Example 13 A wax is contained in the same manner as in Production Example 10 except that 14 parts by weight of the low melting point wax WL-2 shown in Table 1 is pulverized and added into xylene which is a reaction solvent. The low molecular weight resin composition L-4 of the present invention was obtained.

Production Example 14 8 parts by weight of the low melting point wax WL-2 shown in Table 1 and the high melting point wax WH shown in Table 2
A low molecular weight resin composition L-5 of the present invention containing a wax was obtained in the same manner as in Production Example 10 except that 8 parts by weight of -1 was pulverized and added to xylene as a reaction solvent.

Production Example 15 A wax is contained in the same manner as in Production Example 10 except that 14 parts by weight of the high melting point wax WH-1 shown in Table 2 is pulverized and added to xylene which is a reaction solvent. The low molecular weight resin composition L-6 of the present invention was obtained.

Production of Resin Composition for Toner (Production Example 16) High molecular weight resin composition H-obtained in Production Example 1
1 was added to the xylene solution of the low molecular weight resin composition L-3 obtained in Production Example 12 and heated with stirring to obtain a uniform solution. Then, xylene was distilled off under reduced pressure to obtain a toner resin composition B-1 of the present invention.

When the unreacted monomer and xylene were completely removed in the same manner as in Production Example 1 and the temperature at which tan δ became maximum (T _PB ) and the temperature at which tan δ became minimum (T _VB ), T _PB = 70 0.0 ℃, T _VB = 125.0 ℃, 9
It was confirmed to have a shoulder from 0 to 110 ° C. The measurement results are shown in FIG.

B-1 has Mw = 215000 and Mn.
= 6100, Mw / Mn = 35.2, Tg = 5
It was 9.6 ° C.

(Production Example 17) High molecular weight resin composition H-1
Manufactured except that 5 parts by weight of the low melting point wax WL-3 shown in Table 1 and 2 parts by weight of the high melting point wax WH-4 shown in Table 2 were added when the low molecular weight resin composition L-3 and the low molecular weight resin composition L-3 were mixed. In the same manner as in Example 16, the resin composition for toner B- of the present invention
2 was obtained.

(Production Example 18) High molecular weight resin composition H-2
Production Example 16 except that the low molecular weight resin composition L-1 and
In the same manner as described above, a resin composition B-3 for toner of the present invention was obtained.

(Production Example 19) High molecular weight resin composition H-2
Except that 2 parts by weight of the low-melting wax WL-1 shown in Table 1 and 2 parts by weight of the high-melting wax WH-2 shown in Table 2 were added when the low-molecular-weight resin composition L-1 was mixed with In the same manner as in Example 16, the resin composition for toner B- of the present invention
Got 4.

Production Examples 20 to 24 The resin composition for toner of the present invention was prepared in the same manner as in Production Example 16 or 17, except that the high molecular weight resin composition, low molecular weight resin composition and wax shown in Table 3 were used. B-5 to B-9 were obtained.

Production of Comparative High Molecular Weight Resin Composition Except 65 parts by weight of styrene and 35 parts by weight of n-butyl acrylate as monomers and 3 parts by weight of t-amylperoxy 2-ethylhexanoate as a polymerization initiator. Was subjected to a suspension polymerization reaction in the same manner as in Production Example 1 to give T _PH
= 53.7 ° C, T _VH = 92.4 ° C, to obtain a comparative high molecular weight resin composition RH-1.

Production of Comparative Low Molecular Weight Resin Composition In xylene in the same manner as in Production Example 10 except that 100 parts by weight of styrene was used as a monomer and 1.5 parts by weight of di-tert-butyl peroxide was used as a polymerization initiator. By carrying out the solution polymerization reaction, T _PL = 107.3 ° C., T _VL = 1
A comparative low molecular weight resin composition RL-1 having a temperature of 19.8 ° C. was obtained.

Production of Comparative Toner Resin Composition (Comparative Production Example 1) In the same manner as in Production Example 16 except that the comparative high molecular weight resin composition RH-1 and the comparative low molecular weight resin composition RL-1 were used. By mixing in a xylene solution, a comparative toner resin composition RB-1 having T _PB = 58.9 ° C. and T _VB = 104.3 ° C. was obtained.

Comparative Production Example 2 Comparative Production Example 1 except that 5 parts by weight of the comparative low melting point wax RWL-1 and 2 parts by weight of the comparative high melting point wax RWH-1 shown in Table 1 were added to xylene. By mixing in the same manner as described above, a resin composition RB-2 for comparative toner was obtained.

Example 1 Resin composition for toner B-1 of the present invention 100 parts by weight Magnetic material 100 parts by weight Monoazo metal complex 2 parts by weight WL-3 about 71% by weight and WH-4 about 29% by weight 7 parts by weight Crushed product of wax-melted mixture (The wax-melted mixture is a mixture of low-melting wax and high-melting wax mixed in a heated and melted state and homogenized, and is preferably used in the toner of the present invention. An endothermic pattern by various DSC measurements is shown in FIG. 5.)

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

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

Using this toner, a GP-55 digital copying machine (manufactured by Canon Inc.) was used for continuous image output durability of 100,000 sheets, and the image density was 1. When the endurance of 38,100,000 sheets was finished, there was almost no change to 1.42, and there was no change in image quality such as scattering of line images and thickening. Further, when the surface of the photosensitive drum was observed in detail at the end of the 100,000-sheet endurance, no adhered wax was observed and no conspicuous damage was observed on the surface of the photosensitive drum. There was no image defect presumably caused by damage on the surface of the photosensitive drum on the image.

Next, NP-6060 copying machine (manufactured by Canon)
The fixing device is removed, the nip is adjusted to about 3.5 mm, the external driving device is attached, the fixing roller is rotated at 150 mm / sec, the temperature control device is attached, and the temperature is 100 to 250.
It was modified so that the temperature of the fixing roller could be changed in the range of ° C. The fixing test was carried out in a constant temperature bath controlled at a temperature of 3 to 5 ° C., and after confirming that the fixing roller coincided with the temperature in the bath, the power was turned on and the upper roller (heating roller) was set to 13 ° C.
Immediately after reaching 0 ° C., a fixing test was conducted. At this point, the temperature of the lower roller (pressure roller) was about 100 ° C. 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 110 ° C.

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

As a result of the fixing test as described above, 17% immediately after turning on the power, 12% after 20 minutes, and 150% of the transfer paper.
Immediately after passing a single sheet, it was 23%, which was a level with no practical problem. Further, when a blocking resistance test was carried out by leaving it in a constant temperature bath whose temperature was controlled at 50 ° C. for 7 days, it was found that although slight aggregation was observed, it was easily loosened and the fluidity was recovered immediately.

When the glass transition temperature (Tg) of the binder resin of this developer and the melting point of the wax were observed by using DSC, Tg was 58.8 ° C., which was hardly lowered, and the low-melting wax and the high-melting wax were It was confirmed that each had a melting point almost the same as the melting point measured with the wax alone.

Example 2 B as a resin composition for toner
The toner (2) of the present invention was obtained in the same manner as in Example 1 except that the toner (-2) was used.

When the toner of the present invention was evaluated in the same manner as in Example 1, good results were obtained as shown in Table 4.

[Example 3] Resin composition for toner B-2 of the present invention 100 parts by weight Magnetic material 80 parts by weight Imidazole derivative 2 parts by weight 50% by weight of WL-1 and 50% by weight of WH-2 4 Parts by weight Grinded product of molten wax mixture

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.
Magnetic toner of Hydrophobic dry silica (BET 200 m ^{2 /} g) 1.0 is added to 100 parts by weight of this magnetic toner.
Toner (2) of the present invention was obtained by externally adding parts by weight with a Henschel mixer.

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

Using this toner, an NP-4835 copying machine (manufactured by Canon Inc.) was used to continuously print 100,000 sheets, and the image density was 1.42 at the initial stage of durability (1st to 10th sheets). At the end of the 100,000 sheet endurance, the change was 1.43, which was almost unchanged, and there was no change in image quality such as scattering of line images and thickening. Further, when the surface of the photosensitive drum was observed in detail at the end of the 100,000-sheet endurance, no adhered wax was observed and no conspicuous damage was observed on the surface of the photosensitive drum. There was no image defect presumably caused by damage on the surface of the photosensitive drum on the image.

Next, NP-6060 copier (manufactured by Canon)
The fixing device is removed, the nip is adjusted to about 6 mm, an external drive is attached, the fixing roller is rotated at 200 mm / sec, and a temperature control device is attached so that the temperature of the fixing roller can be changed in the range of 100 to 250 ° C. It was modified.
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 temperature of the fixing roller coincided with the temperature inside the bath, the power was turned on and the upper roller (heating roller) was heated to 140 ° C.
Immediately after it reached the fixing test. At this point, the temperature of the lower roller (pressure roller) was about 100 ° C. Next, set the fixing roller to 2 with the heater energized.
A fixing test was conducted by continuing rotation for 0 minutes. The temperature of the lower roller (pressure roller) was about 120 ° C.

Next, in this state, copy paper (75 g
/ M ² ) was passed through a fixing device of 150 sheets at a rate of 40 to 50 sheets / minute, and a fixing test was performed immediately after that.

As a result of the fixing test as described above, 16% immediately after turning on the power, 12% after 20 minutes, and 150% of the transfer paper.
Immediately after passing a single sheet, it was 23%, which was a level with no practical problem. Further, when a blocking resistance test was carried out by leaving it in a constant temperature bath whose temperature was controlled at 50 ° C. for 7 days, it was found that although slight aggregation was observed, it was easily loosened and the fluidity was recovered immediately.

When the glass transition temperature (Tg) of the binder resin of this developer and the melting point of the wax were observed using DSC, Tg did not decrease to 59 ° C., and the low-melting wax and the high-melting wax were each wax. It was confirmed that the melting point was almost the same as the melting point measured alone.

Example 4 B as a resin composition for toner
A toner (4) of the invention was obtained in the same manner as in Example 3 except that -4 was used.

When the toner of the present invention was evaluated in the same manner as in Example 3, good results were obtained as shown in Table 4.

[Examples 5 to 7] Toners (5) to (7) of the present invention were produced in the same manner as in Example 1 by using the resin composition for toner and the wax as shown in Table 4, and the performance was evaluated. evaluated. All were good results.

Comparative Example 1 Resin composition for comparative toner RB-1 100 parts by weight Magnetic material 100 parts by weight Monoazo metal complex 2 parts by weight RWL-1 about 71% by weight and RWH-1 29 to 7 parts by weight A pulverized product of the wax melt mixture (a typical endothermic pattern by DSC measurement is shown in FIG. 6).

Comparative Toner (1) was obtained in the same manner as in Example 1 except that the above materials were used. The results of evaluating the performance of the toner are shown in Table 4.

[Comparative Example 2] Comparative toner (2) was prepared in the same manner as in Example 2 except that the comparative resin composition RB-2 was used.
I got The results of evaluating the performance of the toner are shown in Table 4.

[0218]

[Table 1]

[0219]

[Table 2]

[0220]

[Table 3]

[0221]

[Table 4]

The evaluation ranks in Table 4 are as follows.

(Evaluation of low-temperature fixability) 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% or more

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

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

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

[0227]

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

[Brief description of drawings]

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

FIG. 2 is a graph showing an example of measurement results of tan δ of a high molecular weight resin composition.

FIG. 3 is a graph showing an example of measurement results of tan δ of a low molecular weight resin composition.

FIG. 4 is a graph showing an example of measurement results of tan δ of the resin composition for toner.

FIG. 5 is a graph showing an example of a DSC endothermic pattern of a wax preferably used in the toner of the present invention.

FIG. 6 is a DSC of a comparative wax used for a comparative toner.
It is a graph which shows an example of an endothermic pattern.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsutomu Onuma 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (7)

[Claims] 1. A resin composition for a toner comprising a high molecular weight resin composition and a low molecular weight resin composition, wherein each of the high molecular weight resin composition and the low molecular weight resin composition constituting the resin composition for a toner There is at least one temperature at which the loss tangent, which is the ratio of the loss elastic modulus and the storage elastic modulus, becomes maximum and minimum in the range of 50 to 150 ° C.,
Further, a resin composition for a toner, wherein the relationships represented by the following formulas (1) and (2) are established. [Equation 1] [ _Wherein T _PH , T _PL , and T _PB represent temperatures at which the loss tangents of the high-molecular weight resin composition, the low-molecular weight resin composition, and the resin composition for toner having these are maximum, respectively, and T _VH , T
_VL and _TVB represent temperatures at which the loss tangents of the high-molecular weight resin composition, the low-molecular weight resin composition and the toner resin composition containing them are minimized, respectively. ] 2. The resin composition for a toner according to claim 1, wherein a sub-peak and / or a shoulder are formed at a temperature other than the temperature at which the loss tangent is maximized. 3. The resin composition for toner according to claim 1, which contains a wax. 4. The wax has two kinds of waxes having different melting points, and the following formula (3) is provided between the melting point of the wax having a relatively low melting point and the temperature at which the loss tangent of the resin composition for toner becomes maximum. And the temperature at which the loss tangent of the resin composition for toner has a minimum, and the relationship of the following expression (4) is established. The resin composition for toner according to claim 3. Formula (3) | T _WL −T _PB | ≦ 10 Formula (4) | T _WH −T _VB | ≦ 10 [wherein, T _WL and T _WH are the melting point and relative value of the wax having a relatively low melting point, respectively] Shows the melting point of wax having a high melting point. ] 5. A toner for developing an electrostatic charge image, which comprises at least a binder resin composition having a high molecular weight resin composition and a low molecular weight resin composition and a colorant, and the binder resin composition and the toner constituting the same. There is at least one temperature at which the loss tangent, which is the ratio of the loss elastic modulus and the storage elastic modulus of each of the high-molecular weight resin composition and the low-molecular weight resin composition, is maximum and minimum in the range of 50 to 150 ° C. And a toner for developing an electrostatic charge image, wherein the relationships represented by the following formulas (1) and (2) are established. [Equation 2] [ _Wherein T _PH , T _PL , and T _PB represent temperatures at which the loss tangents of the high-molecular-weight resin composition, the low-molecular-weight resin composition, and the binder resin composition composed of these become maximum, respectively, and T _VH , T _VL ,
T _VB represents the temperature at which the loss tangent of the high molecular weight resin composition, the low molecular weight resin composition, and the binder resin composition composed of these becomes minimum. ] 6. The toner for developing an electrostatic charge image according to claim 5, further comprising a wax. 7. The wax has two kinds of waxes having different melting points, and the following formula (3) is provided between the melting point of the wax having a relatively low melting point and the temperature at which the loss tangent of the binder resin composition is maximized. And the temperature at which the loss tangent of the binder resin composition is minimized, the relationship of the following expression (4) is established. The toner for developing an electrostatic charge image according to claim 7. Formula (3) | T _WL −T _PB | ≦ 10 Formula (4) | T _WH −T _VB | ≦ 10 [wherein, T _WL and T _WH are the melting point and relative value of the wax having a relatively low melting point, respectively] Shows the melting point of wax having a high melting point. ]