JP3376257B2 - Toner for developing electrostatic images - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner used in an image forming method such as an electrophotographic method or an electrostatic recording method.

[0002]

2. Description of the Related Art Generally, in heat fixing toner,
To improve the fixability and anti-offset property, toner particles have been made to contain wax. For example, JP-B-52-3304 discloses a toner containing a wax in JP-B-52-3305 and JP-B-57-52574.

Furthermore, JP-A-3-50559, JP-A-2-79860, JP-A-1-109359, JP-A-62-14166 and JP-A-61-2.
73554, 61-94062, JP-A-6
1-138259, JP-A-60-252361, JP-A-60-252360, and JP-A-60-
JP-A-217366 discloses a toner containing a wax.

The wax is used for improving the offset resistance of the toner at low temperature and high temperature, and for improving the fixing property at low temperature. However, while the wax improves these properties, the blocking resistance of the toner is deteriorated, the developability is deteriorated, and the wax develops a bloom when the toner is left for a long time to deteriorate the developability of the toner. Further, the toner developability may be gradually deteriorated when a large number of sheets are endowed, or the developing sleeve may be contaminated, resulting in a decrease in image density and an increase in fogging.

A toner containing two or more kinds of waxes in order to bring out the effect of wax addition from the low temperature region to the high temperature region is disclosed in JP-B-52-3305.
JP-A-58-21559, JP-A-62-100
775, JP-A-4-124676, JP-A-4-299357, JP-A-4-362953, and JP-A-5-197192.

However, these toners also have some problems. For example, high temperature offset resistance and developability are excellent, but low temperature fixability is low, and low temperature offset resistance and low temperature fixability are excellent, but blocking resistance is slightly poor and developability is low. There is an adverse effect, the offset resistance at low temperature and high temperature cannot be compatible at all, the toner coating on the developing sleeve becomes uneven due to the free wax component, and blotches occur, resulting in image defects. Fog sometimes occurred.

Also, low molecular weight polypropylene (for example,
Viscole 550P, 660 manufactured by Sanyo Kasei Co., Ltd.
Although a toner containing P, etc. is commercially available, a toner having improved high-temperature offset property and improved low-temperature fixability is desired.

[0008]

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

An object of the present invention is to provide a toner for developing an electrostatic charge image which is excellent in fixing property and anti-offset property and is also excellent in development.

A further object of the present invention is to provide a toner for developing an electrostatic charge image, which has less deterioration in developability due to durability.

A further object of the present invention is to provide a toner for developing an electrostatic charge image which is less likely to cause stains on a toner-fixed image fixed on a transfer material.

Another object of the present invention is to provide a toner for developing an electrostatic charge image which is less likely to be wound around a heat fixing member.

[0013]

Specifically, the present invention is
A toner for developing an electrostatic charge image, comprising at least a binder resin, a colorant and a wax, wherein the toner has a DSC endothermic curve at a temperature rise in the range of 30 to 150 ° C. measured by a differential scanning calorimeter, Temperature 70 ~ 90 ℃
Has a maximum endothermic peak (P1) at a temperature of 85 to 115 ° C.
When the height of P1 from the baseline is Hp1 and the height of P2 from the baseline is Hp2, Hp1 and Hp2 are Hp2 / Hp1 ≦ 0. 7 and P2 is a peak instead of a shoulder, the height from the baseline of the lowest valley (V) between P1 and P2 is H.
v, Hp2 and Hv are Hv / Hp2 ≧ 0.
5 and the first maximum value (Max1) on the lowest temperature side in the differential curve of the DSC endothermic curve is the temperature (T1).
The second maximum value (Max2) at 50 to 65 ° C. and then at the low temperature side is at temperature (T2) 65 to 85 ° C.
In the differential curve of the SC endothermic curve, the minimum value (Min1) on the highest temperature side is at a temperature (T3) of 95 ° C. or higher, and relates to the electrostatic charge image developing toner.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION By analyzing a DSC endothermic curve measured by a differential operation calorimeter of toner, it is possible to observe the thermal behavior of the toner, and to know the heat exchange with the toner and the state change of the toner. I can. Therefore, the DSC endothermic curve of the toner provides the knowledge of the electrophotographic characteristics with respect to the heat of the toner. In the present invention, the heat absorption is in the positive direction. This thermal behavior appears due to the interaction between the binder resin and the wax, and the existence state of the binder resin and the wax in the toner particles can be known.
For example, the dispersion state of the wax in the toner particles and the interaction state of the binder resin and the wax can be estimated. These behaviors can be controlled by controlling the structure of the binder resin, the structure of the wax, and the dispersion of the wax in the binder resin. The DSC endothermic curve of the toner will be described with reference to FIGS.

The slope of the increase in the endothermic amount that first appears in the DSC endothermic curve in the temperature range of 30 to 150 ° C. indicates the thermal behavior associated with the glass transition of the toner caused by the interaction between the binder resin and the wax. The point at which the gradient becomes maximum is the point (temperature) at which this transition state becomes maximum. DS
The point (temperature) at which the slope of the C endothermic curve becomes maximum is the point (temperature) at which the DSC endothermic curve shows a maximum value in the differential curve of the time derivative. The temperature (T1) of the first maximum value (Max1) on the lowest temperature side in the differential curve of the time derivative of the DSC endothermic curve is related to the fixability and storage stability of the toner, and the temperature (T1) is 50 to 65. C (preferably 50 to
When the temperature is 60 ° C., the low temperature fixability of the toner can be improved while maintaining the storage stability of the toner. When the toner temperature (T1) is less than 50 ° C, the storage stability of the toner is lowered, while the toner temperature (T1) is 65 ° C.
If it exceeds, the low temperature fixability of the toner will be deteriorated.

In the DSC endothermic curve in the temperature range of 30 to 150 ° C., the second increase in the endothermic amount indicates the thermal behavior associated with the plasticizing effect of the wax on the toner,
The second point (temperature) where the slope of the DSC endothermic curve becomes maximum
Is the point (temperature) at which the plasticizing effect of the wax begins to take effect. The second point (temperature) at which the slope of the DSC endothermic curve becomes maximum is the point (temperature) at which the DSC endothermic curve shows a maximum value in the differential curve. The temperature (T2) of the second maximum value (Max2) that appears after the first maximum value (Max1) in the differential curve of the DSC endothermic curve is also related to the low temperature fixability and the storage stability of the toner, and the temperature (T2 ) Is 65
When the temperature is ˜85 ° C. (preferably 65 to 80 ° C., more preferably 70 to 80 ° C.), the low temperature fixability of the toner can be improved while maintaining the storage stability of the toner. When the toner temperature (T2) is less than 65 ° C., the storage stability of the toner decreases, while the toner temperature (T2)
If the temperature exceeds 85 ° C., the low temperature fixability is deteriorated.

In the DSC endothermic curve of the toner, the maximum endothermic peak (P1) shows the thermal behavior accompanying the melting of the wax, and the peak temperature of the maximum endothermic peak (P1) is
This is the point (temperature) at which the plasticizing effect of the wax on the binder resin is saturated. Therefore, the maximum endothermic peak (P
The temperature of 1) is also related to the low temperature fixability and storage stability of the toner. The temperature of the maximum endothermic peak (P1) of the toner is 7
When the temperature is 0 to 90 ° C. (preferably 70 to 85 ° C.), the low temperature fixability of the toner can be further improved while maintaining the storage stability of the toner. When the temperature of the maximum endothermic peak (P1) of the toner is less than 70 ° C., the storage stability of the toner decreases, while when the temperature of the maximum endothermic peak (P1) of the toner exceeds 90 ° C., the plasticizing effect of the wax Becomes smaller, and the low temperature fixability of the toner deteriorates. Toner D
In the SC endothermic curve, the height of the sub-endothermic peak from the baseline is 0.8 or less than the height of the maximum endothermic peak (P1) from the baseline, in order to further improve the fixing property of the toner. preferable.

In the DSC endothermic curve in the temperature range of 30 to 150 ° C., the point (temperature) at which the gradient appearing on the highest temperature side becomes the minimum is the point (temperature) at which the melting of the wax is almost completed.
And is related to the high temperature offset resistance of the toner.
In the DSC endothermic curve, the point (temperature) at which the gradient appearing on the highest temperature side is the minimum is the point (temperature) on the highest temperature side showing the minimum value (Min1) in the differential curve of the DSC endothermic curve. The temperature (T3) of the minimum value (Min1) on the highest temperature side in the differential curve of the DSC endothermic curve is 95
℃ or more (preferably 100 ℃ or more, more preferably 1
When the temperature is from 0 to 130 ° C, particularly preferably from 100 to 120 ° C, the high temperature offset resistance of the toner is improved. If the temperature (T3) of the minimum value (Min1) on the highest temperature side of the toner is less than 95 ° C., the wax melts at a low temperature, the compatibility with the binder resin becomes good, and the viscosity of the wax becomes too small. , The wax film does not work effectively, and it becomes difficult to exert the releasing effect and the peeling effect. Also, this temperature is 1
If the temperature exceeds 30 ° C., the melting of the wax is insufficient or the viscosity becomes large, and a sufficient wax film cannot be formed, and in this case also, the releasing effect and the releasing effect tend to be difficult to be exhibited. In these cases, the peelability between the heat-fixing member and the transfer material deteriorates, so that the fixed image begins to wrap around the heat-fixing member, and when it is peeled off by the paper discharge separation claw, the fixed image In addition, the traces of the separation claws will start to appear. Then, when it becomes worse, the separation claws cannot separate the transfer material, and the transfer material is wound around the heat fixing member.

Further, in order to make the releasing effect and the releasing effect of the toner from the heat fixing member more effective, 85 to 1
It is preferable to have a subpeak or a shoulder (P2) in the temperature region of 15 ° C (more preferably 90 to 110 ° C). Further, from the viewpoint of improving the fixing property of the toner, the ratio of the height of P2 to the height of P1 (P2 / P1) is preferably 0.7 or less. In particular, the ratio (P2 / P1) is preferably 0.5 or less.

Further, when the temperature difference between T3 and T2 is 25 ° C. or more, a wide temperature (that is, a fixing temperature range) can be taken until the toner is offset from the fixing temperature. It is particularly preferable that this temperature difference is 30 ° C. or more. In addition, the lowest valley between P1 and P2 is V
Then, the ratio of the height of V to P2 (V / P2) is preferably 0.5 or more (more preferably 0.6 or more). In such a case, since a uniform wax film is formed on the surface of the fixed image, the fixed image is not peeled off when the fixed image is rubbed, so that the document material is soiled or other devices are soiled. Never or little. For example, when obtaining a double-sided or multiplex image, the transfer material having the fixed image is not rubbed, and the transfer material above or below the transfer material is not polluted, or less. In addition, since the transfer material having the fixed image does not stain the members in these steps, the transfer material passing thereafter does not stain or is small. Further, when the transfer material having these fixed images is used as an original and the document feeder is used in a copying machine, the same stain as described above may occur due to friction between transfer materials having fixed images or members of the apparatus. None or less.

In the present invention, in the DSC measurement of a toner by a differential scanning calorimeter, it is preferable to use a highly accurate internal heat input compensation type differential scanning calorimeter from the measurement principle. For example, DSC-7 manufactured by Perkin Elmer can be used.

The measuring method is ASTM D3418-82.
Carry out according to. The DSC curve used in the present invention has a temperature rate of 10 ° C /
The DSC curve measured when the temperature is raised at min is used. The temperature range of the DSC curve used is 30-150 ° C. The definition of each temperature is defined as follows. FIG. 1 shows the DSC endothermic curve and its time derivative curve.

The peaks, shoulders, slopes, valleys, baseline maximum values, minimum values, or 0 in the DSC endothermic curve or its differential curve will be described below.

Temperature (T1): When the DSC endothermic curve in the temperature range of 30 to 150 ° C. was analyzed from the low temperature side,
First, the gradient is the temperature at which the maximum is reached, and the differential curve of the DSC endothermic curve is the temperature at which the positive maximum is initially reached.

Temperature (T2): When the DSC endothermic curve in the temperature range of 30 to 150 ° C. was analyzed from the low temperature side,
The slope is the temperature at which the temperature reaches the second maximum, and the fine powder curve of the DSC endothermic curve is the temperature at which the next positive maximum value is reached.

Temperature (T3): When the DSC endothermic curve in the temperature range of 30 to 150 ° C. was analyzed from the low temperature side,
Finally, the slope is a temperature at which the DSC endothermic curve has a minimum value, which is the highest temperature at which the differential curve of the DSC endothermic curve has a negative minimum value.

P1 (maximum endothermic peak): 30 to 150 ° C.
The maximum endothermic peak within the range and the temperature at the peak top is the peak temperature (TP1) of the maximum endothermic peak.

P2 (sub-peak) or S1 (shoulder
-): Within the range of 85 to 115 ° C, the point at which the differential curve of the DSC endothermic curve becomes 0 or the maximum value is the sub-peak or shoulder, and the temperature at this point is the peak or shoulder temperature (TP2). The peak is selected if there is a differential value 0 (differential value 0 for shifting from positive to negative), and if there is no differential value, the shoulder having the negative maximum value is selected. When the shoulder is wide and it is difficult to confirm the sub-peak or the shoulder, the point where the transition from the vicinity of the differential value 0 to the negative is clearly recognized is set as the position of the shoulder. Further, when there are a plurality of sub-peaks or shoulders, the one having the highest temperature is selected.

Peak height: Between T1 and T2, the differential curve of the DSC endothermic curve changes from negative to positive, the point where the differential value becomes 0, or the point where the differential value becomes positive and has a minimum value, and the differential curve at T3 or higher. The point where is almost 0 is connected and this is used as the baseline. The height of each peak, shoulder, or valley from this baseline is the height of each.

When the point on the high temperature side of T3 or higher is set, the DSC endothermic curve up to 200 ° C. and the differential curve can be used.

The wax preferably used is a polyolefin obtained by radically polymerizing an olefin under high pressure;
Polyolefin obtained by purifying low molecular weight by-products obtained at the time of polymerization of high molecular weight polyolefin; polyolefin polymerized by using a catalyst such as Ziegler catalyst and metallocene catalyst under low pressure; polyolefin polymerized by utilizing radiation, electromagnetic waves or light; high molecular weight Low molecular weight polyolefin obtained by pyrolyzing polyolefin; paraffin wax,
Microcrystalline wax, Fischer-Tropsch wax; Synthetic hydrocarbon wax synthesized by a polymerization method such as the Zintor method, Hydrocoal method and Arge method;
Synthetic waxes having a compound of 1 carbon atom as a monomer; hydrocarbon waxes having a functional group such as a hydroxyl group or a carboxyl group at the end are mentioned. It is preferable to use a mixture of these waxes.

Those waxes having a sharp molecular weight distribution obtained by a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a fused liquid crystal deposition method, a fatty acid, an alcohol or a low molecular weight compound. Those obtained by removing other impurities are preferably used.

The endothermic characteristic of the toner, which is a feature of the present invention, is
It is preferable to achieve it by combining several kinds of waxes in an amount of 1 to 20 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the binder resin and dispersing them in the binder resin. The wax is selected such that the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 200 to 5,000 (preferably 25).
0 to 2,000, particularly preferably 300 to 1,500)
And the weight average molecular weight / number average molecular weight (Mw / M
It is preferable to use two or three types of wax having n) of 3.0 or less (preferably 2.0 or less). Further, more preferable results can be obtained by using a wax having a relatively low molecular weight and a wax having a relatively high molecular weight in combination.

In the present invention, the molecular weight distribution of the wax is G
It is measured by the PC under the following conditions.

Apparatus: GPC-150C (Waters Co.) Column: GMH-HT 30 cm 2 series (manufactured by Toso Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1% ionon added) Flow rate: 1.0 ml / min Sample: 0.4 ml injection of 0.15% sample

A molecular weight calibration curve prepared from a 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.

The binder resin used in the toner of the present invention includes the following. The glass transition point of the binder resin is 5
The temperature is preferably 0 to 70 ° C, more preferably 55 to 65 ° C.

The method for measuring the glass transition point of the binder resin is A
Performed according to STM D3418-82. Binder resin D
The SC curve is D measured when the temperature is raised at a temperature rate of 10 ° C./min after the temperature is raised and lowered once and the previous history is taken.
SC curve is used.

The glass transition point (Tg) is DSC at the time of heating.
The temperature at the intersection of the DSC curve and the line connecting the midpoints of the baseline before and after the specific heat change appears in the curve.

Polystyrene as the binder resin; poly-p-
Styrene-substituted homopolymers such as chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic ester copolymers, Styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer; styrene-acrylonitrile-indene copolymer -Based copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum-based resin. A preferable binder resin is a styrene copolymer or a polyester resin.

Comonomers for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid. , Monomethacrylic acid having a double bond such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile and acrylamide; maleic acid, butyl maleate, methyl maleate, maleic acid Dicarboxylic acids having a double bond such as dimethyl acid and substituted compounds thereof; vinyl chloride; vinyl esters such as vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene and butylene. ; Vinyl methyl ketone, such as vinyl vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl propionate ether. These vinyl monomers are used alone or in combination of two or more.

The styrene polymer or styrene copolymer may be crosslinked or may be a mixed resin.

As the crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; divinylaniline and divinyl ether. , A divinyl compound such as divinyl sulfide and divinyl sulfone; and a compound having three or more vinyl groups. These are used alone or as a mixture.

Examples of the method for synthesizing the binder resin include a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method.

In the bulk polymerization method, it is possible to obtain a low molecular weight polymer 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 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 polymerization initiator and the reaction temperature. It is preferable when a low molecular weight product is obtained in the resin composition used.

As the solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol or benzene can be used. If styrene monomers are used, xylene, toluene or cumene are preferred. The solvent is appropriately selected depending on the polymer to be polymerized. The reaction temperature varies depending on the solvent used, the polymerization initiator and the polymer to be polymerized, but is usually 70 ° C to 230 ° C.
It is better to do it at ℃. The solution polymerization is preferably carried out with 30 parts by weight to 400 parts by weight of the monomer per 100 parts by weight of the solvent.

Further, it is also preferable to mix other polymers in the solution at the end of the polymerization, and several polymers can be mixed well.

As a polymerization method for obtaining a high molecular weight component or a gel component, an emulsion polymerization method or a suspension polymerization method is preferable.

Among them, the emulsion polymerization method is a method in which a monomer which is almost insoluble in water is dispersed in an aqueous phase as small particles with an emulsifier and a water-soluble polymerization initiator is used for polymerization. In this method, the heat of reaction can be easily adjusted, and the termination reaction rate is low because the phase in which the polymerization is performed (oil phase consisting of polymer and monomer) and the aqueous phase are different, resulting in a high polymerization rate. A high degree of polymerization can be obtained. Furthermore, because of the relatively simple polymerization process and the fact that the polymerization products are fine particles, they are easy to mix with colorants and charge control agents and other additives in the production of toners. It is advantageous as a method for producing a binder resin for toner, as compared with other methods.

However, suspension polymerization is a simpler method because the resulting polymer tends to become impure due to the added emulsifier and an operation such as salt folding is required to take out the polymer.

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 medium.
0 to 90 parts by weight) is preferable. Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, and calcium phosphate. Generally, 0.05 to 1 part by weight of the dispersant is used with respect to 100 parts by weight of the aqueous medium. The polymerization temperature is suitably 50 to 95 ° C., but it should be appropriately selected depending on the polymerization initiator used and the target polymer. As the polymerization initiator,
Any substance that is insoluble or hardly soluble in water can be used.

As the polymerization initiator, t-butylperoxy-2-ethylhexanoate, cumin perpivalate, t-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di- t-butyl peroxide, t-
Butyl cumyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, 2,2 '
-Azobis (2-methylbutyronitrile), 2,2'-
Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy)
3,3,5-Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxylcarbonyl) cyclohexane, 2,2-bis (t-butylperoxy) Octane,
n-butyl 4,4-bis (t-bitylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl -2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane,
Di-t-butyldiperoxyisophthalate, 2,2-
Bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexahydro Terephthalate, di-t-butylperoxyazelate, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di-t-butylperoxytrimethyl adipate, tris (t-butylperoxy) triazine, Examples thereof include vinyltris (t-butylperoxy) silane, and these can be used alone or in combination.

The amount used is 0.05 parts by weight or more (preferably 0.1 to 15 parts by weight) with respect to 100 parts by weight of the monomer.

Next, the polyester resin will be described.

Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol and 1,5-pentanediol. 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, bisphenol represented by formula (A) and derivatives thereof

[0056]

[Outside 2] (In the formula, R is an ethylene or propylene group, x,
y is an integer of 0 or more, and the average value of x + y is 0 to 10).

A diol represented by the formula (B)

[0058]

[Outside 3] X ′ and y ′ are integers of 0 or more, and
The average value of x '+ y' is 0-10. ) Is mentioned.

Examples of the divalent acid component include phthalic acid,
Benzene dicarboxylic acids or their anhydrides such as terephthalic acid, isophthalic acid and phthalic anhydride, lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or their anhydrides, lower alkyl esters; n- Alkenyl succinic acid or alkyl succinic acid such as dodecenyl succinic acid and n-dodecyl succinic acid, or their anhydrides, lower alkyl esters; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or their anhydrides, lower Examples thereof include dicarboxylic acids such as alkyl ester; and derivatives thereof.

It is preferable to use an alcohol component having a valence of 3 or more and an acid component having a valence of 3 or more, which also serve as a crosslinking component.

As the polyhydric alcohol component having 3 or more valences,
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropynetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,
3,5-trihydroxybenzene etc. are mentioned.

The trivalent or higher polyvalent carboxylic acid component includes
For example, trimellitic acid, pyromellitic acid, 1,2,4-
Benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid,
1,2,4-naphthalene tricarboxylic acid, 1,2,4-
Butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid , Enpol trimer acid, and their anhydrides, lower alkyl esters;

[0063]

[Outside 4] (Wherein, X is an alkylene group having 5 to 30 carbon atoms or an alkenylene group having at least one side chain having 3 or more carbon atoms), a polycarboxylic acid such as an anhydride or a lower alkyl ester thereof. Examples thereof include carboxylic acids and their derivatives.

As an alcohol component, 40 to 60 mol
%, Preferably 45-55 mol%, and 6 as the acid component
It is preferably 0 to 40 mol%, and more preferably 55 to 45 mol%.

Polyvalent components having a valence of 3 or more are 1 to 1 in all components.
It is also preferably 60 mol%.

A styrene-unsaturated carboxylic acid derivative copolymer, from the viewpoints of developing property, fixing property, durability and cleaning property,
Preferred are polyester resins, block copolymers and graft products thereof, and further mixtures of styrene copolymers and polyester resins.

Further, the binder resin used in the toner of the present invention preferably has a peak in a region having a molecular weight of 10 ⁵ or more in the molecular weight distribution measured by GPC, and further has a molecular weight of 3 × 10 ^{3 to} 5. It is preferable to have a peak in the region of 10 ^{4 from} the viewpoints of fixability and durability.

In the case of positively chargeable toner, styrene-acrylic copolymer, styrene-methacrylic-acrylic copolymer, styrene-methacrylic copolymer, styrene-butadiene copolymer, polyester resin, and blocks thereof. Copolymers, graft products and blend resins are preferred. In the case of a negatively chargeable toner, styrene-acrylic copolymer, styrene-methacrylic-acrylic copolymer, styrene-methacrylic copolymer and copolymers of these constituent monomers and maleic acid monoester, polyester resin, Also, these block copolymers, graft products, and blend resins are preferable from the viewpoint of developability.

When a styrene-based copolymer is used as the binder resin, the following toners are preferable in order to sufficiently exert the effect of the wax and prevent the deterioration of the blocking resistance and the developability which are the adverse effects of the plasticizing effect.

In the molecular weight distribution by GPC (gel permeation chromatography) of the soluble component of tetrahydrofuran (THF) of the resin component of the toner, the molecular weight is preferably in the range of 3 × 10 ^{3 to} 5 × 10 ⁴ , more preferably the molecular weight. By having at least one peak in the region of 3 × 10 ^{3 to} 3 × 10 ⁴ , and more preferably in the region of 5 × 10 ³ to 2 × 10 ⁴ , good fixability, developability and blocking resistance are obtained. be able to. If the position of the above-mentioned peak is less than 3 × 10 ³ , the anti-blocking property decreases, while
If the molecular weight exceeds 5 × 10 ⁴ , the fixability will decrease.
Molecular weight of 1 × 10 ⁵ or more, preferably molecular weight of 3 × 1
When at least one peak exists in the region of 0 ^{5 to} 5 × 10 ⁶ , good high temperature offset resistance, blocking resistance, and developability can be obtained. The higher the molecular weight of the peak on the polymer side, the stronger the high temperature offset, but the molecular weight of 5
When a peak exists in a region larger than × 10 ⁶ , there is no problem when using a heat roll to which a large pressure can be applied, but when a large pressure cannot be applied, the elasticity becomes large and the fixing property deteriorates. Come to do. Therefore, in heat fixing with a relatively low pressure used in medium to low speed machines, there is a peak in the molecular weight range of 3 × 10 ⁵ to 2 × 10 ⁶ and this peak is the maximum in the range of molecular weight of 1 × 10 ⁵ or more. It is preferably a peak.

The THF-soluble component having a molecular weight of 1 × 10 ⁵ or less is preferably 50% or more, more preferably 60 to 50%.
90%, particularly preferably 65 to 85% is contained. Due to this, the toner exhibits a good fixing property. When the content of the above components is less than 50%, the fixability is deteriorated, and the pulverizability of the cooled product of the melt-kneaded product during toner production is also decreased. If it exceeds 90%, the plasticizing effect due to the addition of wax decreases.

When a polyester resin is used as the binder resin, the THF-soluble component of the toner preferably has a molecular weight distribution of 3 × 10 ^{3 to} 1.5 in terms of GPC molecular weight distribution.
× 10 ⁴ region, more preferably molecular weight 4 × 10 ³ ~
1.2 × 10 ⁴ , particularly preferably a molecular weight of 5 × 10 ³ to 1 ×
It is preferable that the main peak exists in the region of 10 ⁴ . Further, it is preferable that at least one peak or shoulder is present in a region having a molecular weight of 1.5 × 10 ⁴ or more, or that the component in the region having a molecular weight of 5 × 10 ⁴ or more is 5% or more. Weight average molecular weight of THF-soluble component (M
It is also preferable that the value of w) / number average molecular weight (Mn) is 10 or more.

In the present invention, the molecular weight distribution of the chromatogram of the toner by GPC is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and THF was added as a solvent to the column at this temperature.
(Tetrahydrofuran) at a flow rate of 1 ml / min,
About 100 μl of HF sample solution is injected for measurement. When measuring the molecular weight of a sample, calculate the molecular weight distribution
It is calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared by using several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, the molecular weight of Tosoh or Showa Denko is 1 × 10 ² to
It is suitable to use a standard polystyrene sample of at least about 10 points, using about 10 ⁷ pieces. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns.
For example, Shodex GPC KF- manufactured by Showa Denko KK
801, 802, 803, 804, 805, 806, 8
Combination of 07,800P and TSK Gel manufactured by Tosoh Corporation
G1000H (H _XL ), G2000H (H _XL ), G30
00H (H _XL ), G4000H (H _XL ), G5000H
(H _XL ), G6000H (H _XL ), G7000H
(H _XL ), the combination of TSKguardcolumn can be mentioned.

The sample is manufactured as follows.

After putting the sample in THF and leaving it for several hours, it is shaken sufficiently and well mixed with THF (until the coalescence of the samples disappears), and it is left still for 12 hours or more. At this time T
The time of leaving in HF should be 24 hours or more.
Then sample processing filter (pore size 0.45
μm to 0.5 μm, for example, Mysholydisk H-2
5-5, manufactured by Tosoh Co., Ltd., Excicrodisk 25CR, manufactured by Gelman Science Japan Co., Ltd.) can be used as a GPC sample. The sample concentration is
The resin component is adjusted to 0.5 to 5 mg / ml.

The toner of the present invention preferably contains a charge control agent.

The following substances may be mentioned as substances for controlling the toner to be positively charged.

Modified products of nigrosine and nigrosine fatty acid metal salts; tributylbenzylammonium-1
-Vitroxy-4-naphthosulfonate, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof, (lake forming agents Examples thereof include phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.) higher fatty acid metal salts;
Dibutyltin oxide, dioctyltin oxide,
Diorganotin oxide such as dicyclohexyltin oxide; Diorganotin borate such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate; Guanidine compound, imidazole compound. These can be used alone or in combination of two or more. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. General formula (1)

[0080]

[Outside 5] [Wherein R ₁ represents H or CH ₃ and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably C _{1 to} C ₄ )], a homopolymer of a monomer: A copolymer with a polymerizable monomer such as styrene, acrylic acid ester or methacrylic acid ester can be used as a positive charge control agent. In this case, the homopolymer or copolymer also functions as (all or part of) the binder resin.

Particularly, the compound represented by the following general formula (2) is also preferable as the positive charge control agent.

[0082]

[Outside 6] [Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different from each other, a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group] Represents a group. R ⁷ , R ⁸ and R ⁹ each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, which may be the same or different. A ⁻ is selected from sulfate ion, nitrate ion, borate ion, phosphate ion, hydroxide ion, organic sulfate ion, organic sulfonate ion, organic phosphate ion, carboxylate ion, organic borate ion, and tetrafluoroborate. Shows anions].

The following substances may be mentioned as examples of controlling the toner to be negatively charged.

Organic metal complex, chelate compound, monoazo metal complex, acetylacetone metal complex, metal complex of aromatic hydroxycarboxylic acid, metal complex of aromatic dicarboxylic acid, metal salt of aromatic hydroxycarboxylic acid, aromatic polycarboxylic acid Metal salts, their anhydrides, their esters, and phenol derivatives.

Further, the azo metal complex represented by the general formula (3) shown below is also preferable as the negative charge control agent.

[0086]

[Outside 7] [In the formula, M represents a coordination center metal, and Sc, Ti, V,
Indicates Cr, Co, Ni, Mn or Fe. Ar is an aryl group and represents a phenyl group or a naphthyl group. Ar may have a substituent. The substituent in this case is a nitro group, a halogen group, a carboxyl group, an anilide group, and an alkyl group or an alkoxy group having 1 to 18 carbon atoms.
X, X ', Y and Y'represent -O-, -CO-, -NH- or -NR- (R is an alkyl group having 1 to 4 carbon atoms).

[0087]

[Outside 8] Represents a cation ion and is hydrogen, sodium, potassium, ammonium or aliphatic ammonium. Cationic ions are not necessary. ].

In particular, Fe or Cr is preferable as the central metal, halogen, an alkyl group or an anilide group is preferable as the substituent, and hydrogen, alkali metal ammonium or aliphatic ammonium is preferable as the counter ion. Also, a mixture of complex salts having different counter ions is preferably used.

The basic organic acid metal complex represented by the following general formula (4) is also preferable as the negative charge control agent.

[0090]

[Outside 9]

Particularly, as the central metal, Fe, Cr, Si,
Zn or Al is preferable, the substituent is an alkyl group,
Anilide group, aryl group or halogen is preferable, and the counter ion is preferably hydrogen, ammonium or aliphatic ammonium.

As a method of incorporating the charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally. The amount of these charge control agents used is determined according to the type of binder resin, the presence or absence of other additives, and the toner manufacturing method including the dispersion method, and is not uniquely limited. It is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin.

In the toner of the present invention, the charging stability,
It is preferable to externally add silica fine powder in order to improve developability, fluidity and durability.

The silica fine powder has a specific surface area of 20 m ² / g or more (particularly 30 to 4) by nitrogen adsorption measured by the BET method.
Those in the range of 00 m ² / g) give good results.
Silica fine powder 0.01 per 100 parts by weight of toner particles
-8 parts by weight, preferably 0.1-5 parts by weight.

Further, the silica fine powder is a silicone varnish, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silanes having a functional group, if necessary, for the purpose of hydrophobizing or controlling chargeability. It is also preferably treated with a treating agent such as a coupling agent or other organosilicon compound.
Plural kinds of treatment agents may be used.

It is also preferable to add another inorganic powder in order to improve the developability and durability. For example, magnesium, zinc, aluminum, cerium, cobalt,
Oxides of metals such as iron, zirconium, chromium, manganese, strontium, tin and antimony; complex metal oxides such as calcium titanate, magnesium titanate and strontium titanate; metal salts such as calcium carbonate, magnesium carbonate and aluminum carbonate. Clay minerals such as kaolin; phosphoric acid compounds such as apatite; silicon compounds such as silicon carbide and silicon nitride; carbon powders such as carbon black and graphite. Of these, zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate or magnesium titanate is preferable.

Further, the following lubricant powder may be externally added. For example, fluororesin powder such as Teflon and polyvinylidene fluoride; powder of fluorine compound such as carbon fluoride; powder of fatty acid metal salt such as zinc stearate; powder of fatty acid derivative such as fatty acid and fatty acid ester; sulfide such as molybdenum sulfide. Powders of amino acids and amino acid derivatives.

The toner of the present invention can be used as a two-component developer in combination with a carrier, and as the carrier for use in the two-component developing method, any conventionally known carrier can be used. Specifically, particles having an average particle size of 20 to 300 μm, such as surface-oxidized or unoxidized metals such as iron, nickel, cobalt, manganese, chromium, and rare earths, and alloys or oxides thereof are used.

Those in which a resin such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin or a polyester resin is adhered or coated on the surface of the carrier particles is preferably used.

The toner of the present invention may further contain a magnetic material to be used as a magnetic toner. In this case, the magnetic material also serves as a coloring agent. Magnetic materials contained in the magnetic toner include iron oxides such as magnetite, maghemite, and ferrite; metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, and zinc. Antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium,
Alloys with metals such as titanium, tungsten, vanadium and mixtures thereof may be mentioned.

The number average particle diameter of these magnetic materials is 2 μm.
Below, those having a thickness of 0.1 to 0.5 μm are preferable. The amount contained in the toner is about 20 to 200 parts by weight with respect to 100 parts by weight of the binder resin, and particularly preferably 40 to 150 parts by weight with respect to 100 parts by weight of the binder resin component.

Examples of the non-magnetic colorant that can be used in the toner of the present invention include pigments and dyes. Examples of pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, red iron oxide, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient for maintaining the optical density of the fixed image, and the amount added is 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the binder resin. . Examples of the dye include azo dyes, anthraquinone dyes,
Examples of the xanthene dyes and methine dyes are 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the binder resin.

To prepare the toner for developing an electrostatic charge image of the present invention, a binder resin, a wax, a pigment as a colorant, a dye or a magnetic material, a charge control agent, and other additives, if necessary, are used. After thoroughly mixing with a mixer such as a ball mill, melt kneading with a heat kneader such as a heating roll, kneader, or extruder to make the resins compatible with each other, and disperse the wax, pigment, dye, and magnetic material in the resin. Alternatively, the toner can be obtained by dissolving, cooling and solidifying, and then pulverizing and classifying.

Further, if desired, desired additives may be sufficiently mixed with toner particles by a mixer such as a Henschel mixer to obtain a toner.

Further, in producing the toner, it is preferable to disperse the wax finely and uniformly in the binder resin in order to obtain the DSC curve which is the feature of the present invention. When the dispersed state is non-uniform, dispersed with large particles, or free wax is present, a desirable DSC curve may not be exhibited, and the toner performance may not be fully exhibited. There is. In order to obtain such a dispersed state, it is preferable to carry out the melt kneading in the next step using a melt-kneaded mixture of wax and a binder resin before the melt-kneading at the time of producing the toner. Further, it is preferable that the binder resin is dissolved in a solvent, the wax is wet-mixed in the solvent, the solvent is removed, the product is dried and crushed, and then the wax is used in the melt-kneading step. It is also preferable to raise the solvent temperature when mixing the wax and mix the wax in the molten state with the binder resin.

[0106]

EXAMPLES The present invention will be described in more detail below with reference to production examples and examples.

Production Example 1 styrene 70 parts by weight n-butyl acrylate 26 parts by weight divinylbenzene 0.5 parts by weight 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane 0.2 parts by weight di -Tert-butyl peroxide 0.8 parts by weight

The above raw materials were dropped into 200 parts by weight of xylene in a reaction vessel over 4 hours, and solution polymerization was further carried out under reflux of xylene. After the completion of the polymerization, 4 parts by weight of wax B and 2 parts by weight of wax E shown in Table 1 were added to the xylene solution, and the mixture was mixed with the styrene copolymer component while dissolving the wax at the reflux temperature. 100 mmH
Binder resin composition No. 1 consisting of a styrene-n-butyl acrylate copolymer having a crosslinked structure and a wax was obtained by distilling off xylene while reducing the pressure to g. Got 1. The obtained binder resin composition was dried, pulverized and used in the melt-kneading step described later.

The styrene-n-butyl acrylate copolymer having a crosslinked structure used as a binder resin before adding wax has a glass transition point of 60 ° C. and contains 5% by weight of THF insoluble matter. The THF-soluble component has a weight average molecular weight (Mw) of 180,000, a number average molecular weight (Mn) of 9,200, and an Mw / Mn of 19.
6 and the main peak in the molecular weight distribution is 1
6000, and the sub-peak was at a molecular weight of 240,000.

[0110]

[Table 1]

The polymethylene wax is a Fischer-Tropsch wax synthesized by the Arge process using carbon monoxide and hydrogen derived from natural gas as raw materials to obtain waxes A, B and C by vacuum distillation, and by fractional crystallization. Waxes D, E and F were obtained.

Binder Resin Composition Nos. Nos. 1 to 16 were produced in the same manner as in Production Example 1 except that the waxes were changed as shown in Table 2. 2 to 16 were prepared.

[0113]

[Table 2]

Example 1 Binder Resin Composition No. 1 100 parts by weight Magnetite (number average diameter 0.2 μ) 90 parts by weight Triphenylmethane compound (positive charge control agent) 2 parts by weight

The above materials were premixed by a Henschel mixer and then kneaded by a twin-screw kneading extruder set at 110 ° C. The obtained kneaded product is cooled and roughly crushed with a cutter mill, then finely crushed with a crusher using a jet stream, and classified with a multi-division classifier utilizing the Coanda effect to obtain a weight average diameter of 7. 0 μm positively chargeable magnetic toner particles were obtained.
To 100 parts by weight of the magnetic toner particles, 0.9 parts by weight of positively-charged hydrophobic silica was externally added and mixed by a Henschel mixer, and magnetic toner No. It was set to 1. This magnetic toner No. 1 DSC
The characteristics are shown in Table 3.

Examples 2 to 6 Binder resin composition No. Example 1 except using 2 to 6
Magnetic toner No. 2 to 6 were obtained. Magnetic toner No. Table 3 shows the DSC characteristics of Nos. 2 to 6.

Comparative Examples 1 to 10 Binder Resin Composition No. In the same manner as in Example 1 except that the magnetic toner Nos. 7 to 16 were obtained. Magnetic toner No. Table 3 shows the DSC characteristics of Nos. 7 to 16.

[0118]

[Table 3]

A fixing test, an offset test, a development endurance test, a winding test, and an image endurance test were conducted using the toners of Examples 1 to 6 and Comparative Examples 1 to 10. The results are shown in Table 4. With the toner of Example 1, good fixing characteristics and developing characteristics were obtained, and there were no traces of separation nails on the image due to winding of the fixing roller and stains on the original when the copied image was used as the original.

Fixability and Offset Test Electrophotographic copying machine NP-6030 (manufactured by Canon Inc.)
An unfixed image was obtained by a modified machine in which the fixing device of 1 was removed.
On the other hand, the taken-out fixing device was modified to perform a fixing property test of an unfixed image and an offset resistance test as a temperature roller variable fixing device.

The nip of the external fixing device is set to 5.0 mm and the process speed is set to 180 mm / sec.
The unfixed image is fixed at each temperature by controlling the temperature in the temperature range of 50 ° C at intervals of 5 ° C.
The point where the image density reduction rate before and after the rubbing was 10% or less was determined as the fixing start temperature by rubbing with a sillbon paper applied with m2 weight 5 times.

Regarding the offset, the low temperature offset free starting point was the temperature at which the image was not contaminated by toner, and the highest temperature without offset was the high temperature offset free ending point.

Development durability test Electrophotographic copying machine NP-6030 (manufactured by Canon Inc.)
Using, the image density stability of the copy image was evaluated by intermittently printing an image of 20,000 sheets on an A4 size transfer paper with an A4 size image area ratio of 6% at a process speed of 200 mm / sec. In the endurance mode, two sheets were continuously imaged every 15 seconds, the operation was continued for 8 hours, and the operation was continued for 16 hours. A: There is no density unevenness on the image, and the density is stable and good. B: There is no density unevenness on the image, but there is a slight decrease in density. C: There is uneven density on the image, and there is a decrease in density.

Fixing roller winding test Electrophotographic copying machine NP-6030 (manufactured by Canon Inc.)
With A3 size and 100% of the image area ratio
20 sheets were continuously printed on 3 sizes of transfer paper, and the winding property was evaluated by the presence / absence of the fixing and discharging separation claw marks.
If the fixing roller is not wound tightly, the transfer paper will be peeled off from the fixing roller by relying on the separating claws, so that claw marks are generated on the image. If the releasability from the fixing roller is good, it can be easily peeled off by the separating claw, so that no nail mark is generated. A: Separation claw marks are not generated in the solid image. B: Separation claw marks are slightly generated on the solid image. C: Separation claw marks are generated on the solid image.

Original smear test Electrophotographic copying machine NP-6030 (manufactured by Canon Inc.)
The image smearing when the copied image was developed was tested by using the auto document feeder of. 40 sheets of A4 size image having an image area ratio of 6% obtained in the developability durability test were continuously passed through an auto document feeder five times to evaluate the stain on the original. A: The original did not stain. B: The document was slightly soiled. C: The original is stained.

[0126]

[Table 4]

The toner of Comparative Example 1 was inferior to the toner of Example 1 in high temperature offset resistance, a slight decrease in image density was observed when many sheets were used, and separation nail marks were observed in the solid black image area. .

The toner of Comparative Example 2 was inferior in fixing property to the toner of Example 1, and some stains were generated on the original in the original stain test.

The toners of Comparative Examples 3 to 5 and 9 were particularly inferior to the toner of Example 1 in the winding resistance.

The toners of Comparative Examples 6 to 8 and 10 were inferior in fixability and low temperature offset resistance to the toner of Example 1.

[0131]

The toner of the present invention contains a wax,
It has excellent low-temperature fixability, high-temperature offset resistance, multi-sheet durability, and wrapping resistance due to its specific heat absorption characteristics.

[Brief description of drawings]

FIG. 1 is a diagram showing a DSC endothermic curve of a toner and a differential curve of the DSC endothermic curve.

FIG. 2 is a diagram for explaining each parameter of a DSC endothermic characteristic of toner.

FIG. 3 is a diagram for explaining a height of an endothermic peak in a DSC endothermic curve of toner.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Fujikawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-8-234480 (JP, A) (58) Survey Fields (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (15)

(57) [Claims] 1. A least a binder resin, a toner for developing electrostatic images having a colorant and a wax, the toner is the temperature 3 as measured by differential scanning calorimetry
In the DSC endothermic curve at the time of temperature rise in the range of 0 to 150 ° C, the maximum endothermic peak (P1) is at a temperature of 70 to 90 ° C, and the sub-endothermic peak or the show at a temperature of 85 to 115 ° C.
It has a rudder (P2), and the height of P1 from the baseline is Hp1, the baseline
Hp1 and Hp2 when the height of P2 from
And Hp2 / Hp1 ≦ 0.7 are satisfied and P2 is a peak instead of a shoulder, P
Baseline of the lowest valley (V) between 1 and P2
When the height from is Hv, Hp2 and Hv are Hv
/Hp2≧0.5, and the first maximum value (Max1) on the lowest temperature side in the differential curve of the DSC endothermic curve is the temperature (T1) 50 to 65 ° C.
The second maximum value (Max2) on the low temperature side is at the temperature (T2) of 65 to 85 ° C., and the minimum value (Min1) on the highest temperature side is the temperature on the differential curve of the DSC endothermic curve. (T3) An electrostatic charge image developing toner having a temperature of 95 ° C. or higher. 2. In the differential curve of the DSC endothermic curve of the toner, the first maximum value (Max1) is at a temperature (T1) of 50 to 50.
The toner of claim 1, which is at 60 ° C. 3. In the differential curve of the DSC endothermic curve of the toner, the temperature (T3) of the first minimum value (Min1) and the second minimum value (Min1)
3. The toner according to claim 1, wherein the temperature (T2) having the maximum value (Max2) of 1 satisfies the following condition T3-T2 ≧ 25 ° C. 4. In the toner DSC endothermic curve, the maximum endothermic peak (P1) is at a temperature of 70 to 85 ° C., and in the differential curve of the toner DSC endothermic curve, the second maximum value (Max2) is the temperature (T2). The toner according to claim 1, wherein the toner has a minimum value (Min1) of 65 to 80 ° C. and a temperature (T3) of 100 ° C. or more. 5. In the differential curve of the DSC endothermic curve of the toner, the temperature (T3) of the first minimum value (Min1) and the second minimum value (Min1)
The toner (1) according to any one of claims 1 to 4 , wherein the temperature (T2) of the maximum value (Max2) of the following condition T3−T2 ≧ 30 ° C. is satisfied. 6. The differential curve of the DSC endothermic curve of the toner, or the toner of claims 1 to 5 local minimum (Min1) is in a temperature 100 to 120 ° C.. 7. A wax may be any toner of claims 1 to 6 is contained 1 to 20 parts by weight of the binder resin 100 parts by weight per. 8. wax, either toner of claims 1 to 6 is contained 1 to 10 parts by weight per 100 parts by weight of the binder resin. 9. The wax has a number average molecular weight (Mn) of 2
The toner according to any one of claims 1 to 8 , wherein the toner has an Mw / Mn of 3.0 or less and is 0.00 to 5,000. 10. The wax has a Mn of 250 to 2000.
The toner according to claim 9, which is 11. The wax has a Mn of 300 to 1500.
The toner according to claim 9, which is 12. wax, either toner of claims 1 to 11, which is a polymethylene wax. 13. The wax has a Mn of 200 to 600, a polymethylene wax (i) of Mw / Mn of 1.2 to 2.1, and an Mn of 700 to 1500, and Mw / Mw /
The toner according to claim 12, which is a mixed wax with a polymethylene wax having Mn of 1.2 to 2.0. 14. The toner according to claim 13 , wherein the wax is a mixed wax of polymethylene wax (i) and polymethylene wax (ii) in a weight ratio of 9: 1 to 3: 7. 15. The toner according to claim 13 , wherein the wax is a mixed wax of polymethylene wax (i) and polymethylene wax (ii) in a weight ratio of 8: 2 to 3: 7.