JP2012163606A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner having excellent durable stability and low-temperature fixability in high speed printing without affecting long-term preservation stability.SOLUTION: The toner comprises toner particles, each of which contains binder resin and a coloring agent. In a DSC curve measured by a differential scanning calorimeter, the toner has the glass-transition temperature which is 50.0°C or more and 70.0°C or less, has the maximum value in a temperature range of 110.0°C or more and 145.0°C or less, and also has the minimum value in a temperature range of 150.0°C or more and 200.0°C or less. The toner contains 20.0 mass% or more and 50.0 mass% or less of tetrahydrofuran (THF) insoluble matter derived from the binder resin. An extraction residual which is made through Soxhlet extraction using tetrahydrofuran (THF) for 16 hours has the maximum value in a temperature range 110.0°C or more and 150.0°C or less in the DSC curve measured by the differential scanning calorimeter.

Description

  The present invention relates to an electrophotographic image forming method for developing an electrostatic charge image, and a toner used in a toner jet.

Image forming apparatuses using electrophotography have been sought more rapidly and with higher reliability, and light printing that requires higher reliability (from document editing to copying and bookbinding on a personal computer) It has begun to be used for print-on-demand applications capable of printing a small amount of varieties. On the other hand, there is a high demand for energy saving of the apparatus, and excellent low-temperature fixing performance of toner is strongly demanded in order to meet these demands. Generally, the low-temperature fixing performance is related to the viscosity of the toner, and a property of being quickly melted by heat at the time of fixing (so-called sharp melt property) is required. However, the toner satisfying such a low-temperature fixing performance is weak against external stresses such as stirring in the developing device and temperature rise of the main body, and problems such as deterioration in durability due to embedding of external additives and adhesion to members. It is easy to produce. That is, it is very difficult to achieve both high speed and low temperature fixing performance, especially in applications where reliability is strictly required, such as for light printing.
In general, the temperature inside the image forming apparatus is designed to be lower than the glass transition temperature of the toner. However, it becomes difficult to keep the temperature inside the apparatus low as the size and speed increase. It is coming. Furthermore, the glass transition temperature may be exceeded instantaneously.
In Patent Document 1, two types of resins with different softening points are used as the main components of the binder resin, and low-melting crystalline polyester is added thereto to improve low-temperature fixability while maintaining offset resistance and blocking resistance. Proposals that can be made have been made. However, in such a case, not only the compatibility with the binder resin is increased and the anti-blocking property and the anti-offset property are deteriorated, but when used in a higher-speed image forming apparatus, particularly in an image having a low image ratio. When printing is performed, toner deterioration and development sleeve contamination are likely to occur.
On the other hand, Patent Document 2 has been proposed as a method for solving the problem of compatibility of such crystalline substances. That is, by using a block polyester composed of a crystalline block and an amorphous block as a binder resin, it is resistant to mechanical stress and can secure a sufficient fixing property (fixing strength) in a wide temperature range. Proposals that can provide toner have been made. However, even in such a case, it is necessary to lower the melting point of the crystalline block in order to cope with higher speed and energy saving, and it is very difficult to keep the crystalline state without being compatible in the resin. is there.
Further, Patent Document 3 proposes that a coating layer formed by recrystallization is formed at the time of fixing and a scratch resistance is improved by using a binder resin in which a crystalline polyester and an amorphous polyester are used in combination. Also in this case, since the binder resin becomes compatible during the toner manufacturing process, no exothermic peak is detected from the toner. Therefore, there is room for improvement in order to achieve both higher speed and energy saving.
Further, Patent Document 4 proposes a toner using a partially crystalline resin. Even in such a case, a fixed effect is exhibited, but there is still room for improvement in order to cope with further increase in speed. Moreover, it is important to improve the dispersibility of other raw materials in order to keep the quality stable over a long period of time. In particular, in the manufacturing method of the pulverized toner, the balance is maintained by optimizing the kneading process, but it is extremely difficult to maintain the crystalline state of the crystalline substance as described above even after kneading.
As described above, there are many technical problems to achieve both energy saving and speedup, and there is room for improvement.

Japanese Patent No. 3963673 JP 2004-191921 A Japanese Patent Laying-Open No. 2005-189808 Japanese Patent No. 2988703

The present invention provides a toner that solves the above problems.
The present invention provides a toner that has good durability stability and low-temperature fixability in high-speed printing without affecting long-term storage stability.

  The present invention relates to a toner having toner particles containing a binder resin and a colorant, and the toner has a glass transition temperature of 50.0 ° C. or higher and 70.0 ° C. in a DSC curve measured by a differential scanning calorimeter. The toner has a maximum value at a temperature of 110.0 ° C. or more and 145.0 ° C. or less, a minimum value at a temperature of 150.0 ° C. or more and 200.0 ° C. or less, and the toner is derived from a binder resin. An extract residue containing 20.0 mass% or more and 50.0 mass% or less of insoluble content of tetrahydrofuran (THF) and extracted by Soxhlet extraction with tetrahydrofuran (THF) for 16 hours is a DSC measured by a differential scanning calorimeter. The present invention relates to a toner having a maximum value in a curve at a temperature of 110.0 ° C. or higher and 150.0 ° C. or lower.

  According to the present invention, a toner having good durability stability and low-temperature fixability in high-speed printing can be obtained without affecting long-term storage stability.

It is a DSC curve of the binder resin 1 used for the Example of this invention. 2 is a DSC curve of the toner (T-1) of Example 1 of the present invention.

In order to obtain a toner having good durability and stability during high-speed printing (particularly an image with a low printing rate), it is necessary to increase the mechanical strength of the toner. In general, as a technique for increasing the mechanical strength of a toner, the direction of increasing the viscosity of the binder resin, such as increasing the molecular weight of the binder resin, which is the main component of the toner, or containing an ultra-high molecular weight component called gel is known. It has been. However, the response to increasing the viscosity of the binder resin (so-called toner hardening direction) has a great influence on the low-temperature fixability. Furthermore, in order to obtain a toner that does not adhere to a member such as a developing sleeve, it is necessary to eliminate the adhering component (mainly the low molecular weight component of the binder resin). Since the binder resin generally has a distribution in molecular weight, known methods for eliminating low molecular weight components include increasing the overall molecular weight and sharpening the distribution. However, this method also has a great influence on the low-temperature fixability.
On the other hand, in order to obtain a toner having good low-temperature fixability, it is necessary to quickly melt the toner in a short time passing through the nip of the fixing device. Generally, as a technique for rapidly melting toner, it is known to control the melting characteristics of a binder resin that is a main component of the toner. However, when the melting characteristics of the binder resin itself are controlled, the influence on the offset resistance at high temperatures, the offset characteristics at low temperatures, and the blocking resistance is very large.
Therefore, various methods for controlling the melting property of the binder resin by a plastic effect using a fixing aid (additives such as low melting point wax and crystalline polyester) have been studied. Since the addition of another substance as described above is largely due to the compatibility with the binder resin, the improvement of the low-temperature fixability and the resistance to offset and blocking at high temperatures are There are often trade-offs.
As described above, technical hurdles are extremely high in order to achieve both durability stability and low-temperature fixability at a high level. As a result of investigations to solve the above-mentioned trade-off items, the present inventors have found that the toner is very strong until it passes through the fixing device, and rapidly melts as soon as it receives heat from fixing. I came up with the idea that the above contradiction could be resolved.
That is, the toner of the present invention has a glass transition temperature of 50.0 ° C. or higher and 70.0 ° C. or lower and a maximum value of 110.0 ° C. or higher and 145.0 ° C. or lower in a DSC curve measured by a differential scanning calorimeter. It has a minimum value at a temperature of 150.0 ° C. or higher and 200.0 ° C. or lower.
In general, toner undergoes a phase transition from a glass state to a supercooled liquid state at a glass transition temperature, and its melting characteristics slightly change. Thereafter, since the movement of the polymer in the toner becomes active according to the temperature, the melting characteristics of the toner are lowered according to the temperature. This decrease in melting characteristics is closely related to fixability, but it is difficult to greatly improve fixability because melting characteristics at temperatures exceeding the glass transition temperature are related to reduced durability and contamination of components. It becomes. As a result of the study by the present inventors, in the DSC curve measured by the differential scanning calorimeter, the glass transition temperature is 50.0 ° C. or higher and 70.0 ° C. or lower, and the temperature is 110.0 ° C. or higher and 145.0 ° C. or lower. It has been found that a toner having a maximum value and having a minimum value at a temperature of 150.0 ° C. to 200.0 ° C. can achieve both durability and fixability.
The presence of a maximum value in the DSC curve measured by the differential scanning calorimeter indicates that recrystallization tends to proceed rapidly in the process of raising the temperature of the toner. In general, when a crystalline substance such as crystalline polyester is dispersed in a binder resin or the like, recrystallization does not occur unless annealing or the like is performed for a long time at a temperature lower than the melting point. It has been. Further, when a highly crystalline substance such as wax is dispersed in the binder resin, it is known that crystallization occurs in the cooling process, so that it already exists in a crystalline state in the toner at normal temperature. In contrast, the toner of the present invention is in an amorphous state up to the glass transition temperature, but is characterized in that crystallization proceeds rapidly as the molecular motion becomes active. In addition, having a minimum value immediately after recrystallization occurs makes it possible to achieve a rapid viscosity drop. Furthermore, the fact that crystals are easily formed means that the orientation of the binder resin in the toner is likely to occur. In general, since the orientation of the resin is likely to occur when the molecular weight is low, a low molecular weight substance that is disadvantageous for adhesion of the member is preferentially crystallized. Therefore, it has become clear that recrystallization causes suppression of member adhesion.
When the glass transition temperature is less than 50.0 ° C., the binder resin in the toner starts to move at a temperature close to room temperature. In such a case, the storage stability of the toner is deteriorated. Further, the durability stability is deteriorated, and the image density is lowered and the developing sleeve is contaminated.
On the other hand, when the glass transition temperature is higher than 70.0 ° C., it indicates that the binder resin in the toner starts moving slowly, and in such a case, the low-temperature fixability deteriorates.
Moreover, when the maximum value is less than 110.0 ° C., it indicates that the crystallization proceeds rapidly after the glass transition temperature. When the crystallization speed is high, the compatibility with other toner raw materials tends to deteriorate, and the durability developability under high temperature and high humidity is lowered. On the other hand, when the maximum value is higher than 145.0 ° C., it indicates that the progress of crystallization after the glass transition temperature is slow. When crystallization is slow, it means that the binder resin starts to move in the toner to a high temperature. Therefore, toner deterioration and member adhesion during durability are likely to occur.
Furthermore, the present invention is characterized in that a minimum value exists at a temperature of 150.0 ° C. or more and 200.0 ° C. or less in a DSC curve measured by a differential scanning calorimeter. When the minimum value is less than 150.0 ° C., the melting point of the crystalline part obtained by the orientation of the binder resin present in the toner is low, which is advantageous for the fixability. However, it is generally known that a crystalline substance has a lower melting point when its orientation is weak and its crystallinity is low. As a result, the orientation of the binder resin in the toner is performed slowly, and as a result, toner deterioration and member adhesion during durability tend to occur.
On the other hand, when the minimum value is higher than 200.0 ° C., the orientation tends to be strong and the crystallinity tends to be high. Therefore, not only the low-temperature fixability is deteriorated but also the familiarity with other toner raw materials tends to be deteriorated, and the durability developability under high temperature and high humidity is lowered.

Furthermore, it has been clarified that the durability stability can be drastically improved by incorporating a part of the binder resin having such characteristics into the gel.
That is, the toner of the present invention contains 20.0% by mass or more and 50.0% by mass or less of tetrahydrofuran (THF) insoluble matter derived from the binder resin, and is extracted when extracted by Soxhlet extraction with tetrahydrofuran (THF) for 16 hours. The residue has a maximum value at a temperature of 110.0 ° C. or more and 150.0 ° C. or less in a DSC curve measured by a differential scanning calorimeter.
It is known that a polymer component generally called gel is effective in improving durability and suppressing high temperature offset. As a result of studies by the present inventors, it has been found that durability stability can be improved by imparting the recrystallization property described above to the gel.
When the THF-insoluble content derived from the binder resin in the toner is less than 20.0% by mass, high temperature offset tends to occur. Further, since the durability strength of the toner is lowered, there is a tendency that the durability is lowered particularly when the durability is carried out for a long time with an image having a low printing ratio. On the other hand, when the THF-insoluble content is more than 50.0% by mass, the low-temperature fixability is lowered.
On the other hand, when the maximum value of the extraction residue when extracted for 16 hours by Soxhlet extraction with tetrahydrofuran (THF) is less than 110.0 ° C., it indicates that the crystallization proceeds rapidly. When the crystallization speed is high, it tends to be difficult to blend with other toner raw materials, and the durability developability under high temperature and high humidity is lowered. On the other hand, when the maximum value is higher than 150.0 ° C., it indicates that the progress of crystallization after the glass transition temperature is slow. When crystallization is slow, it means that the binder resin starts to move in the toner to a high temperature. Therefore, toner deterioration and member adhesion during durability are likely to occur.
As described above, both the low-temperature fixability and the durability can be achieved by controlling the structure of the binder resin that occupies most of the toner. In other words, by controlling the speed at which a part of the binder resin is recrystallized, it is possible to obtain a toner that is very strong until it passes through the fixing device and melts rapidly upon receiving heat from fixing. It becomes possible.

The above characteristics of the toner of the present invention can be imparted, for example, by including (1) a binder resin (A) and a binder resin (B) described later as the binder resin of the toner. is there.
The toner of the present invention may be used by mixing the binder resin (A) and the binder resin (B) having different softening points in that the portion to be recrystallized is effectively finely dispersed in the toner. More preferred. When these two types of resins are used in combination, the mass ratio of the binder resin (A): binder resin (B) is preferably 20:80 to 60:40. If the ratio is within this range, the dispersibility of the recrystallized crystalline part is particularly good, and the tendency of developing sleeve contamination tends to be good, and the low-temperature fixability is improved.
The binder resin (A) used in the present invention preferably has a softening point (Tm) of 90.0 ° C. or higher and 105.0 ° C. or lower, and the binder resin (B) has a softening point (Tm) of 120. It is preferably 0 ° C. or higher and 155.0 ° C. or lower. Further, the difference (ΔTm) in softening point between the two types of binder resins (A) and (B) is particularly preferably from 15.0 ° C. to 50.0 ° C. in order to improve dispersibility.

The binder resin (A) has a glass transition temperature of 50.0 ° C. or higher and 60.0 ° C. or lower and a maximum of 110.0 ° C. or higher and 145.0 ° C. or lower in a DSC curve measured by a differential scanning calorimeter. It is preferable that the endothermic amount of the maximum value is 3.0 J / g or more and 15.0 J / g or less, and the temperature has a minimum value of 150.0 ° C. or more and 200.0 ° C. or less.
When the glass transition temperature is less than 50.0 ° C., it indicates that the binder resin in the toner starts to move at a temperature close to room temperature. In such a case, the storage stability of the toner tends to decrease. Further, the durability stability is deteriorated, and there is a high possibility that the image density is lowered and the developing sleeve is contaminated. On the other hand, when the glass transition temperature is higher than 60.0 ° C., it indicates that the binder resin in the toner starts moving slowly, and in such a case, the low-temperature fixability tends to be lowered.
Moreover, when the maximum value is less than 110.0 ° C., it indicates that the crystallization proceeds rapidly after the glass transition temperature. When the crystallization speed is high, it tends to be difficult to blend with other toner raw materials, and the durability developability under high temperature and high humidity tends to be lowered. On the other hand, when the maximum value is higher than 145.0 ° C., it indicates that the progress of crystallization after the glass transition temperature is slow. When crystallization is slow, it means that the binder resin starts to move in the toner to a high temperature. Therefore, there is a possibility that toner deterioration and member adhesion during the endurance easily occur.
Further, when the maximum endothermic amount is less than 3.0 J / g, it indicates that the crystallinity is low, and in such a case, toner deterioration may occur during the durability. On the other hand, when the endothermic amount of the maximum value is larger than 15.0 J / g, the crystallinity is very strong. In such a case, the toner tends to be less compatible with other toner raw materials, and the durability developability under high temperature and high humidity tends to decrease.
Further, when the minimum value is less than 150.0 ° C., the melting point of the crystalline part obtained by the orientation of the binder resin present in the toner is low, which is advantageous for the fixability. However, since it is known that the melting point decreases when the orientation is weak and the crystallinity is low, it means that the movement of the binder resin in the toner continues to a high temperature. As a result, there is a tendency that toner deterioration and member adhesion during the endurance easily occur. On the other hand, when the minimum value is higher than 200.0 ° C., the orientation tends to be strong and the crystallinity tends to be high. For this reason, not only the low-temperature fixability is deteriorated, but also tends to be less compatible with other toner raw materials, and the durability developability under high temperature and high humidity is reduced.

As the binder resin (A) used in the present invention, a polyester resin is preferable in that a part of the molecule is oriented to impart crystallinity, and among these, a linear polyester is more preferable. The components of the linear polyester resin particularly preferably used in the present invention are as follows.
Examples of the divalent acid component include the following dicarboxylic acids or derivatives thereof. Benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or their anhydrides or lower alkyl esters thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or their anhydrides or lower thereof Alkyl esters; alkenyl succinic acids or alkyl succinic acids such as n-dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides thereof or lower alkyl esters thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid Or its anhydride or its lower alkyl ester.
The present invention is characterized in that the crystallization speed is controlled by orienting a part of the polymer chain of the binder resin. Therefore, an aromatic dicarboxylic acid that has a solid planar structure and is abundant in electrons delocalized by the π-electron system, and is easily molecularly oriented by π-π interaction, is preferable. Particularly preferred are terephthalic acid and isophthalic acid, which are easily linear. The content of the aromatic dicarboxylic acid is preferably 50 mol% or more, more preferably 70 mol% or more, in 100 mol% of the acid component constituting the polyester resin. Within this range, it is preferable in terms of easy control of the crystallization rate.
The following are mentioned as a bivalent alcohol component. Ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5 -Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol (CHDM), hydrogenation Bisphenol A, bisphenol represented by formula (1) and derivatives thereof: and diols represented by formula (2).

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ、ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０乃至１０である。）

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

Among these, aliphatic straight-chain alcohols having 2 to 6 carbon atoms that can easily form a straight-chain structure are preferable from the viewpoint of controlling the crystallization speed by orienting a part of the polymer chain. For this purpose, neopentyl glycol, 2-methyl-1,3-propanediol, 1,2-propanediol and the like having a substituent in the side chain that can have a steric crystal structure while taking a linear structure Is particularly preferred. These alcohol components are preferably 20 to 50 mol% and more preferably 25 to 40 mol% in 100 mol% of all alcohol components constituting the polyester resin.
The polyester resin used in the present invention includes a monovalent carboxylic acid compound, a monovalent alcohol compound, a trivalent or higher carboxylic acid compound, in addition to the above-mentioned divalent carboxylic acid compound and divalent alcohol compound. You may contain the alcohol compound more than a valence as a structural component. Examples of the monovalent carboxylic acid compound include aromatic carboxylic acids having 30 or less carbon atoms such as benzoic acid and p-methylbenzoic acid, and aliphatic carboxylic acids having 30 or less carbon atoms such as stearic acid and behenic acid. .
Examples of monovalent alcohol compounds include aromatic alcohols having 30 or less carbon atoms such as benzyl alcohol, and aliphatic alcohols having 30 or less carbon atoms such as lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol. It is done.
Although it does not restrict | limit especially as a trivalent or more carboxylic acid compound, A trimellitic acid, trimellitic anhydride, pyromellitic acid, etc. are mentioned. Examples of the trivalent or higher alcohol compound include trimethylolpropane, pentaerythritol, and glycerin.

About the manufacturing method of the said polyester resin, it does not restrict | limit in particular, A well-known method can be used. For example, the aforementioned carboxylic acid compound and alcohol compound are charged together and polymerized through an esterification reaction or a transesterification reaction and a condensation reaction to produce a polyester resin. Although it is not particularly necessary to polymerize the polyester resin, for example, a polymerization catalyst such as titanium tetrabutoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, or germanium dioxide should be used. Can do. The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C. or higher and 290 ° C. or lower.
Further, the binder resin (A) has at least one peak in a region having a molecular weight of 5000 or more and 10,000 or less in a molecular weight distribution measured by gel permeation chromatography (GPC) of a THF-soluble component, and has a molecular weight of 3000 The following area is preferably 20% or less with respect to the entire area. Furthermore, the ratio [Mw / Mn] of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 1 or more and 30 or less. When the peak is less than 5000, the tendency to decrease the blocking resistance is observed, and when the molecular weight exceeds 10,000, the fixability tends to decrease. On the other hand, when the area having a molecular weight of 3000 or less is larger than 20% with respect to the entire area, there is a tendency that the storage stability tends to be deteriorated because the amount of change in the molecule becomes large at a low temperature. Further, when the molecular weight distribution is very sharp such that [Mw / Mn] is less than 1, the high temperature offset tends to deteriorate, and when [Mw / Mn] is greater than 30, the low temperature fixability tends to decrease. is there.
Furthermore, the acid value of the binder resin (A) is preferably 5 mgKOH / g or more and 40 mgKOH / g or less. When the acid value is less than 5 mgKOH / g, the interaction with other raw materials (especially charge control agents such as organometallic complexes) tends to be reduced, and it may be difficult to maintain the crystalline state after toner formation. is there. When the acid value is larger than 50 mgKOH / g, it tends to be affected by moisture in a high-temperature and high-humidity environment, so that the durability developability under high-temperature and high-humidity tends to decrease.

On the other hand, the binder resin (B) used in the present invention preferably has a softening point of 120.0 ° C. or higher and 155.0 ° C. or lower. Within this range, the dispersibility of the recrystallized crystalline part is particularly good.
The binder resin (B) contains 20.0% by mass or more and 50.0% by mass or less of tetrahydrofuran (THF) insoluble matter, and the extraction residue when extracted by Soxhlet extraction with tetrahydrofuran (THF) for 16 hours is In the DSC curve measured by a differential scanning calorimeter, it is preferable that the temperature has a maximum value of 110.0 ° C. or more and 150.0 ° C. or less.
Furthermore, the binder resin (B) is preferably a hybrid resin in which a polyester unit (polyester structure) and a vinyl copolymer unit (vinyl copolymer structure) are chemically bonded. In general, a polyester unit with excellent low-temperature fixability and a vinyl copolymer unit with excellent high-temperature offset resistance and high compatibility with a release agent are included, and the molecular weight distribution of the two different binder resins. By arbitrarily controlling the physical properties, a gel structure having the above characteristics can be easily designed.
The mixing ratio of the polyester unit and the vinyl copolymer unit is preferably 50:50 to 90:10 mass ratio from the viewpoint of control of the crosslinked structure at the molecular level. When the amount of the polyester unit is less than 50% by mass, it is difficult to obtain low-temperature fixability. When the amount of the polyester unit is more than 90% by mass, the preservability and the dispersion state of the release agent are likely to occur.
The binder resin (B) has a peak molecular weight (Mp) by GPC of tetrahydrofuran (THF) soluble content of 5000 to 15000, a weight average molecular weight (Mw) of 5000 to 300000, a weight average molecular weight (Mw) and a number. The ratio [Mw / Mn] to the average molecular weight (Mn) is preferably 5-50. When Mp and Mw are small and the distribution is sharp, high temperature offset is likely to occur. Further, when Mp and Mw are large and the distribution is broad, the desired low-temperature fixability tends to be difficult to obtain. The glass transition temperature of the binder resin (B) is preferably 53.0 to 62.0 ° C. from the viewpoints of fixability and storage stability.
As the polyester unit that can be used as the binder resin (B) and the polyester unit in the case of the hybrid resin, known polyester resin components can be used as the binder resin for toner. Specifically, a polyester resin obtained by polycondensation of the following acid component / alcohol component can be used.
Divalent carboxylic acids include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride or derivatives thereof; oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid , Succinic acid, aliphatic dicarboxylic acids such as adipic acid and derivatives thereof, and acid anhydrides thereof.
Examples of the trivalent or higher polyvalent carboxylic acid or its anhydride include the following. 1,2,4-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides or lower alkyl esters thereof.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, Aliphatic diols such as 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol; hydrogenated bisphenol A; bisphenol derivatives represented by the following formula (A), and represented by the following formula (B) Diols are mentioned.

（式中、Ｒはエチレン又はプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）

(In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

  Examples of the trihydric or higher polyhydric alcohol include 1,2,3-propanetriol, trimethylolpropane, hexanetriol, and pentaerythritol. 1,2,4-benzenetricarboxylic acid and its anhydride are preferred.

As the vinyl copolymer unit when the binder resin (B) is a hybrid resin, a known vinyl resin component may be used as a binder resin for toner. Specific examples of the monomer for forming the vinyl copolymer unit include the following.
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- n-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene Styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene, p-nitrostyrene.
Acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, acrylate-n-butyl, acrylate isobutyl, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid Acrylic acid and acrylic acid esters such as 2-chloroethyl and phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid -n- Α-methylene aliphatic monocarboxylic acids such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Bisono esters or acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide.
Furthermore, the following are mentioned as a monomer of a vinyl-type copolymerization unit. Acrylic acid or methacrylic acid esters such as 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 2-hydroxylpropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) (Hexyl) A monomer having a hydroxyl group such as styrene.
In the vinyl copolymer unit, various monomers capable of vinyl polymerization can be used in combination as required. Examples of such monomers include the following. ethylene,
Unsaturated monoolefins such as propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate, vinyl propionate, Vinyl esters such as vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether: vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl N-vinyl compounds such as carbazole, N-vinylindole and N-vinylpyrrolidone; vinyl naphthalenes; and other compounds such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid. Japanese dibasic acids; unsaturated dibasic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride; methyl maleate half ester, ethyl half ester maleate, butyl maleate Unsaturated bases such as half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester Half ester of acid; unsaturated basic acid ester such as dimethylmaleic acid and dimethylfumaric acid; acid anhydride of α, β-unsaturated acid such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; Anhydrous of unsaturated acids and lower fatty acids A monomer having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.
The vinyl copolymer unit may be a polymer cross-linked with a cross-linkable monomer as exemplified below if necessary. The following are mentioned as a crosslinkable monomer. Aromatic divinyl compounds, diacrylate compounds linked by alkyl chains, diacrylate compounds linked by alkyl chains containing ether bonds, diacrylate compounds linked by chains containing aromatic groups and ether bonds, polyesters Type diacrylates and polyfunctional crosslinking agents.
Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene.
Examples of diacrylate compounds linked by an alkyl chain include the following. Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and more A compound in which acrylate is replaced with methacrylate.
The following are mentioned as diacrylate compounds connected with the alkyl chain containing an ether bond. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate.
Examples of diacrylate compounds connected by a chain containing an aromatic group and an ether bond include the following. Polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and acrylates of the above compounds Is replaced with methacrylate. As a polyester type diacrylate, a brand name MANDA (Nippon Kayaku) is mentioned.
The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallyl cyanurate, triallyl trimellitate .
These crosslinkable monomers can be used in an amount of 0.01% by mass to 10% by mass (more preferably 0.03% by mass to 5% by mass) with respect to 100% by mass of the other monomer components. Among these cross-linkable monomers, those which are preferably used from the viewpoint of fixability and offset resistance are aromatic divinyl compounds (particularly divinylbenzene) and divalent groups connected by a chain containing an aromatic group and an ether bond. Examples include acrylate compounds.
The vinyl copolymer unit may be a resin manufactured using a polymerization initiator. These initiators are preferably used in an amount of 0.05 to 2 parts by mass with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.
Examples of such a polymerization initiator include the following. 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-carbamoylazoisobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane), methyl ethyl ketone peroxide, Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α '-Bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tri Oil peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyi Propyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodeca Noate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate.
The hybrid resin more preferably used as the binder resin in the present invention is a resin in which a polyester unit and a vinyl copolymer unit are chemically bonded directly or indirectly. The hybrid resin can be obtained by reacting the raw material monomer of the polyester unit and the raw material monomer of the vinyl copolymer unit simultaneously or sequentially.
In addition to the binder resins (A) and (B), the binder resin of the toner of the present invention contains a binder resin constituting a known toner to the extent that the effects of the present invention are not impaired. Is possible.

The toner of the present invention may be a magnetic toner or a non-magnetic toner. When used as a magnetic toner, it is preferable to use magnetic iron oxide. As the magnetic iron oxide, iron oxides such as magnetite, maghemite, and ferrite are used.
In addition, for the purpose of improving the fine dispersibility in the toner particles, it is preferable that the magnetic iron oxide is subjected to a treatment for applying a shearing force to the slurry during production to loosen the magnetic iron oxide.
In the present invention, the amount of magnetic iron oxide contained in the toner is preferably 25% by mass or more and 45% by mass or less, more preferably 30% by mass or more and 45% by mass in the toner.
These magnetic materials have a magnetic force of 795.8 kA / m applied, a coercive force of 1.6 or more and 12.0 kA / m or less, a saturation magnetization of 50.0 or more and 200.0 Am ² / kg or less, (
More preferably, it is 50.0 or more and 100.0 Am ² / kg or less), and the remanent magnetization is preferably 2.0 or more and 20.0 Am ² / kg or less.
The magnetic properties of magnetic iron oxide can be measured using a vibration type magnetometer, for example, VSM P-1-10 (manufactured by Toei Kogyo Co., Ltd.).
In the case of a magnetic toner, the magnetic material can be used as a colorant. However, in the case of using it as a non-magnetic toner, carbon black and other conventionally known pigments and dyes are used as the colorant. More than seeds can be used.
The colorant is preferably from 0.1 to 100.0 parts by mass, more preferably from 0.5 to 90.0 parts by mass, with respect to 100.0 parts by mass of the resin component.

In the present invention, a release agent (wax) can be used as necessary in order to impart releasability to the toner. As the wax, it is easy to disperse in the toner and has high releasability. Therefore, hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax are preferred. If necessary, a small amount of one or two or more kinds of waxes may be used in combination. Examples include the following:
Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanate wax; and deoxidation Deoxidized part or all of fatty acid esters such as carnauba wax. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; long-chain alkyl alcohols; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscaprin Saturated fatty acid bisamides such as acid amide, ethylene bislauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl Unsaturated fatty acid amides such as dipinamide, N, N-dioleyl sebacic acid amide; aromatic bisamides such as m-xylenebisstearic acid amide, N, N-distearylisophthalic acid amide; calcium stearate, laur Fatty acid metal salts such as calcium phosphate, zinc stearate, magnesium stearate (generally referred to as metal soap); waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid A partially 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 a vegetable oil.
Examples of the release agent particularly preferably used in the present invention include aliphatic hydrocarbon waxes. Examples of such aliphatic hydrocarbon waxes include the following. Low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst under low pressure; alkylene polymer obtained by thermal decomposition of high molecular weight alkylene polymer; synthesis gas containing carbon monoxide and hydrogen Synthetic hydrocarbon waxes obtained from the distillation residue of hydrocarbons obtained from the aging method from the above, and synthetic hydrocarbon waxes obtained by hydrogenating them; press sweating method, solvent method, vacuum distillation of these aliphatic hydrocarbon waxes Sorted according to the use of and the fractional crystallization method.
Examples of the hydrocarbon as the matrix of the aliphatic hydrocarbon wax include the following. Carbonization synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system of two or more types) (for example, the Gintor method, Hydrocol method (using a fluidized catalyst bed)) Hydrogen compounds); hydrocarbons having up to about several hundred carbon atoms obtained by the age method (using an identified catalyst bed) in which a large amount of waxy hydrocarbons can be obtained; hydrocarbons obtained by polymerizing alkylene such as ethylene with a Ziegler catalyst. Among such hydrocarbons, in the present invention, it is preferable that the hydrocarbon is a linear hydrocarbon having a small number of branches and a small length and a long saturation. In particular, hydrocarbons synthesized by a method not based on polymerization of alkylene are also preferred from the molecular weight distribution.
Specific examples include the following. Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries), high wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals) ), Sazole H1, H2, C80, C105, C77 (Schumann Sazol), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiki Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark), Unicid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite), wood wax, beeswax, rice wax, candelilla wax Carnauba wax (available from Celerica NODA).
The timing of adding the release agent may be added at the time of melt-kneading during toner production or may be at the time of binder resin production, and is appropriately selected from existing methods. These release agents may be used alone or in combination.
The release agent is preferably added in an amount of 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the binder resin. If the amount is less than 1 part by mass, the desired release effect may not be obtained sufficiently. When the amount exceeds 20 parts by mass, dispersion in the toner particles is poor, and toner adhesion to the photoreceptor and surface contamination of the developing member and cleaning member tend to occur, and the toner image tends to deteriorate.

In the toner of the present invention, a charge control agent can be used in order to stabilize the charging property. Although the charge control agent varies depending on the type and physical properties of other toner particle constituent materials, it is generally preferable that the charge control agent is contained in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the binder resin. More preferably, it is contained in an amount of 0.1 to 5 parts by mass. As such a charge control agent, an organometallic complex or a chelate compound in which an acid group or a hydroxyl group present at the terminal of the binder resin used in the present invention easily interacts with a central metal is effective. Examples thereof include monoazo metal complexes; acetylacetone metal complexes; metal complexes or metal salts of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids.
As specific examples, Spiron Black TRH, T-77, T-95 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E-84, E-88, E-89 (Orient Chemical). Moreover, charge control resin can also be used together with the above-described charge control agent.

In the toner of the present invention, as an inorganic fine powder, a fluid having a high fluidity-imparting ability on the surface of toner particles and a BET specific surface area smaller than the number average particle diameter of primary particles is 50 m ² / g or more and 300 m ² / g or less. It is preferable to use a property improver. The fluidity improver can be used without particular limitation as long as the fluidity can be increased by externally adding the toner particles to the toner particles before and after the addition. For example, the following are mentioned. Hydrophobic-treated silica obtained by subjecting wet-process silica, fine-powder silica such as dry-process silica, surface treatment with silica, silane coupling agent, titanium coupling agent, or silicone oil. A preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is referred to as dry process silica or fumed silica. For example, the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen is utilized, and the reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl
Further, in this production process, a composite fine powder of silica and another metal oxide obtained by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound may be used. The particle diameter is preferably in the range of 0.001 μm to 2 μm as the number average particle diameter of the primary particle diameter, and particularly preferably silica fine powder in the range of 0.002 μm to 0.2 μm is used. Good to do.
Furthermore, it is preferable to use a hydrophobized silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halogen compound. In the hydrophobized silica fine powder, it is particularly preferable to treat the silica fine powder so that the degree of hydrophobicity titrated by the methanol titration test is in the range of 30 to 80.
As a hydrophobizing method, it is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with 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 include the following. Hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α- Chlorethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1 -Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyl Examples include rudisiloxane and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and one hydroxyl group in the terminal unit Si. These are used alone or in a mixture of two or more. The inorganic fine powder may be treated with silicone oil as described above, or may be treated in combination with the hydrophobic treatment.
As a preferable silicone oil, one having a viscosity at 25 ° C. of 30 mm ² / s or more and 1000 mm ² / s or less is used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil are particularly preferred.
Examples of the method for treating silicone oil include the following methods. A method in which silica fine powder treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer; a method in which silicone oil is sprayed on a silica fine powder as a base; A method in which after dissolving or dispersing oil, silica fine powder is added and mixed to remove the solvent. More preferably, the silicone oil-treated silica is heated to 200 ° C. or higher (more preferably 250 ° C. or higher) in an inert gas to stabilize the surface coating after the silicone oil treatment.
A preferred silane coupling agent is hexamethyldisilazane (HMDS). In the present invention, the silica is preferably treated by a method in which silica is treated with a coupling agent and then treated with silicone oil, or a method in which silica is treated with a coupling agent and silicone oil at the same time.
The inorganic fine powder is used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the toner particles.
Other external additives may be added to the toner of the present invention as necessary. For example, there are resin fine particles and inorganic fine particles that function as a charge auxiliary agent, conductivity imparting agent, fluidity imparting agent, anti-caking agent, release agent at the time of fixing with a heat roller, lubricant, and abrasive.
Examples of the lubricant include polyethylene fluoride powder, zinc stearate powder, and polyvinylidene fluoride powder. Of these, polyvinylidene fluoride powder is preferred. Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder. These external additives can be sufficiently mixed using a mixer such as a Henschel mixer to obtain the toner of the present invention.

The method for producing the toner of the present invention is not particularly limited, and a known method can be used. For example, binder resin and colorant, and other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer and a ball mill, and then melt-kneaded using a heat kneader such as a heating roll, kneader, extruder, After cooling and solidification, pulverization and classification are performed, and if necessary, desired additives are sufficiently mixed by a mixer such as a Henschel mixer to obtain the toner of the present invention. As the kneader used in the melt-kneading step, a twin-screw extruder is preferably used for the reason that continuous production is possible.

A method for measuring physical properties of the toner of the present invention is as follows. Examples described later are also based on this method.
<Maximum value, minimum value and endothermic value of DSC curve of toner, extraction residue and binder resin>
The maximum value, the minimum value, and the endothermic value of the DSC curves of the toner, the extraction residue, and the binder resin are measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 5 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. A specific heat change is obtained in this temperature rising process.
At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature (Tg) of the binder resin.
In this temperature raising process, in the temperature range of 30 ° C. to 250 ° C., the exothermic peak obtained immediately after the glass transition temperature (Tg) is the maximum value, and the endothermic peak obtained by further raising the temperature is the minimum value. On the other hand, the endothermic amount ΔH of the exothermic peak and endothermic peak can be obtained by obtaining the integrated value of the exothermic peak and endothermic peak.

<Measurement of THF-insoluble matter derived from binder resin>
The tetrahydrofuran (THF) insoluble matter derived from the binder resin in the present invention is measured by the following method.
About 2.0 g of toner is weighed (W1 g), put in a cylindrical filter paper (for example, No. 86R size 28 × 100 mm, manufactured by Toyo Filter Paper Co., Ltd.), subjected to a Soxhlet extractor, and extracted for 16 hours using 200 ml of THF as a solvent. At this time, the extraction is performed at a reflux rate such that the solvent extraction cycle is about once every 4 to 5 minutes. After the extraction is completed, the cylindrical filter paper is taken out and vacuum-dried at 40 ° C. for 8 hours, and the amount of the extraction residue is weighed (W2 g). Next, the weight of incinerated residual ash in the toner is determined (W3 g). The incineration residual ash content is obtained by the following procedure. About 2 g of a sample is placed in a 30 ml magnetic crucible that has been precisely weighed in advance, and weighed accurately, and the mass (Wag) of the sample is precisely weighed. The crucible is put in an electric furnace, heated at about 900 ° C. for about 3 hours, allowed to cool in the electric furnace, and allowed to cool in a desiccator for 1 hour or more at room temperature, and the mass of the crucible is precisely weighed. The incineration residual ash content (Wbg) is obtained from here.
(Wb / Wa) × 100 = Incineration residual ash content (mass%)
The mass (W3g = (Wb / Wa) × W1) of the incinerated residual ash of the sample is determined from this content.
The THF-insoluble content can be obtained from the following formula.
THF insoluble matter (mass%) = [W2-W3] / [W1-W3] × 100
In addition, the measurement of the THF-insoluble content of the sample not containing any component other than the resin such as the binder resin was performed by obtaining the extraction residue (W2g) in the same process as described above for the resin weighed in a predetermined amount (W1g). Desired. THF insoluble matter (mass%) = W2 / W1 × 100

<Measurement of molecular weight distribution by GPC of resin, etc.>
The column is stabilized in a heat chamber at 40 ° C., THF is flowed through the column at this temperature as a solvent at a flow rate of 1 ml / min, and about 100 μl of the THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is suitably used, and at least about 10 standard polystyrene samples are used. The detector uses an RI (refractive index) detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, a combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK, or manufactured by Tosoh Corporation TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ) be able to.
Moreover, a sample is produced as follows.
Place the sample in THF and leave it at 25 ° C. for several hours, then shake it well, mix well with THF (until the sample is no longer integrated), and let stand for more than 12 hours. At that time, the standing time in THF is set to 24 hours. After that, a sample processed filter (pore size 0.2 to 0.5 μm, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation) can be used) is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

<Measurement method of weight average particle diameter (D4)>
The weight average particle diameter (D4) of the toner is a precision particle size distribution measuring apparatus “Coulter Counter Multisizer by pore electrical resistance method equipped with an aperture tube of 100 μm.
3 ”(registered trademark, manufactured by Beckman Coulter) and attached dedicated software“ Beckman Coulter Multisizer 3 Version 3.51 ”(manufactured by Beckman Coulter, Inc.) for measurement condition setting and measurement data analysis, Measure with 25,000 effective measurement channels, analyze and calculate the measurement data.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the (1) round bottom beaker installed in the sample stand, the (5) aqueous electrolyte solution in which the toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to about 5%. The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measurement of acid value of binder resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of the pulverized binder resin sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. . Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Measurement of magnetic properties of magnetic iron oxide particles>
Using a vibrating sample magnetometer VSM-P7 manufactured by Toei Industry Co., Ltd., measurement is performed at a sample temperature of 25 ° C. and an external magnetic field of 795.8 kA / m.
<Measurement of number average particle size of primary particles such as magnetic iron oxide particles and inorganic fine powder>
The number average particle diameter of primary particles is determined by observing each particle with a scanning electron microscope (magnification 40000 times), measuring the ferret diameter of 200 particles, and determining the number average particle diameter. In this example, S-4700 (manufactured by Hitachi, Ltd.) was used as the scanning electron microscope.

Hereinafter, the present invention will be specifically described based on examples. However, this does not limit the embodiment of the present invention. Note that “parts” and “%” in the following formulations are based on mass unless otherwise specified.

<Example of production of binder resin 1>
-95 mol part of terephthalic acid-5 mol part of fumaric acid-70 mol part of ethylene glycol-30 mol part of neopentyl glycol The above polyester monomer is charged into a 5-liter autoclave together with an esterification catalyst. A reflux condenser, a water separator, an N ₂ gas introduction tube, a thermometer, and a stirring device were attached thereto, and a polycondensation reaction was performed at 230 ° C. while introducing N ₂ gas into the autoclave. The reaction time was adjusted so that the desired softening point was obtained. After completion of the reaction, the reaction time was taken out from the container, cooled and pulverized to obtain a binder resin 1. Various physical properties of these resins are as shown in Table 2. FIG. 1 shows a DSC chart of the binder resin 1.

<Production example of binder resins 2 to 11>
The monomer shown in Table 1 was charged into a 5 liter autoclave together with an esterification catalyst, and a reflux condenser, a water separator, an N ₂ gas introduction pipe, a thermometer and a stirring device were attached, and N ₂ gas was introduced into the autoclave. A polycondensation reaction was performed at 230 ° C. The reaction time was adjusted so as to obtain a desired softening point, and after completion of the reaction, the reaction solution was taken out from the container, cooled and pulverized to obtain binder resins 2 to 11. Various physical properties of these resins are as shown in Table 2.

<Example of production of binder resin 12>
・ Bisphenol A ethylene oxide adduct (average addition mol number 2.2 mol)
48.5 mol parts, 34.5 mol parts of terephthalic acid, 8.0 mol parts of adipic acid, 5.0 mol parts of trimellitic anhydride, 4.0 mol parts of acrylic acid Then, a nitrogen gas introducing device, a temperature measuring device, and a stirring device are attached, and stirring is performed at 160 ° C. in a nitrogen atmosphere. There, a vinyl copolymer monomer (styrene: 85.0 mol parts and 2 ethylhexyl acrylate: 15.0 mol parts) and a polymerization initiator so that the polyester monomer: vinyl copolymer monomer is 8: 2 (mass basis). As benzoyl peroxide 2.0 mol
What mixed the part was dripped over 4 hours from the dropping funnel. Then, after reacting at 160 ° C. for 5 hours, the temperature is raised to 230 ° C. and 0.2% by mass of dibutyltin oxide is added, and the reaction time is adjusted so that the THF-insoluble content becomes 40% by mass, and the binder resin is obtained. 12 was obtained. Various physical properties of these resins are as shown in Table 2.

<Example of production of binder resin 13>
A binder resin 13 was obtained in the same manner as the binder resin 12 except that the reaction time was adjusted so that the THF-insoluble content was 60% by mass. Various physical properties of these resins are as shown in Table 2.

<Example of production of binder resin 14>
・ Bisphenol A ethylene oxide adduct (average addition mol number 2.2 mol)
48.5 mol parts / terephthalic acid 34.5 mol parts / dodecenyl succinic acid 8.0 mol parts / trimellitic anhydride 5.0 mol parts / fumaric acid 4.0 mol parts Using the above polyester monomer, the THF insoluble content is 50% by mass. The binder resin 14 was obtained in the same manner as the binder resin 12 except that the reaction time was adjusted. Various physical properties of these resins are as shown in Table 2.

<Example of production of binder resin 15>
In a 2-liter four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, 90 parts by mass of binder resin 1 and 10 parts by mass of binder resin 6 were mixed, and benzoyl 0.1 parts by weight of peroxide was added. The binder resin 15 was obtained by adjusting the reaction time so that the temperature of the mixed solution was 80 ° C. and the THF-insoluble content was 40% by mass. Various physical properties of these resins are as shown in Table 2.

<Example of production of binder resin 16>
In a 2-liter four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, 90 parts by mass of binder resin 4 and 10 parts by mass of binder resin 6 were mixed, and benzoyl 0.1 parts by weight of peroxide was added. The binder resin 16 was obtained by adjusting the reaction time so that the temperature of the mixed solution was 80 ° C. and the THF-insoluble content was 30% by mass. Various physical properties of these resins are as shown in Table 2.

[Example 1]
Binder resin 1 30 parts by mass Binder resin 12 70 parts by mass Magnetic iron oxide particles 90 parts by mass (average particle size 0.20 μm, Hc = 11.5 kA / m, σs = 88 Am ² / kg, σr = 14 Am ² / kg)
-Commercially available low molecular weight polypropylene wax 4 parts by mass (Biscol 660-P: Sanyo Chemical Industries)
Charge control agent (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 2 parts by mass The above materials were premixed with a Henschel mixer and then melt kneaded with a biaxial kneading extruder. The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, then pulverized with a jet mill, and the obtained finely pulverized powder is classified using a multi-division classifier utilizing the Coanda effect, and the weight average particle diameter (D4) 7.0 μm negatively chargeable magnetic toner particles were obtained. Hydrophobic silica fine powder 1 [BET specific surface area 150 m ² / g with respect to 100 parts by mass of magnetic toner particles, 30 parts by mass of hexamethyldisilazane (HMDS) and 10 parts by mass of dimethyl silicone oil with respect to 100 parts by mass of silica fine powder. Hydrophobic treatment] 1.0 parts by mass and 3.0 parts by mass of strontium titanate fine powder (D50: 1.0 μm) were externally added and sieved with a mesh having an opening of 150 μm, and toner (T-1) was added. Obtained. Table 3 shows the toner formulation and the physical properties obtained. FIG. 2 shows a DSC chart of the toner (T-1).

The fixing evaluation of this toner was performed as follows. Commercial copy machine (imageRUNNER)
ADVANCE 8105 (manufactured by Canon Inc.) was taken out, and the external fixing device was used. The external fixing device operates outside the printer, can arbitrarily set the fixing roller temperature, and is modified so that the process speed is 600 mm / sec. The low-temperature fixability was evaluated by using 80 g / m ² paper and passing a solid black unfixed image. The high temperature offset property was evaluated by passing an unfixed image in which a 4-dot horizontal line pattern latent image (latent image line width of about 190 μm) of 600 dpi was written at 1 cm intervals using 80 g / m ² paper.
For low-temperature fixability, a load of 50 g / cm ² was applied, the fixed image was rubbed with sylbon paper, and the temperature at which the image density reduction rate before and after rubbing was less than 10% was defined as the fixing temperature. Further, for high temperature offset property, the reproducibility of the line after fixing was visually confirmed, and the temperature at which the disturbance of the line could be confirmed was defined as the offset generation temperature. The temperature range between the fixing temperature and the offset generation temperature was defined as a fixing region. The evaluation results are shown in Table 4.
A: Very good (fixing area 70 ° C. or higher)
B: Good (50 ° C. or higher and lower than 70 ° C.)
C: Normal (20 ° C or higher and lower than 50 ° C)
D: Inferior (less than 20 ° C)

With respect to the temporal stability of the toner, 10 g of the toner was weighed into a 50 cc polycup, and the blocking property after being left in a constant temperature and humidity chamber at 40 ° C. and 95% for 30 days was visually evaluated using the following evaluation criteria. . The evaluation results are shown in Table 4.
A: There is no solidified state B: There is a lump, but it gets smaller and loosens as you turn the cup C: A lump remains even if you unscrew the cup D: There is a larger lump, turn the cup I can't unravel

Evaluation of toner developability was performed as follows. A continuous copying test of 200,000 sheets was performed using a commercially available copying machine (imageRUNNER ADVANCE 8105, manufactured by Canon Inc.) in a 30 ° C., 80% RH environment using a test chart with a printing ratio of 5%. The image density was measured with a Macbeth densitometer (manufactured by Macbeth) using an SPI filter to measure reflection density, and a 5 mm square image was measured. These evaluations were initially performed at 200,000 sheets, and durability stability was evaluated based on the difference in reflection density ([Density transition (30 ° C., 80%) in Table 4)].
Further, a continuous print test of 50,000 sheets was performed using a test chart with a print ratio of 1% in an environment of 30 ° C. and 80% RH. The image density was measured with a Macbeth densitometer (manufactured by Macbeth) using an SPI filter to measure reflection density, and a 5 mm square image was measured. These evaluations were initially performed at the time of 50000 sheets, and durability stability at a low image ratio ([density transition (low duty 30 ° C., 80%) in Table 4]) was evaluated based on the density difference of reflection density. The evaluation results are shown in Table 4.
A: Very good (density difference less than 0.10)
B: Good (density difference of 0.10 or more and less than 0.20)
C: Normal (density difference of 0.20 or more and less than 0.30)
D: Inferior (density difference of 0.30 or more)
On the other hand, development sleeve contamination evaluation ([sleeve contamination (low duty 30 ° C., 80%) in Table 4)] is the image density after continuous printing test of 50,000 sheets, and the development sleeve is cleaned once with Sylbon paper and the test chart is again The evaluation was based on the difference from the image density when the image was taken out. The evaluation results are shown in Table 4.
A: Very good (density difference less than 0.05)
B: Good (density difference 0.05 or more, less than 0.10)
C: Normal (density difference 0.10 or more, less than 0.20)
D: Inferior (density difference of 0.20 or more)

[Examples 2 to 11]
Toners (T-2) to (T-11) were prepared in the same manner as in Example 1 according to the formulation described in Table 3. The physical properties of the toner thus obtained are shown in Table 3, and the results of the same tests as in Example 1 are shown in Table 4.

[Comparative Examples 1 to 8]
Toners (T-12) to (T-20) were prepared in the same manner as in Example 1 according to the formulation described in Table 3. The physical properties of the toner thus obtained are shown in Table 3, and the results of the same tests as in Example 1 are shown in Table 4.

Claims (4)

A toner having toner particles containing a binder resin and a colorant,
The toner has a glass transition temperature of 50.0 ° C. or higher and 70.0 ° C. or lower and a maximum value of 110.0 ° C. or higher and 145.0 ° C. or lower in a DSC curve measured by a differential scanning calorimeter. The temperature has a minimum value between 150.0 ° C. and 200.0 ° C.,
The toner contains 20.0% by mass or more and 50.0% by mass or less of tetrahydrofuran (THF) insoluble matter derived from the binder resin, and the extraction residue when extracted by Soxhlet extraction with tetrahydrofuran (THF) for 16 hours is: A toner having a maximum value at a temperature of 110.0 ° C. or higher and 150.0 ° C. or lower in a DSC curve measured by a differential scanning calorimeter.   The toner according to claim 1, wherein the binder resin contains a binder resin (A) and a binder resin (B) having different softening points. In the DSC curve measured by a differential scanning calorimeter, the binder resin (A) has a glass transition temperature of 50.0 ° C. or higher and 60.0 ° C. or lower, and a temperature of 110.0 ° C. or higher and 145.0 ° C. or lower. It has a maximum value, has a minimum value at a temperature of 150.0 ° C or more and 200.0 ° C or less,
The toner according to claim 1, wherein the endothermic amount of the maximum value is 3.0 J / g or more and 15.0 J / g or less.   The toner according to any one of claims 1 to 3, wherein the binder resin (B) is a hybrid resin in which a polyester unit and a vinyl copolymer unit are chemically bonded.

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