JP2005234255A - Toner and method of manufacturing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner having excellent balance in fixing property and offset resistance, giving a high-quality image for a long time with less fog in any environment, causing no contamination of a toner contact member and having high durability. <P>SOLUTION: The toner contains at least a binder resin, a colorant and wax, wherein the wax contains a nonpolar wax having no polarity and a polar wax having a polar group. The nonpolar wax is added during preparing the binder resin, and the polar wax is added when the binder resin and the colorant are melted and kneaded. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method, and the like, and a manufacturing method thereof.

  Various methods and apparatuses have been developed for the process of fixing a toner image to a sheet such as paper in an electrophotographic image forming method for developing an electrostatic image. There have been proposed a pressure heating method using a heat roller and a heat fixing method in which a pressure member is in close contact with a heating body via a film.

  In this roller heating type fixing device, the surface of the heat roller or film and the toner image of the fixing sheet are in contact with each other, so that the thermal efficiency when fixing the toner image on the fixing sheet is extremely good, and the fixing is performed quickly. It can be done and is very good in electrophotographic copiers or printers.

  However, in the above method, since the heat roller or film surface and the toner image are in contact with each other in a molten state, a part of the toner image adheres to and is transferred to the fixing roller or film surface, and this is transferred again to the next fixing sheet. As a result, an offset phenomenon may occur, and the fixing sheet may be soiled. One of the important conditions of the heat fixing method is to prevent the toner from adhering to the heat fixing roller and the film surface.

  Conventionally, for the purpose of preventing the toner from adhering to the surface of the fixing roller, for example, the roller surface is formed of a material such as silicone rubber or fluorine-based resin having excellent releasability with respect to the toner. In order to prevent fatigue, the roller surface is coated with a thin liquid film having good releasability such as silicone oil. However, this method is extremely effective in preventing toner offset, but has a problem that the fixing device becomes complicated because a device for supplying the liquid for preventing offset is required. In addition, this is opposite to the reduction in size and weight, and silicone oil may evaporate due to heat and contaminate the interior of the machine.

  Therefore, instead of using a silicone oil supply device, instead of supplying an offset prevention liquid from the toner during heating, a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner particles is proposed. Has been. However, if such an additive is added in a large amount in order to obtain a sufficient effect, filming on the photoconductor and the surface of a toner carrier such as a carrier and a developing sleeve are contaminated, causing deterioration of the image.

  For this reason, a small amount of a release agent is added to the toner particles so as not to deteriorate the image, and a small amount of releasable oil is supplied or an offset toner is used in an apparatus using a member such as a roll-up type web. A cleaning device is used in combination. However, considering recent demands for miniaturization, weight reduction, and high reliability, it is necessary and preferable to remove these auxiliary devices. Accordingly, in order to further improve the toner fixing property and offset resistance, further improvements in the toner binder resin and the release agent are necessary.

  It is known to include a wax as a release agent in toner particles. For example, it is disclosed in Patent Documents 1 to 3.

  These waxes are used to improve the offset resistance of toner at low and high temperatures. However, while these performances are improved, the blocking resistance is lowered or the developability is lowered.

  Further, as a toner containing two or more kinds of waxes in order to exhibit the effect of adding wax from a low temperature region to a high temperature region, for example, techniques such as Patent Documents 4 to 10 are disclosed.

  However, none of these toners can satisfy all of the performances, causing some problems. For example, high-temperature offset resistance and developability are excellent, but low-temperature fixability is still one step, low-temperature offset resistance and low-temperature fixability are excellent, but blocking resistance is slightly inferior and developability is low There were harmful effects such as. Further, it is difficult to uniformly disperse each wax component in the toner, which may cause an increase in fog due to poor dispersion, a deterioration in developability, and a bad image due to contamination of the developer carrying member.

  Furthermore, as means for improving the dispersion of the release agent, Patent Documents 11 to 17 propose that the polymerization of the resin composition is performed in the presence of the release agent. Patent Document 18 proposes a method in which the first wax is added at the time of polymerizing the synthetic resin and the second wax is added at the time of toner melt melting and kneading.

  However, in these methods, the release agent component is completely compatible or very finely dispersed in the resin, so that the originally required releasability is impaired, and a fixing device called blob It has been difficult to obtain satisfactory performance because the offset toner is accumulated on the member (for example, the separation claw or thermistor member) and the image is contaminated. Further, when two types of waxes are used, it is difficult to disperse both of them appropriately, which may cause an increase in fog due to poor dispersion or an image defect due to contamination of the developer carrying member.

  Patent Document 19 discloses a technique for modifying the shape and surface properties of a toner produced by a pulverization method by thermal or mechanical impact. However, when the shape of the toner is modified by this method, an excessive amount of heat is applied to the toner surface, so that the surface of the toner is covered with wax, and the fixing member or the like may be soiled.

Japanese Patent Publication No.52-3304 Japanese Patent Publication No.52-3305 Japanese Patent Publication No.57-52574 JP-A-4-124676 JP-A-4-299357 JP-A-4-362953 JP-A-5-197192 JP-A-8-278657 JP-A-8-334919 JP-A-9-304966 Japanese Patent Laid-Open No. 9-281748 Japanese Patent Laid-Open No. 10-123753 JP-A-11-158336 JP-A-11-160911 JP 2002-162786 A JP 2002-278155 A JP 2003-5431 A JP-A-4-358159 JP-A-11-149176

  It is an object of the present invention to provide a toner having an excellent balance between fixing property and non-offset property, and capable of providing a high-quality image with less fog in any environment over a long period of time. It is an object of the present invention to provide a highly durable toner and a toner manufacturing method without contaminating members.

  The present invention relates to a toner obtained by using a wax-containing resin composition containing a nonpolar wax as a binder resin, melt-kneading the binder resin, constituent materials necessary for the toner such as a colorant, and polar wax. An average circularity of 3 μm or more of the toner measured by a flow type particle image measuring device of the toner particles, which is manufactured through a process of setting the composition to a desired particle size, is 0.930 to 0.990. Accordingly, the present invention relates to a toner characterized in that an external additive is added and mixed, and a toner manufacturing method.

  According to the present invention, low-temperature melting and offset resistance are compatible, and it is stable against environmental changes, and image formation is highly prevented from adverse effects caused by fogging and contamination of the developer carrying member. Is possible.

  The toner of the present invention comprises a wax-containing binder resin containing a nonpolar wax, a constituent material necessary for the toner such as a colorant, and a toner composition obtained by melt-kneading the polar wax with a desired particle size. The toner has a mean circularity of 3 μm or more measured by a flow type particle image measuring device of the toner particles of 0.930 to 0.990, and is externally added as necessary. An agent is added and mixed.

The wax-containing binder resin is
1) A wax-containing resin in which a resin and a non-polar wax are mixed in the presence of a solvent, and the solvent is removed to contain a wax. 2) A wax-containing resin in which the resin and the non-polar wax are melt-kneaded to contain a wax. It is characterized by being.

  By incorporating wax into the toner by this method, it is possible to contribute to stable electrophotographic characteristics and low-temperature melting of the toner, and to achieve high offset resistance at high temperatures, and in any environment However, it is possible to highly prevent image defects caused by fogging and contamination of the developer carrying member.

  That is, by containing two or more kinds of waxes, offset resistance and low-temperature fixability can be satisfied at the same time, and releasability can be achieved in a wide temperature range. It is possible to achieve a high level of offset resistance in the region. Further, by adopting the above-described method for adding wax, it becomes possible to appropriately control the dispersion of each wax, and fogging and developability deterioration due to a decrease in wax dispersion, contamination of the developer carrying member due to the release of wax. It has become possible to prevent the deterioration of releasability and resin elasticity due to the compatibilization of the wax with the resin.

  Including two or more kinds of waxes in the toner has various advantages as described above, but it is difficult to appropriately disperse two kinds of waxes in the resin. However, simply melting and kneading in the toner will significantly reduce the viscosity of the kneaded product at the temperature at which one of the waxes melts, making it difficult to apply kneading shear and disperse the remaining wax components. It becomes difficult. Deterioration of wax dispersibility impairs charging uniformity of toner, causes deterioration of fog and developability, and offset resistance deteriorates due to release of wax, and fixing members called blobs (for example, separation nails and thermistor members) As a result, the offset toner is accumulated and the image is contaminated.

  In order to improve the dispersibility, a method of polymerizing the binder resin in the presence of wax was also considered, but when polymerized in the presence of wax, the wax becomes compatible with the resin, and the original function of the wax is reduced. A certain releasability is impaired, and blobs can be seen, and the polymerization of the binder resin is easily affected, which is not preferable.

  In order to achieve good dispersion of the wax component, two or more kinds of waxes are added separately during the preparation of the binder resin and during toner production (when melt-kneaded with the binder resin and the colorant), This makes it possible to highly control the dispersion in the toner.

  By controlling the dispersion diameter of the wax in the toner, the dispersion of the wax can be controlled. By adding a nonpolar wax during the preparation of the binder resin and adding the polar wax during toner production, the dispersion diameter of each wax can be controlled to an appropriate size.

  If a non-polar wax is added together with a polar wax during toner production, the dispersion diameter becomes large and poor dispersion of the wax and free wax are likely to occur, the uniformity of charging of the toner is impaired, fogging and contamination of the developer carrying member, and development. It tends to cause sexual deterioration.

  If a polar wax is added together with a nonpolar wax during the preparation of the binder resin, the dispersion diameter becomes small, the effect of the wax cannot be fully exhibited, and the fixability and offset resistance are affected.

  By adding non-polar wax during the preparation of the binder resin and adding polar wax during toner production, the dispersion of each wax can be controlled to a high degree, with stable electrophotographic characteristics and low-temperature melting of the toner. In addition to being able to achieve high offset resistance in a high temperature range, it has become possible to highly prevent image damage caused by fogging and contamination of the developer carrying member in any environment.

  The method for adding the wax will be further described.

  First, after polymerization of the binder resin used for the toner, the resin and the nonpolar wax are mixed in the presence of a solvent, or the resin and the nonpolar wax are melt-kneaded, and the nonpolar wax is added.

  If wax is added at the time of binder resin polymerization, it becomes compatible with the binder resin and the effect of the wax cannot be fully exerted. However, addition of the wax at the above time affects the polymerization of the binder resin. And can be finely dispersed in the toner. In the sense that the dispersion state is more strictly controlled, it may be added separately during each step, and further during the binder resin polymerization.

  Further, when the binder resin is a mixed system of a high molecular weight component and a low molecular weight component, the addition of the nonpolar wax is performed when the resin A and the resin B are mixed with the solution to prepare the binder resin. Alternatively, it is performed when the binder resin is prepared by melt-kneading the resin A and the resin B.

  Further, polar wax is added during toner production (when melt-kneading with a binder resin and a colorant).

  By using a polar wax having a high affinity for the toner binder resin component, the wax can be uniformly present in the toner, and the action of the wax can be effectively exhibited.

  Nonpolar waxes used in the present invention include the following.

  Examples thereof include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax.

  Examples of the polar wax used in the present invention are as follows.

  Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, and alcohols obtained by hydrolyzing these oxides, or block copolymers of these oxides; candelilla wax, carnauba wax, wax, rice wax, Plant waxes such as jojoba wax; animal waxes such as beeswax, lanolin and whale wax; mineral waxes such as ozokerite, ceresin and petrolactam; waxes based on fatty acid esters such as montanate ester and castor wax; The fatty acid ester such as deoxidized carnauba wax is partially or completely deoxidized. Furthermore, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinal acid; stearyl alcohol Saturated alcohols such as eicosyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol, or long chain alkyl alcohols having a long chain alkyl group; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid Fatty acid amides such as amides and lauric acid amides; saturated fatty acid bisamides such as methylene bisstearic acid amides, ethylene biscapric acid amides, ethylene bislauric acid amides and hexamethylene bisstearic acid amides; Unsaturated fatty acid amides such as lenbis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; Aromatic bisamides such as N, N'-distearylisophthalamide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soap); aliphatic hydrocarbons Wax grafted with vinyl monomers such as styrene and acrylic acid; partially esterified products of aliphatic and polyhydric alcohols such as behenic acid monoglyceride; hydroxyl groups obtained by hydrogenating vegetable oils and fats Methyl Este with Compounds.

  The nonpolar wax used in the present invention is preferably a hydrocarbon wax because of its influence on dispersibility in the toner and chargeability of the toner. For example, paraffin wax, Fischer-Tropsch wax, low-molecular polyolefin obtained by polymerizing olefin with radical polymerization under high pressure or Ziegler catalyst or metallocene catalyst under low pressure, polyolefin obtained by thermal degradation of high molecular weight polyolefin, monoxide Examples include Fischer-Tropsch waxes such as synthetic hydrocarbons obtained from the distillation components of hydrocarbons obtained from the synthesis gas composed of carbon and hydrogen by the age method or by hydrogenation thereof. An antioxidant may be added. Furthermore, the thing which fractionated the hydrocarbon wax by the use of the press perspiration method, the solvent method, vacuum distillation, or a fractional crystallization method is preferably used. The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) (even if the raw material is coal, it is natural gas) For example, the Jintole method, Hydrocol method (using a fluidized catalyst bed), or the Age method (using a fixed catalyst bed) in which a large amount of waxy hydrocarbons can be obtained up to about several hundred carbon atoms And hydrocarbons obtained by polymerizing olefins such as ethylene with a Ziegler catalyst or a metallocene catalyst are preferred because they are straight-chain hydrocarbons with little branching and long saturation.

  As the nonpolar wax, Fischer-Tropsch wax is preferably used from the viewpoint of dispersibility in the toner and releasability.

  The polar wax suitably used in the present invention is preferably an alcohol-modified wax obtained by acid-modifying an aliphatic hydrocarbon wax or hydrolyzing an oxide. Alcohol-modified waxes that are less affected by nonpolar wax and that can be well dispersed in the toner are more preferred.

  An example of producing an alcohol-modified wax is obtained by, for example, subjecting an aliphatic hydrocarbon wax to liquid phase oxidation with a molecular oxygen-containing gas in the presence of boric acid and boric anhydride. As the catalyst, a mixture of boric acid and boric anhydride can be used. The mixing ratio of boric acid and boric anhydride (boric acid / boric anhydride) is 1.0 to 2.0, preferably 1.2 to 1.7 in terms of molar ratio. When the proportion of boric anhydride is less than the above range, an excess of boric acid is not preferable because it causes a decrease in aggregation. On the other hand, if the proportion of boric anhydride is more than the above range, the powder substance derived from boric anhydride is recovered after the reaction, and excess boric acid does not contribute to the reaction, which is not preferable from an economical viewpoint.

  The addition amount of boric acid and boric anhydride used is preferably 0.001 to 10 mol, particularly preferably 0.1 to 1.0 mol with respect to 1 mol of the aliphatic hydrocarbon as a raw material when the mixture is converted to boric acid. . As the molecular oxygen-containing gas blown into the reaction system, oxygen, air, or a wide range of those diluted with an inert gas can be used, but the oxygen concentration is preferably 1 to 30% by volume, more preferably. Is 3-20% by volume. The liquid phase oxidation reaction is usually carried out in the molten state of the starting aliphatic hydrocarbon without using a solvent. The reaction temperature is 120 to 280 ° C, preferably 150 to 250 ° C. The reaction time is preferably 1 to 15 hours. It is preferable that boric acid and boric anhydride are mixed in advance and added to the reaction system. If only boric acid is added alone, a dehydration reaction of boric acid or the like occurs, which is not preferable. Moreover, the addition temperature of the mixed solvent of boric acid and boric anhydride is preferably 100 ° C. to 180 ° C., preferably 110 ° C. to 160 ° C. When the temperature is lower than 100 ° C., it is caused by moisture remaining in the system. This is not preferable because the catalytic function of boric anhydride is lowered.

  After completion of the reaction, water is added to the reaction mixture, and the resulting borate ester of the wax is hydrolyzed and purified to obtain the desired wax.

  The wax used in the present invention will be further described.

  The melting point (Tm1) of the nonpolar wax used in the present invention is preferably in the range of 90 to 150 ° C, more preferably in the range of 90 to 120 ° C.

The melting point (Tm2) of the polar wax preferably satisfies the following formula.
50 ≦ Tm2 (° C.) (Formula 1)

  Tm2 is more preferably from 50 to 120 ° C, and still more preferably from 70 to 95 ° C.

  When the melting point of the nonpolar wax is less than 90 ° C., the offset resistance of the toner is lowered and the developer carrying member is likely to be contaminated, and when it is 150 ° C. or more, the toner fixing performance may be adversely affected. If the melting point of the polar wax is less than 50 ° C., the blocking resistance of the toner may deteriorate, and if it exceeds 120 ° C., the fixing performance of the toner may be adversely affected. Also, if the melting point of the nonpolar wax is smaller than the melting point of the polar wax, the viscosity at the time of toner melting and kneading is remarkably lowered, so that kneading share is difficult to be applied and it is difficult to disperse the polar wax component. There is a case.

  By using a wax having a melting point in the above range for the toner, the effect of the wax plasticizing the toner can be further improved, and the fixing property of the toner can be improved. Further, by being within the above range, when the fixing member is overheated excessively, the wax easily exudes from the toner, and the high temperature offset resistance of the toner can be improved.

Furthermore, it is preferable that the relationship between Tm1 and Tm2 satisfies the following formula 2-1, more preferably the relationship of formula 2-2.
0 ≦ Tm1 (° C.) − Tm2 (° C.) ≦ 70 (Formula 2-1)
10 ≦ Tm1 (° C.) − Tm2 (° C.) ≦ 50 (Formula 2-2)

  If the difference in melting point is less than 0 ° C, the effect of each wax added in each step is difficult to clarify, and if the difference exceeds 70 ° C, each wax tends to be separated from each other and behave easily. , It is easy to cause the release of wax and poor dispersion.

The melting point of the wax in the present invention was measured according to the following conditions using a differential scanning calorimeter (DSC measuring device) and Q-1000 (manufactured by TA Instruments Japan).
Sample: 5-20 mg, preferably 10 mg
Measurement method: Place the sample in an aluminum pan, and use an empty aluminum pan as a reference.
Temperature curve: Temperature increase I (20 ° C. → 180 ° C., temperature increase rate 10 ° C./min.)
Temperature drop I (180 ° C. → 10 ° C., temperature drop rate 10 ° C./min.)
Temperature increase II (10 ° C. → 180 ° C., temperature increase rate 10 ° C./min.)
An endothermic peak measured at temperature rise II is used.

  The melt viscosity at 135 ° C. of the nonpolar wax used in the present invention is 1 to 100 mPa · s or less, preferably 1 to 50 mPa · s or less, more preferably 1 to 20 mPa · s or less. The melt viscosity at 120 ° C. of the polar wax is 5 to 500 mPa · s or less, preferably 5 to 200 mPa · s or less, more preferably 5 to 100 mPa · s or less. The melt viscosity of the nonpolar wax is more than the melt viscosity of the polar wax. Is preferably smaller.

  When the melt viscosity of the nonpolar wax exceeds 100 mPa · s, the releasability becomes inferior, affects the excellent offset resistance as a toner, and easily causes contamination of the developer carrying member. When it becomes below, blocking resistance will be inferior and it will affect the durability as a toner. When the melt viscosity of the polar wax exceeds 500 mPa · s, the plasticity and the releasability become inferior, and the excellent fixability as a toner and the offset resistance are affected. The blocking resistance becomes inferior, and the developability and storage stability as a toner are affected. In addition, since the melt viscosity of the nonpolar wax is smaller than the melt viscosity of the polar wax, the viscosity at the time of toner melt-kneading becomes moderate, so that the toner has an appropriate share and the polar wax is easily dispersed. .

  The melt viscosity of the wax in the present invention was measured according to JIS K-6862-7.2.

  The softening point of the nonpolar wax used in the present invention is 80 to 140 ° C, preferably 80 to 120 ° C, and the softening point of the polar wax is 60 to 100 ° C, preferably 60 to 90 ° C. It is preferable that the softening point of the polar wax is lower than the softening point.

  When the softening point of the nonpolar wax exceeds 140 ° C., the excellent fixability as a toner is affected, and when it is 80 ° C. or less, the developability as a toner is affected. When the softening point of the polar wax exceeds 110 ° C., it exerts an influence on the excellent offset resistance as a toner, and the developer carrying member is liable to be contaminated. When the temperature becomes 60 ° C. or less, the storage stability as a toner is affected. It will be affected. In addition, since the softening point of the polar wax is lower than the softening point of the nonpolar wax, an appropriate share is applied when the toner is melt-kneaded, and the polar wax is easily dispersed.

  The penetration at 25 ° C. of the wax used in the present invention is 0 to 5, preferably 0 to 3.0 for nonpolar wax, 2 to 15, preferably 2 to 12, more preferably 3 for polar wax. It is preferable that the non-polar wax penetration is smaller than that of the polar wax.

  When the penetration of the nonpolar wax is 5 or more, it tends to change at low temperatures, which may affect the storage stability and developability of the toner. When the penetration of the polar wax is 15 or more, the blocking property as the toner is deteriorated and the storage stability is deteriorated, and when it is 2 or less, the fixing property as the toner may be affected. Further, since the penetration of the nonpolar wax is smaller than the penetration of the polar wax, an appropriate share is applied when the toner is melt-kneaded, and the polar wax is easily dispersed.

  The penetration of the wax in the present invention was measured according to JIS K-2235-5.4.

  The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the wax used in the present invention is in terms of polyethylene, the nonpolar wax is 300 to 2000, preferably 600 to 1500, and the polar wax is 100 The molecular weight of the polar wax is smaller than that of the nonpolar wax.

  When the molecular weight of the nonpolar and polar wax is smaller than the above value, it is excessively susceptible to thermal influences, resulting in poor blocking resistance and developability. When the molecular weight of the nonpolar wax is larger than 1200, heat from the outside is removed. When the molecular weight of the polar wax is 3000 or more, excellent offset resistance cannot be obtained because it cannot be effectively used and excellent fixability cannot be obtained. Further, since the molecular weight of the polar wax is smaller than that of the nonpolar wax, it becomes easy to disperse uniformly in the toner.

The molecular weight in the present invention was measured according to the following conditions.
Apparatus: GPC-150C (manufactured by Waters)
Column: GMH-HT (manufactured by Tosoh Corporation) Duplex temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 ml / min.
Sample: 0.4 ml of sample having a concentration of 0.15% by mass is measured under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Furthermore, the molecular weight of the wax is calculated by conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

The addition amount of the wax in the present invention is 0.5 to 5 parts by mass, preferably 1 to 4 parts by mass with nonpolar wax, and 1 to 15 parts by mass with polar wax, preferably 100 parts by mass of the binder resin. 2 to 10 parts by mass. It is preferable that the addition amount of nonpolar wax (Add1) and the addition amount of polar wax (Add2) satisfy the following formula 3).
Add1 <Add2 (Formula 3)

  When the addition amount of the nonpolar wax is less than 0.5 parts by mass, the offset resistance as a toner is lowered and the developer carrying member is easily contaminated. When the amount exceeds 5 parts by mass, the fixability as a toner is lowered. When the amount of the polar wax added is less than 1 part by mass, the fixability as a toner is lowered, and when it exceeds 15 parts by mass, the offset resistance tends to be lowered. Further, when the addition amount of the nonpolar wax is larger than the addition amount of the polar wax, it becomes difficult to disperse well in the toner, and the fog and the developer carrying member are liable to be contaminated.

  The hydroxyl value of the polar wax used in the present invention is 5-150 mgKOH / g, preferably 10-100 mgKOH / g, more preferably 20-90 mgKOH / g. When the hydroxyl value of the polar wax is less than 5 mgKOH / g, the wax is not sufficiently finely dispersed and the toner fixing property is lowered. On the other hand, if the hydroxyl value is larger than 150 mgKOH / g, the plasticizing effect of the wax becomes too great and the blocking resistance of the toner is lowered.

  Moreover, it is preferable that the wax has an acid value in order to further improve the constant temperature fixability and wax dispersibility. The acid value is preferably 1 to 30 mgKOH / g (more preferably 1 to 15 mgKOH / g, still more preferably 1 to 10 mgKOH / g). When the wax has an acid group, the interfacial adhesive force with other components constituting the toner is increased, and the effect that the wax plasticizes the toner is easily obtained, so that the fixing property of the toner is improved. When the acid value of the wax is less than 1 mgKOH / g, the interfacial adhesive force with other components constituting the toner becomes small, and the release of the wax tends to occur, and the effect of the wax may not be sufficiently obtained. On the other hand, if the acid value of the wax is larger than 30 mgKOH / g, the interfacial adhesive force is excessively increased, and the plasticization of the toner proceeds greatly, so that sufficient releasability may not be maintained.

The measurement of the hydroxyl value in the present invention was carried out as follows.
・ Devices and instruments Measuring cylinder (100ml)
Full pipette (5ml)
Flat bottom flask (200ml)
Glycerin bath / reagent Acetylation reagent (25 g of acetic anhydride is placed in a 100-ml flask, and pyridine is added to bring the total volume to 100 ml.)
Phenolphthalein solution 0.5 kmol / m ³ Potassium hydroxide ethanol solution ・ Measurement method (a) 0.5-6.0 g of hydrocarbon wax is precisely weighed into a flat bottom flask, and 5 ml of acetylating reagent is pipetted into the whole volume. Add using.
(B) Place a small funnel on the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at a temperature of 95-100 ° C. and heat. In order to prevent the temperature of the neck of the flask from rising due to the heat of the glycerin bath, a cardboard disc with a round hole in it is put on the base of the neck of the flask.
(C) After 1 hour, the flask is removed from the glycerin bath, and after standing to cool, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride.
(D) Further, in order to complete the decomposition, the flask is heated again in the glycerin bath for 10 minutes, and after cooling, the funnel and the wall of the flask are washed with 5 ml of ethanol (95).
(E) A few drops of phenolphthalein solution is added as an indicator, and titrated with 0.5 kmol / m ³ potassium hydroxide ethanol solution. The end point is when the indicator lightly continues for about 30 seconds.
(F) In the blank test, (a) to (e) are performed without adding the hydrocarbon wax (a).
(G) If the sample is difficult to dissolve, add a small amount of pyridine, or add xylene or toluene to dissolve.
Calculation A = [{(BC) × 28.05 × f} / S] + D
Where A: hydroxyl value (mgKOH / g)
B: 0.5 kmol / m ³ potassium hydroxide ethanol solution used for the blank test
Liquid volume (ml)
C: 0.5 kmol / m ³ potassium hydroxide ethanol solution used for titration
Amount (ml)
f: Factor of 0.5 kmol / m ³ potassium hydroxide ethanol solution S: Mass of hydrocarbon wax (g)
D: Acid value 28.05: Formula weight of potassium hydroxide 56.11 × 1/2

  The acid value in the present invention was measured as follows.

(Devices and instruments)
・ Erlenmeyer flask (300 ml)
・ Bullet (25ml)
・ Water bath or hot plate

(reagent)
· 0.1 kmol / m ³ HCl · 0.1 kmol / m ³ potassium hydroxide ethanol solution (orientation takes Erlenmeyer flask 0.1 kmol / m ³ HCl 25ml with whole pipette, phenolphthalein solution is added, Titrate with 0.1 kmol / m ³ potassium hydroxide ethanol solution, and determine the factor from the amount required for neutralization.)
-Phenolphthalein solution solvent (diethyl ether and ethanol (99.5) mixed in a volume ratio of 1: 1 or 2: 1. These were added just a few drops of phenolphthalein solution as an indicator just before use. Neutralize with 1 kmol / m ³ potassium hydroxide ethanol solution.)

(Measurement method)
(A) Weigh accurately 1 to 20 g of wax into an Erlenmeyer flask.
(B) Add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the wax is completely dissolved in a water bath.
(C) Titrate with a 0.1 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the indicator lightly red for 30 seconds.

(Calculation)
The acid value of the wax is calculated according to the following formula.
A = 5.611 × B × f / S
However,
A: Acid value (mgKOH / g)
B: Amount of 0.1 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml)
f: Factor of 0.1 kmol / m ³ potassium hydroxide ethanol solution S: Mass of wax (g)
5.611: Formula weight of potassium hydroxide 56.11 × 1/10

  The toner of the present invention can be produced by a known method. As a method for producing the toner of the present invention, the toner constituent materials are sufficiently mixed with a ball mill or other mixer, then kneaded well using a thermal kneader such as a hot roll kneader or an extruder, cooled and solidified, and then mechanically It is preferable to pulverize the pulverized powder and classify the pulverized powder.

  The toner of the present invention can be used as both a magnetic toner and a non-magnetic toner, but a weight average diameter of 2.5 to 10 μm promotes charging uniformity and reduces toner cohesion. In view of improving the image density and improving the developability by improving the fog, it is preferable. In particular, the effect is remarkable in a toner having a weight average diameter of 2.5 to 8.0 μm, and an extremely fine image can be obtained. A weight average diameter of 2.5 μm or more is preferable because a sufficient image density can be obtained. The weight average diameter can be adjusted by a toner production method and production conditions, classification work, and the like.

  The weight average particle diameter and particle size distribution of the toner of the present invention can be measured using the Coulter method, and for example, Coulter Multisizer (manufactured by Coulter Co.) can be used. In this measurement method, an electrolytic solution is used. For this electrolytic solution, for example, a 1% NaCl aqueous solution prepared using primary sodium chloride or ISOTON R-II (manufactured by Coulter Scientific Japan) is used. it can.

  As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. This was dispersed for about 1 to 3 minutes with an ultrasonic disperser to disperse the sample. Using a 100 μm aperture as the aperture, the volume and number of toner particles of 2.00 μm or more were measured with the measuring device, and the volume distribution and The number distribution is calculated. Then, a weight-based weight average diameter (D4) obtained from the volume distribution according to the present invention is calculated.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Use 13 channels less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm.

  The average circularity of 3 μm or more of the toner measured by the flow particle image measuring apparatus for toner particles used in the present invention is preferably 0.930 to 0.990, more preferably 0.935 to 0.960, More preferably, it is 0.940-0.955.

  The average circularity of the toner is obtained by using an apparatus that thermally or mechanically treats the toner surface, such as a faculty (manufactured by Hosokawa Micron Corporation) or a hybridizer (manufactured by Nara Machinery Co., Ltd.). Can be achieved.

  By adopting the wax addition method as described above, the average circularity of the toner is in the above range, so that a high-quality image with excellent balance of fixing property and non-offset property and little fogging in any environment. Can be provided over a long period of time, and a highly durable toner can be obtained without contaminating the toner contact member.

  When the circularity of the toner particles increases, the fluidity of the toner increases, so that the individual toners can move freely. Toner developed on a transfer material such as paper has a higher probability of being developed for each toner unit as the toner has a higher degree of circularity, so the image height on the transfer material becomes lower and the toner is fixed. This increases the thermal efficiency and makes it easier to fix. Further, since the wax is uniformly dispersed in the toner particles, even if the image height on the transfer material is low, the effect can be sufficiently exerted.

  If the circularity of the toner particles is not sufficiently high, the toner tends to behave as an agglomerate, and as a result, the chargeability of the toner becomes non-uniform and fog tends to deteriorate.

  If the average circularity of the toner is 0.970 or more, the toner is applied non-uniformly on the sleeve due to excessive supply of toner on the developing sleeve, and as a result, the fog is deteriorated. If the average circularity of the toner is less than 0.935, the height of the developed image becomes high, the fixability is likely to deteriorate, and the toner tends to behave as an agglomerate and fog is deteriorated. It becomes easy to do.

The average circularity in the present invention is used as a simple method for quantitatively expressing the particle shape. In the present invention, the flow type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation is used at 23 ° C. and 60%. Measurement is performed under the environment of RH, and particles within a circle equivalent diameter of 0.60 μm to 400 μm are measured. The circularity of the measured particle is obtained by the following equation (1), and further, the circle equivalent diameter is 3 μm to 400 μm. In the following particles, the value obtained by dividing the total circularity by the total number of particles is defined as the average circularity.
Circularity a = L0 / L
[In the formula, L0 represents the circumference of a circle having the same projection area as the particle image, and L represents the particle projection image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). Indicates the perimeter. ]

  Furthermore, the toner of the present invention can be produced by sufficiently mixing the toner particles obtained by these methods described above with a mixer such as a Henschel mixer as required.

  Examples of the binder resin used in the present invention include styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and a homopolymer of a substituted product thereof; styrene-p-chlorostyrene copolymer, styrene. -Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer Polymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Styrene copolymers such as coalesced; poly Vinyl chloride, phenol resin, natural modified phenolic 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 resin and the like can be used.

  Examples of the comonomer 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. Monocarboxylic acid having a double bond such as acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide and the like; for example, maleic acid, butyl maleate , Dicarboxylic acids having a double bond such as methyl maleate, dimethyl maleate, and the like; and substituted products thereof; for example, vinyl esters such as vinyl chloride, vinyl acetate, vinyl benzoate, and the like, such as ethylene, propylene Vinyl olefins such as vinyl methyl ketone, vinyl hexyl ketone, etc .; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; Monomers are used alone or in combination.

  The acid value of the resin used in the present invention is preferably 1.0 to 60 mgKOH / g (more preferably 1.0 to 50 mgKOH / g, still more preferably 2.0 to 40 mgKOH / g). If it is less than 1.0 mgKOH / g, the chargeability of the toner tends to deteriorate and fog tends to deteriorate. If it exceeds 60 mgKOH / g, it tends to be affected by environmental fluctuations and the image density is lowered. However, fog tends to increase.

  The acid value of the binder resin in the present invention was measured according to JIS K-0070.

  The glass transition temperature (Tg) of the resin used in the present invention is preferably 40 to 70 ° C. When Tg is less than 40 ° C., the blocking resistance of the toner tends to deteriorate, and when it exceeds 70 ° C., the toner fixing property tends to deteriorate.

  The resin used in the present invention preferably has a number average molecular weight of 1,000 to 40,000 from the viewpoint of achieving good fixability, and from the viewpoint of achieving good offset resistance and blocking resistance. The weight average molecular weight is preferably 10,000 to 1,000,000.

  The resin used in the present invention preferably has a low molecular weight component and a high molecular weight component. From the viewpoint of achieving good fixability, the peak molecular weight of the low molecular weight component is preferably 4,000 to 30,000, preferably From the viewpoint of achieving excellent offset resistance and blocking resistance, the peak molecular weight of the high molecular weight component is preferably 50,000 to 1,000,000. When both the low molecular weight component and the high molecular weight component satisfy the above molecular weight distribution range, both the low-temperature fixability and the offset resistance can be achieved to a higher degree.

  Furthermore, the resin used in the present invention preferably has a THF-insoluble content of 40% by mass or less, and more preferably 25% by mass or less, from the viewpoint of improving the dispersibility of the toner constituent components.

  As the colorant used in the present invention, various known colorants such as a magnetic substance, a non-magnetic dye, and a pigment can be used. When the toner of the present invention is applied to a magnetic one-component toner, the toner contains a magnetic substance.

  Examples of magnetic materials used in the present invention 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, zinc, antimony, Metal alloys such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof are used, and those containing non-ferrous elements on the surface or inside of the magnetic material are preferable. Further, the toner of the present invention is preferably a magnetic toner containing 30 to 200 parts by mass of a magnetic material with respect to 100 parts by mass of the binder resin. In this case, a sufficient coloring effect can be obtained by the magnetic material.

  Examples of magnetic materials used in the present invention 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, manganese, selenium, and titanium. Alloys with metals such as tungsten and vanadium and mixtures thereof are used, and those containing non-ferrous elements on the surface or inside of the magnetic material are preferred.

  As the magnetic material used in the present invention, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements and mixtures thereof are preferably used. Among them, lithium, beryllium, boron, magnesium, aluminum, silicone, phosphorus, germanium, titanium, zirconium, tin, lead, zinc, calcium, barium, scandium, vanadium, chromium, manganese, cobalt, copper, nickel, gallium, cadmium, indium It is preferably a magnetic iron oxide containing at least one element selected from silver, palladium, gold, mercury, platinum, tungsten, molybdenum, niobium, osmium, strontium, yttrium, technetium, ruthenium, rhodium, and bismuth. . In particular, lithium, beryllium, boron, magnesium, aluminum, silicone, phosphorus, germanium, zirconium, tin, and a transition metal element of the fourth period are preferable elements.

  These elements may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as oxides, or may exist on the surface as oxides or hydroxides. Among these forms, the preferred form is contained as an oxide.

  In some cases, the magnetic iron oxide used in the toner of the present invention may be treated with a silane coupling agent, a titanium coupling agent, titanate, aminosilane, or the like.

  These magnetic iron oxides are preferably used in an amount of 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of making both coloring power and magnetism related to developability and transportability compatible with each other. More preferably, it is used at 40 to 150 parts by mass.

  Examples of the colorant used in the present invention include any appropriate pigment or dye in addition to the above magnetic iron oxide. Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and the blending amount varies depending on the type and the like, but is 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin. Preferably, it is 0.2-10 mass parts.

  For the same purpose, a dye is further used. Examples of the dye include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes. The amount of the dye varies depending on the type and the like, but is 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin. It is preferable that it is 0.3-10 mass parts.

  The toner of the present invention preferably contains a charge control agent. For controlling the toner to be negatively charged, for example, organometallic complexes and chelate compounds are effective, and monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acid metal complexes, and others. And aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, phenol derivatives such as bisphenol, and the like. As the charge control agent for controlling the toner to be negatively charged, an azo metal complex represented by the following general formula (2) is preferable.

  In the charge control agent represented by the general formula (2), in particular, Fe or Cr is preferable as the central metal, halogen, alkyl group, or anilide group is preferable as the substituent, and hydrogen or alkali metal ammonium is preferable as the counter ion. Aliphatic ammonium is preferred. A mixture of complex salts having different counter ions is also preferably used.

  Examples of the charge control agent for controlling the toner to be negatively charged include a basic organic acid metal complex represented by the following general formula (3).

  In the charge control agent represented by the general formula (3), in particular, Fe, Cr, Si, Zn, and Al are preferable as the central metal, and an alkyl group, anilide group, aryl group, and halogen are preferable as the substituent, The counter ion is preferably hydrogen, ammonium, or aliphatic ammonium.

  Among the charge control agents represented by the general formula (3), an azo metal complex is more preferable, and an azo iron complex represented by the following general formula (4) is most preferable.

  Specific examples of the azo metal complex represented by the general formula (4) include the following structural formulas (5) to (10).

  For controlling the toner of the present invention to be positively charged, for example, modified products of nigrosine and fatty acid metal salts, etc .; four kinds of tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, etc. Onium salts such as quaternary ammonium salts and phosphonium salts thereof, and their lake pigments, triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdenum) Acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), higher fatty acid metal salts; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; Over DOO, dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate; guanidine compounds, imidazole compounds and the like can be used alone or in combination. Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used.

  Further, a homopolymer of a monomer represented by the following general formula (11); a copolymer with a polymerizable monomer such as styrene, acrylic acid ester or methacrylic acid ester described above can be used as a positive charge control agent. . In this case, these charge control agents also have an action as a binder resin (all or a part thereof).

［式中、Ｒ₁はＨ又はＣＨ₃を示し、Ｒ₂及びＲ₃は置換又は未置換のアルキル基（好ましくはＣ₁〜Ｃ₄）を示す。］

[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 ). ]

  As the positively chargeable charge control agent, a compound represented by the following general formula (12) is particularly preferable.

  As a method of incorporating a 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 by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. The amount is preferably 0.1 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  In the toner of the present invention, it is preferable to externally add particles having a small particle size as external additives to toner particles containing at least a binder resin and a colorant. Examples of such external additives include inorganic oxides such as silica, alumina, and titanium oxide, and fine particles such as carbon black and carbon fluoride.

  In particular, silica, alumina and titanium oxide fine powder are preferable because they have a great effect of improving the fluidity of the toner. From such a viewpoint, the number average particle diameter of the inorganic oxide particles is preferably 5 to 200 nm, and more preferably 10 to 100 nm.

The particles of the inorganic oxide is preferably a specific surface area by nitrogen adsorption measured by BET method is 30 m ² / g or more, more preferably 60~400m ² / g. The inorganic oxide particles may be used after hydrophobizing the surface, and the specific surface area of the surface-treated inorganic oxide particles is preferably 20 m ² / g or more, It is more preferable that it is 40-300 m < ² > / g.

  The application amount of the inorganic oxide particles is preferably 0.03 to 5 parts by mass with respect to 100 parts by mass of the toner particles in order to appropriately coat the surface of the toner particles with the particles.

  The inorganic oxide particles preferably have a degree of hydrophobicity of 30% or more, more preferably 50% or more in terms of methanol wettability. Preferred hydrophobizing agents include silane compounds that are silicon-containing surface treating agents and silicone oils.

  Examples of the silane compound include alkyl alkoxysilanes such as dimethyldimethoxysilane, trimethylethoxysilane, and butyltrimethoxysilane, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, and allylphenyldichloro. Examples include silane compounds such as silane, benzyldimethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane. Moreover, as a silicone oil, a well-known thing can be used. Silane compounds and silicone oils can be used in combination.

  In addition, from the viewpoint of improving the developability and durability of the toner, it is also preferable to add other inorganic powder as an external additive to the toner of the present invention. Examples of such inorganic powder include metal oxides such as magnesium, zinc, aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin, and antimony; calcium titanate, magnesium titanate, strontium titanate Composite metal oxides such as: 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 powder such as carbon black and graphite Is mentioned. Of these, zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate, magnesium titanate and the like are preferable.

  Furthermore, a lubricant powder such as a fluororesin such as polyvinyl fluoride or polyvinylidene fluoride; a fluorine compound such as carbon fluoride can be added to the toner of the present invention as an external additive.

  The equipment used for producing the toner of the present invention is not particularly limited. For example, as a mixer, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); a super mixer (manufactured by Kawata Corporation); Ribocorn (manufactured by Okawara Seisakusho Co., Ltd.) ); Nauter mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron Corporation); spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.);

  As a kneading machine, for example, KRC kneader (manufactured by Kurimoto Iron Works); Bus co-kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works) PCM kneading machine (Ikegai Iron Works); Three roll mill, mixing roll mill, kneader (Inoue Seisakusho); Needex (Mitsui Mining); MS pressure kneader, Nider Ruder (Moriyama Seisakusho) A Banbury mixer (manufactured by Kobe Steel).

  Examples of the pulverizer include a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); a kryptron (manufactured by Kawasaki Heavy Industries); a turbo mill (manufactured by Turbo Industry); and a super rotor (manufactured by Nisshin Engineering).

  Classifiers include, for example, a class seal, a micron classifier, a speck classifier (manufactured by Seishin Enterprise); a turbo classifier (manufactured by Nisshin Engineering); a micron separator, a turboplex (ATP), a TSP separator (manufactured by Hosokawa Micron) ); Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Industrial Co., Ltd.); YM Microcut (manufactured by Yaskawa Shoji Co., Ltd.).

  Examples of sieving devices used to screen coarse particles include Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokuju Kosakusha Co., Ltd.); Vibrasonic System (Dalton Co., Ltd.); Examples include a turbo screener (manufactured by Turbo Industry); a micro shifter (manufactured by Hadano Sangyo); and a circular vibrating sieve.

  According to the present invention, as described above, a high-quality image that can be durable for a long period of time without contaminating the toner contact member, has excellent fixing properties and offset resistance, and has little fogging. A toner that can be provided over a period of time can be obtained.

  Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited thereto. The number of parts in the examples is part by mass.

  First, the wax used in the present invention will be described.

[Synthesis example of nonpolar wax]
The hydrocarbon wax synthesized by the age method was subjected to fractional crystallization to obtain wax 1, wax 2, and wax 3. Table 1 shows the physical properties of the waxes 1 to 3. Further, a polyethylene wax having physical properties as shown in Table 1 was used as the wax 4.

[Synthesis example of wax having polar group]
Synthesis example A:
Fischer-Tropsch wax (number average molecular weight (Mn) 721, average carbon number 49.4) 1000 g as a raw material was placed in a glass cylindrical reactor and 140 ° C. while blowing a small amount of nitrogen gas (3.5 l / min). The temperature was raised to. After adding 26.1 g (0.41 mol) of mixed catalyst of boric acid / boric anhydride = 1.44 (molar ratio), blowing air (20 liter / min) and nitrogen (15 liter / min), The reaction was performed at 180 ° C. for 2 hours. After completion of the reaction, an equal amount of warm water (95 ° C.) is added to the reaction mixture, the reaction mixture is hydrolyzed, and left to stand to separate the hydrocarbon wax separated into the upper layer, and the separated hydrocarbon wax is removed. Washed with water to obtain wax A. Wax A has a hydroxyl value of 50.2 mgKOH / g, an ester value of 12.6 mgKOH / g, an acid value of 7.4 mgKOH / g, a melting point of 85 ° C., a penetration of 6, a viscosity of 13.2 mPa · s, and softening The point was 93 ° C. and Mn was 617.

Synthesis example B:
Wax B (Mn = 734) was obtained in the same manner as in Synthesis Example A, except that 1000 g of polyethylene wax (Mn = 851) was used as a raw material and the synthesis conditions were changed. Table 2 shows the physical properties of Wax B.

Synthesis example C:
A wax C (Mn = 325) was obtained in the same manner as in Synthesis Example A except that 1000 g of paraffin wax (Mn = 399) was used as a raw material and the synthesis conditions were changed. Table 2 shows the physical properties of Wax C.

Synthesis example D:
An ester wax having physical properties as shown in Table 2 was used as wax D.

  The binder resin used in this example will be described.

<Example of production of binder resin polymer component>
In a four-necked flask,
180 parts deaerated water 20 parts 2% by weight aqueous solution of polyvinyl alcohol 70 parts styrene 25 parts n-butyl acrylate 5 parts monobutyl maleate 0.002 parts divinylbenzene 2,2-bis (4 , 4-Di-tert-butylperoxycyclohexyl) propane
0.2 parts of the above components were added, and the inside of the four-necked flask was sufficiently replaced with nitrogen, and then the temperature was raised to 85 ° C. to initiate polymerization, and the temperature was maintained for 24 hours. This was filtered off, washed with water and dried to obtain a high molecular weight polymer H. When this was analyzed, they were Mw = 910,000, PMw = 780,000, Mw / Mn = 2.5, and Tg = 61 ° C.

<Production example of binder resin low-molecular component>
500 parts of xylene was put into a four-necked flask, and the inside of the container was sufficiently replaced with nitrogen while stirring, and then heated to reflux.

Under this reflux,
-Styrene 80 parts-Acrylic acid-n-butyl 15 parts-Monobutyl maleate 5 parts, and di-tert-butyl peroxide: 2.0 parts of a mixed solution was added dropwise over 4 hours and held for 2 hours. . This was separated by filtration, washed with water and dried to obtain a low molecular weight polymer L. When this was analyzed, it was Mw = 15000, PMw = 16400, Mw / Mn = 2.4, Tg = 60 degreeC.

<Example of production of styrene-based binder resin A>
Resin H: 70.0 parts Resin L: 30.0 parts Wax 1: 2.0 parts The above components were mixed in a xylene solution to obtain a binder resin A.

<Example of production of styrene-based binder resin B>
Resin H: 70.0 parts Resin L: 30.0 parts The above components were mixed in a xylene solution to obtain a binder resin B.

<Example of production of styrene-based binder resin E>
Binder resin B: 92 parts Wax 1: 2 parts The above components were mixed with a Henschel mixer, kneaded at 180 ° C. with a biaxial kneading extruder, cooled and pulverized, and binder resin E was obtained.

<Example of production of styrene-based binder resin F>
Binder resin F was obtained in the same manner as in Production Example E, except that the amount of wax 1 added to the raw material was changed from 2 parts to 4 parts.

<Example of production of styrene-based binder resin G>
A binder resin G was obtained in the same manner as in Production Example E, except that the raw material was changed from wax 1 to wax 2.

<Example of production of styrene-based binder resin H>
Binder resin H was obtained in the same manner as in Production Example A, except that the raw material wax 1: 2 part was changed to wax 2: 3 part.

<Production example of styrene-based binder resin I>
Binder resin I was obtained in the same manner as in Production Example A, except that the raw material wax 1: 2 part was changed to wax 3: 3 part.

<Production example of styrene-based binder resin J>
Binder resin J was obtained in the same manner as in Production Example A, except that the raw material wax 1: 2 part was changed to wax B: 4 part.

<Example of production of styrene-based binder resin K>
Binder resin K was obtained in the same manner as in Production Example A, except that the raw material wax 1: 2 part was changed to wax D: 3 part.

<Example of production of styrene-based binder resin L>
Binder resin L was obtained in the same manner as in Production Example A, except that the raw material wax 1: 2 part was changed to wax C: 10 part.

[Example 1]
-Binder resin E: 102 parts-Magnetite: 95 parts-Wax A: 5 parts-Azo-based iron compound represented by the structural formula (5): 2 parts After the above materials were mixed with a Henschel mixer, the mixture was heated to 100 ° C. It melt-kneaded with the set biaxial kneading extruder. The obtained kneaded product is cooled, coarsely pulverized with a cutter mill, and then pulverized with a mechanical pulverizer. The resulting finely pulverized product is further classified with an air classifier, and classified fine powder having a weight average diameter of 6.8 μm. A body (toner particles) was obtained. Thereafter, the surface of the toner was treated with a faculty (manufactured by Hosokawa Micron Corporation).

  A negatively chargeable magnetic toner 1 was prepared by adding 1.2 parts of negatively chargeable hydrophobic silica to 100 parts of the toner particles with a Henschel mixer and sieving with a mesh having a mesh size of 150 μm.

[Example 2]
Toner 2 was obtained in the same manner as in Example 1 except that the raw material was changed from binder resin E to binder resin A.

Example 3
Toner 3 was prepared in the same manner as in Example 1 except that the binder resin E: 102 parts of the raw material was changed to 104 parts of the binder resin F and the addition amount of the wax A was changed from 5 parts to 3 parts. Obtained.

Example 4
Toner 4 was obtained in the same manner as in Example 1 except that the raw material was changed from binder resin E to binder resin G.

Example 5
Toner 5 was obtained in the same manner as in Example 1 except that 102 parts of binder resin E as a raw material was changed to 103 parts of binder resin H and 5 parts of wax A was changed to 4 parts of wax B. It was.

Example 6
Toner 6 was obtained in the same manner as in Example 1 except that 102 parts of binder resin E as a raw material was changed to 103 parts of binder resin I, and 5 parts of wax A was changed to 4 parts of wax C. It was.

[Comparative Example 1]
-Binder resin B: 100 parts-Magnetite: 95 parts-Wax 4: 3 parts-Wax C: 4 parts-Azo-based iron compound represented by the structural formula (5): 2 parts The above materials are mixed with a Henschel mixer Then, the mixture was melt kneaded by a biaxial kneading extruder set at 100 ° C. The obtained kneaded product is cooled, coarsely pulverized with a cutter mill, then finely pulverized using a fine pulverizer using a jet stream, and the resulting finely pulverized product is further classified with an air classifier, and the weight average diameter A fine powder (toner particles) of 6.8 μm was obtained.

  To 100 parts of the toner particles, 1.2 parts of negatively chargeable hydrophobic silica was externally added and mixed with a Henschel mixer, and sieved with a mesh having a mesh size of 150 μm to prepare a negatively chargeable magnetic toner 7.

[Comparative Example 2]
Toner 8 is obtained in the same manner as in Comparative Example 1 except that 100 parts of binder resin B of the raw material is changed to 104 parts of binder resin J and 4 parts of wax C is changed to 4 parts of wax D. It was.

[Comparative Example 3]
Binder resin B: 100 parts of the raw material was changed to binder resin K: 103 parts, wax 4: 3 parts were changed to wax 3: 4 parts, and wax C was removed, and was the same as in Comparative Example 1. Thus, toner 9 was obtained.

[Comparative Example 4]
Toner 10 is obtained in the same manner as in Comparative Example 1 except that the raw material is changed from binder resin E to binder resin L, wax 4: 3 parts is changed to wax 4: 5 parts, and wax C is removed. It was.

[Comparative Example 5]
Toner 11 was obtained in the same manner as in Comparative Example 1 except that the raw material wax C: 4 parts was changed to wax C: 10 parts and the addition of wax 4 was omitted.

  Table 3 shows the wax used for each toner, the addition timing of the wax, and the number of added parts.

  Table 4 shows the average circularity of the toner particles measured by a flow type particle image measuring apparatus of 3 μm or more.

(Evaluation)
<Printout test>
Using a commercially available laser beam printer Laserjet 9000 (process speed 225 mm / sec; manufactured by HP) in an environment of high temperature and high humidity (32.5 ° C., 80% RH), each process was charged with 1500 g of each toner. The sample was allowed to stand for 1 day to allow the toner to adjust to humidity and temperature, and then a printout test was conducted. The obtained images were evaluated for the following items.

(1) Image density In a high-temperature and high-humidity environment (32.5 ° C., 80% RH), 10000 sheets / day were printed on ordinary copying machine plain paper (75 g / m ² ) for 3 days. Evaluation was made by maintaining the image density at the end of the 10,000th day, the 20,000th day and the 30,000th day. Except when checking the image, durability was performed in a mode in which a grid pattern with a 5% printing rate was intermittent for 2 seconds after passing two sheets. The image density was measured by using a “Macbeth reflection densitometer” (manufactured by Macbeth Co., Ltd.) to measure a relative density with respect to a printout image of a white background portion having a document density of 0.00.

(2) Fog In a low-temperature and low-humidity environment (15 ° C., 10% RH), a commercially available laser beam printer LaserJet 9000 (process speed 225 mm / sec; manufactured by HP) and a sleeve-drum distance set to 235 μm Then, after allowing the toner to adjust to humidity and temperature by allowing it to stand for 1 day in the environment, the fog was calculated from the comparison of the solid white after the endurance printing of 20000 sheets with the whiteness of the transfer paper after printing.

  The whiteness was measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.).

(3) Fixability Fixability is an image obtained immediately after starting up LBP in a low-temperature, low-humidity environment (10 ° C., 15% RH) using 90 g / m ² basis weight plain paper for copying machines. Was applied with a pressure of 4.9 kPa, and the fixed image was rubbed with a soft thin paper, and evaluated by the reduction rate (%) of the image density before and after rubbing. The applied amount of toner was 5 g / m ² .
A: Less than 2% B: 2 to 4%
C: 4-8%
D: 8-12%
E: 13% or more

(4) Anti-offset property Anti-offset property is a sample image with an image area ratio of about 5% printed on A5 size paper in a high temperature environment (32.5 ° C) and then passed through A4 size paper. The evaluation was based on the degree of contamination on the image at that time. Copy paper (64 g / m ² ) was used as a test paper.
A: Not generated B: Slightly generated when looked closely C: Degree of offset although it is offset, but apparently offset generated

(5) Blocking After weighing 10 g of toner in a cup of polypropylene or the like and flattening the surface, spread the medicine-wrapped paper, put 10 g of iron powder carrier on it and leave it in a 50 ° C. environment for 5 days to change the toner blocking state. evaluated.
A: When the cup is tilted, the toner flows smoothly.
B: When the cup is rotated, the toner surface gradually collapses and becomes a smooth powder.
C: When force is applied from the outside while turning the cup, the toner surface collapses and gradually begins to flow.
D: A blocking sphere is generated. It collapses when pecked with a pointed object.
E: Blocking spheres are generated. Even if it sticks, it is hard to collapse.

(6) Evaluation of image black spots caused by adhesion of magnetic toner to fixing member The pressure roller and the image after printing out 30000 sheets in a low temperature and low humidity environment (temperature 15 ° C., 10% RH) were visually evaluated.
A Black spots are not seen.
B Toner adheres to the fixing roller but does not appear on the image.
C One or two black spots are seen on the image.
D There are 3 or more black spots on the image.

  Table 5 shows the evaluation results for the above six items.

Claims (8)

  A toner composition obtained by using a wax-containing resin composition containing a non-polar wax as a binder resin, melt-kneading the binder resin, constituent materials necessary for the toner such as a colorant, and polar wax is desired. The toner has an average circularity of 3 μm or more measured by a flow type particle image measuring device for the toner particles of 0.930 to 0.990, and an external additive as necessary. A method for producing a toner, comprising adding and mixing the toner.   A resin and a non-polar wax are mixed in the presence of a solvent, and the wax-containing resin composition obtained by removing the solvent is used as a binder resin, and the binder resin and a constituent material necessary for the toner, such as a colorant, A method for producing a toner, comprising producing a toner composition obtained by melt kneading polar wax through a step of obtaining a desired particle size.   A wax-containing resin composition obtained by melt-kneading a resin and a non-polar wax is used as a binder resin, and the binder resin, a constituent material necessary for a toner such as a colorant, and a polar wax are melt-kneaded. A method for producing a toner, comprising producing the obtained toner composition through a step of obtaining a desired particle size.   4. The method for producing a toner according to claim 1, wherein the nonpolar wax is a hydrocarbon wax.   The method for producing a toner according to claim 1, wherein the polar wax is a hydrocarbon wax obtained by alcohol modification or acid modification. The melting point (Tm1) measured by a differential scanning calorimeter (DSC) of the nonpolar wax has a relationship of the following formula with the melting point (Tm2) measured by DSC of the polar wax. The method for producing a toner according to any one of 1 to 5.
50 ≤ Tm2 (° C)
0 <Tm1 (° C.) − Tm2 (° C.) ≦ 70   The method for producing a toner according to claim 1, wherein the wax-containing resin composition contains two or more kinds of resins and a wax.   A toner composition obtained by using a wax-containing resin composition containing a non-polar wax as a binder resin, melt-kneading the binder resin, constituent materials necessary for the toner such as a colorant, and polar wax is desired. And a toner having an average circularity of 0.930 to 0.990 having an average circularity of 3 μm or more.