JP5035026B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention is for developing an electrostatic latent image in an electrophotographic method, an electrostatic recording method, an electrophotographic copying machine using an electrostatic printing method, a laser beam printer, and an electrostatic recording device using an electrostatic recording method. It relates to the toner used. More specifically, the present invention relates to an electrostatic charge image developing toner having excellent copy quality, long life, and environmental stability.

  Conventionally, in an electrophotographic copying machine, a laser beam printer, an electrostatic recording apparatus, and the like, an electrostatic charge image is formed by various means on an electrostatic charge image carrier such as an electrophotographic photosensitive member or an electrostatic recording body. The electrostatic image formed on the charge image carrier is dry-developed using powder toner in which a colorant, magnetic powder, etc. are dispersed in a binder resin together with carrier particles as necessary, and then the toner image is formed. In general, a desired copy or data is ejected by transferring the toner image to a transfer material such as transfer paper, and then subjecting the transferred toner image to heat and pressure fixing or flash fixing. As a method for developing an electrostatic image, a dry development method using a powder toner has been mainly employed in recent years.

  By the way, electrophotographic copying machines, laser beam printers, and the like have recently been made smaller and more personalized, but at the same time, there has been a demand for higher speed due to the demand for on-demand printing, and further reduction in energy is required. ing. Therefore, various attempts have been made to improve these apparatuses for forming a reliable and high-quality image at a high speed and with a low energy over a long period of time by a mechanism as simple as possible. In addition to such improvements in the apparatus, various attempts have been made to improve the toner used for development.

  For example, regarding a fixing method for fixing a toner image to a transfer sheet such as paper, a heat-pressure fixing method using a heating roller, a roll-shaped or long heat-resistant film (hereinafter referred to as a fixing belt) In this method, a heating member and a transfer sheet developing surface are opposed to each other through the fixing belt, and the transfer sheet is conveyed from the back while being pressed by a pressure roller and heat-fixed. In these methods, when the toner image is fixed, the heat roller or the fixing belt is in direct contact with the toner image, so that the heat is efficiently propagated to the toner. Therefore, the toner is melted quickly and smoothly with low energy. be able to. However, in such a method, at the time of fixing, the melted toner and the heat roller or the fixing belt are in direct contact with each other. Therefore, a part of the melted toner is transferred and adhered to the surface of the heat roller or the fixing belt. When the roller or the fixing belt comes into contact with the transfer sheet again, the transferred and adhered toner is transferred again to the transfer sheet, or when there is no transfer sheet, the transferred and adhered toner is transferred to the pressure roll, There is a problem of causing a so-called offset phenomenon such as adhesion of the transfer sheet to the back surface of the transfer sheet when it passes through the fixing device, thereby making the transfer sheet dirty.

  In order to prevent such a toner offset phenomenon, the surface of a conventional heat roll is formed of a releasable material such as silicone rubber or fluororesin, and a liquid having good releasability such as silicone oil is applied to the surface. Generally, the surface of a hot roll is covered with a releasable liquid film layer. According to this method, the occurrence of the offset phenomenon can be substantially prevented, but a problem arises in that a releasable liquid coating apparatus is required, and the silicone oil evaporates due to heat and contaminates the inside of the apparatus. Also, providing such a releasable liquid coating apparatus is incompatible with the downsizing of the apparatus. For this reason, the releasable liquid is not applied by a coating device, but the toner itself contains a releasable substance, the releasable substance is melted by heating during fixing, and the releasable liquid is supplied from the toner. In order to prevent the offset phenomenon, low molecular weight polyethylene, low molecular weight polypropylene, hydrocarbon waxes, natural waxes, modified waxes obtained by modifying these, and carnauba are proposed as release agents (release agents). As is well known, many waxes such as waxes and Fischer-Tropsch waxes have been proposed.

  Conventional toners for developing electrostatic images used in dry development methods use styrene resins or thermoplastic polyester resins as binder resins. Colorants such as dyes and pigments, charge control agents, waxes are used as binder resins. After a mold release agent such as is melt-kneaded and cooled, particles having an average particle diameter of about 1 to 15 μm are obtained through pulverization and classification steps. At this time, it is also well known that magnetic toner such as magnetite is added to and contained in the toner as necessary. When the magnetic powder is contained in the toner, it is not necessary to use a colorant because the magnetic powder also functions as a colorant. However, if necessary, a colorant may be further added. Normally, toner for developing an electrostatic image is manufactured through such a process. However, waxes added to impart releasability to the toner are poorly compatible with the binder resin in the first place and are uniform in the toner. It is difficult to disperse. In addition, if a large amount of wax is added to the toner to prevent the toner offset phenomenon, the wax is unevenly distributed and the wax is liberated when the toner is finely pulverized. Filming occurs, the developed image deteriorates, and problems such as a decrease in toner fluidity and blocking occur.

  Studies have been made so far to improve the compatibility between the toner binder resin and the release agent and to obtain a toner having no problems as described above. For example, it has been proposed to use a wax having a specific physical property or molecular structure such as a fatty acid wax having a polar group in the molecular structure or a modified wax having a polar group introduced in the molecule. In addition, the wax is dispersed in the binder resin in advance by, for example, removing the solvent after dissolving the binder resin and the wax in the solvent, or by polymerizing the binder resin in the presence of the wax. There has also been proposed a method of manufacturing a product and melt-kneading this and other components of the toner (for example, see Patent Document 1). Regarding the former, it cannot be said that the problem of uneven distribution or release of wax has been sufficiently improved, and the latter can be said to be a method that can be adopted when producing a styrene-based resin. In the present situation, it is difficult to produce a toner having good characteristics.

  Furthermore, it has been proposed to use a compatibilizing agent in order to improve the compatibility of the wax with the binder resin. As a method using such a compatibilizing agent, a method using a graft polymer obtained by grafting a vinyl polymer to an ethylene-glycidyl methacrylate copolymer as a compatibilizing agent for a binder resin made of a polymer having a carboxyl group (Patent Document 2). And a method of using an alkylene-glycidyl methacrylate copolymer as a compatibilizing agent for resin particles containing a hydroxyl group or an acid group such as a thermoplastic polyester resin (see Patent Document 3).

  A toner using rosin is also known in the past. For example, in order to improve the low-temperature fixability of the toner, it has been proposed to use a rosin ester obtained by esterifying a carboxylic acid of rosin with a monovalent or divalent alcohol. The softening point of the toner is preferably 70 to 120 ° C., and it is disclosed that the transparency of the toner can be expressed by using a rosin ester, and that the rosin ester is compatible with a release agent (Patent Document 4). reference). However, when a rosin ester obtained by esterifying a carboxylic acid with a monohydric or dihydric alcohol as described in Patent Document 4 was examined, the effect as expected in the uniform dispersion and compounding of the release agent was obtained. Couldn't get. In order to obtain a low-temperature fixing toner, it has also been proposed to use a rosin resin (rosin ester, rosin maleic resin, rosin-modified phenol resin, etc.) having a softening temperature of 130 ° C. or less as a binder resin for the toner ( (See Patent Document 5). Furthermore, a toner for developing an electrostatic charge image comprising a binder resin, a colorant, a charge control agent, and colored particles containing a rosin ester having an acid value of 2 or less and an external additive has also been proposed (see Patent Document 6). . However, these Patent Documents 5 and 6 do not disclose the use of rosin resin or rosin ester as a compatibilizing agent for a binder resin and a release agent.

JP-A-6-95433 JP-A-7-64323 JP 7-199542 A JP-A-10-307419 WO00 / 18840 JP 2003-322997 A

  In these methods, particularly when a polyester resin is used as the binder resin, it cannot be said that the low-temperature fixability and offset resistance of the toner are sufficient, the problem of uneven distribution of the release agent in the toner, and the release during fine pulverization. The problem of mold release has not been sufficiently solved. In general, the improvement in the compatibility of the release agent can be obtained to some extent for the styrene resin, but when the binder resin is a polyester resin, At present, it is difficult to obtain the same improvement in characteristics. Further, in the method using the above polymer as a compatibilizing agent, even when the compatibility is improved when a thermoplastic polyester resin is used as the binder resin, the charge amount and the resistance value change due to the addition of the compatibilizing agent. The toner performance deteriorates, such as a decrease in fixing performance, and there is a problem in terms of practicality. These materials are difficult to be miniaturized by ordinary methods, and need to be pulverized by means of freeze pulverization. In addition, since the compatibilizer used is also expensive, there is a problem in using it for a low-cost general-purpose toner because of the complexity of the production method and the cost.

  Furthermore, in recent years, from the viewpoint of environmental safety, it has been recommended to use a polyester that does not use a bisphenol A derivative. However, as a binder resin, in particular, neopentyl glycol, ethylene glycol or the like is used as an alcohol instead of a bisphenol A derivative. When used as a component, the compatibility between such a polyester resin and a release agent is very poor, and as a result, the amount of the release agent component is liberated during pulverization in the toner manufacturing process. In addition, if the compatibility between the binder resin and the release agent is not sufficient, the composition of the classified fine powder and the classified product (toner mother particles) that are separated when the toner is pulverized, in particular, the content of the release agent is different. There is also a problem that it is difficult to reuse fine powder as a toner material.

  On the other hand, regarding the release agent, release agents having a polar group such as carnauba wax have relatively good compatibility, but in the case of low molecular weight polypropylene, the compatibility is poor, and in particular, non-oxidation type low The molecular weight polypropylene was further incompatible. In addition, low-viscosity and high-melting point Fischer-Tropsch wax, which has a high effect of improving low-temperature fixability and offset resistance, has extremely poor compatibility, and improving compatibility with polyester resins is a major issue. Met.

  Furthermore, when a styrene acrylic resin is used as the binder resin, the effect of improving the compatibility / dispersibility of the release agent can be obtained by adding a release agent during the production of the binder resin. It was difficult to obtain improvements. Specifically, there is a problem that filming of the release agent component on the photosensitive member, the developing sleeve, and the carrier occurs, and a wave pattern (wave pattern) is generated in the toner layer on the developing sleeve. This problem is conspicuous in the case of low molecular weight polypropylene, and is a problem to be improved particularly when non-oxidized low molecular weight polypropylene is used. In addition, a styrene acrylic resin internally added with a release agent complicates the manufacturing process and leads to an increase in cost.

  The present invention has been made in view of the above circumstances, and in any binder resin, only a toner forming material is kneaded and compared with a conventionally proposed method, a low molecular weight polypropylene used as a release agent. The compatibility and dispersibility of Fischer-Tropsch wax are further improved, and there is no uneven distribution of low-molecular-weight polypropylene or Fischer-Tropsch wax in the toner, and no release of low-molecular-weight polypropylene or Fischer-Tropsch wax from the toner, so that the photoreceptor and the developing sleeve There are no problems such as filming on the carrier, development image deterioration, toner fluidity reduction, blocking, etc., and excellent charging characteristics, low-temperature fixability, offset resistance, and good development images over a long period of time. To provide an electrostatic charge image developing toner that can be formed It is an target.

  In addition, the present invention uses a polyester resin obtained by using a composition using neopentyl glycol, ethylene glycol or the like without using a bisphenol A derivative as an alcohol component, particularly considering environmental safety. In the toner, the compatibility with the low molecular weight polypropylene or Fischer-Tropsch wax used as a release agent is very good, the low-molecular weight polypropylene or Fischer-Tropsch wax in the toner is not unevenly distributed or liberated, and the same excellent effects as described above are obtained. It is an object of the present invention to provide a toner for developing an electrostatic image.

  As a result of intensive studies to solve the above problems, the present inventors have found that in an electrostatic charge developing toner containing at least a binder resin, a colorant, and a low molecular weight polypropylene or Fischer-Tropsch wax as a release agent, By adding a rosin-modified maleic acid resin having an acid value of 40 mgKOH / g or less to the toner, the compatibility and dispersibility of the low molecular weight polypropylene or Fischer-Tropsch wax in the binder resin are remarkably improved, and the low in the toner. There is no uneven distribution of molecular weight polypropylene or Fischer-Tropsch wax or liberation of low-molecular-weight polypropylene or Fischer-Tropsch wax from the toner, so that filming on the photoconductor, developing sleeve, and carrier, development image degradation, and toner fluidity decrease The No problems such Kkingu, and charging characteristics, low-temperature fixing property, excellent in offset resistance, found that it is possible to form a good developed image over a long period of time. In addition, such an effect is also obtained when the binder resin is a polyester resin using neopentyl glycol, ethylene glycol or the like having at least an alcohol component as an alcohol component, which is particularly poor in compatibility with a conventional release agent. I also found that it was played. The present invention has been made based on these findings.

That is, the present invention relates to the following inventions (1) to (18).
(1) In a toner for electrostatic charge development containing at least a binder resin, a colorant, and a low molecular weight polypropylene or Fischer-Tropsch wax as a release agent, the toner has an acid value of 40 mgKOH / g or less. An electrostatic charge image developing toner comprising an acid resin.
(2) The toner for developing an electrostatic charge image according to (1) above, wherein the rosin-modified maleic resin has a softening temperature of 120 to 150 ° C. by a ring and ball method.
(3) The electrostatic image developing toner according to (1) or (2) above, wherein the rosin-modified maleic resin has an acid value of 10 to 40 mgKOH / g.
(4) The content of the rosin-modified maleic resin is in the range of 0.3 to 3.5 times the content of the low molecular weight polypropylene, any of the above (1) to (3) The electrostatic image developing toner according to claim 1.
(5) The electrostatic image as described in (4) above, wherein the content of the rosin-modified maleic resin is in the range of 0.4 to 1.6 times the content of the low molecular weight polypropylene. Development toner.
(6) The low molecular weight polypropylene has a number average molecular weight in a range of 2,000 to 10,000 according to a vapor osmotic pressure method (VPO method), as described in any one of (1) to (5) above Toner for developing electrostatic images.
(7) The electrostatic image developing toner according to any one of (1) to (6) above, wherein the low molecular weight polypropylene has an acid value of 2 mgKOH / g or less.
(8) Any of (1) to (3) above, wherein the content of the rosin-modified maleic resin is in the range of 0.2 to 4.0 times the content of the Fischer-Tropsch wax. The electrostatic image developing toner according to claim 1.
(9) The electrostatic image according to (8) above, wherein the content of the rosin-modified maleic resin is in the range of 0.3 to 3.5 times the content of the Fischer-Tropsch wax. Development toner.

(10) The electrostatic charge image development according to any one of (1) to (3), (8) and (9) above, wherein the Fischer-Tropsch wax has a DSC melting point of 80 to 120 ° C. Toner.
(11) The electrostatic image developing toner according to any one of (1) to (10), wherein the binder is a polyester resin.
(12) The electrostatic image developing toner according to (11), wherein the polyester resin is a polyester resin containing at least neopentyl glycol and ethylene glycol as alcohol components.
(13) The electrostatic image developing toner according to (11) or (12) above, wherein the alcohol component of the polyester resin is a linear polyester resin containing no bisphenol A derivative.
(14) The electrostatic image developing toner according to any one of (11) to (13), wherein the acid component of the polyester resin is terephthalic acid.
(15) The toner for developing an electrostatic charge image according to any one of (11) to (14) above, wherein the polyester resin has an acid value of 5 to 20 mgKOH / g.
(16) The electrostatic charge developing toner according to any one of (1) to (10), wherein the binder resin is a styrene acrylic resin.
(17) The electrostatic image developing toner according to any one of (1) to (16) above, wherein the colorant is magnetic iron oxide.
(18) The electrostatic image developing toner according to any one of (1) to (17), which is obtained through at least a melt-kneading step, a pulverizing step, and a classification step.

  The toner for developing an electrostatic charge image of the present invention has excellent distribution properties (compoundability) and charging characteristics of low molecular weight polypropylene or Fischer-Tropsch wax, and good storage stability of classified products. Filming of low molecular weight polypropylene or Fischer-Tropsch wax on the developing sleeve and carrier does not occur, toner fluidity is not lowered, blocking and the like occur, and a good developed image can be formed over a long period of time. In addition, when the toner image formed by using the toner for developing an electrostatic charge image of the present invention is fixed through a fixing roller and a fixing sheet, no occurrence of offset is observed, and the low-temperature fixing property is good. Can be reduced in size and energy.

  Further, in the toner for developing an electrostatic charge image of the present invention, the low molecular weight polypropylene or Fischer-Tropsch wax has good dispersibility and distribution, so the content of the low-molecular weight polypropylene or Fischer-Tropsch wax in the classified product and classified fine powder. Shows almost the same value. Therefore, the classified fine powder can be reused as a toner forming material.

  Further, a polyester resin that does not use a bisphenol A derivative as an alcohol component has environmental safety, is inexpensive, and has a merit that the toner consumption can be reduced because the specific gravity of the polyester resin is small. Since it does not have an aromatic functional group, the compatibility with the release agent is particularly bad, and there is a drawback that a lot of released release agent is generated in the pulverization process at the time of toner production. By adding a rosin-modified maleic resin having an amount of 40 mg KOH / g or less, a release agent is uniformly distributed and blended in a polyester resin using, for example, neopentyl glycol and ethylene glycol as main components as an alcohol component. It is possible to obtain a toner with excellent dispersibility and distribution of the agent and excellent development characteristics. The reduction in the specific gravity of the toner can be expected the effect of toner consumption suppressed. Therefore, in the electrostatic image developing toner of the present invention, it is possible to obtain a toner having excellent quality without using a bisphenol A derivative in the alcohol component of the polyester resin.

In summary, the following excellent effects can be obtained in the present invention.
(A) Regardless of the binder resin, the low molecular weight polypropylene or Fischer-Tropsch wax in the toner is uniformly mixed, and the content of the low molecular weight polypropylene or Fischer-Tropsch wax in the classified product (toner base particles) and the classified fine powder As a result, the classified fine powder generated in the classification process can be recycled again as a raw material.
(B) Since low molecular weight polypropylene or Fischer-Tropsch wax is uniformly dispersed and blended in the binder resin, more low-molecular weight polypropylene or Fischer-Tropsch wax can be added to the toner than in the past. .
(C) By uniformly dispersing and blending low molecular weight polypropylene or Fischer-Tropsch wax in the toner, non-uniformity as a toner is eliminated, fluidity and chargeability are stabilized, and the photoconductor and development during development Generation of filming of low molecular weight polypropylene or Fischer-Tropsch wax on the sleeve or carrier and generation of a wave pattern (wave pattern) of the toner layer on the developing sleeve do not occur, and scumming (fogging) of the non-image area is also reduced. In addition, there is obtained a toner that has no problems such as deterioration of the developed image, decrease in fluidity of the toner, blocking, etc., is excellent in charging characteristics, low-temperature fixability, and offset resistance, and can form a good developed image over a long period of time. It is done. This is particularly effective as a toner used for one-component development without using a carrier.
(D) Even when a highly environmentally safe polyester resin using at least neopentyl glycol and ethylene glycol as the alcohol component instead of the bisphenol A derivative is used as the binder resin, the composition of the release agent becomes uniform, and the characteristics Therefore, it is possible to provide a toner for developing an electrostatic image having excellent environmental safety and a toner not using such a bisphenol A derivative has a low density.

  As described above, the present invention relates to an electrostatic charge developing toner containing at least a binder resin, a colorant, and a low molecular weight polypropylene or Fischer-Tropsch wax as a release agent, and the toner has an acid value of 40 mgKOH / g or less. A rosin-modified maleic acid resin. Hereinafter, materials used for the toner for developing an electrostatic charge according to the present invention will be described in detail sequentially from the rosin-modified maleic resin that characterizes the present invention.

  The rosin-modified maleic resin used in the present invention is an additive formed by Diels-Alder reaction of rosin and maleic acid (in the present invention, maleic acid includes maleic anhydride and fumaric acid). An alkyd resin obtained by reacting a polyhydric alcohol such as erythritol or ethylene glycol. The acid value is determined by the blending ratio of the polyhydric alcohol to be reacted with the adduct of rosin and maleic acid and the degree of esterification. However, the rosin modified maleic resin used in the present invention can be obtained by setting the acid value to 40 mgKOH / g or less. In addition to the polyhydric alcohol, a polybasic acid may be used in combination, and a long chain alkyd resin may be bonded to the rosin skeleton. Here, maleic acid and maleic anhydride and fumaric acid can be used in the same manner. In the present invention, rosin-modified fumaric acid resin is also included in rosin-modified maleic acid resin.

  Examples of the rosin component of the rosin-modified maleic resin include tall oil rosin, gum rosin, wood rosin and the like mainly composed of abietic acid, dehydroabietic acid, neoabietic acid, parastrinic acid, pimaric acid, and isopimaric acid.

  Examples of the polyhydric alcohol to be reacted with the rosin and maleic acid adduct include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol. When a polybasic acid used as a raw material for the alkyd resin is used together with these polyhydric alcohols, the polybasic acid may be phthalic anhydride, terephthalic acid, isophthalic acid, adipic acid, maleic acid, itaconic acid, succinic acid. And sebacic acid.

  Examples of commercially available rosin-modified maleic acid resins having an acid value of 40 mgKOH / g or less that can be used in the present invention include Marquide No1, Marquide No2, Marquide No5, Marquide No6, Marquide No8 (above, manufactured by Arakawa Chemical Industries, Ltd.) ) Etc.

  The acid value of the rosin-modified maleic resin is preferably 40 mgKOH / g or less, and more preferably 10 to 40 mgKOH / g or less. If the acid value is within this range, the low molecular weight polypropylene and the Fischer-Tropsch wax are uniformly dispersed in the binder resin, and the blending amount of the low molecular weight polypropylene and the Fischer-Tropsch wax in the toner can be made uniform. When the acid value is larger than 40 mgKOH / g, the effect of uniformly dispersing and distributing the low molecular weight polypropylene and the Fischer-Tropsch wax in the binder resin is reduced. In particular, when the toner is finely pulverized, the low molecular weight polypropylene and the Fischer-Tropsch wax are liberated, and filming occurs due to adhesion to the photoreceptor, the developing sleeve, and the carrier, resulting in deterioration of the developed image. In addition, there is a low molecular weight polypropylene or Fischer-Tropsch wax released in the toner, which causes problems such as a decrease in toner fluidity and blocking.

  In the present invention, the content of the rosin-modified maleic resin is preferably in the range of 0.3 to 3.5 times (weight basis) with respect to the content of the low molecular weight polypropylene, A range of 1.6 times is more preferable. If it is less than 0.3 times, the effect of improving dispersibility and compatibility cannot be obtained, and there may be cases where low molecular weight polypropylene is liberated. On the other hand, if it exceeds 3.5 times, the rosin-modified maleic resin becomes excessive, and the toner formulation cannot be controlled, causing problems such as deterioration of image characteristics and deterioration of fixing performance (occurrence of hot offset). .

  Furthermore, the content of the rosin-modified maleic resin of the present invention is preferably in the range of 0.2 to 4.0 times the Fischer-Tropsch wax content, and in the range of 0.3 to 3.5 times. It is more preferable that If it is less than 0.2 times, the effect of improving dispersibility and compatibility cannot be obtained, and the Fischer-Tropsch wax may be released. On the other hand, if the ratio exceeds 4.0 times, the rosin-modified maleic resin becomes excessive and the toner formulation cannot be controlled, causing problems such as deterioration of image characteristics and deterioration of fixing performance (occurrence of hot offset). .

  In consideration of fixing property and storage stability as a toner, the softening temperature of the rosin-modified maleic resin of the present invention by the ring and ball method (JIS K 5903) is preferably in the range of 120 to 150 ° C. When the temperature is lower than 120 ° C., storage stability is deteriorated and hot offset is caused. When the temperature is higher than 150 ° C., it is difficult to melt and does not serve as a compatibilizing agent, resulting in poor fixing properties.

  The true density of the rosin-modified maleic resin used in the present invention is preferably in the range of 1.08 to 1.25 (g / cc). This value indicates that the true density of low molecular weight polypropylene and Fischer-Tropsch wax is about 0.9 (g / cc), and the true density of the polyester resin is about 1.1 to 1.3 (g / cc). Therefore, it is an intermediate numerical value between the two, and is an effective numerical range for achieving compatibilization.

  In the present invention, the reason why the dispersibility and distribution of low molecular weight polypropylene or Fischer-Tropsch wax are greatly improved by the addition of a rosin-modified maleic resin having an acid value of 40 mgKOH / g or less is completely elucidated. It has not been. The present inventors presume as follows, but the present invention is not limited by the following description. That is, the improvement in dispersibility and distribution of low molecular weight polypropylene or Fischer-Tropsch wax is considered to be in the structure of the rosin-modified maleic resin. The rosin-modified maleic acid resin is an adduct of tribasic acid made from rosin (main component is abietic acid) and maleic acid, and esterified with polyhydric alcohol. Of the rosin skeleton. The part of the polar group having this acid is the part of the carboxyl group derived from unreacted abietic acid and the carboxyl group of maleic acid, and is compatible with the polar group of the binder resin. It reacts and is compatible with the part. In addition, the nonpolar rosin skeleton having a conjugated double bond is compatible with low molecular weight polypropylene or Fischer-Tropsch wax. As a result, the effect of uniformly dispersing and distributing the low molecular weight polypropylene or the Fischer-Tropsch wax in the binder resin can be obtained. For this reason, it is particularly effective in the use of non-oxidized low molecular weight polypropylene having no polarity and having an acid value of 2 mgKOH / g or less as low molecular weight polypropylene.

  Next, the release agent used in the toner of the present invention will be described. In the present invention, low molecular weight polypropylene and Fischer-Tropsch wax are used as the release agent. First, low molecular weight polypropylene, but there are two types of low molecular weight polypropylene, a non-oxidized type and an oxidized type. In the present invention, it is preferable to use a non-oxidized low molecular weight polypropylene. The non-oxidized type means herein an acid value having a numerical value of 2 mgKOH / g or less. The molecular weight of the low molecular weight polypropylene is preferably in the range of 2,000 to 10,000 as measured by the molecular weight by the vapor osmotic pressure method (VPO method). Moreover, it is preferable that a softening temperature is a numerical value of 130-150 degreeC. As such non-oxidized low molecular weight polypropylene, for example, Hymer TP-32, Biscol 550P, 660P, 330P manufactured by Sanyo Chemical Industries, Ltd., NP055, NP056, NP105, NP505 manufactured by Mitsui Chemicals, Inc. can be preferably used. . By using a rosin-modified maleic resin having a softening temperature in the range of 120 to 150 ° C., the value becomes close to the softening temperature of low-molecular weight polypropylene, and the compatibility between the rosin-modified maleic resin and low-molecular weight polypropylene is improved. It is.

  The low molecular weight polypropylene used in the electrostatic image developing toner of the present invention is preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of the binder resin. When the content of the low molecular weight polypropylene exceeds 8 parts by weight, the release agent can be uniformly mixed and dispersed in the binder resin by the action of the rosin-modified maleic resin, but the content of the low molecular weight polypropylene is Excessive amount causes adhesion of low molecular weight polypropylene component to the developing sleeve and the photosensitive drum, spent to the carrier, etc., causes scattering of toner in the machine, increased fog, image deterioration, and quality deteriorates. . On the other hand, when the amount is less than 0.5 parts by weight, the effect of adding low molecular weight polypropylene is not observed, that is, the fixing performance is deteriorated and offset is likely to occur. As described above, the addition amount of the rosin-modified maleic resin is also determined in consideration of the balance with the addition amount of the low molecular weight polypropylene.

  On the other hand, the Fischer-Tropsch wax used in the present invention has been conventionally produced by the Fischer-Tropsch method using coal as a raw material. However, due to the problems of resource depletion and the complexity of the production process, alternative raw materials are used on a global scale. As a result, the raw material has been shifted from coal to environmentally friendly natural gas, and the manufacturing process has been changed to an easy one. Using natural gas consisting of methane, ethane, propane, butane, etc. as raw materials, these are converted into synthesis gas consisting of carbon monoxide and hydrogen by autothermal reforming. Fischer-Tropsch wax is produced by a Fischer-Tropsch synthesis method using this synthesis gas as a raw material. Thus, Fischer-Tropsch wax is a wax-like hydrocarbon synthesized by catalytic hydrogenation of carbon monoxide, and is a linear paraffinic wax with few methyl branches structurally. Among paraffin waxes, it is particularly hard, has a high molecular weight and high crystallinity, is characterized by a high freezing point and low viscosity when melted, and is excellent in low-temperature fixability and offset resistance compared to other release agents. Specifically, Sasol-made paraflint H1-N4, HI-N6, A3, Shell MDS FT-100, MDP-7000, MDP-7010, and the like can be used. Among them, H1-N4, FT-100 Is preferred because of its low-temperature fixability and storage stability. Moreover, the thing whose melting | fusing point by a differential scanning calorimeter (henceforth DSC) is 80-120 degreeC is preferable. When the melting point is lower than 80 ° C., problems are likely to occur in the storage stability of the toner, and the fluidity tends to be poor. On the other hand, when the temperature is higher than 120 ° C., the effect of lowering the melt viscosity of the toner is small, and it becomes difficult to obtain the low-temperature fixability of the toner. Further, the penetration at 25 ° C. measured by JIS K-2235 is preferably 3 or less, and more preferably 2 or less. If the penetration is greater than 3, the fluidity tends to deteriorate when toner is formed, and problems such as storage stability and tribocharging with carrier particles tend to occur.

  The melting point by DSC in the present invention is the peak temperature of absorbed heat, and the temperature is raised between 20 and 150 ° C. at a rate of 10 ° C./min using DSC-60 manufactured by Shimadzu Corporation. The process of rapidly cooling from 150 ° C. to 20 ° C. is repeated twice, and the peak temperature of the second heat absorption is measured.

  The Fischer-Tropsch wax used in the toner for developing an electrostatic charge image of the present invention is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin. If the Fischer-Tropsch wax content exceeds 10 parts by weight, the content of the Fischer-Tropsch wax becomes excessive, although the rosin-modified maleic resin can be uniformly mixed and dispersed in the binder resin. As a result, adhesion of the Fischer-Tropsch wax component to the developing sleeve and the photosensitive drum, spent to the carrier, and the like are caused, scattering of the toner in the machine, increase of fogging, image deterioration, and quality are deteriorated. On the other hand, if the amount is less than 0.5 parts by weight, the effect of adding the Fischer-Tropsch wax is not seen, that is, the fixing performance is lowered, and offset is likely to occur. As described above, the addition amount of the rosin-modified maleic resin is also determined in consideration of the balance with the addition amount of the Fischer-Tropsch wax.

  In the present invention, the acid values of rosin-modified maleic resin and Fischer-Tropsch wax can be measured according to the method of JIS K-0070. The acid value is expressed in mg of potassium hydroxide necessary to neutralize 1 g of the sample.

  As the binder resin used in the toner for developing an electrostatic charge image of the present invention, any conventionally known binder resin for toner can be used. Binder resins that can be used include homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer Polymer, styrene-vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl Styrenes such as methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Copolymer or crosslinked Styrene copolymer: polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, Examples thereof include an epoxy resin, a xylene resin, a polyvinyl butyral, a terpene resin, a coumarone indene resin, and a petroleum resin. Of these, polyester resins and styrene copolymers are preferably used. In the case of a styrene copolymer, a styrene acrylic resin is preferred.

  Examples of the alcohol component constituting the polyester resin that can be preferably used in the toner of the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4- Butanediol, 2,3-butanediol, 1,4-butenediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexane Diols such as diol, bisphenol A, hydrogenated bisphenol A, 1,4-bis (hydroxymethyl) cyclohexane, bisphenol derivatives represented by the following general formula (1), glycerol, diglycerol, sorbit, sorbitan, butanetriol Trimethylol ethane, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, polyhydric alcohols and the like. These may be used alone or in combination of two or more.

(In the formula, R is 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.)

  It is particularly preferable that the polyester resin used in the electrostatic image developing toner of the present invention contains at least neopentyl glycol and ethylene glycol as alcohol components. By using a polyester resin having at least neopentyl glycol and ethylene glycol as alcohol components together with the rosin-modified maleic acid resin having an acid value of 40 mgKOH / g or less, the release agent can be uniformly distributed and blended in the toner. In the case of a linear polyester resin having no crosslinking component, the function of a rosin-modified maleic acid resin having an acid value of 40 mgKOH / g or less is effective in uniformly distributing the release agent.

  As an alcohol component of the polyester resin containing at least neopentyl glycol and ethylene glycol as alcohol components, in addition to neopentyl glycol and ethylene glycol which are essential components, 1,2-propylene glycol, 1, 3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,4-butenediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6- Hexanediol, 2-ethyl-1,3-hexanediol, glycerol, diglycerol, sorbit, sorbitan, butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythris Torr, it is possible to use tripentaerythritol, a polyhydric alcohol and the like. Of these, diethylene glycol is preferably used as an optional component. On the other hand, bisphenol A derivatives such as bisphenol A, hydrogenated bisphenol A, and 1,4-bis (hydroxymethyl) cyclohexane increase the amount of consumption when toner is produced due to environmental problems and large specific gravity. It has disadvantages and is preferably not used.

  And when the whole polyester is 100 mol% (including 50 mol% of the acid component and 50 mol% of the alcohol component), the alcohol component, neopentyl glycol and ethylene glycol, are preferably 35 to 50 mol%, more preferably 40 to 48 mol%. Diethylene glycol is preferably used as the remaining alcohol component.

  Examples of the acid component of the polyester resin used in the toner for developing an electrostatic charge image of the present invention include divalent carboxylic acids such as benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; Alkyl dicarboxylic acids such as acids, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; and succinic acid or anhydrides further substituted with an alkyl group having 16 to 18 carbon atoms; fumaric acid, maleic acid, citraconic acid, Examples of unsaturated dicarboxylic acids such as itaconic acid and glutaconic acid or anhydrides thereof; cyclohexanedicarboxylic acid; naphthalenedicarboxylic acid; diphenoxyethane-2,6-dicarboxylic acid, and the like. Is trimellitic acid, pyromellitic acid, naphthalenetri Carboxylic acid, butane tricarboxylic acid, hexane tricarboxylic acid, tetra (methylene carboxyl) methane, octane tetracarboxylic acid, and benzophenone tetracarboxylic acid anhydride, and the like. These may be used alone or in combination of two or more.

  Preferred acid components include phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-dodecenyl succinic acid or its anhydride, dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, trimellitic acid or its anhydrous Tricarboxylic acids such as products.

  In the electrostatic charge image developing toner of the present invention, the polyester resin preferably has an acid value in the range of 5 to 20 mgKOH / g. When the acid value of the polyester resin is less than 5 mgKOH / g, the reactivity with the rosin-modified maleic acid resin (compatibilizing agent) is lowered, which may cause a problem of liberation of low molecular weight polypropylene. When the acid value of the polyester resin exceeds 20 mgKOH / g, the storage stability and development characteristics of the obtained toner at high temperature and high humidity may be deteriorated.

  In the present invention, the acid value of the binder resin can be measured according to the method of JIS K-0070. The acid value is represented by the number of mg of potassium hydroxide required to neutralize 1 g of toner. However, when the toner contains a magnetic substance, the residue obtained by eluting the magnetic substance with an acid is 1 g of toner.

  The polyester resin may be a homopolyester or a copolyester alone or a blend of two or more of these. The polyester resin preferably has a weight average molecular weight (Mw) of 5,000 or more in terms of molecular weight measured by gel permeation chromatography (GPC) from the viewpoint of offset resistance and low-temperature fixability. More preferably, 1,000,000,000. When the weight average molecular weight of the polyester resin decreases, the offset resistance of the toner tends to decrease, and when the weight average molecular weight increases, the fixability tends to decrease. In addition, the polyester resin used has a type having a molecular weight distribution curve of two peaks composed of a specific low molecular weight condensation polymer component and a specific high molecular weight condensation polymer component, or has a single molecular weight distribution curve. Any type.

  In the styrene copolymer that can be preferably used in the toner of the present invention, the comonomer for the styrene monomer includes acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, acrylic acid Monocarboxylic acid having a double bond such as 2-ethylhexyl, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, or a substituted product thereof; Dicarboxylic acids having a double bond such as maleic acid, methyl maleate, butyl maleate, and dimethyl maleate and their substituted products; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; Ren, propylene, ethylenic olefins such as butylene; vinyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl monomers such as vinyl ethers such as vinyl isobutyl ether. These may be used alone or in combination of two or more. In particular, in the present invention, it is preferable to use a styrene acrylic resin which is a copolymer of styrene and butyl acrylate, acrylate-2-ethylhexyl, methyl methacrylate or butyl methacrylate.

  As a crosslinking agent used when producing a crosslinked styrene copolymer, a compound having two or more polymerizable double bonds is mainly used, and an aromatic divinyl compound such as divinylbenzene or divinylnaphthalene; Carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and three These compounds having a vinyl group are used alone or as a mixture.

The styrene copolymer has at least one peak in the region of 3 × 10 ^{3 to} 5 × 10 ⁴ in the molecular weight distribution measured by GPC, and at least one other peak or shoulder in the region of 10 ⁵ or more. A styrene-acrylic copolymer having a molecular weight is preferred from the viewpoint of fixability. If a peak is present in a region smaller than 3 × 10 ^{3 in} terms of molecular weight, although low-temperature fixability is good, hot offset or toner fusing is likely to occur, and the toner component adheres to the developing sleeve and the photoreceptor. As a result, image contamination occurs. Further, if there is no peak in the region of 3 × 10 ^{3 to} 5 × 10 ⁴ and the peak exceeds 5 × 10 ⁴ , the fixing performance is deteriorated. As for the molecular weight of the styrene acrylic resin used in the present invention, Mw is preferably 10 × 10 ⁴ to 30 × 10 ⁴ , and Mn is preferably 0.2 × 10 ^{4 to} 1.0 × 10 ⁴ .

  In the production of the vinyl polymer, a polymerization initiator is used. Any conventionally known polymerization initiator can be used. Polymerization initiators include benzoyl peroxide, lauroyl peroxide, tertiary butyl hydroperoxide, tertiary butyl peroxybenzoate, ditertiary butyl peroxide, cumene hydroperoxide, dicumyl peroxide, azoisobutyrate. Ronitrile, azobisvaleronitrile, and the like have been preferably used conventionally. The use ratio of the polymerization initiator to the vinyl monomer is generally 0.2 to 5% by mass. The polymerization temperature is appropriately selected according to the type of monomer and initiator used.

  In the present invention, the binder resin is preferably 40 to 95 parts by weight per 100 parts by weight of the toner.

  The glass transition temperature (Tg) of the binder resin is preferably in the range of 50 to 70 ° C. In the present invention, the glass transition temperature (Tg) is an extension of the baseline below Tg when measured with a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation) at a heating rate of 10 ° C./min. The value of the intersection with the tangent of the endothermic curve near Tg was determined and measured.

  As the colorant used in the electrostatic image developing toner of the present invention, the following organic pigments of yellow, magenta, cyan, and black, carbon black, and magnetic materials, which are used in conventional toners, are preferably used. These can be used alone or in admixture of two or more.

  As the yellow organic pigment, compounds represented by benzimidazolone compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex compounds, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 139, 147, 150, 168, 174, 176, 180, 181, 191 and the like are preferably used. Among them, it is preferable to use a benzimidazolone compound.

  As magenta organic pigments, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, 255 and the like are preferably used. Among them, it is preferable to use a quinacridone compound.

  As the cyan organic pigment, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are preferably used. Among these, it is preferable to use a copper phthalocyanine compound.

  As carbon black, various types such as furnace black, channel black, acetylene black, etc. can be used. However, furnace black carbon is preferable because it has the effect of reducing fog (soil on the white background) in image characteristics. It is.

  Further, in the electrostatic image developing toner of the present invention, magnetic powder is internally added as necessary to obtain a magnetic toner. Examples of these magnetic powders include magnetic iron oxides such as magnetite, maghemite and ferrite, or compounds of divalent metals and iron oxides, metals such as iron, cobalt and nickel, or aluminums of these metals, cobalt, copper, Examples include powders of alloys of metals such as lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures of these powders. These magnetic powders preferably have an average particle size of about 0.1 to 2 μm, more preferably about 0.1 to 0.5 μm. The content of the magnetic powder in the toner is about 20 to 200 parts by weight, preferably 40 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Further, the saturation magnetization of the toner is preferably 15 to 35 emu / g (measuring magnetic field: 1 kilo-Oersted). In the electrostatic image developing toner of the present invention, the magnetic powder also functions as a colorant.

  The electrostatic image developing toner as described above is required to hold positive or negative charges depending on the polarity of the electrostatic latent image to be developed. A charge control agent is added to and contained in the toner as necessary in order to impart a desired polarity of charge to the electrostatic image developing toner.

  As the charge control agent used for the positively chargeable toner, nigrosine dye, fatty acid metal derivative, triphenylmethane dye, quaternary ammonium salt compound, diorganotin oxide, diorganotin borate, etc. alone or in combination of two or more. Can be used. Of these, nigrosine dye is preferably used. The charge control agent is used in an amount of 0.5 to 10 parts by weight with respect to 100 parts of the binder resin, and 0.7 to 8 parts by weight is preferable in that it can maintain and stabilize excellent chargeability.

  The nigrosine dye is preferably nigrosine base, or a nigrosine base modified with maleic acid resin, xylene resin, or the like. Specifically, N-01, N-04, N-07, Nigrosine Base EX manufactured by Orient Chemical Industries, Ltd. CCA-1, CCA-3 manufactured by Chuo Synthetic Chemical Co., Ltd. Specific examples of the quaternary ammonium salt compound include P-51 and P-53 manufactured by Orient Chemical Industries, and TP-302 and TP-415 manufactured by Hodogaya Chemical Co., Ltd.

Examples of the charge control agent used in the negatively chargeable toner include a metal salt compound of an aromatic hydroxycarboxylic acid, the same metal complex, a metal complex of a monoazo dye, and a phenol-based condensate such as calixarene. Among them, it is preferable to use a metal salt compound of an aromatic hydroxycarboxylic acid or a metal complex of a monoazo dye. In the metal salt compound of aromatic hydroxycarboxylic acid, the aromatic hydroxycarboxylic acid is preferably salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-hydroxy-2-naphthoic acid, or 3-phenylsalicylic acid, and the central metal Includes Cr, Zn, Ca, Al, Fe, Zr and the like.
Moreover, the said charge control agent is used by 0.5-10 weight part with respect to 100 weight part of polyester resins, and 0.7-8 weight part is preferable at the point which can maintain and stabilize the outstanding charging property.

  Specific examples of the charge control agent used in the negatively chargeable toner include a metal salt compound of an aromatic hydroxycarboxylic acid and a metal complex of the same, Bontron E-81, E-82, E-84 manufactured by Orient Chemical Industries, Ltd. Examples include TN-105 manufactured by Hodogaya Chemical Co., Ltd., and compounds described in Japanese Patent Nos. 2885238 and 3785975. Examples of the metal complex of the monoazo dye include Bontron S-34 and S-44 manufactured by Orient Chemical Industries, and Spiron Black TRH, T-77 and T-95 manufactured by Hodogaya Chemical Co., Ltd. As another negative charge control agent, Clariant copy charge N4P may be mentioned.

  Among these, a charge control agent preferably used in combination with a rosin-modified maleic acid resin having an acid value of 40 mgKOH / g or less is a metal salt compound of an aromatic hydroxycarboxylic acid. The reason is that the alcohol group (—OH group) of the metal salt compound of the aromatic hydroxycarboxylic acid reacts with the acid component of the rosin-modified maleic resin, so that the metal salt compound of the aromatic hydroxycarboxylic acid is contained in the polyester resin. Is preferably dispersed. As a result, low molecular weight polypropylene, Fischer-Tropsch wax, and a charge control agent are uniformly dispersed in the toner.

  In the charge control agent used in the present invention, the volume average particle size (D50: median diameter) of the charge control agent is preferably in the range of 3 to 10 μm. (The particle size distribution is a value measured by Beckman Coulter Multisizer) By satisfying this range, the charge control agent is uniformly dispersed in the binder resin, and a stable charge amount as a toner is maintained. Is possible. If the particle size D50 of the charge control agent exceeds 10 μm, it becomes difficult to uniformly disperse the charge control agent in the binder resin, resulting in a bias in the content of the charge control agent. This may cause fogging of the image and scattering in the aircraft. On the other hand, if the particle size D50 of the charge control agent is smaller than 1 μm, the specific surface area of the charge control agent per unit weight increases, which causes an excessive increase (charge up) of the charge amount of the toner. A wave pattern on the developing sleeve is generated in a low temperature and low humidity environment, which leads to image defects, which is not preferable.

  In the toner for developing an electrostatic image of the present invention, known additives used in the production of the toner, such as a lubricant, a fluidity improver, an abrasive, a conductivity imparting agent, and an image peeling preventing agent, as necessary. Can be added internally or externally. Examples of these additives include polyvinylidene fluoride and zinc stearate as a lubricant, and silica, aluminum oxide, titanium oxide, silicon aluminum co-oxide produced by a dry method or a wet method as a fluidity improver. , Silicon-titanium co-oxide and those hydrophobized, etc., and abrasives include silicon nitride, cerium oxide, silicon carbide, strontium titanate, tungsten carbide, calcium carbonate, and those hydrophobized. Examples of the conductivity imparting agent include carbon black and tin oxide. In addition, fine powders of fluorine-containing polymers such as polyvinylidene fluoride are preferable from the viewpoints of fluidity, abrasiveness, charge stability, and the like.

  As the fluidity improver, it is preferable to contain hydrophobized silica, silicon aluminum co-oxide, and silicon titanium co-oxide fine powder as external additives. Examples of the hydrophobizing treatment of these fine powders include treatment with a silane coupling agent such as silicone oil and tetramethyldisilazane. Further, positively charged silica having a positive tribo charge relative to the iron powder carrier when measured by the blow-off method can also be used. In order to obtain this positively chargeable silica, it may be treated with a silicone oil having an organo group having at least one nitrogen atom in the side chain, or a nitrogen-containing silane coupling agent. The amount of the hydrophobized fine powder such as silica subjected to hydrophobization treatment is 0.01 to 20%, preferably 0.03 to 5%, based on the developer weight.

  Specific examples of the surface treatment agent for the fluidity improver used in the present invention include organoalkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, dimethyldichlorosilane, trimethylchlorosilane, octadecyltrichlorosilane, and t-butyldimethylchlorosilane. Organochlorosilanes such as hexamethyldisilazane, etc., organoaminosilanes such as bis (dimethylamino) dimethylsilane, dimethyl silicone oil, methylphenyl silicone oil, straight silicone oil such as methyl hydrogen silicone oil, modified silicone Oil etc. can be used. Examples of the modifying group used in the modified silicone oil include a methylstyrene group, a long-chain alkyl group, a polyether group, a carbinol group, an amino group, an epoxy group, a carboxyl group, a higher fatty acid group, a mercapto group, and a methacryl group. .

  In the toner for developing an electrostatic image of the present invention, the above materials are premixed by a dry blender, a Henschel mixer, a ball mill or the like, and then the mixture is heat kneaded by a hot roll, a kneader, a uniaxial or biaxial extruder, or the like. It is preferable to produce the mixture by melt kneading with a machine, pulverizing the obtained kneaded product after cooling, and classifying it to a desired particle size as necessary. For example, in order to disperse low molecular weight polypropylene in a binder resin such as a polyester resin and to obtain the effect of a rosin-modified maleic acid resin, the kneading temperature is 120 to 180 ° C. (measure the temperature at the time of discharge). Is preferred. If it is out of these ranges, the function as a compatibilizer of the rosin-modified maleic resin cannot be brought out. If the temperature exceeds 180 ° C., the share of kneading cannot be applied, and the dispersion of the low molecular weight polypropylene and the charge control agent becomes worse. If the temperature is lower than 120 ° C., the low molecular weight polypropylene does not melt and cannot be dispersed.

  The toner base particles (classified product) obtained by classification are finally added with an external additive in a post-processing step to become a toner. However, regarding the method for producing the toner for developing an electrostatic charge image of the present invention, the production of the toner base particles is not limited to this kneading and pulverization method. For example, after the toner constituent material is dispersed in the binder resin solution , By spray drying, or by any of the conventionally known methods such as a method in which a predetermined material is mixed with a monomer that constitutes the binder resin to obtain an emulsified suspension, followed by polymerization to obtain toner. Of course, it is also good. The electrostatic charge image developing toner of the present invention preferably has a volume average particle size of 3 to 15 μm, more preferably 5 to 12 μm.

  In the post-treatment step, a Henschel mixer, a super mixer, etc. are usually used. The post-processing step is an important step in controlling the adhesion state of the external additive on the toner surface. The adhesion state of these external additives varies greatly depending on the post-treatment process conditions. Usually, it is preferable to mix under conditions of 10 to 40 m / sec. At the peripheral speed of the mixer. When mixed under conditions exceeding 40 m / sec., The external additive is embedded in the toner base particles and does not function. If it is lower than the range, the external additive will be liberated, and the external additive effect will not work.

  As a final step after adding and mixing the external additive, the toner is manufactured through a sieving step for the purpose of removing foreign matters in the toner. As the type of sieve, a vibration sieve, an ultrasonic vibration sieve, a gyro shifter, or the like can be used. At that time, the mesh openings used for sieving affect the toner quality. In the present invention, it is preferable to use a sieve mesh having an opening of 40 to 300 μm. Furthermore, the range of 45-180 micrometers is preferable. When toner is manufactured using a mesh having a mesh size larger than 300 μm, coarse particles contained in the toner base particles are mixed in the toner, and aggregates of external additives are contained in the toner. .

  In the toner for developing an electrostatic charge image of the present invention, a toner (toner mother particle) having a weight average particle diameter of 3 to 15 μm is preferable, and in particular, 12 to 60% by number of toner particles having a particle diameter of 5 μm or less. 1 to 33% by number of toner particles having a particle diameter of 8 to 12.7 μm are contained, 2.0% by weight or less of toner particles having a particle diameter of 16 μm or more are contained, and the weight average particle diameter of the toner is 4 to 10 μm is more preferable from the viewpoint of development characteristics. The toner particle size distribution can be measured using, for example, a Coulter counter (Multisizer 3).

  When the toner for developing an electrostatic image of the present invention is used as a two-component dry developer, a carrier is included. The carrier used together with the toner for developing an electrostatic charge image of the present invention may be any carrier conventionally used in a two-component dry developer, for example, a ferromagnetic metal such as iron powder or an alloy powder of a ferromagnetic metal. Ferrite powder and magnetite powder composed of elements such as nickel, copper, zinc, magnesium and barium are preferred. These carriers may be coated with a resin such as a styrene / methacrylate copolymer, a styrene polymer, or a silicone resin. As a method of coating the carrier with a resin, a coating resin is dissolved in a solvent, and this is applied onto the core particles by a dipping method, a spray method, a fluidized bed method, etc., dried, and then heated and applied as necessary. Any known method such as a method of curing the film can be used. The average particle diameter of the carrier is usually 15 to 200 μm, preferably 20 to 100 μm.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the embodiments of the present invention are not limited to these examples. In the following, all parts represent parts by weight. In addition, detailed conditions and results of the following Examples and Comparative Examples are shown in Tables 1 to 15 below.

  The binder resin, release agent, and rosin-modified maleic resin used in the following examples and comparative examples are as follows.

<Binder resin>
(Polyester resin)
Thermoplastic polyester resin 1
Polyester resin composed of terephthalic acid, isophthalic acid, trimellitic acid, propylene oxide-added bisphenol A, and ethylene glycol.
Acid value: 10 mgKOH / g
OH value: 43 mg KOH / g
Tg: 58 ° C
Molecular weight Mw: 28200 Mn: 2500
Thermoplastic polyester resin 2
Polyester resin composed of terephthalic acid, isophthalic acid, trimellitic acid, propylene oxide-added bisphenol A, and ethylene glycol.
Acid value: 18 mgKOH / g
OH value: 36 mgKOH / g
Tg: 59 ° C
Molecular weight Mw: 32000 Mn: 2600

Polyester resin 3
A linear polyester resin composed of terephthalic acid (50 mol%), neopentyl glycol (25 mol%), ethylene glycol (20 mol%), diethylene glycol (5 mol%).
Acid value: 11 mgKOH / g
Tg: 57 ° C
Weight average molecular weight Mw: 700,000
Polyester resin 4
A linear polyester resin composed of terephthalic acid (45 mol%), isophthalic acid (5 mol%), neopentyl glycol (30 mol%), and ethylene glycol (20 mol%).
Acid value: 14 mgKOH / g
Tg: 60 ° C
Weight average molecular weight Mw: 850,000

(Styrene acrylic resin)
Styrene acrylic resin 1
Styrene / Butyl Acrylate Copolymer CPR-100 (Mitsui Chemicals)
Tg: 60 ° C
Molecular weight Mw: 172,000, Mn: 2,300, Mw / Mn 75
Low molecular weight peak: 4200, High molecular weight peak: 327,000
Styrene acrylic resin 2
Styrene / butyl acrylate / butyl methacrylate copolymer CPR-200 (Mitsui Chemicals)
Tg: 58 ° C
Molecular weight Mw: 126,000, Mn: 3,100, Mw / Mn 41
Low molecular weight peak: 5,200 High molecular weight peak: 226,000

<Release agent>
(Low molecular weight polypropylene)
Biscol 550-P (non-oxidized low molecular weight polypropylene; manufactured by Sanyo Chemical Industries)
Acid value: not having nil Average molecular weight (vapor pressure osmotic pressure method): 4,000
Heimer TP-32 (non-oxidized low molecular weight polypropylene; manufactured by Sanyo Chemical Industries)
Acid value: not having nil Average molecular weight (vapor pressure osmotic pressure method): 8,200
Biscol 660-P (non-oxidized low molecular weight polypropylene; manufactured by Sanyo Chemical Industries)
Acid value: not having nil Average molecular weight (vapor pressure osmotic pressure method): 3000

(Fischer Tropsch wax)
Paraflint H1-N4 (Sazol)
Melting point: 2 peaks of 95.8 ° C and 111.8 ° C 25 ° C penetration: 1.8
Melt viscosity: 10.6 (mPa / S · 120 ° C)
Paraflint H1-N6 (Sazol)
Melting point: 22.7 ° C. and 105.2 ° C. 2 peaks 25 ° C. penetration: 1.0
Melt viscosity: 10.9 (mPa / S · 120 ° C)
FT-100 (manufactured by Shell MDS)
Melting point: 98.0 ° C
25 ° C. penetration: 1.0
Melt viscosity: 10.2 (mPa / S · 120 ° C)

Carnauba wax (manufactured by Celerica NODA, refined carnauba wax No. 1 (P))
Melting point: 85 ° C
Penetration: 1.0 or less Viscosity: 21.6 (cp) (100 ° C.)

<Rosin-modified maleic resin>
Marquide No. 1 (Arakawa Chemical Industries)
Acid value: 12 (mgKOH / g)
Softening point: 126 (° C)
True density: 1.12 (g / cc)
Marquide No. 5 (Arakawa Chemical Industries)
Acid value: 20 (mgKOH / g)
Softening point: 144 (° C)
True density: 1.12 (g / cc)
Marquide No. 6 (Arakawa Chemical Industries)
Acid value: 35 (mgKOH / g)
Softening point: 149 (° C)
True density: 1.15 (g / cc)
Marquide No. 32 (Arakawa Chemical Industries)
Acid value: 71 (mgKOH / g)
Softening point: 136 (° C)
True density: 1.17 (g / cc)
Marquide No. 34 (Arakawa Chemical Industries)
Acid value: 265 (mg KOH / g)
Softening point: 144 (° C)
True density: 1.11 (g / cc)
Marquide No. 3002 (Arakawa Chemical Industries)
Acid value: 90 (mgKOH / g)
Softening point: 175 (° C)
True density: 1.17 (g / cc)

Example 1
Thermoplastic polyester resin 1 56.5 parts Charge control agent (3,5-di-tert-
Trivalent chromium salt compound of butylsalicylic acid) 0.5 part Magnetic material (magnetic powder) (EPT-1000 manufactured by Toda Kogyo Co., Ltd.) 38.0 parts Low molecular weight polypropylene (Biscol 550-P manufactured by Sanyo Chemical Industries, Ltd.) 2.5 parts 2.5 parts of rosin-modified maleic resin (Marquide No. 5 manufactured by Arakawa Chemical Industries)

  The above materials are mixed with a Henschel mixer, melted and kneaded with a twin-screw kneading extruder (Ikegai PCM30), extruded, cooled and solidified, coarsely pulverized with a hammer mill, and then an I-type jet mill (IDS manufactured by Nippon Pneumatic Industry Co., Ltd.). -2 type) and finely pulverized using a classifier (DS-2 type manufactured by Nippon Pneumatic Industry Co., Ltd.) to obtain a classified product (toner base particle) having a weight average particle diameter of about 8.5 μm. The calorific value of the low molecular weight polypropylene of this classified product and the classified fine powder is measured, and the distribution property indicating the blending state of the low molecular weight polypropylene from the value of (low molecular weight polypropylene calorific value of the classified fine powder) / (low molecular weight polypropylene calorific value of the classified product) evaluated. The results are shown in Table 2.

  In Table 2, when the value of the partitionability of the low molecular weight polypropylene is 1.5 or less, the partitionability can be evaluated as good. In Table 2, the calorific value of the low molecular weight polypropylene was measured using a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation, and after raising the temperature to 200 ° C. once and lowering to room temperature, the heat history was taken. Using the DSC curve when the temperature was raised at 10 ° C./min, the calorific value corresponding to the melting peak of the low molecular weight polypropylene was defined as the calorific value of the low molecular weight polypropylene.

  Next, 100 parts of the classified product obtained above, 0.4 parts of hydrophobic silica (RY200S manufactured by Nippon Aerosil Co., Ltd.) and 0.8 part of calcium titanate (CT manufactured by Fuji Titanium Co., Ltd.) were mixed with a Henschel mixer, After passing through a sieving step, a toner was obtained. Using this toner, a live-action test was performed using a commercially available copying machine (NP-6550 manufactured by Canon Inc.) having a structure of a hot-pressure roll as a fixing device, and toner fixing property, offset resistance, developing property (initial and The developed image density value and fog after 100,000 sheets, the wave pattern on the developing sleeve (whether the wave pattern was generated) and other image characteristics were evaluated. The results are shown in Table 3.

Regarding the fixing property, the fixed image was rubbed with an eraser (dragonfly pencil MONO), and the value calculated by [image density after rubbing / image density before rubbing] × 100 was expressed as fixing strength.
In addition, the anti-offset property was evaluated based on the condition of white paper smearing after 20 sheets of fixing test images were continuously copied and stopped for 5 minutes, and then passed through 20 white paper sheets. The evaluation results were indicated as “◯” when no paper stain occurred, “Δ” when only the first few sheets, slightly paper stain occurred, and “X” when paper stain occurred on all 20 sheets.

  The image density was measured using a Macbeth photometer. The image density may be a density of 1.35 or more. The fog was measured by measuring the reflectance with a photovolt. 1.5% or less is a good value. Further, regarding the evaluation of the image defect due to the toner adhesion to the photoconductor during the image test, the case where the image defect did not occur was evaluated as ◯, and the case where the image defect occurred was evaluated as x. Fixing strength, offset resistance, measurement of image density and fog, evaluation of image defects due to toner adhesion to the photoconductor, presence or absence of wave pattern on the developing sleeve, and other image characteristics are evaluated in the following examples and comparison. All the examples were performed in the same manner.

Examples 2-8 and Comparative Examples 1-4
A classified product and a toner were obtained in the same manner as in Example 1 except that the materials and amounts described in Examples 2 to 8 and Comparative Examples 1 to 4 in Table 1 were used. These classified products and toners were evaluated in the same manner as in Example 1 for low molecular weight polypropylene distribution properties (compoundability), toner fixing properties, offset resistance, and developability. The results are shown in Table 2 and Table 3.
In the comparative example, the image test was stopped after printing 30,000 sheets because of the poor dispersibility of the release agent and the occurrence of a wave pattern on the sleeve.

Example 9
Polyester resin 3 56.5 parts Charge control agent (3,5-di-tert-
Trivalent chromium salt compound of butylsalicylic acid) 0.5 part Magnetic material (magnetic powder) (EPT-1000 manufactured by Toda Kogyo Co., Ltd.) 38.0 parts Low molecular weight polypropylene (Biscol 550-P manufactured by Sanyo Chemical Industries, Ltd.) 2.5 parts 2.5 parts of rosin-modified maleic resin (Marquide No. 5 manufactured by Arakawa Chemical Industries)

  The above materials are mixed with a Henschel mixer, melted and kneaded with a twin-screw kneading extruder (Ikegai PCM30), extruded, cooled and solidified, coarsely pulverized with a hammer mill, and then an I-type jet mill (IDS manufactured by Nippon Pneumatic Industry Co., Ltd.). -2 type) and finely pulverized using a classifier (DS-2 type manufactured by Nippon Pneumatic Industry Co., Ltd.) to obtain a classified product (toner base particle) having a weight average particle diameter of about 8.5 μm. The calorific value of the low molecular weight polypropylene of this classified product and the classified fine powder is measured, and the distribution property indicating the blending state of the low molecular weight polypropylene from the value of (low molecular weight polypropylene calorific value of the classified fine powder) / (low molecular weight polypropylene calorific value of the classified product) evaluated. The results are shown in Table 5.

  In Table 5, when the value of the partitioning property of the low molecular weight polypropylene is 1.5 or less, the partitioning property can be evaluated as good. In Table 5, the calorific value of the low molecular weight polypropylene is measured using a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation, and after heating up to 200 ° C. and then down to room temperature, the heat history is taken. Using the DSC curve when the temperature was raised at 10 ° C./min, the calorific value corresponding to the melting peak of the low molecular weight polypropylene was defined as the calorific value of the low molecular weight polypropylene.

  Next, 100 parts of the classified product obtained above, 0.4 parts of hydrophobic silica (RY200S manufactured by Nippon Aerosil Co., Ltd.) and 0.8 part of calcium titanate (CT manufactured by Fuji Titanium Co., Ltd.) were mixed with a Henschel mixer, After passing through a sieving step, a toner was obtained. Using this toner, a live-action test was performed using a commercially available copying machine (NP-6550 manufactured by Canon Inc.) having a structure of a hot-pressure roll as a fixing device, and toner fixing property, offset resistance, developing property (initial and The developed image density value and fog after 100,000 sheets, the wave pattern on the developing sleeve (whether the wave pattern was generated) and other image characteristics were evaluated. The results are shown in Table 6.

Examples 10-16 and Comparative Examples 5-8
A classified product and a toner were obtained in the same manner as in Example 9 except that the materials and amounts described in Examples 10 to 16 and Comparative Examples 5 to 8 in Table 4 were used. These classified products and toners were evaluated in the same manner as in Example 9 in terms of low molecular weight polypropylene dispersibility (compoundability), toner fixing properties, offset resistance, and developability. The results are shown in Tables 5 and 6.
In the comparative example, the image test was stopped after printing 30,000 sheets because of the poor dispersibility of the release agent and the occurrence of a wave pattern on the sleeve.

Example 17
Styrene acrylic resin 1 (CPR-100 manufactured by Mitsui Chemicals) 53.0 parts Charge control agent (Nigrosine) 2.0 parts Low molecular weight polypropylene (Biscol 550-P manufactured by Sanyo Chemical Industries) 2.0 parts Rosin-modified maleic acid Resin (Marquide No. 5 manufactured by Arakawa Chemical Industries) 2.0 parts

  The above materials are mixed with a Henschel mixer, melted and kneaded with a twin-screw kneading extruder (Ikegai PCM30), extruded, cooled and solidified, coarsely pulverized with a hammer mill, and then an I-type jet mill (IDS manufactured by Nippon Pneumatic Industry Co., Ltd.). -2 type) and finely pulverized using a classifier (DS-2 type manufactured by Nippon Pneumatic Industry Co., Ltd.) to obtain a classified product (toner base particle) having a weight average particle diameter of about 8.5 μm. The calorific value of the low molecular weight polypropylene of this classified product and the classified fine powder is measured, and the distribution property indicating the blending state of the low molecular weight polypropylene from the value of (low molecular weight polypropylene calorific value of the classified fine powder) / (low molecular weight polypropylene calorific value of the classified product) evaluated. The results are shown in Table 8.

  In Table 8, when the value of the partitioning property of the low molecular weight polypropylene is 1.5 or less, the partitioning property can be evaluated as good. In Table 8, the calorific value of the low molecular weight polypropylene was measured using a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation, and after raising the temperature to 200 ° C. once and lowering to room temperature, the heat history was taken. Using the DSC curve when the temperature was raised at 10 ° C./min, the calorific value corresponding to the melting peak of the low molecular weight polypropylene was defined as the calorific value of the low molecular weight polypropylene.

  Next, 100 parts of the classified product obtained above, 0.4 parts of hydrophobic silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) and 1.0 part of calcium titanate (CT manufactured by Fuji Titanium Co., Ltd.) were mixed with a Henschel mixer. After passing through a sieving step, a toner was obtained. Using this toner, a live-action test was conducted using a commercially available copying machine (Canon Image Runner IR-600) having a structure of a hot-pressing roll as a fixing device, and toner fixing property, offset resistance, developing property ( The development image density value and fog at the initial stage and after 50,000 sheets), the wave pattern on the developing sleeve (whether or not wave pattern was generated), and other image characteristics were evaluated. The results are shown in Table 9.

Examples 18-24 and Comparative Examples 9-12
Classified products and toners were obtained in the same manner as in Example 17 except that the materials and amounts described in Examples 18 to 24 and Comparative Examples 9 to 12 in Table 4 were used. These classified products and toners were evaluated in the same manner as in Example 17 in terms of the low molecular weight polypropylene dispersibility (compoundability), toner fixability, offset resistance, and developability. The results are shown in Table 8 and Table 9.
In the comparative example, the image test was stopped after printing 30,000 sheets because of the poor dispersibility of the release agent and the occurrence of a wave pattern on the sleeve.

Example 25
Thermoplastic polyester resin 1 56.5 parts Charge control agent (3,5-di-tert-
Trivalent chromium salt compound of butylsalicylic acid) 0.5 part Magnetic substance (magnetic powder) (EPT-1000 manufactured by Toda Kogyo Co., Ltd.) 38.0 parts Paraflint H1-N4 (manufactured by Sazol) 2.5 parts Rosin-modified maleic acid Resin (Marquide No. 5 manufactured by Arakawa Chemical Industries) 2.5 parts

  The above materials are mixed with a Henschel mixer, melted and kneaded with a twin-screw kneading extruder (Ikegai PCM30), extruded, cooled and solidified, coarsely pulverized with a hammer mill, and then an I-type jet mill (IDS manufactured by Nippon Pneumatic Industry Co., Ltd.). -2 type) and finely pulverized using a classifier (DS-2 type manufactured by Nippon Pneumatic Industry Co., Ltd.) to obtain a classified product (toner base particle) having a weight average particle diameter of about 8.5 μm. The calorific value of this classified product and the finer Fischer-Tropsch wax is measured, and the distribution property indicating the blending state of Fischer-Tropsch wax is calculated from the value of (Fischer-Tropsch wax calorific value of the classified fine powder) / (Fischer-Tropsch wax calorific value of the classified product). evaluated. The results are shown in Table 11.

  In Table 11, when the value of the distribution property of Fischer-Tropsch wax is 1.5 or less, the distribution property can be evaluated as good. Further, in Table 11, the calorific value of Fischer-Tropsch wax is measured using a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation, and after heating up to 200 ° C. once and taking down a thermal history after cooling down to room temperature. Using the DSC curve when the temperature was raised at 10 ° C./min, the calorific value corresponding to the melting peak of Fischer-Tropsch wax was defined as the calorific value of Fischer-Tropsch wax.

  Next, 100 parts of the classified product obtained above, 0.4 parts of hydrophobic silica (RY200S manufactured by Nippon Aerosil Co., Ltd.) and 0.8 part of calcium titanate (CT manufactured by Fuji Titanium Co., Ltd.) were mixed with a Henschel mixer, After passing through a sieving step, a toner was obtained. Using this toner, a live-action test was performed using a commercially available copying machine (NP-6080 manufactured by Canon Inc.) having a hot-pressure roll structure as a fixing device, and toner fixing property, offset resistance, developing property (initial and The developed image density value and fog after 100,000 sheets, the wave pattern on the developing sleeve (whether the wave pattern was generated) and other image characteristics were evaluated. The results are shown in Table 12.

Examples 26 to 33 and Comparative Examples 13 to 16
Classified products and toners were obtained in the same manner as in Example 25 except that the materials and amounts described in Examples 26 to 33 and Comparative Examples 13 to 16 in Table 10 were used. These classified products and toners were evaluated in the same manner as in Example 25 for Fischer-Tropsch wax distribution (mixing properties), toner fixing properties, offset resistance, and developing properties. The results are shown in Table 11 and Table 12.
In the comparative example, the image test was stopped after printing 30,000 sheets because of the poor dispersibility of the release agent and the occurrence of a wave pattern on the sleeve.

Example 34
Polyester resin 3 56.5 parts Charge control agent (3,5-di-tert-
Trivalent chromium salt compound of butylsalicylic acid) 0.5 part Magnetic substance (magnetic powder) (EPT-1000 manufactured by Toda Kogyo Co., Ltd.) 38.0 parts Paraflint H1-N4 (manufactured by Sazol) 2.5 parts Rosin-modified maleic acid Resin (Marquide No. 5 manufactured by Arakawa Chemical Industries) 2.5 parts

  The above materials are mixed with a Henschel mixer, melted and kneaded with a twin-screw kneading extruder (Ikegai PCM30), extruded, cooled and solidified, coarsely pulverized with a hammer mill, and then an I-type jet mill (IDS manufactured by Nippon Pneumatic Industry Co., Ltd.). -2 type) and finely pulverized using a classifier (DS-2 type manufactured by Nippon Pneumatic Industry Co., Ltd.) to obtain a classified product (toner base particle) having a weight average particle diameter of about 8.5 μm. The calorific value of this classified product and the finer Fischer-Tropsch wax is measured, and the distribution property indicating the blending state of Fischer-Tropsch wax is calculated from the value of (Fischer-Tropsch wax calorific value of the classified fine powder) / (Fischer-Tropsch wax calorific value of the classified product). evaluated. The results are shown in Table 14.

  In Table 14, when the value of the distribution property of Fischer-Tropsch wax is 1.5 or less, the distribution property can be evaluated as good. Further, in Table 14, the calorific value of Fischer-Tropsch wax is measured using a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation, and after heating up to 200 ° C. and then down to room temperature, a heat history is obtained. Using the DSC curve when the temperature was raised at 10 ° C./min, the calorific value corresponding to the melting peak of Fischer-Tropsch wax was defined as the calorific value of Fischer-Tropsch wax.

  Next, 100 parts of the classified product obtained above, 0.4 parts of hydrophobic silica (RY200S manufactured by Nippon Aerosil Co., Ltd.) and 0.8 part of calcium titanate (CT manufactured by Fuji Titanium Co., Ltd.) were mixed with a Henschel mixer, After passing through a sieving step, a toner was obtained. Using this toner, a live-action test was performed using a commercially available copying machine (NP-6080 manufactured by Canon Inc.) having a hot-pressure roll structure as a fixing device, and toner fixing property, offset resistance, developing property (initial and The developed image density value and fog after 100,000 sheets, the wave pattern on the developing sleeve (whether the wave pattern was generated) and other image characteristics were evaluated. The results are shown in Table 15.

Examples 35-41 and Comparative Examples 17-20
A classified product and a toner were obtained in the same manner as in Example 34 except that the materials and amounts described in Examples 35 to 41 and Comparative Examples 17 to 20 in Table 13 were used. These classified products and toners were evaluated in the same manner as in Example 34 for the Fischer-Tropsch wax distribution properties (compoundability), toner fixing properties, offset resistance, and developing properties. The results are shown in Table 14 and Table 15.
In the comparative example, the image test was stopped after printing 30,000 sheets because of the poor dispersibility of the release agent and the occurrence of a wave pattern on the sleeve.

  From Tables 1 to 15, by adding and containing a rosin-modified maleic acid resin having an acid value of 40 mgKOH / g or less to the electrostatic charge image developing toner, not only polystyrene resin but also conventional low molecular weight polypropylene components and Fischer-Tropsch Polyester resins such as polyester resins using neopentyl glycol, ethylene glycol, etc., without using bisphenol A derivatives as alcohol components, which were poorly compatible with the wax component and difficult to uniformly disperse these components in the toner. It can also be seen that uniform distribution and blending of the low molecular weight polypropylene component or Fischer-Tropsch wax component in the toner is possible. Since the low molecular weight polypropylene component and the Fischer-Tropsch wax component are uniformly distributed and blended in the toner, there is little difference between the composition of the classified fine powder and the composition of the toner base particles, and is therefore collected during the classification of the toner. Recycling of classified fine powder is also easy. Further, it is considered that the presence state of low molecular weight polypropylene or Fischer-Tropsch wax in the toner is uniform, but the toner having a low molecular weight polypyropylene or Fischer-Tropsch wax as a release agent has an acid value of 40 mgKOH / g or less. It can also be seen that the toner of the present invention obtained by adding and containing a certain rosin-modified maleic resin is excellent in durability, printing durability and image quality with satisfactory image characteristics.

Claims (18)

  In an electrostatic charge developing toner containing at least a binder resin, a colorant, and a low molecular weight polypyropylene or Fischer-Tropsch wax as a release agent, the toner contains a rosin-modified maleic acid resin having an acid value of 40 mgKOH / g or less. An electrostatic charge image developing toner, comprising:   The electrostatic image developing toner according to claim 1, wherein the rosin-modified maleic resin has a softening temperature of 120 to 150 ° C. according to a ring and ball method.   The electrostatic image developing toner according to claim 1, wherein the rosin-modified maleic resin has an acid value of 10 to 40 mg KOH / g.   The electrostatic charge according to any one of claims 1 to 3, wherein the content of the rosin-modified maleic resin is in the range of 0.3 to 3.5 times the content of the low molecular weight polypropylene. Toner for image development.   5. The electrostatic image developing toner according to claim 4, wherein the content of the rosin-modified maleic resin is in a range of 0.4 to 1.6 times the content of the low molecular weight polypropylene.   6. The electrostatic image developing toner according to claim 1, wherein the low molecular weight polypropylene has a number average molecular weight in a range of 2,000 to 10,000 according to a vapor osmotic pressure method (VPO method). .   7. The electrostatic image developing toner according to claim 1, wherein the low molecular weight polypropylene has an acid value of 2 mgKOH / g or less.   The electrostatic charge according to any one of claims 1 to 3, wherein the content of the rosin-modified maleic resin is in a range of 0.2 to 4.0 times the content of the Fischer-Tropsch wax. Toner for image development.   9. The electrostatic image developing toner according to claim 8, wherein the content of the rosin-modified maleic resin is in the range of 0.3 to 3.5 times the content of the Fischer-Tropsch wax.   The toner for developing an electrostatic charge image according to claim 1, wherein the Fischer-Tropsch wax has a melting point by DSC of 80 to 120 ° C. 10.   The electrostatic image developing toner according to claim 1, wherein the binder is a polyester resin.   The electrostatic charge image developing toner according to claim 11, wherein the polyester resin is a polyester resin containing at least neopentyl glycol and ethylene glycol as alcohol components.   13. The electrostatic image developing toner according to claim 11, wherein the alcohol component of the polyester resin is a linear polyester resin not containing a bisphenol A derivative.   The electrostatic charge image developing toner according to claim 11, wherein the polyester resin contains at least terephthalic acid as an acid component.   15. The toner for developing an electrostatic charge image according to claim 11, wherein the acid value of the polyester resin is 5 to 20 mg KOH / g.   The electrostatic charge developing toner according to claim 1, wherein the binder resin is a styrene acrylic resin.   The toner for developing an electrostatic image according to claim 1, wherein the colorant is magnetic iron oxide.   18. The electrostatic image developing toner according to claim 11, wherein the toner is developed through at least a melt-kneading step, a pulverizing step, and a classification step.