JP4649276B2 - toner - Google Patents

Description

  The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method, particularly a toner suitable for oilless fixing.

  In recent years, electrophotographic image forming apparatuses such as copiers and laser beam printers have been pursued strictly for small size, light weight, high speed, high image quality, and high reliability due to demands for space saving and energy saving. Image forming apparatuses have come to be configured with simpler elements in various respects. As a result, the performance required for the toner becomes higher, and if the improvement in toner performance cannot be achieved, a superior image forming apparatus cannot be realized. In recent years, demands for full-color image output have increased rapidly due to various needs, and further higher image quality and higher resolution are desired.

  For normal full-color toners, improvement in color reproducibility and transparency of OHP images are important, and sharp melt, low molecular weight polyester resins are used as binder resins, and color toners of each color are sufficiently mixed in the fixing process. Designed to be. However, such a resin having a sharp melt property has a problem that a self-aggregation force is weak and a high temperature offset phenomenon occurs in which a molten toner adheres to a fixing roller or the like. Therefore, conventionally, silicone oil or the like has been uniformly applied to the fixing roller for the purpose of preventing the high temperature offset phenomenon, but an image obtained with such a configuration has excessive silicone oil or the like on the surface. Since it adheres, especially in an OHP image, a user feels uncomfortable when using it, which is not preferable.

  Many black toners used in the market contain a low melting point wax to prevent offset, and it is not necessary to apply silicone oil to the fixing roller. In recent years, attempts have been made to include a low molecular weight, low melting point wax having an average carbon number of less than 50 in the toner for full color. For example, a polyester toner containing a hydrocarbon wax having an average carbon number of 30 to 40 as a wax has been devised (see, for example, Patent Document 1).

  Also, a method of incorporating a carboxylic acid-modified paraffin wax into the toner (for example, Patent Document 2), a method of incorporating a carboxylic acid-modified paraffin wax having a specific acid value and a polyester resin having a specific acid value into the toner (For example, Patent Document 3), a method in which polyethylene is oxidized to form a long-chain alkyl alcohol type wax, and a long-chain alkyl carboxylic acid type wax obtained by further oxidizing this is added to the toner (for example, Patent Document 4) Reference).

  Further, a method of incorporating an alcohol type wax obtained by boric acid oxidation of an α-olefin, which is a linear hydrocarbon having a double bond at a terminal (see, for example, Patent Document 5), the alcohol type wax and isocyanate, There has been devised a method in which a urethanized wax obtained by reacting with a toner is contained in a toner (for example, see Patent Document 6).

  Various studies have also been made on a copolymer of an α-olefin and maleic anhydride. For example, a method of containing a copolymer of an α-olefin and maleic anhydride in a toner (for example, Patent Document 7). , And 8), a method in which a copolymer of an α-olefin and maleic anhydride is further cross-linked with a polyhydric alcohol, and this is contained in a toner (for example, see Patent Document 9), α-olefin and maleic anhydride Has been devised in which a copolymer is further esterified with a long-chain alcohol and then incorporated into a toner (see, for example, Patent Documents 10 and 11).

JP 2001-051445 A Japanese Patent Laid-Open No. 03-050560 JP 2004-029160 A Japanese Patent Laid-Open No. 08-030028 JP 2000-267347 A JP 2001-042560 A Japanese Patent Laid-Open No. 05-0621240 Japanese Patent Application Laid-Open No. 08-082954 JP 11-012396 A Japanese Patent Laid-Open No. 09-120177 Japanese Patent Laid-Open No. 11-015187

  However, in the case of the polyester toner containing the hydrocarbon wax having an average carbon number of 30 to 40, the compatibility between the highly polar polyester resin and the nonpolar hydrocarbon wax is poor, so As a result, there was room for improvement in toner developability, durability, fixability, storage stability, and the like.

  In addition, from the above-mentioned carboxylic acid-modified paraffin wax, long-chain alkyl carboxylic acid type wax, alcohol type wax obtained by boric acid oxidation of α-olefin, and alcohol type wax, which have been devised to solve such wax dispersion failure Since the toner containing the derived urethanized wax has a polar group in the wax molecular structure due to modification, the wax can be dispersed relatively well in the highly polar polyester resin. However, in order to modify the wax raw material, severe reaction conditions such as high temperature or addition of a large excess of catalyst are necessary, such as a coupling reaction between wax molecules, a molecular chain scission of the wax molecule, etc. Various undesirable side reactions may occur. For example, the melt viscosity is increased by increasing the molecular weight of the wax, and the melting point is decreased by decreasing the molecular weight of the wax molecule. For this reason, there are cases where not only the low-temperature fixability and high-temperature offset resistance are insufficient, but there is room for improvement in developability and storage stability. Also, when applied to color toners, there may be problems with color reproducibility and transparency.

  Further, a toner containing a copolymer of α-olefin and maleic anhydride and a toner containing an esterified product of the copolymer have relatively good dispersibility of carbon black in the toner. C., which is a typical colorant used in other colorants such as cyan toner. I. There was room for improvement in the dispersibility of Pigment Blue 15: 3. In addition, there are cases where the low-temperature fixability in a low-temperature and low-humidity environment is insufficient, and the image density stability in a high-temperature and high-humidity environment is also problematic.

  Therefore, the present invention provides a toner having good storage stability, excellent low-temperature fixability, uniformly dispersing a colorant in the toner, and capable of stably forming an image satisfying high definition regardless of environmental changes. More specifically, an object of the present invention is to provide a toner having a high coloring power, a clear color and a good color mixing property, and an excellent transparency.

  As a result of intensive studies on a toner containing at least a binder resin and a colorant, the present inventors have found that the above-described problem can be achieved by incorporating a reaction composition having specific physical properties of an α-olefin and a carboxylic acid into the toner. Has found that can be solved.

That is, the present invention relates to a toner containing at least a binder resin, a colorant, and a reaction composition of an α-olefin and a carboxylic acid .
Before SL reaction composition, the double methylene group hydrogens adjacent to the coupling is pulled alpha-olefin and the carboxylic acids include compounds obtained by adding a reaction at the site where the hydrogen of the alpha-olefin is withdrawn (except, alpha- A reaction composition containing at least a olefin (co) polymer) , wherein a carboxyl group derived from the carboxylic acid remains in the molecule,
The present invention relates to a toner wherein the reaction composition has a polyethylene-converted weight average molecular weight (Mw) in the range of 200 to 2800 by gel permeation chromatography (GPC).

  According to the present invention, a toner having excellent storage stability, low-temperature fixability, and high-temperature offset resistance, and a high coloring power in which a colorant is uniformly dispersed in the toner can be easily obtained. Regardless of environmental changes, it is possible to provide a full-color image having a clear color, good color mixing, and excellent transparency.

  Hereinafter, the present invention will be described in detail.

  It is essential that the toner of the present invention contains at least a reaction composition of an α-olefin and a carboxylic acid. The reaction composition of an α-olefin and a carboxylic acid used in the present invention is adjacent to an α-olefin double bond by using, for example, an organic peroxide having an ability to extract hydrogen. It can be obtained by extracting the hydrogen of the methylene group and the hydrogen bonded to the carbon adjacent to the carbonyl group of the carboxylic acid to generate a radical and subjecting them to an addition reaction.

  The toner of the present invention contains a reaction composition having specific physical properties of an α-olefin and a carboxylic acid, so that the storage stability is good and the fixing performance such as low-temperature fixability and high-temperature offset resistance is excellent. The pigment dispersion in the particles can be good. As described above, for example, when paraffin wax is modified with carboxylic acid, it is necessary to forcibly remove hydrogen from non-reactive paraffin, so that reaction conditions become severe, and molecular coupling and molecular chain scission are caused. For example, the melt viscosity increases due to the high molecular weight of the wax and the melting point decreases due to the low molecular weight of the wax molecules, making it difficult to achieve both low temperature fixability and storage stability. . On the other hand, in the case of α-olefin, the hydrogen of the methylene group adjacent to the double bond is an active hydrogen, and since it is easily extracted, an extra side reaction hardly occurs, and both fixing property and storage stability can be achieved. It becomes easy. In addition, the reaction composition contains a reactant having both a non-polar long-chain hydrocarbon moiety derived from an α-olefin and a polar carboxyl group derived from a carboxylic acid in the molecular structure. Pigment particles such as C.I. I. Pigment Blue 15: 3 can be easily dispersed in the binder resin.

The reaction composition contained in the toner of the present invention does not necessarily have to be a reaction of all α-olefin and carboxylic acid, and contains at least an addition reaction product of α-olefin and carboxylic acid. Just do it. In addition, α-olefin, carboxylic acids, or both may remain in the reaction composition, but 50% by mass or more of the reaction composition has a molar ratio of α-olefin to carboxylic acids of 1: 1 addition product is preferable because the effect of the present invention is more remarkably exhibited. Further, an α-olefin (co) polymer may be contained in the reaction composition as long as the effects of the present invention are not impaired. Incidentally, an addition product having a molar ratio of α-olefin and carboxylic acids contained in the reaction composition of 1: 1, an addition product having a molar ratio other than 1: 1, an α-olefin, and an α-olefin. The composition ratio of the (co) polymer, etc. can be determined by a conventionally known method such as nuclear magnetic resonance spectrum (H ¹ and C ¹³ -NMR), liquid chromatography (HPLC), gel permeation chromatography (GPC), red It can be quantified by an analysis means using an external spectrum (IR), an ultraviolet spectrum (UV) or the like.

  Carboxylic acids that are raw materials for producing a reaction composition of an α-olefin and carboxylic acids used in the present invention are not particularly limited, but aliphatic carboxylic acids having 3 to 30 carbon atoms are preferably used. Specifically, propionic acid, n-butanoic acid, 2-methylpropionic acid, n-pentanoic acid, 2-methylbutanoic acid, n-hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methyl Pentanoic acid, 2-ethylbutanoic acid, heptanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, 2-ethylhexanoic acid, lauric acid, myristic acid, Palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, 1,10-decanedicarboxylic acid, maleic acid, Malic acid, succinic acid, alkenyl succinic acid, (meth) acrylic acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, etc., and sodium salts, potassium salts, esters or anhydrides of these acids, etc. Illustrated. Among these, the use of aliphatic carboxylic acids that do not contain an unsaturated group in the molecule does not cause the formation of a polymer due to a polymerization reaction. It is done. Among aliphatic carboxylic acids that do not contain an unsaturated group in the molecule, it is more preferable to use linear aliphatic carboxylic acids having no branched structure in the molecular structure, specifically, propionic acid, n -Butanoic acid, n-pentanoic acid, n-hexanoic acid, heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and these Examples include sodium salts, potassium salts, esters of acids, and anhydrides of these acids.

  When the reaction composition produced using an aliphatic carboxylic acid having 3 to 30 carbon atoms is contained in the toner, the chargeability of the toner is stabilized regardless of environmental fluctuations, and the durability is good. The image density transition.

  In addition, the α-olefin, which is a raw material for producing a reaction composition of an α-olefin and a carboxylic acid, is an internal olefin or olefin for the purpose of reducing the content of an extremely low melting point component in the reaction composition. Those having a small content of impurities such as branched olefins are preferably used, and those having these impurities removed may be used as necessary. In addition, α-olefins having an average carbon number of 10 to 50 are preferably used, and α-olefins having an average carbon number of 20 to 40 are more preferably used. When the reaction composition produced using an α-olefin having an average carbon number of 10 to 50 is contained in the toner, a toner having both low-temperature fixability and storage stability is easily obtained. Moreover, it is preferable to use what refine | purified the alpha-olefin which is a raw material for manufacturing the reaction composition of alpha-olefin and carboxylic acids, More preferably, the penetration at 25 degreeC is 1-50. It is good to use the alpha olefin which is the range. Specific examples of the purification method include conventionally known purification methods such as a high vacuum distillation method, press sweating method, hot melt filtration separation method, solvent deoiling method, solvent extraction method, recrystallization method, and chromatographic separation method. These may be selected as appropriate, and purification may be performed by combining these methods as necessary.

  The reaction composition of α-olefin and carboxylic acids used in the present invention needs to have a polyethylene-converted weight average molecular weight (Mw) in the range of 200 to 2800 as measured by gel permeation chromatography (GPC). More preferably, it is the range of 200-2000, Most preferably, it is the range of 300-1000. When the weight average molecular weight exceeds 2800, it becomes difficult to control the charge of the toner. For example, when a large number of images are output at high speed in a low temperature and low humidity environment, the charge amount of the toner becomes excessively high. Decrease and fogging occur. Moreover, since the melt viscosity of the reaction composition is increased, the low-temperature fixability is insufficient. On the contrary, when the weight average molecular weight is less than 200, the viscosity of the reaction composition is extremely lowered when the reaction composition is melted. The difference becomes too large, and as a result, the miscibility of the reaction composition into the binder resin is deteriorated, the dispersibility of the pigment is deteriorated, and the storage stability and the fixability are insufficient. Further, in a high-temperature and high-humidity environment, the chargeability of the toner may be insufficient and toner scattering may occur.

  When the toner of the present invention is applied to an image forming apparatus having a high process speed, the release of inorganic fine powder externally added to the toner particles (hereinafter referred to as external addition) is suppressed, and the inorganic fine powder on the photosensitive drum is suppressed. It is difficult for filming of the powder to occur.

  If a large amount of the inorganic fine powder externally added to the toner particles is liberated, it is considered that filming of the inorganic fine powder on the photosensitive drum is caused by the following mechanism. That is, first, a part of the inorganic fine powder released from the toner particles adheres on the photosensitive drum. Since the inorganic fine powder has a very small particle size compared to the toner, it easily slips through the cleaning blade and remains on the photosensitive drum without being collected in the waste toner container. The photosensitive drum is repeatedly rubbed with the cleaning blade, rubbed with the charging roller, rubbed with the intermediate transfer member or the transfer material at the transfer unit, or rubbed with the developing roller at the developing unit. The inorganic fine powder remaining on the surface is repeatedly rubbed against the surface of the photosensitive drum, and eventually causes filming. When filming on the photosensitive drum occurs, charging failure of the photosensitive drum and exposure inhibition occur, and image defects such as white spots and image streaks tend to occur.

  When the toner of the present invention contains a reaction composition of an α-olefin and a carboxylic acid in the toner, when applied to an image forming apparatus having a high process speed, filming on the photosensitive drum hardly occurs. The reason why the toner of the present invention hardly causes filming is not clear, but the present inventors presume as follows. An addition product having a 1: 1 molar ratio of α-olefin to carboxylic acid present in the reaction composition of α-olefin and carboxylic acid is a carboxyl group that is a polar group derived from carboxylic acid, α- It is a compound that has both nonpolar (hydrophobic) long-chain hydrocarbon moieties derived from olefins in the molecule. The binder resin mainly constituting the toner, particularly the polyester resin, is a highly polar organic compound having a number of ester bonds in the molecule, and the surface of the inorganic fine powder externally added to the toner is a silane compound or silicone. Hydrophobic fine particles treated with a hydrophobizing agent such as oil. Therefore, the addition product of α-olefin and carboxylic acids contained in the toner has a non-polar part in the molecule having a strong interaction with the hydrophobic inorganic fine powder, and the polar part in the molecule is polar. As a result, the toner particles (binder resin) and the inorganic fine powder are strongly bonded to each other, and the release of the inorganic fine powder from the toner particles can be suppressed. As a result, the photosensitive drum It is considered that the filming of the inorganic fine powder is less likely to occur.

  When the weight average molecular weight of the reaction composition used in the present invention exceeds 2800, filming on the photosensitive drum tends to occur. The reason for this is that the polymer chain has the property of curling in a bowl shape, so that the interaction between the non-polar part of the long-chain hydrocarbon and the inorganic fine powder, and the interaction between the polar part of the carboxyl group and the binder resin. This is thought to be because the action becomes difficult to work effectively and the release of the inorganic fine powder from the toner particles cannot be suppressed.

  The content of the reaction composition of α-olefin and carboxylic acids contained in the toner of the present invention is preferably in the range of 1.0 to 10.0 parts by mass, more preferably 100 parts by mass of the binder resin. Is in the range of 2.0 to 7.0 parts by weight. When the content of the reaction composition contained in the toner is less than 1.0 part by mass per 100 parts by mass of the binder resin, the low-temperature fixability and the high-temperature offset resistance are insufficient, or the pigment in the toner Dispersibility may deteriorate and coloring power may be insufficient. In addition, when applied to a high-speed image forming apparatus having a process speed of 140 mm / s or more, the initial image density may be lowered, or the release of inorganic fine powder externally added to the toner particles may be significant. On the contrary, when the content of the reaction composition contained in the toner exceeds 10.0 parts by mass per 100 parts by mass of the binder resin, the fixing stability and coloring power are sufficient, but the storage stability of the toner deteriorates. For example, in image output under a high-temperature and high-humidity environment, toner may be fused on the developing sleeve, and the image density may decrease with image output.

  The reaction composition of α-olefin and carboxylic acids used in the present invention preferably has a peak temperature of the maximum endothermic peak in a differential scanning calorimeter (DSC) in the range of 55 to 99 ° C., more preferably 65 to 90. It is in the range of ° C. When the peak temperature of the maximum endothermic peak in DSC of the reaction composition contained in the toner is lower than 55 ° C., a problem occurs in the storage stability of the toner. A part of the reaction composition may bloom on the toner surface to deteriorate developability, or the toner may aggregate due to temperature rise in the image forming apparatus main body during image output, resulting in poor developability. . Conversely, if the peak temperature of the maximum endothermic peak in DSC is higher than 99 ° C., the above-mentioned storage stability is good, but the low-temperature fixability may be insufficient.

  Although the penetration degree in 25 degreeC of the reaction composition of the alpha olefin and carboxylic acids used by this invention is not specifically limited, Preferably it is the range of 1-9, More preferably, it is the range of 1-5. When the penetration is less than 1, sharp melting cannot be performed when the toner is fixed. For example, the color reproducibility of the secondary color is deteriorated, and the good color mixing property and low temperature fixing property which are the effects of the present invention are obtained. It may not be expressed. On the other hand, if the penetration at 25 ° C. exceeds 9, for example, a problem may occur in the storage stability and development stability of the toner in a high temperature and high humidity environment.

  Furthermore, the onset temperature on the low temperature side of the maximum endothermic peak in the DSC of the reaction composition of the α-olefin and carboxylic acids used in the present invention is preferably in the range of 50 to 90 ° C. If the onset temperature is less than 50 ° C., there may be a problem in storage stability of the toner, or a fusing or the like may occur on the developing sleeve or the photosensitive drum, resulting in an image defect. On the other hand, if the onset temperature exceeds 90 ° C., the low-temperature fixability may be insufficient and the color mixing property may deteriorate. The onset temperature here refers to the temperature at the intersection of the tangent line and the base line at the point where the differential value on the low temperature side of the endothermic curve of the DSC peak is maximum.

  You may refine | purify and use the reaction composition of the alpha olefin and carboxylic acids used for this invention as needed. Specific examples of the purification method include conventionally known methods such as a high vacuum distillation method, press sweating method, hot melt filtration separation method, solvent deoiling method, solvent extraction method, recrystallization method, and chromatographic separation method. Can be combined as needed.

  The toner of the present invention contains at least a binder resin.

  As the binder resin contained in the toner of the present invention, those conventionally used for toners are used. For example, styrene-acrylic resins, polyester resins, epoxy resins and the like are exemplified. . In the present invention, it is preferable to use a polyester resin as a binder resin, a hybrid resin having a polyester unit and a vinyl copolymer unit, or a polyester resin, or a mixture of a vinyl copolymer and a hybrid resin, Or it is preferable that it is either the mixture of a vinyl-type copolymer and a polyester resin, and it is more preferable in 50 mass% or more of the whole binder resin being resin which has a polyester unit. By using a resin having a polyester unit in 50% by mass or more of the total binder resin, the toner has better sharp melt properties, high coloring power, clear color and good color mixing, and excellent transparency. It can be expressed more significantly. In addition, it is particularly preferable that 50% by mass or more of the total binder resin has a polyester unit as a hybrid resin, because the toner has good wax dispersibility and good high-temperature offset resistance.

  In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl copolymer unit” refers to a portion derived from a vinyl copolymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component, and the monomer constituting the vinyl copolymer unit is a monomer component having a vinyl group.

  In addition to the interaction between the above-described pigment and the reaction composition, the toner of the present invention has a pigment in the toner due to the interaction between the reaction composition and a polyester resin, particularly a hybrid resin, which is a binder resin. And the dispersion of both of the reaction compositions is in an optimal state. As a result, as compared with conventionally known polyester-based toners containing nonpolar waxes, images that are more likely to develop due to non-uniform charging are developed with excellent toner developability. The image density is stable even when a large number of images are output in a low-temperature and low-humidity environment with little fogging on the background. Furthermore, the stability is improved against environmental fluctuations, and for example, a stable image density is expressed even in a low temperature and low humidity environment or a high temperature and high humidity environment.

  When a polyester resin or a hybrid resin having a polyester unit is used as the binder resin contained in the toner of the present invention, a polyhydric alcohol and a polyvalent alcohol are used as a polyester monomer for producing a polyester unit of the polyester resin or the hybrid resin. Carboxylic acid, its anhydride, or ester of polyvalent carboxylic acid can be used as a raw material monomer. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Bisphenol A alkylene oxide adducts such as bis (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1 , 2-Propylene glycol, 1,3-propylene glycol, 1,4-butanediol Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

  Examples of the divalent carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyl dicarboxylic acids such as succinic acid, dodecenyl succinic acid, adipic acid, sebacic acid and azelaic acid, or anhydrides thereof. And succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and citraconic acid, or anhydrides thereof.

  Examples of the trivalent or higher carboxylic acid component include trimellitic acid, pyromellitic acid, 1,2,4-naphthalene tricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, and anhydrides and ester compounds thereof. Is mentioned. The amount of the trivalent or higher polyvalent carboxylic acid component is preferably 0.1 to 10 mol% based on the total monomer.

  Among the above, in particular, a carboxylic acid component (for example, fumaric acid) comprising a bisphenol derivative represented by the formula (1) as a diol component and a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof. Particularly preferred is a polyester resin obtained by condensation polymerization of acid, maleic acid, maleic anhydride, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid) as an acid component. The polyester resin having this composition has good charging characteristics.

  When a vinyl resin or a hybrid resin having a vinyl copolymer unit is used as the binder resin contained in the toner of the present invention, a vinyl copolymer or a vinyl copolymer unit of the hybrid resin is generated. The following can be used as the vinyl monomer for the purpose. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene and its derivatives such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinylidene chloride, vinyl bromide, vinyl Vinyl halides such as vinyl halide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n methacrylate -Α-methylene aliphatic monocarboxylic acid esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, acrylic acid Ethyl, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid 2 Acrylic esters such as chloroethyl and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl compounds such as N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Unsaturated dibasic acid half esters such as alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; dimethyl maleic acid, dimethyl fumaric acid and the like; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group, such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof. Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  When a hybrid resin having a vinyl copolymer or a vinyl copolymer unit is used as the binder resin to be included in the toner of the present invention, these resins are crosslinked with a crosslinking agent having two or more vinyl groups. It may be. The following are mentioned as a crosslinking agent used in this case. Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol di Examples include acrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate; linked by alkyl chains containing ether linkages. Examples of the diacrylate compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol # 400 diacrylate. Acrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and acrylates of the above compounds in place of methacrylate; diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, Polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and acrylates of the above compounds The thing replaced with a methacrylate is mentioned. Other polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; Examples include allyl cyanurate and triallyl trimellitate.

  When a binder resin containing a vinyl copolymer unit or a polyester unit is contained in the toner of the present invention, the vinyl copolymer unit or the polyester unit contains a monomer component that can react with both resin components. It is preferable to include. Examples of the monomer constituting the polyester unit that can react with the vinyl copolymer unit include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl copolymer unit, those capable of reacting with the polyester unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method for obtaining a reaction product of a vinyl copolymer unit and a polyester unit, a polymer containing a monomer component capable of reacting with each of the vinyl copolymer unit and the polyester unit described above exists. A method obtained by polymerizing one or both of the resins is preferred.

  Examples of radical polymerization initiators used for producing a vinyl resin or a hybrid resin having a vinyl copolymer unit include 2,2′-azobisisobutyronitrile and 2,2′-azobis. (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2, 2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane) 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone Ketone peroxides such as oxide, acetylacetone peroxide, cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3- Tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl Peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate Di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxy Butyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2 Ethylhexanoate, di -t- butyl peroxy hexahydro terephthalate, di -t- butyl peroxy azelate and the like.

  Examples of the method for producing a hybrid resin that can be contained in the toner of the present invention include the following production methods (1) to (6).

  (1) A method in which a vinyl copolymer, a polyester resin and a hybrid resin component are blended after production, and the blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling the organic solvent. . The hybrid resin component is prepared by separately producing a vinyl copolymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. Synthesized ester compounds can be used.

  (2) A method of producing a polyester unit and a hybrid resin component in the presence of a vinyl copolymer unit in the presence of the vinyl copolymer unit. The hybrid resin component is produced by a reaction between a vinyl copolymer unit (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used.

  (3) A method of producing a vinyl copolymer unit and a hybrid resin component in the presence of the polyester unit after the production thereof. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer and / or vinyl copolymer unit.

  (4) After producing the vinyl copolymer unit and the polyester unit, a hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used.

  (5) After producing the hybrid resin component, a vinyl monomer unit and / or a polyester monomer (alcohol, carboxylic acid) are added to perform addition polymerization and / or polycondensation reaction, whereby a vinyl copolymer unit and a polyester unit are obtained. Manufactured. In this case, as the hybrid resin component, those produced by the production methods (2) to (4) can be used, and those produced by a known production method can be used as necessary. Furthermore, an organic solvent can be used as appropriate.

  (6) A vinyl copolymer unit, a polyester unit, and a hybrid resin component are produced by mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing an addition polymerization and a condensation polymerization reaction. . Furthermore, an organic solvent can be used as appropriate.

  In the production methods of (1) to (5) above, the vinyl copolymer unit and / or the polyester unit can use a plurality of polymer units having different molecular weights and cross-linking degrees.

  The binder resin used in the production of the toner of the present invention has a peak molecular weight (Mp) of 2000 to 2000 in a molecular weight distribution measured by gel permeation chromatography (GPC) of a component soluble in tetrahydrofuran (THF). 40000, and the ratio Mw / Mn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 5 or more. When the Mp of the binder resin is less than 2000, there is a problem in storage stability of the toner, high temperature offset resistance is insufficient, and fusion and filming to the photoreceptor are likely to occur. There's a problem. On the other hand, if Mp exceeds 40000, the low-temperature fixability may be insufficient, the image gloss may be too low, or a problem may occur in color mixing. Moreover, when Mw / Mn is less than 5.0, a problem may occur in high temperature offset resistance.

  In the toner of the present invention, the molecular weight distribution in GPC of the binder resin component soluble in THF contained in the toner is preferably such that Mp is in the range of 2000 to 40000, and Mw / Mn is 10 or more. Is preferred. If Mp is less than 2000, there may be a problem in storage stability of the toner, high temperature offset resistance may be insufficient, and fusion to the photosensitive drum may occur easily. On the other hand, if Mp exceeds 40000, the low-temperature fixability may be insufficient, the image gloss may be too low, or a problem may occur in color mixing. Further, when Mw / Mn is less than 10, there may be a problem in high temperature offset resistance.

  In order to make the Mp of the binder resin component soluble in THF contained in the toner of the present invention in the range of 2000 to 40000, the binder resin having an Mp of 2000 to 40000 in the THF soluble component is used. What is necessary is just to use as a raw material. In order to set Mw / Mn to 10 or more, a binder resin having Mw / Mn of 10 or more may be used, or a binder resin having an Mw / Mn of less than 10 and an aromatic carboxylic acid described later. Mw / Mn can be 10 or more by metal-crosslinking an organic metal compound such as a metal compound in a kneading process which is one of the toner manufacturing processes. Moreover, when adjusting Mw / Mn using this method by metal bridge | crosslinking, Mw / Mn can be adjusted by adjustment of the kind of organometallic compound, the addition amount, and the temperature at the time of kneading | mixing.

  The glass transition temperature (Tg) of the binder resin contained in the toner of the present invention is preferably in the range of 40 to 90 ° C., more preferably in the range of 50 to 80 ° C. If the Tg of the binder resin is less than 40 ° C., the low-temperature fixability is good, but the storage stability and durability of the toner may deteriorate. Conversely, if the Tg of the binder resin exceeds 90 ° C. Although the storage stability and durability of the toner are improved, the low-temperature fixability may be deteriorated.

  The acid value of the binder resin contained in the toner of the present invention is not particularly limited, but is preferably in the range of 1 to 40 mgKOH / g. When the acid value of the binder resin is less than 1 mg KOH / g, there is a tendency that metal crosslinking with the organometallic compound at the time of the above-mentioned melt-kneading cannot be sufficiently performed, and preferable high-temperature offset resistance may not be obtained. . On the other hand, if the acid value exceeds 40 mgKOH / g, it may be difficult to control the charge of the toner, or the metal crosslinking reaction may proceed excessively, which may adversely affect the low-temperature fixability.

  The toner of the present invention contains a colorant for cyan toner, magenta toner, yellow toner or black toner.

  For example, as a colorant for cyan toner, C.I. I. Pigment blue 2,3,15: 1,15: 2,15: 3,16,17, C.I. I. Acid Blue 6, C.I. I. Examples thereof include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of the color pigment for magenta toner include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 155, 163, 202, 206, 207, 209, 238, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned. Further, as a dye for magenta toner, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1; I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28 are listed.

  Examples of the color pigment for yellow toner include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 93, 94, 95, 97, 109,110,111,120,127,128,129,147,151,154,155,168,174,175,176,180,181,191,194, C.I. I. Bat yellow 1, 3, 20, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, and the like. Further, as a dye for yellow, C.I. I. Solvent yellow 9, 17, 24, 31, 35, 58, 93, 100, 102, 103, 105, 112, 162, 163 and the like.

  As the colorant for black toner, carbon black, acetylene black, lamp black, graphite, iron black, aniline black, cyanine black, etc., or the yellow colorant, magenta colorant, cyan colorant, and the like exemplified above are further required. Accordingly, a black colorant mixed with the above-described black colorant is used.

  The amount of these colorants used is 1 to 15 parts by mass, preferably 3 to 10 parts by mass with respect to 100 parts by mass of the binder resin, from the balance between the reproducibility of the intermediate color and the coloring power. good. When the content of the colorant is more than 15 parts by mass, the transparency is lowered, and in addition, the reproducibility of intermediate colors as typified by human skin color is likely to be lowered, and further, the charging property of the toner is stabilized. And the target charge amount is difficult to obtain. Further, when the content of the colorant is less than 1 part by mass, it is difficult to obtain the desired coloring power and it is difficult to obtain a high-quality image with a high image density.

  Furthermore, the toner of the present invention uses a magnetic material as a black colorant and can also be used as a magnetic toner. Magnetic materials that can be used in this case include iron oxides such as magnetite, maghematite, and ferrite, metals such as iron, cobalt, and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, and zinc of these metals. Metal alloys such as antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

These magnetic materials have an average particle size of 0.5 μm or less, preferably about 0.1 to 0.3 μm. The amount of the magnetic substance to be contained in the toner particles is 30 to 150 parts by mass, particularly preferably 50 to 120 parts by mass with respect to 100 parts by mass of the binder resin. In addition, the magnetic characteristics when 795.8 kA / m (10 K oersted) is applied are coercive force (Hc) 1.6 to 24 kA / m (20 to 300 oersted), saturation magnetization (σs) Am ² / kg (50 to 200 emu / kg). g), a magnetic material having residual magnetization (σr) Am ² / kg ( ^{2 to 20} emu / g) is preferable.

  The toner of the present invention may contain a conventionally known wax in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  Examples of the wax that can be contained in the toner of the present invention include the following. Oxides of aliphatic hydrocarbon waxes such as polyethylene wax, polypropylene wax, olefin copolymer wax, microcrystalline wax, Fischer-Tropsch wax, paraffin wax, and aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or the like Block copolymers; waxes based on fatty acid esters such as carnauba wax and montanic acid ester wax; ester waxes that are synthetic reaction compositions of higher fatty acids such as behenyl behenate and behenyl stearate and higher alcohols; and The fatty acid esters such as deoxidized carnauba wax are partially or wholly deoxidized.

  Furthermore, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis laurin Saturated fatty acid bisamides such as acid amide and hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N ′ dioleyl seba Unsaturated fatty acid amides such as acid amides; Aromatic bisamides such as m-xylene bis-stearic acid amide and N, N ′ distearyl isophthalic acid amide; Calcium stearate, calcium laurate, zinc stearate, magnesium stearate, etc. Aliphatic metal salts (generally referred to as metal soaps); waxes obtained by grafting vinyl monomers such as styrene and acrylic acid to aliphatic hydrocarbon waxes; fatty acids such as behenic acid monoglycerides and polyhydric alcohol moieties Esterified product: methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable oil or the like.

  Moreover, the peak temperature of the maximum endothermic peak in DSC of the wax described above is preferably in the range of 50 to 120 ° C, more preferably in the range of 60 to 90 ° C. If the peak temperature of the maximum endothermic peak of the wax is less than 50 ° C., for example, the storage stability of the toner may be inferior, and conversely if the peak temperature exceeds 120 ° C., the effect as a fixing aid is diminished. It may be difficult to perform low-temperature fixing that is desired from the viewpoint.

  The toner of the present invention preferably has one or more endothermic peaks in the range of 30 to 200 ° C. in DSC, and the peak temperature of the maximum endothermic peak in the endothermic peak is preferably in the range of 50 to 120 ° C. More preferably, it is the range of 60-90 degreeC. If the peak temperature of the maximum endothermic peak of the toner is within this range, the balance between excellent low-temperature fixability and developability will be good. When the peak temperature of the maximum endothermic peak of the toner is less than 50 ° C., the storage stability of the toner may be inferior, and conversely, when the peak temperature exceeds 120 ° C., low temperature fixing desired from the viewpoint of energy saving may be performed. It can be difficult. In order to set the peak temperature of the maximum endothermic peak of the toner to 50 to 120 ° C., a reaction composition of an α-olefin and a carboxylic acid having a peak temperature of the maximum endothermic peak in the range of 50 to 120 ° C., if necessary Further, this can be achieved by adding a wax having a peak temperature of 50 to 120 ° C. to the toner.

  The toner of the present invention may further contain a charge control agent. As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Specific compounds include aromatic carboxylic acid derivatives selected from aromatic oxycarboxylic acids and aromatic alkoxycarboxylic acids such as salicylic acid, naphthoic acid and dicarboxylic acid as negative charge control agents, and aromatic carboxylic acid derivatives. Metal compounds, polymer compounds having a sulfonic acid or carboxylic acid group in the side chain, boron compounds, urea compounds, silicon compounds, calixarene, and the like. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound. However, in the present invention, the addition of a charge control agent is not essential. When the two-component development method is used, frictional charging between the toner and the carrier is used, and when the one-component development method is used, the toner and By actively utilizing frictional charging between the blade member and the toner and the sleeve member, it is not always necessary to include a charge control agent in the toner.

  In the present invention, the inclusion of an organometallic compound among the above charge control agents is more preferable in that the charge level can be adjusted, the rising of charge can be improved, and the thermal melting characteristics of the toner can be improved. . The organometallic compound contained in the toner of the present invention is preferably an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, and a metal compound of the aromatic carboxylic acid derivative. The metal is preferably a divalent or higher metal atom. As the aromatic carboxylic acid derivative, a salicylic acid derivative is preferable.

A metal compound of an aromatic carboxylic acid can be produced by a conventionally known method described in, for example, Japanese Patent Publication No. 8-10360. That is, an aromatic carboxylic acid (for example, 3,5-di-t-butylsalicylic acid) is added to an aqueous sodium hydroxide solution, heated to about 60 ° C., stirred, and completely dissolved. Next, an aqueous solution (for example, an aluminum sulfate aqueous solution) containing a divalent or higher metal ion is gradually dropped into the aromatic carboxylic acid aqueous solution. After dropping, the temperature is raised to about 90 ° C. and stirred for 30 minutes, then the pH is adjusted to about 3 and cooled to about 40 ° C. The precipitated crystals are filtered, the crystals are washed with water until the pH of the filtrate becomes neutral, and dried at about 90 ° C. to obtain a metal compound of an aromatic carboxylic acid. The divalent or higher metal ions that can be used at this time are Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , Cu ^2+. Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Ni ³⁺ , Zr ⁴⁺ . Among these divalent or higher valent metal ions, preferred are Sr ²⁺ , Zn ²⁺ , Ca ²⁺ , Mg ²⁺ , Al ³⁺ , Cr ³⁺ , Zr ⁴⁺ , and particularly preferred are Al ³⁺ and Zr ⁴⁺ .

  When the organometallic compound is contained in the toner of the present invention, the organometallic compound is preferably contained in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. Since it can be adjusted, it becomes easy to obtain an absolute charge amount necessary for development, and the heat melting property of the toner can be improved.

  In the toner of the present invention, it is preferable that an inorganic fine powder having an average primary particle diameter of 4 to 80 nm is externally added to the toner particles as a fluidizing agent. The inorganic fine powder is added to improve the fluidity of the toner and make the toner uniform. When the inorganic fine powder having an average primary particle size of 80 nm or less is not added, the fluidity of the toner is insufficient, and the charging of the toner particles is likely to be nonuniform, resulting in increased fog, decreased image density, Problems such as toner scattering are likely to occur. In addition, when the average primary particle diameter of the inorganic fine powder is smaller than 4 nm, the inorganic fine powder is easily agglomerated to form a strong aggregate, and the inorganic fine powder is uniformly adhered to the toner particle surface. And the uniformity of charging between the toner particles is deteriorated, for example, fog is deteriorated.

  In the present invention, the measurement method of the average primary particle size of the inorganic fine powder is a photograph of the toner magnified by a scanning electron microscope. Further, the inorganic fine powder is measured by an elemental analysis means such as XMA attached to the scanning electron microscope. The number average diameter can be determined by measuring 100 or more primary particles of inorganic fine powder adhering to or liberating from the toner surface while contrasting the photograph of the toner mapped with the contained element.

As the inorganic fine powder used in the present invention, silica fine powder by a wet production method, silica fine powder such as a silica fine powder by a dry production method, these silica fine powders are treated with a treatment agent such as a silane compound, a titanium coupling agent, and silicone oil. Examples include treated silica fine powder, titanium oxide fine powder, alumina fine powder, treated titanium oxide fine powder, treated alumina oxide fine powder and the like that have been subjected to surface treatment. The inorganic fine powder externally added to the toner particles is preferably one whose surface is subjected to a hydrophobic treatment, and the surface hydrophobic treatment improves the adjustment of the charge amount of the toner and the environmental stability. As treatment agents for hydrophobic treatment, treatment agents such as silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds may be used alone or in combination. And may be processed. Among them, those treated with silicone oil are preferable, and more preferably, the inorganic fine powder treated with silicone oil at the same time as or after hydrophobizing treatment maintains a high charge amount of toner particles even in a high humidity environment. In addition, it is good for preventing toner scattering. The silicone oil preferably has a viscosity at 25 ° C. of 3000 to 80000 mm ² / s. As the silicone oil used, for example, dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, fluorine-modified silicone oil and the like are particularly preferable. As a method for treating silicone oil, for example, inorganic fine powder treated with a silane compound and silicone oil may be directly mixed using a mixer, or a method of spraying silicone oil onto inorganic fine powder may be used. Also good. Alternatively, after dissolving or dispersing silicone oil in a suitable solvent, silica fine powder may be added and mixed to remove the solvent. A method using a sprayer is more preferable in that the formation of aggregates of inorganic fine powder is relatively small. The processing amount of silicone oil is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the inorganic fine powder.

  The addition amount of the inorganic fine particles having an average primary particle size of 4 to 80 nm is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles. If the amount exceeds 5.0 parts by mass, the fixability may be deteriorated.

  Toner applied to a high-speed image forming apparatus having a process speed of 140 mm / s or more is subjected to strong rubbing at a high speed from, for example, a developing sleeve or a toner layer regulating member, so that high durability is required. As a means for improving the durability of the toner, there is a method of increasing the amount of the inorganic fine powder added to the toner particles. However, in such a case, the inorganic fine powder is more easily released from the toner particles, filming on the photosensitive drum becomes remarkable, and image defects are likely to occur. However, the toner of the present invention is one in which release of the inorganic fine powder from the toner particles is suppressed. Even if a toner to which a relatively large amount of inorganic fine powder is externally added is applied to a high-speed image forming apparatus, the photoreceptor Filming of the inorganic fine powder on the drum is suppressed, and as a result, image defects are hardly generated.

  The toner of the present invention includes toner particles containing at least a binder resin, a colorant, and a reaction composition of an α-olefin and a carboxylic acid as essential components, and external additives such as inorganic fine powders externally added to the toner particles. It consists of an agent. When the toner particles in the present invention are produced by a pulverization method, they can be obtained by the method described below. That is, at least a binder resin, a colorant, a reaction composition of an α-olefin and a carboxylic acid, and if necessary, other optional components such as a wax and an organometallic compound are mixed with a mixer such as a Henschel mixer or a ball mill. Mix well, melt, knead and knead using a kneader such as a kneader or extruder, cool and solidify the melt-kneaded product, grind the solidified product, and classify the pulverized product to obtain a predetermined average particle size Toner particles can be obtained. Further, for example, when the toner particles of the present invention are produced by a polymerization method, a vinyl monomer such as styrene or n-butyl acrylate, a colorant, a reaction composition of an α-olefin and a carboxylic acid, and further necessary Accordingly, after the wax, polar resin, crosslinking agent, charge control agent, chain transfer agent, and other additives are uniformly dissolved or dispersed to form a polymerizable monomer composition, this polymerizable monomer composition Is granulated in an aqueous medium containing a dispersion stabilizer such as calcium phosphate using an appropriate high-speed stirrer, and the temperature is adjusted to 50 to 100 ° C. using an azo or peroxide polymerization initiator in a nitrogen atmosphere. The suspension polymerization reaction is completed at a temperature, and after cooling, the toner particles are filtered, washed, and dried to obtain toner particles having a desired particle size. Further, when the toner particles of the present invention are produced by the emulsion aggregation method, a vinyl-based monomer such as styrene, acrylic acid or n-butyl acrylate, and a chain transfer agent such as thiols, if necessary, are added to alkylbenzene. Emulsified in water using a surfactant such as sodium sulfonate or a polymer dispersant such as polyvinyl alcohol or methyl cellulose, and a polymerization initiator such as potassium persulfate is used in combination with a reducing agent such as sodium sulfite if necessary. Polymerization is performed at a temperature of 0 to 100 ° C. in a nitrogen atmosphere to obtain a resin emulsion. A colorant pulverized or dispersed to an appropriate particle size, a reaction composition of an α-olefin and a carboxylic acid, and, if necessary, a wax, a charge control agent, other additives, etc. Other materials are added and the resin emulsion is aggregated using an aggregating agent or the like, and then thermally associated to obtain toner particles having a desired particle size.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 4.0 to 9.0 μm. Thus, by reducing the weight average particle diameter of the toner, the reproducibility in the development of the contour portion of an image, particularly a character image or a line pattern is improved. When the weight average particle size is less than 4.0 μm, for example, the adhesion force to the surface of the photosensitive drum is increased, which tends to cause uneven image unevenness due to transfer defects. Further, the charge amount per unit mass of the toner becomes high, and the image density may be lowered in a low temperature and low humidity environment, for example. Furthermore, due to a decrease in fluidity and an increase in adhesion to a member, for example, frictional charging with a carrier is difficult to be performed smoothly, toner that cannot be sufficiently charged increases, and fogging of non-image areas becomes conspicuous. . Also, if the weight average particle size exceeds 9.0 μm, there is a merit that the fluidity of the toner is excellent, but the reproducibility of character images and line patterns is reduced because there are fewer fine particles that can contribute to higher image quality. For example, the reproducibility of the highlight portion may be lowered, and the resolution may be further lowered. Further, when 3 to 40% by number of toner having a particle diameter of 4.0 μm or less is contained and 15% by volume or less of toner having a particle diameter of 10.0 μm or more is contained, the balance between developability and transferability is improved. It is particularly preferable because it is easy to obtain a removed toner.

  The toner of the present invention preferably has an average circularity in the range of 0.920 to 0.990, more preferably 0.925 to 0.985 in particles having an equivalent circle diameter of 2 μm or more. By setting the average circularity of the toner within the above range, the fluidity, transferability, and chargeability of the toner can be improved. If the average circularity is less than 0.920, the transferability, particularly the transfer efficiency, may be deteriorated. Conversely, if the average circularity is more than 0.990, the shape becomes too spherical. There may be image defects due to poor cleaning, such as untransferred toner passing through the cleaning blade. If the average circularity is greater than 0.990, the inorganic fine powder tends to be liberated from the toner particles when applied to an image forming apparatus having a high process speed.

  The means for adjusting the average circularity of the toner of the present invention to 0.920 to 0.990 is not particularly limited. For example, the toner particles are made spherical by applying a mechanical impact force to the toner particles produced by the pulverization method. Method, a method of obtaining a spherical toner particle by atomizing a molten mixture into air using a disk or a multi-fluid nozzle, suspending a toner composition dissolved in a solvent in water, and then distilling off the solvent to obtain spherical toner particles. A method of obtaining, adding other materials such as a colorant to the emulsion obtained by emulsion polymerization, and agglomerating and associating the emulsion to obtain spherical toner particles, and directly obtaining spherical toner particles by suspension polymerization. Various methods such as a polymerization method can be employed. As the mechanical impact method, known devices are used. For example, a hybridizer manufactured by Nara Machinery Co., Ltd., a mechanofusion system manufactured by Hosokawa Micron Co., a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., and Nisshin Engineering Co., Ltd. There are super rotors made of steel.

  In the toner of the present invention, by adjusting the toner particle size distribution and the average circularity as described above, the charge distribution becomes sharper, thereby improving the development efficiency and reducing fogging. Furthermore, it is possible to faithfully reproduce the latent image formed on the photosensitive drum, and is excellent in the reproducibility of a minute dot latent image such as a halftone dot and a digital image. A toner image having excellent resolution can be provided. In addition, even when image output is continued, high image quality is maintained, and even in the case of high density images, it is possible to perform good development with a small amount of toner consumption, and color reproducibility with a clear color over a long period of time. A good full color image is obtained.

  The toner of the present invention can also be applied to an image forming apparatus provided with an intermediate transfer member. An image forming apparatus provided with an intermediate transfer member can be applied to a wide variety of transfer materials, and has been rapidly spreading in recent years. In the case of an image forming apparatus provided with an intermediate transfer member, the transfer process is performed twice, so that a decrease in transfer efficiency causes a decrease in toner utilization efficiency and becomes a problem. However, the toner of the present invention achieves high transferability by adjusting the particle size distribution and average circularity as described above, and can be suitably used for an image forming apparatus provided with an intermediate transfer member. If the toner of the present invention having such a high transferability is used, transfer defects such as transfer omissions that tend to occur in a system using an intermediate transfer member hardly occur, so the color reproducibility and color tone of the secondary color are extremely high. Even when a wide variety of transfer materials are used, a beautiful full-color image can be obtained.

  The toner of the present invention can be used as a one-component developer or a two-component developer, but when used as a two-component developer, a clear full-color image can be easily obtained over a long period of time, which is particularly preferable. .

  When the toner of the present invention is used as a two-component developer, the toner of the present invention and a magnetic carrier may be mixed to form a two-component developer. As the carrier, for example, surface-oxidized or non-oxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, calcium, magnesium, rare earth and other metals and their alloys or oxides and magnetic ferrite can be used.

  Moreover, the resin coat carrier which coat | covered the surface of the said carrier with resin etc. is used suitably in this invention. As a method for producing a resin-coated carrier, a conventionally known method can be adopted and is not particularly limited.For example, a method of forming a coat film on the surface of a carrier by spraying a resin solution while causing the carrier to float and flow, Examples include a spray drying method, a method in which a coating material such as a resin is dissolved or suspended in a solvent and mixed with a carrier, and the solvent is gradually volatilized while applying a shear stress, or a method in which powder and a carrier are simply mixed. .

  Examples of the carrier coating material include resins having a low surface energy, such as silicone resin and fluorine-based resin, which are considered to be useful for preventing toner fusion and the like from being spent on the carrier. Resin, acrylic resin, polyamide, polyvinyl butyral, aminoacrylate resin and the like are exemplified, and these are used alone or in combination.

  Moreover, in order to improve the adhesiveness with respect to a carrier, it is preferable to use various additives together and to improve the toughness of a film. In particular, when coating a silicone resin, the durability and charging characteristics of the resulting coated carrier are further improved by adding water to the coating resin dilution solvent to be used. This is because the crosslinking point of the curable silicone resin and the hydrolysis of the silane coupling agent are accelerated, the curing reaction proceeds further, and the surface energy of the silicone resin increases for a short time, and the adhesion to the carrier. This is due to the improvement.

  The amount of coating resin applied to the carrier is such that the resin solid content is 0.05 to 10 parts by mass per 100 parts by mass of the carrier.

  The average particle size (D50) based on the volume distribution of the carrier is preferably 25 to 80 μm, more preferably 30 to 65 μm. The average particle size based on the volume distribution of the carrier can be measured by any laser diffraction type particle size distribution meter as long as the measurement range is from submicron to several hundred microns, and may be either dry or wet. For example, it can be measured using a laser diffraction particle size distribution analyzer SALD-3000 (trade name, manufactured by Shimadzu Corporation). When the average particle size based on the volume distribution of the carrier is smaller than 25 μm, mixing with the toner becomes difficult. On the other hand, if the average particle size based on volume distribution exceeds 80 μm, the specific surface area of the carrier is small, so that the charging ability at the time of toner replenishment is inferior, which may cause fogging and toner scattering.

  When the two-component developer is prepared by mixing the toner of the present invention and the carrier of the above-mentioned form, the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. Then usually good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease. If the toner concentration exceeds 15% by mass, fogging or in-machine scattering tends to occur, and the useful life of the developer tends to decrease.

  Next, an image forming method to which the toner of the present invention is applied will be described below with reference to the drawings.

  FIG. 1 shows an image forming apparatus for a two-component developer. Developers 4-1, 4-2, 4-3, and 4-4 are respectively introduced with a developer having cyan toner, a developer having magenta toner, a developer having yellow toner, and a developer having black toner. Then, the electrostatic charge image formed on the photosensitive drum 1 is developed by the magnetic brush developing method, and each color toner image is formed on the photosensitive drum 1.

  The toner of the present invention can be mixed with a magnetic carrier and developed using, for example, developing means as shown in FIG. Specifically, it is preferable to perform development in a state where the magnetic brush is in contact with the photosensitive drum 13 while applying an alternating electric field. The distance B between the developer carrying member (developing sleeve) 11 and the photosensitive drum 13 is 100 to 1000 μm.

  The voltage (Vpp) between the peaks of the alternating electric field is preferably 500 to 5000 V, the frequency (f) is 500 to 10000 Hz, and various waveforms such as a triangular wave, a rectangular wave, a sine wave, or a waveform with a changed duty ratio can be selected. Can be used. The contrast potential is preferably 200 V to 500 V so that a sufficient image density can be obtained.

  The contact width (development nip C) of the magnetic brush on the developing sleeve 11 with the photosensitive drum 13 is preferably 3 to 8 mm in order to obtain a sufficient image density, excellent dot reproducibility, and development without carrier adhesion. To.

  The toner of the present invention can be developed using a developing means as shown in FIG. 3, for example, without being mixed with a magnetic carrier. FIG. 3 is a schematic view of an image forming apparatus for nonmagnetic one-component development. In FIG. 3, reference numeral 25 denotes an electrostatic charge image carrier (photosensitive drum), and latent image formation is formed by electrophotographic process means. Reference numeral 24 denotes a toner carrier (developing sleeve). A bias power source 26 applies a bias between the photosensitive drum 25 and an alternating electric field. When an alternating electric field is applied, Vpp is 200 to 3000 V, f is 500 to 5000 Hz, and a waveform such as a rectangular wave, a sine wave, a sawtooth wave, and a triangular wave can be applied. It is also preferable to superimpose a DC bias. The developing sleeve 24 is preferably a cylinder made of stainless steel, aluminum or the like, and the surface may be coated with a resin in which fine particles such as metals, carbon black, and a charge control agent are dispersed, if necessary. The gap α between the photosensitive drum 25 and the developing sleeve 24 is set to 50 to 500 μm in the case of jumping development, and in the case of contact development, the photosensitive drum 25 and the developing sleeve 24 are in contact (that is, α = 0) or The developing nip width is preferably set to 0.2 to 8.0 mm with a gap narrower than the toner layer. In the case of contact development, a so-called elastic roller having an elastic layer on the surface is preferably used as the developing sleeve, and the hardness of the material of the elastic layer used is 30 to 60 degrees (asker-C / load). 1 kg) is preferably used. The substantially right half circumferential surface of the developing sleeve 24 is always in contact with the toner reservoir in the toner container 21, and the toner near the developing sleeve surface is attached and held on the developing sleeve surface by electrostatic force.

  By setting the surface roughness Ra (μm) of the toner carrier to 1.5 or less, the toner layer on the toner carrier is thinned. The surface moving speed of the toner carrier is set to be 1.05 to 3.0 times the surface moving speed of the electrostatic image carrier. When the surface moving speed of the toner carrying member is less than 1.05 times the surface moving speed of the electrostatic latent image carrying member, the stirring effect received by the toner layer becomes insufficient, and good image formation cannot be expected. . In addition, when developing an image that requires a large amount of toner over a wide area, such as a solid black image, the amount of toner supplied to the electrostatic latent image is insufficient and the image density becomes low. On the other hand, when it exceeds 3.0 times, in addition to various problems caused by excessive charging of the toner, the deterioration of the toner due to mechanical stress and the toner fixing to the toner carrying member are generated and promoted, which is not preferable. .

  The toner T is stored in the hopper 21 and is supplied onto the developing sleeve by the supply member 22. As the supply member, a supply roller made of a foamed material such as a porous elastic body, for example, a flexible polyurethane foam, is preferably used. The supply roller is rotated at a relative speed in the forward or reverse direction with respect to the developing sleeve, and the toner is supplied onto the developing sleeve. The toner after development (undeveloped toner) on the sleeve is also peeled off. At this time, the contact width of the supply roller to the developing sleeve is preferably 2.0 to 10.0 mm and more preferably 4.0 to 6.0 mm in consideration of the balance between toner supply and stripping. Moreover, as a supply member, you may use the brush member which consists of resin fibers, such as nylon and rayon.

  The toner supplied onto the developing sleeve is applied thinly and uniformly by the regulating member 23. The regulating member is a metal blade, magnetic blade, or other doctor blade arranged with a certain gap from the developing sleeve, or a rigid roller or sleeve using metal, resin, ceramics or the like instead of the doctor blade. Also good. Further, an elastic body such as an elastic blade or an elastic roller for press-fitting toner may be used as the regulating member. Furthermore, a DC electric field and / or an AC electric field can also be applied to the regulating member and the supply member. For example, by applying an electric field to the regulating member, a toner loosening action occurs on the developing sleeve, and uniform thin layer coating properties The uniform chargeability is further improved, and by applying an electric field to the supply member, the supply / peeling of the toner can be performed more smoothly, achieving a sufficient image density and obtaining a good quality image.

  For example, in FIG. 3, the elastic blade 23 is fixedly held at its base, which is the upper side, on the toner container 21 side, and the lower side is bent in the forward or reverse direction of the developing sleeve 24 against the elasticity of the blade. In this state, the inner surface of the blade (the outer surface in the case of the reverse direction) is brought into contact with the surface of the sleeve 24 with an appropriate elastic pressure. According to such an apparatus, it is possible to obtain a dense toner layer that is stable against environmental changes. For the elastic body, it is preferable to select a triboelectric material suitable for charging the toner to a desired polarity. A rubber elastic body such as silicone rubber, urethane rubber or NBR; a synthetic resin elastic body such as polyethylene terephthalate. A metal elastic body such as stainless steel, steel or phosphor bronze can be used. Moreover, those composites may be sufficient. Further, when durability is required for the elastic body and the toner carrying body, it is preferable that the metal elastic body is bonded or coated with a resin or rubber so as to contact the sleeve contact portion. The contact pressure between the elastic blade and the toner carrier is effectively 0.1 to 30 kPa as the linear pressure in the generatrix direction of the toner carrier. As a result, it is possible to effectively loosen toner aggregation, and it is possible to instantly raise the charge amount of the toner. When the contact pressure is less than 0.1 kPa, it is difficult to uniformly apply the toner, and the toner charge amount distribution becomes broad, which may cause fogging or scattering. On the other hand, when the contact pressure exceeds 30 kPa, a large pressure is applied to the toner, and the toner may be deteriorated or toner aggregates may be generated.

  Hereinafter, various physical property measuring methods used in the present invention will be described.

<Measurement of molecular weight distribution of reaction composition of α-olefin and carboxylic acid>
The molecular weight distribution of the reaction composition of the α-olefin and the carboxylic acid is measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-150C (trade name, manufactured by Waters)
Column: Shodex KF-80M 2 series (trade name, manufactured by Showa Denko KK)
Eluent: o-dichlorobenzene (2,6-di-t-butyl-4-methylphenol
(BHT) 0.1% addition)
Flow velocity: 1.0 ml / min
Oven temperature: 135 ° C
Sample injection amount: 0.40 ml
Measurement is performed under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used in calculating the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.

  Samples are prepared as follows.

  Place the sample in o-dichlorobenzene and heat the sample bottle on a hot plate set at 150 ° C. to dissolve the sample. When the sample melts, put it in a preheated filter unit and place it on the main unit. The sample passed through the filter unit is used as the GPC sample. The sample concentration is adjusted to 0.15% by mass.

<Measurement of peak temperature and onset temperature of maximum endothermic peak>
The peak temperature of the maximum endothermic peak of the reaction composition of α-olefin and carboxylic acids, wax and toner is measured using a differential scanning calorimeter (DSC) according to ASTM D3418-82. The measurement sample is precisely weighed 2 to 10 mg. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min within a measurement temperature range of 30 to 200 ° C. In the measurement, the temperature is increased and then the temperature is decreased once, and then the temperature is increased again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. The maximum endothermic peak at. The onset temperature refers to the temperature at the intersection of the tangent line and the base line at the point where the differential value on the low temperature side of the endothermic curve of the maximum endothermic peak in DSC is maximum.

<Measurement of penetration of reaction composition of α-olefin and carboxylic acid>
The penetration of the reaction composition of α-olefin and carboxylic acid is measured according to JIS K-2207. Specifically, the penetration depth when a needle having a conical tip with a diameter of about 1 mm and an apex angle of 9 ° is vertically entered with a constant load is read in units of 0.1 mm, and is a value obtained by multiplying this by 10 times. Is the penetration. The test conditions in the present invention are a sample temperature of 25 ° C., a load of 100 g, and an entry time of 5 seconds.

<Measurement of acid value of reaction composition of α-olefin and carboxylic acid>
A sample 1.0-1.5 g is precisely weighed in an Erlenmeyer flask, 20 ml of xylene is added thereto, and then dissolved by heating. After dissolution, 20 ml of dioxane is added, and titrated as soon as possible with a 1% by weight phenolphthalein solution as an indicator with a 0.1 mol / l potassium hydroxide standard methanol solution while the solution does not become cloudy or hazy. Perform a blank test at the same time.
Acid value = [5.61 × (AB) × f] / S

  However, A: ml number of 0.1 mol / l potassium hydroxide standard methanol solution required for this test, B: ml number of 0.1 mol / l potassium hydroxide standard methanol solution required for blank test, f: Factor of 0.1 mol / l potassium hydroxide standard methanol solution, S: sample amount of reaction composition (g)

<Measurement of melt viscosity of reaction composition of α-olefin and carboxylic acid>
The beaker containing the sample is immersed in an oil bath maintained at 120 ° C. and stirred well when the reaction composition is dissolved. Then, the viscosity is measured using a Brookfield rotational viscometer.

<Measurement of Weight Average Particle Size (D4) and Particle Size Distribution of Toner>
The weight average particle diameter (D4) and particle size distribution of the toner are measured using various measuring devices such as Coulter Counter TA-II type (trade name, manufactured by Coulter) or Coulter Multisizer (trade name, manufactured by Coulter). Is possible. In the present invention, a Coulter Multisizer is used, and an interface (manufactured by Nikka Ki Bios Co., Ltd.) for outputting the number distribution and volume distribution is connected to the personal computer. The electrolyte used for the measurement of the Coulter Multisizer is a solution in which sodium chloride is dissolved in ion-exchanged water so as to have a concentration of 1% by mass, such as ISOTON R-II (trade name, Coulter Scientific) Can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzenesulfonate is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser “Tetora 150 type” (trade name, manufactured by Nikka Ki Bios), and a 100 μm aperture was used as an aperture by the Coulter Multisizer. The volume distribution and the number distribution are calculated by measuring the volume and the number of toner particles of 2 μm or more.

  Then, the weight average particle diameter (D4: the median value of each channel is the representative value of the channel) obtained from the volume distribution according to the present invention can be obtained.

<Measurement of average circularity of toner>
The average circularity of the toner is measured using a flow type particle image measuring device “FPIA-2100” (trade name, manufactured by Sysmex Corporation), and is calculated using the following equation.

  Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define. The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).

  In the present invention, the circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity.

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles.

  In addition, “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity. 1.0 is divided into classes equally divided every 0.01, and the average circularity is calculated using the center value of the division points and the number of measured particles.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a means for dispersing, an ultrasonic disperser “Tetora150 type” (trade name, manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours.

  To measure the circularity of the toner particles, the flow type particle image measuring device is used, and the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 particles / μl. Measure more than one. After the measurement, using this data, data having an equivalent circle diameter of less than 2 μm is cut to determine the average circularity of the toner particles.

  Furthermore, “FPIA-2100”, which is a measuring apparatus used in the present invention, improves the magnification of the processed particle image, compared with “FPIA-1000” that has been used to calculate the shape of the toner. The accuracy of toner shape measurement has been improved by improving the processing resolution of the captured image (256 × 256 → 512 × 512), thereby achieving more reliable capture of fine particles. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA-2100 that can obtain information on the shape more accurately is more useful.

<Measurement of molecular weight distribution of resin component in binder resin and toner>
Measurement of the molecular weight distribution of the resin component soluble in tetrahydrofuran (THF) by gel permeation chromatography (GPC) may be performed as follows.

  A predetermined amount of binder resin or toner and THF are placed in a glass sample bottle and allowed to stand at room temperature for 24 hours to dissolve the resin component. This solution is filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm (for example, trade name “Maeshori Disc”, manufactured by Tosoh Corporation) to obtain a sample solution, which is measured under the following conditions. In addition, sample preparation adjusts so that the density | concentration of the component soluble in THF may be 0.4-0.6 mass%.

Equipment: High-speed GPC HLC8120 GPC (trade name, manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805, 80
7 series of 6,807 (trade name, manufactured by Showa Denko)
Eluent: THF
Flow velocity: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measurement of glass transition temperature of binder resin>
The glass transition temperature (Tg) of the binder resin is measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC).

  The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. It is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min within a measurement range of 30 to 200 ° C. In this temperature raising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature of the resin of the present invention.

<Measurement of acid value of binder resin>
The acid value of the binder resin is measured as follows according to JIS K0070.
2-10 g of sample is weighed into a 200-300 ml Erlenmeyer flask and about 50 ml of a mixed solvent of methanol and toluene (volume ratio 30/70) is added to dissolve the resin. If solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% by mass of bromthymol blue and phenol red, titration with a standardized 0.1 mol / l potassium hydroxide standard methanol solution is carried out, and the amount of consumption of the potassium hydroxide standard methanol solution is then calculated. The acid value is obtained by the calculation of
Acid value = [5.61 × (AB) × f] / S
However, A: ml number of 0.1 mol / l potassium hydroxide standard methanol solution required for this test, B: ml number of 0.1 mol / l potassium hydroxide standard methanol solution required for blank test, f: Factor of 0.1 mol / l potassium hydroxide standard methanol solution, S: Sample amount of resin (g)

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

<Production example of reaction composition of α-olefin and carboxylic acid>
<Reaction Composition Production Example 1>
Α-Olefin A purified by solvent deoiling treatment (average carbon number: 31, polyethylene-converted weight average molecular weight: 432, peak temperature of maximum endothermic peak by DSC: 72 ° C., low temperature side onset temperature: 63 ° C., 25 ° C. Penetration at 5, 120 ° C. with Brookfield viscometer: 11 mPa · s, α-olefin content: 96%) 300 parts by mass and 60 parts by mass of butanoic acid were charged into an autoclave and nitrogen gas was used. The solution was thoroughly replaced and dissolved by heating at 180 ° C. with stirring. Thereto, 5 parts by mass of di-t-butyl peroxide which is an organic peroxide was dropped over 30 minutes, and α-olefin A and butanoic acid were subjected to an addition reaction. After cooling, the reaction composition in the flask was taken out, dried under reduced pressure overnight at 25 ° C. and 2.0 Pa, and then the atmosphere temperature was gradually raised to 40 ° C. to perform perspiration treatment. Further, the sweating product is heated and dissolved in a mixed solvent of methyl ethyl ketone / toluene with stirring, and this dissolved solution is cooled to 5 ° C. with stirring to precipitate crystals, which are filtered with a pressure filter equipped with a membrane filter. did. The crystal is transferred to another container equipped with a stirring blade and a distillation apparatus, heated and melted to 205 ° C. with stirring, and subjected to vacuum distillation at 2.0 Pa for 4 hours to remove a light fraction, and α -Reaction composition A of olefin A and butanoic acid was obtained.

  When this reaction composition A was analyzed by NMR and HPLC, the content of the product obtained by reacting α-olefin A and butanoic acid at a molar ratio of 1: 1 was 99% by mass, and the content of unreacted α-olefin A was contained. The rate was less than 1% by mass. In addition, the weight average molecular weight in terms of polyethylene is 520, the peak temperature of the maximum endothermic peak by DSC is 78 ° C., the low temperature side onset temperature is 68 ° C., and the penetration is 2, 120 ° C. Brookfield viscometer The viscosity was 13 mPa · s, and the acid value was 36 mgKOH / g.

<Reaction Composition Production Example 2>
A reaction composition B was obtained in the same manner as in Production Example 1 except that the amount of butanoic acid added was changed to 38 parts by mass.

<Reaction Composition Production Example 3>
Reaction composition C was obtained in the same manner as in Production Example 1 except that the amount of butanoic acid added was changed to 24 parts by mass.

<Reaction Composition Production Example 4>
α-olefin B instead of α-olefin A (average carbon number: 37, weight average molecular weight in terms of polyethylene is 539, peak temperature of maximum endothermic peak by DSC is 78 ° C, low temperature side onset temperature is 65 ° C, 25 ° C In the same manner as in Production Example 1 except that 60 parts by weight of decanoic acid was used in place of butanoic acid, using a viscosity of 4 at 120 ° C. and a viscosity of 18 mPa · s at 120 ° C. and an α-olefin content of 90%. The reaction composition D was obtained.

<Reaction Composition Production Example 5>
α-olefin C instead of α-olefin A (average carbon number 43, weight average molecular weight in terms of polyethylene is 630, peak temperature of maximum endothermic peak by DSC is 83 ° C, low temperature side onset temperature is 70 ° C, 25 ° C Behenic acid with a purity of 90% by mass instead of butanoic acid (higher fatty acid with different carbon chain length as an impurity) using a penetration of 4 at 120 ° C. and a viscosity of 21 mPa · s at 120 ° C. and an α-olefin content of 86% The reaction composition E was obtained in the same manner as in Production Example 1 except that 82 parts by mass) was used.

<Production Example 6 of Reaction Composition>
α-olefin D instead of α-olefin A (average carbon number is 24, weight average molecular weight in terms of polyethylene is 284, peak temperature of maximum endothermic peak by DSC is 54 ° C, low temperature side onset temperature is 42 ° C, 25 ° C The reaction composition F was obtained in the same manner as in Production Example 1 except that the penetration at 18 was 12, the viscosity at 120 ° C. was 9 mPa · s, and the α-olefin content was 95%.

<Reaction Composition Production Example 7>
300 parts by mass of the α-olefin A and 35 parts by mass of maleic anhydride were charged into an autoclave and sufficiently substituted with nitrogen gas. Thereafter, the mixture was heated and dissolved at a temperature of 180 ° C. with stirring, and maintained for 12 hours to cause addition reaction between α-olefin A and maleic anhydride. Then, it refine | purified like manufacture example 1 and the reaction composition G was obtained.

<Reaction Composition Production Example 8>
300 parts by mass of α-olefin A and 35 parts by mass of maleic anhydride were charged into an autoclave and sufficiently substituted with nitrogen gas. Thereafter, the mixture was heated and melted at a temperature of 190 ° C. with stirring, and 20 parts by mass of di-t-butyl peroxide was added dropwise over 2 hours to cause a reaction. Then, it refine | purified like manufacture example 1 and the reaction composition H was obtained.

<Reaction Composition Production Example 9>
A reaction composition I was obtained in the same manner as in Production Example 8, except that the amount of di-t-butyl peroxide added was 10 parts by mass.

<Reaction Composition Production Example 10>
A reaction composition J was obtained in the same manner as in Production Example 8 except that the amount of di-t-butyl peroxide added was 3 parts by mass.

<Production Example 11 of Reaction Composition>
A reaction composition K was obtained in the same manner as in Production Example 8 except that the amount of di-t-butyl peroxide added was 3 parts by mass and the heating and melting temperature (reaction temperature) was 175 ° C.

  The physical properties of the reaction compositions A to K are summarized in Table 1.

<Example of binder resin production>
<Production example of resin A (hybrid resin)>
In a reaction vessel equipped with a thermometer, stirring blades, condenser and nitrogen introduction tube, 47 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2 ) -2,2-bis (4-hydroxyphenyl) propane 28 parts by mass, terephthalic acid 23 parts by mass, trimellitic anhydride 11 parts by mass, fumaric acid 1 part by mass and dibutyltin oxide 0.005 part by mass After replacing the inside of the container with nitrogen gas, the temperature was gradually raised while stirring and maintained at a temperature of 145 ° C. On the other hand, 4.18 parts by mass of styrene, 1.15 parts by mass of 2-ethylhexyl acrylate, 0.52 parts by mass of fumaric acid, 0.12 parts by mass of dimer of α-methylstyrene, 0.20 mass of dicumyl peroxide The parts were mixed well at room temperature and added dropwise to the previous reaction vessel over 4 hours. Thereafter, the reaction solution was heated to 200 ° C. and reacted for 6 hours to obtain Resin A (hybrid resin). Mp of the obtained resin A was 12000, Mw / Mn was 24, and Tg was 62 ° C. The acid value was 28.

<Production example of resin B (polyester resin)>
In a reaction vessel equipped with a thermometer, stirring blades, condenser and nitrogen introduction tube, 47 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2 ) -2,2-bis (4-hydroxyphenyl) propane 18 parts by mass, dodecenyl succinic acid 18 parts by mass, terephthalic acid 18 parts by mass, trimellitic anhydride 3 parts by mass and dibutyltin oxide 0.01 parts by mass After replacing the inside of the container with nitrogen gas, the temperature was gradually raised while stirring, the temperature was raised to 210 ° C., and the mixture was reacted for 6 hours to obtain polyester resin B. Mp of the obtained resin B (polyester resin) was 8000, Mw / Mn was 11, and Tg was 60 ° C. The acid value was 26.

<Toner Production Example 1>
-Resin A 100.0 parts by mass-C.I. I. Pigment Blue 15: 3 5.0 parts by mass / Reaction Composition A 5.0 parts by mass / aluminum 3,5-di-t-butylsalicylate compound 1.0 part by mass The above materials were sufficiently premixed by a Henschel mixer. . Thereafter, the mixture is melt-kneaded with a twin-screw extruder kneader, and the kneaded product is cooled and roughly pulverized to about 1 to 2 mm using a hammer mill, and then finely pulverized to a particle size of 20 μm or less with an air jet type pulverizer. . Thereafter, the above finely pulverized product is treated for 3 minutes at a rotation speed of 100 s ⁻¹ with a surface modification (spheroidizing) treatment device “Hybridizer” (trade name, manufactured by Nara Machinery Co., Ltd.) using mechanical impact force. Thereafter, the toner was classified with an air classifier “Elbow Jet Classifier” (trade name, manufactured by Nittetsu Mining Co., Ltd.) so that the weight average particle diameter was about 7 μm, and cyan toner particles 1 of the present invention were obtained. To 100 parts by mass of the toner particles 1, 2.5 parts by mass of hydrophobized silica fine powder (average primary particle diameter: 12 nm) was externally added to obtain the cyan toner 1 of the present invention. The hydrophobized silica fine powder was subjected to a surface treatment with 10 parts by mass of hexamethyldisilazane with respect to 100 parts by mass of silica fine powder obtained by a dry process, and then with 10 parts by mass of dimethyl silicone oil. It has been surface treated.

<Toner Production Example 2>
Cyan toner particles 2 of the present invention and cyan toner 2 of the present invention were obtained in the same manner as in Toner Production Example 1 except that the reaction composition B was used instead of the reaction composition A.

<Toner Production Example 3>
Cyan toner particles 3 of the present invention and cyan toner 3 of the present invention were obtained in the same manner as in Toner Production Example 1 except that the reaction composition C was used in place of the reaction composition A.

<Toner Production Example 4>
Cyan toner particles 4 of the present invention and cyan toner 4 of the present invention were obtained in the same manner as in Toner Production Example 1 except that the reaction composition D was used instead of the reaction composition A.

<Toner Production Example 5>
Cyan toner particles 5 of the present invention and cyan toner 5 of the present invention were obtained in the same manner as in Toner Production Example 1 except that reaction composition E was used in place of reaction composition A.

<Toner Production Example 6>
Cyan toner particles 6 of the present invention and cyan toner 6 of the present invention were obtained in the same manner as in Toner Production Example 1 except that the reaction composition F was used instead of the reaction composition A.

<Toner Production Example 7>
Cyan toner particles 7 of the present invention and cyan toner 7 of the present invention were obtained in the same manner as in Toner Production Example 1 except that the reaction composition G was used instead of the reaction composition A.

<Toner Production Example 8>
Cyan toner particles 8 of the present invention and cyan toner 8 of the present invention were obtained in the same manner as in Toner Production Example 1 except that the reaction composition H was used instead of the reaction composition A.

<Toner Production Example 9>
Cyan toner particles 9 of the present invention and cyan toner 9 of the present invention were obtained in the same manner as in Toner Production Example 1 except that the reaction composition I was used in place of the reaction composition A.

<Toner Production Example 10>
The cyan toner particles 10 of the present invention and the cyan toner 10 of the present invention were obtained in the same manner as in Toner Production Example 1 except that the resin B was used instead of the resin A.

<Toner Production Example 11>
The amount of reaction composition A used was changed from 5.0 parts by weight to 1.0 parts by weight, and normal paraffin wax (average carbon number 35, polyethylene equivalent weight average molecular weight 497, peak temperature of maximum endothermic peak by DSC) Is 75 ° C., low-temperature onset temperature is 72 ° C., penetration at 25 ° C. is 7, viscosity at 120 ° C. is 7 mPa · s), and 4.0 parts by mass is used in the same manner as in Toner Production Example 1. Thus, cyan toner particles 11 of the present invention and cyan toner 11 of the present invention were obtained.

<Toner Production Example 12>
The cyan toner particles 12 of the present invention and the cyan toner 12 of the present invention are obtained in the same manner as in Toner Production Example 1 except that the amount of the reaction composition A used is changed from 5.0 parts by mass to 0.4 parts by mass. It was.

<Toner Production Example 13>
Except having changed the usage-amount of the reaction composition A from 5.0 mass parts to 2.0 mass parts, it carried out similarly to the manufacture example 1 of a toner, and obtained the cyan toner particle 13 of this invention, and the cyan toner 13 of this invention. It was.

<Toner Production Example 14>
Except having changed the usage-amount of the reaction composition A from 5.0 mass parts to 9.0 mass parts, it carried out similarly to the manufacture example 1 of a toner, and obtained the cyan toner particle 14 of this invention, and the cyan toner 14 of this invention. It was.

<Toner Production Example 15>
The cyan toner particles 15 of the present invention and the cyan toner 15 of the present invention are obtained in the same manner as in Toner Production Example 1 except that the amount of the reaction composition A used is changed from 5.0 parts by mass to 12.0 parts by mass. It was.

<Toner Production Example 16>
The cyan toner particles 16 of the present invention and the cyan toner 16 of the present invention were prepared in the same manner as in Toner Production Example 1 except that the condition of the surface modification treatment by the hybridizer was changed to a rotation speed of 120 s ⁻¹ and a treatment time of 7 minutes. Obtained.

<Toner Production Example 17>
The cyan toner particles 17 of the present invention and the cyan toner 17 of the present invention were prepared in the same manner as in Toner Production Example 1 except that the condition of the surface modification treatment by the hybridizer was changed to a rotation speed of 90 s ⁻¹ and a treatment time of 1 minute. Obtained.

<Toner Production Example 18>
The cyan toner particles 18 of the present invention and the cyan toner 18 of the present invention were obtained in the same manner as in the toner production example 1 except that the surface modification treatment by the hybridizer was not performed.

<Toner Production Example 19>
The kneaded product was roughly pulverized in the same manner as in Toner Production Example 1, and then the pulverization pressure conditions of the air jet pulverizer were weakened to obtain a finely pulverized product having a coarse pulverized particle size. Furthermore, the finely pulverized product was treated for 3 minutes at a rotation speed of 100 s ^-1 with a surface modification (spheronization) treatment device, and classified so that the weight average particle diameter was about 10 μm with an air classification device. Thus, cyan toner particles 19 of the present invention were obtained. Thereafter, hydrophobized silica fine powder was externally added in the same manner as in Toner Production Example 1 to obtain cyan toner 19 of the present invention.

<Toner Production Example 20>
The kneaded product was roughly pulverized in the same manner as in Toner Production Example 1, and then the pulverization pressure conditions of the air jet pulverizer were increased to obtain a finely pulverized product having a fine pulverized particle size. Furthermore, the finely pulverized product was treated for 3 minutes at a rotation speed of 100 s ⁻¹ with a surface modification (spheronization) treatment device, and classified so that the weight average particle diameter was about 4 μm with an air classification device. Thus, cyan toner particles 20 of the present invention were obtained. Thereafter, hydrophobized silica fine powder was externally added in the same manner as in Toner Production Example 1 to obtain cyan toner 20 of the present invention.

<Toner Production Example 21>
In a four-necked flask, 700 parts by mass of ion-exchanged water and 800 parts by mass of an aqueous sodium phosphate solution having a concentration of 0.1 mol / l were added and heated to 60 ° C. While stirring this at 170 s ^-1 with a TK homomixer (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd.), 70 parts by mass of an aqueous calcium chloride solution having a concentration of 1.0 mol / l was added to form a slightly water-insoluble solution. An aqueous dispersion medium containing a dispersant (calcium phosphate) was prepared.

  On the other hand, a mixture consisting of the following was dispersed for 4 hours at room temperature using an attritor (trade name, manufactured by Mitsui Miike Chemical Co., Ltd.) to prepare a uniform polymerizable monomer composition.

-Styrene 78.0 mass parts-N-butyl acrylate 22.0 mass parts-Divinylbenzene 0.2 mass part-C.I. I. Pigment Blue 15: 3 5.0 parts by mass / Reaction Composition A 5.0 parts by mass / aluminum 3,5-di-t-butylsalicylate compound 1.0 part by mass / 2,2-azobis (2,4-dimethyl) Valeronitrile) 5.0 parts by mass

Next, the polymerizable monomer composition was put into the aqueous dispersion medium and granulated by stirring with a homomixer for 10 minutes in a nitrogen atmosphere at an internal temperature of 60 ° C. Thereafter, the stirring device is changed to a paddle stirring blade, and the mixture is held at 60 ° C. for 5 hours while being stirred at 3.3 s ⁻¹ , and further heated to 80 ° C. and held for 5 hours to obtain a suspension of toner particles. It was.

  Thereafter, the suspension was cooled, diluted hydrochloric acid was added, and the mixture was stirred for 2 hours to dissolve the dispersant (calcium phosphate) adhering to the toner particle surfaces. Further, the suspension was filtered, and the toner particles were repeatedly washed with water. Thereafter, the obtained water-containing toner particles were dried with hot air at 40 ° C. for 3 days to obtain cyan toner particles 21 of the present invention. Further, cyan toner 21 of the present invention was obtained in the same manner as in toner production example 1.

<Toner Production Example 22>
An oil phase was prepared by mixing 2500 parts by mass of styrene, 300 parts by mass of n-butyl acrylate, 56 parts by mass of acrylic acid, 110 parts by mass of dodecanethiol, and 30 parts by mass of carbon tetrabromide. On the other hand, 43 parts by mass of polyoxyethylene nonylphenyl ether and 59 parts by mass of sodium alkylbenzene sulfonate are dissolved in 3500 parts by mass of ion-exchanged water in a flask, and then the above oil phase is dispersed and emulsified, and slowly stirred for 10 minutes. While mixing, 700 parts by mass of ion-exchanged water in which 29 parts by mass of ammonium persulfate was dissolved was added to perform nitrogen substitution. Thereafter, the contents are heated in an oil bath while stirring the flask until the temperature reaches 70 ° C., and emulsion polymerization is continued for 6 hours. An anionic resin fine particle dispersion (1) having an average particle diameter of the dispersed resin fine particles of 155 nm is obtained. Obtained.

  1940 parts by mass of styrene, 830 parts by mass of n-butyl acrylate, and 57 parts by mass of acrylic acid were mixed to prepare an oil phase. On the other hand, 43 parts by mass of polyoxyethylene nonylphenyl ether and 90 parts by mass of sodium alkylbenzene sulfonate are dissolved in 3500 parts by mass of ion-exchanged water in a flask, and then the above oil phase is dispersed and emulsified, and slowly stirred for 10 minutes. Then, 700 parts by mass of ion-exchanged water in which 15 parts by mass of ammonium persulfate was dissolved was added and nitrogen substitution was performed. Thereafter, the contents are heated in an oil bath while stirring the flask until the content reaches 70 ° C., and emulsion polymerization is continued as it is for 6 hours. An anionic resin fine particle dispersion (2) having an average particle diameter of the dispersed resin fine particles of 100 nm Got.

  C. I. Pigment Blue 15: 3 210 parts by mass, 42 parts by mass of sodium alkylbenzenesulfonate, and 1400 parts by mass of water were mixed and dissolved, and passed through an ultrasonic disperser 10 times to obtain a pigment dispersion.

  440 parts by mass of the reaction composition A, 53 parts by mass of sodium alkylbenzene sulfonate, and 1400 parts by mass of water were heated to 95 ° C. and subjected to dispersion treatment using a homogenizer Ultra Turrax T50 (trade name, manufactured by IKA). Thereafter, the mixture was cooled to room temperature at a rate of about 2 ° C. per minute with stirring. Thereafter, using a pressure discharge type homogenizer 15MR type (trade name, manufactured by APV GAULIN), dispersion treatment was performed again at a pressure of 49 MPa to obtain a wax dispersion.

  18 parts by mass of an aqueous polyaluminum chloride solution having a concentration of 10% by mass and 162 parts by mass of an aqueous nitric acid solution having a concentration of 0.1% by mass were dispersed for 5 minutes using a homogenizer to obtain a dispersed flocculant aqueous solution.

  835 parts by mass of resin fine particle dispersion (1), 550 parts by mass of resin fine particle dispersion (2), 210 parts by mass of pigment dispersion, 117 parts by mass of wax dispersion, and 4300 parts by mass of water are sufficient at room temperature in a stirring tank with a heating jacket. Then, 180 parts by mass of the flocculant aqueous solution was added over 3 minutes from the upper part of the stirring tank, and then stirring was continued for 10 minutes.

  Next, the liquid temperature was heated to 48 ° C. with the heating jacket of the stirring tank and held for 60 minutes. To this mixed solution, 430 parts by mass of the resin fine particle dispersion (1) was gradually added, and the mixture was further maintained for 1 hour. Subsequently, 150 parts by mass of a 4% by mass sodium hydroxide aqueous solution was added and heated to 97 ° C., and further 100 parts by mass of a 2% by mass nitric acid aqueous solution was added and held for 6 hours. Thereafter, the mixture was cooled to room temperature, filtered, sufficiently washed with water, and then vacuum dried to obtain cyan toner particles 22 of the present invention. Further, cyan toner 22 of the present invention was obtained in the same manner as in toner production example 1.

<Toner Production Example 23>
C. I. Pigment Blue 15: 3 Instead of 5 parts by mass, C.I. I. Magenta toner particles 23 of the present invention and magenta toner 23 of the present invention were obtained in the same manner as in Toner Production Example 1 except that 6 parts by mass of Pigment Red 122 was used.

<Toner Production Example 24>
C. I. Pigment Blue 15: 3 Instead of 5 parts by mass, C.I. I. Yellow toner particles 24 of the present invention and yellow toner 24 of the present invention were obtained in the same manner as in Toner Production Example 1 except that 7 parts by mass of Pigment Yellow 177 was used.

<Toner Production Example 25>
-Resin B 100.0 parts by mass-C.I. I. Pigment Blue 15: 3 5.0 parts by mass / reaction composition J 5.0 parts by mass / aluminum 3,5-di-t-butylsalicylate compound 1.0 part by mass The above materials were sufficiently premixed by a Henschel mixer. . Thereafter, the mixture is melt-kneaded with a twin-screw extruder kneader, and the kneaded product is cooled and roughly pulverized to about 1 to 2 mm using a hammer mill, and then finely pulverized to a particle size of 20 μm or less with an air jet type pulverizer. . Thereafter, the particles were classified by an air classifier so that the weight average particle diameter was about 7 μm, and toner particles 25 for comparison were obtained. Further, a comparative cyan toner 25 was obtained in the same manner as in Toner Production Example 1.

<Toner Production Example 26>
A comparative cyan toner particle 26 and a comparative cyan toner 26 were obtained in the same manner as in Toner Production Example 25 except that the reactive composition K was used instead of the reactive composition J.

<Toner Production Example 27>
With reference to Japanese Patent Laid-Open No. 03-0505560 (the above-mentioned Patent Document 2), a carboxylic acid-modified paraffin wax to be contained in the toner for the comparative example was produced as follows.

  Normal paraffin wax (average carbon number 35, polyethylene equivalent weight average molecular weight 497, maximum endothermic peak temperature by DSC is 75 ° C., low temperature side onset temperature is 72 ° C., penetration at 25 ° C. is 7,120 300 parts by mass of a viscosity of 7 mPa · s at 8 ° C. and 8 parts by mass of maleic anhydride were dissolved by heating and dispersed in 500 parts by mass of xylene. And 15 mass parts of dicumyl peroxide was added, and it heated up, and was made to react at xylene boiling point temperature for 4 hours. Thereafter, xylene was distilled off, cooled, and the reaction product in the flask was taken out, dried under reduced pressure overnight at 25 ° C. and 2.0 Pa, and then the atmosphere temperature was gradually raised to 40 ° C. to perform perspiration treatment. . Further, the sweated product is heated and dissolved in a mixed solvent of methyl ethyl ketone / toluene while stirring, and this solution is cooled to 5 ° C. with stirring to precipitate crystals, which is filtered with a pressure filter equipped with a membrane filter. did. The crystals are transferred to another container equipped with a stirring blade and a distillation apparatus, heated and melted to 205 ° C. with stirring, and subjected to vacuum distillation at 2.0 Pa for 4 hours to remove light fractions, An acid-modified paraffin wax was obtained. The resulting carboxylic acid-modified paraffin wax has a weight average molecular weight of 420 in terms of polyethylene, a peak temperature of the maximum endothermic peak by DSC of 76 ° C., a low temperature onset temperature of 43 ° C., and a penetration at 25 ° C. The viscosity at 8 and 120 ° C. was 23 mPa · s, and the acid value was 30 mgKOH / g.

  Using this carboxylic acid-modified paraffin wax, a comparative toner was produced as follows.

-Resin B 100.0 parts by mass-C.I. I. Pigment Blue 15: 3 5.0 parts by mass, the carboxylic acid-modified paraffin wax 5.0 parts by mass, and 3,5-di-t-butylsalicylic acid aluminum compound 1.0 part by mass Mixed. Thereafter, the mixture is melt-kneaded with a twin-screw extruder kneader, and the kneaded product is cooled and roughly pulverized to about 1 to 2 mm using a hammer mill, and then finely pulverized to a particle size of 20 μm or less with an air jet type pulverizer. . Thereafter, the particles were classified by an air classifier so that the weight average particle diameter was about 7 μm, and toner particles 27 for comparison were obtained. Further, a comparative cyan toner 27 was obtained in the same manner as in Toner Production Example 1.

<Toner Production Example 28>
C. I. Pigment Blue 15: 3 Instead of 5 parts by mass, C.I. I. A comparative magenta toner particle 28 and a comparative magenta toner 28 were obtained in the same manner as in Toner Production Example 27 except that 6 parts by mass of Pigment Red 122 was used.

<Toner Production Example 29>
C. I. Pigment Blue 15: 3 Instead of 5 parts by mass, C.I. I. A comparative yellow toner particle 29 and a comparative yellow toner 29 were obtained in the same manner as in Toner Production Example 27 except that 7 parts by mass of Pigment Yellow 177 was used.

  Table 2 shows internal prescriptions and physical properties of the toners 1 to 24 of the present invention produced in the toner production examples 1 to 24 and the comparative toners 25 to 29 produced in the toner production examples 25 to 29.

<Preparation of two-component developer>
With respect to each of the toners 1 to 24 of the present invention produced in the toner production examples 1 to 24 and the comparative toners 25 to 29 produced in the toner production examples 25 to 29, the magnetic carrier particles and the toner concentration are 10% by mass. The two-component developers 1 to 24 of the present invention and the comparative two-component developers 25 to 29 were prepared. The magnetic carrier particles used for the preparation of the two-component developer are Mn-Mg ferrite particles whose surface is coated with 0.2 parts by mass of a fluorine-modified acrylic resin with respect to 100 parts by mass of the ferrite particles. The average particle size (D50) based on volume distribution is 60 μm.

<Examples 1-7 , Reference Examples 8 and 9, Examples 10-22 , Comparative Examples 1-3>
The image forming apparatus used in this embodiment will be described. FIG. 1 is a schematic view of an image forming apparatus applied to this embodiment, and FIG. 2 is a schematic view of a developing unit of the image forming apparatus.

  In FIG. 1, a photosensitive drum 1 has a photosensitive layer 1a having an organic optical semiconductor on a substrate 1b, and rotates in the direction of an arrow and rotates against and in contact (conductive elastic layer 2a, cored bar 2b). ) To uniformly charge the photosensitive drum 1. The exposure 3 is turned on and off according to digital image information on the photosensitive member by a polygon mirror to form an electrostatic charge image. The toner is developed on the photoreceptor 1 by reversal development using the developing units 4-1 to 4-4. The toner image on the photosensitive drum is transferred onto the intermediate transfer member 5, and the untransferred toner on the photosensitive drum 1 is collected in a waste toner container 9 by the cleaner member 8.

  The intermediate transfer member 5 is obtained by coating an elastic layer 5a in which carbon black is sufficiently dispersed in nitrile-butadiene rubber (NBR) on a pipe-shaped metal core 5b.

  The outer diameter of the transfer roller 7 is 20 mm, and the transfer roller 7 sufficiently disperses carbon black in a foam of ethylene-propylene-diene terpolymer (EPDM) on a core metal 7b having a diameter of 10 mm. It has the elastic layer 7a produced | generated by coating a thing.

  As the heat fixing device 11, a heat roll type fixing device having no oil application function was used. At this time, both an upper roller and a lower roller having a fluororesin surface layer were used, and the diameter of the roller was 65 mm. The fixing temperature was set to 180 ° C. and the nip width was set to 6 mm.

Each of the above-described two-component developers 1-22 of the present invention and the comparative two-component developers 25-27 are put in a developing device and are kept overnight at room temperature and normal humidity (23 ° C., 50% RH). I left it alone. Thereafter, a developing device was set in the image forming apparatus. Next, while continuously replenishing the toner so that the toner density becomes constant, plain paper for color copying machines (80 g / m ² , manufactured by Canon Inc.) is used as a transfer material, and a strip-shaped image 1000 having an image area ratio of 20%. The sheets were output in a single color mode and at a process speed (peripheral speed of the photosensitive drum) of 160 mm / s (A4 horizontal 32 sheets / min). Thereafter, the image forming apparatus was moved together with the developing device in an environment of normal temperature and low humidity (23 ° C., 5% RH) and left for 3 days, and then 1000 sheets of belt-like images having an image area ratio of 5% were output. Furthermore, after moving with a developing device in a high temperature and high humidity (30 ° C., 80% RH) environment and leaving it overnight, 1000 belt-shaped images having an image area ratio of 30% were output.

  Next, each evaluation item will be described. The evaluation results are shown in Table 3.

(1) Storage stability 5 g of toner is put in a 50 ml plastic cup and left in a hot air dryer set at 55 ° C. After 48 hours, it was taken out and allowed to cool to room temperature, and then the plastic cup was gently rotated and visually judged according to the following criteria.
A: Very good (flowability is not impaired)
B: Good (The fluidity is lowered, but the fluidity is restored when the cup is rotated.)
C: Normal (coagulation and coarsening are observed)
D: Bad (caking)

(2) Low-temperature fixability The first image in a normal temperature and normal humidity environment was evaluated as follows.

The belt-shaped image part is rubbed 5 times with a soft thin paper (for example, “Dasper”, manufactured by Ozu Sangyo Co., Ltd.) while applying a load of 4.9 kPa, and the image density before and after the rubbing is determined. Measurement was performed, and the reduction rate ΔD (%) of the image density was calculated by the following equation. The image density was measured with an X-Rite color reflection densitometer (Color reflection densitometer X-Rite 404A).
ΔD (%) = (Image density before rubbing−Image density after rubbing) × 100 / Image density before rubbing

And low temperature fixability was evaluated on the following reference | standard about (DELTA) D.
A: Very good (less than 5%)
B: Good (5% or more and less than 10%)
C: Normal (10% or more, less than 20%)
D: Bad (more than 20%)

(3) High-temperature offset resistance Measure the worst value of the whiteness of the non-image area of 100 images and the whiteness of unused plain paper in a high-temperature and high-humidity environment. The high temperature offset resistance was evaluated. The whiteness was measured by a reflectometer equipped with an amber filter ("REFLECTOMETER MODEL TC-6DS" manufactured by Tokyo Denshoku Co., Ltd.).
A: Very good (less than 1.0%)
B: Good (1.0% or more and less than 2.0%)
C: Normal (2.0% or more and less than 4.0%)
D: Poor (4.0% or more)

(4) Transparency Using an OHP sheet “CG3700” (trade name, manufactured by 3M) as a transfer material, a solid monochrome image having a toner loading on a cyan monochrome OHP sheet of 0.60 to 0.65 mg / cm ² is obtained. The image is output by the image forming apparatus shown in FIG. Subsequently, the image on the OHP sheet was projected onto a white screen with a transmission type OHP “95550” (trade name, manufactured by 3M), and visually evaluated as follows.
A: Transparency is very excellent.
B: Transparency is slightly inferior, but it is a good level.
C: Transparency is still one, but at a practical level.
D: The transparency is poor and dull.

(5) Image density The evaluation was based on the image density of the 500th sheet in a room temperature and humidity environment. The image density was measured with the above-described X-Rite color reflection densitometer.
A: Very good (over 1.60)
B: Good (from 1.40 to less than 1.60)
C: Normal (1.20 or more, less than 1.40)
D: Bad (less than 1.20)

(6) Fog After the image output in the low-temperature and low-humidity environment is finished, a solid white image is output, the image forming apparatus is forcibly stopped during the solid white image formation, and the solid white image portion on the photosensitive drum is removed. Taped with a transparent polyester adhesive tape and affixed to white paper. Only the unused tape was stuck on the same white paper, and the whiteness of each was measured, and the fog was calculated from the difference in whiteness. The whiteness was measured with the above-described reflectometer.
A: Very good (less than 2.0%)
B: Good (2.0% or more and less than 4.0%)
C: Normal (4.0% or more and less than 6.0%)
D: Poor (6.0% or more)

(7) Environmental stability The image density of the 900th sheet was measured under a normal temperature and low humidity environment and a low temperature and low humidity environment, and the density difference between them was calculated. This density difference was used as an indicator of the environmental stability of the toner. The image density was measured with the above-described X-Rite color reflection densitometer.
A: Very good (less than 0.10)
B: Good (0.10 or more and less than 0.20)
C: Normal (0.20 or more, less than 0.40)
D: Poor (0.40 or more)

(8) Durability stability The image densities of the 10th sheet and the 900th sheet were measured in a high temperature and high humidity environment, and the density difference was calculated. This density difference was used as an index of the durability stability of the toner. The image density was measured with the above-described X-Rite color reflection densitometer.
A: Very good (less than 0.10)
B: Good (0.10 or more and less than 0.15)
C: Normal (0.15 or more, less than 0.25)
D: Bad (over 0.25)

(9) Filming For filming on the photosensitive drum, after all image output is completed, five halftone images are output continuously in a room temperature and humidity environment, and images such as white spots and image streaks are output. By visually observing the state of the defect, it was judged according to the following criteria.
A: Very good (no image defects at all)
B: Good (there is a slight image defect)
C: Normal (there are some image defects)
D: Bad (there is considerable image defect)

(10) Cavity Cavity is shown in FIG. 4a using plain paper for color copying machines (80 g / m ² , manufactured by Canon Inc.) as a transfer material after image output under normal temperature and humidity conditions is completed. The “surprise” character pattern image was output, and the “surprise” character pattern dropout (state of FIG. 4 b) was visually evaluated.
A: Very good (almost no occurrence)
B: Good (slight)
C: Normal (some occurrence)
D: Bad (occurs considerably)

<Example 23 and Comparative Example 4>
In Example 23, a commercially available full color copier CLC5000 (manufactured by Canon Inc.) was used as it was without modification. The cyan, magenta, and yellow developing devices are removed from the copying machine main body, and the internal developer is extracted. The two-component developer 1 of the present invention is used for the cyan developing device, and the two-component developer 23 of the present invention is used for the magenta developing device. The two-component developer 24 of the present invention was filled in the yellow developing device (the black developing device used the developer incorporated in the CLC5000 as it was).

Then, plain paper for color copiers (80 g / m ² , manufactured by Canon Inc.) is used as a transfer material, and landscape images (manuscript charts with strong green and blue colors) and portraits (manufactures with strong flesh, red, and yellow colors) The original (chart) was copied, and the color reproducibility of the obtained copied image was visually evaluated.

  Similarly, in Comparative Example 4, the two-component developer 27 for comparison is used for the cyan developer, the two-component developer 28 for comparison is used for the magenta developer, and the two-component developer for comparison is used for the yellow developer. The system developer 29 was filled and evaluated in the same manner.

  As a result, the images obtained with the two-component developers 1, 23 and 24 of the present invention were both clear images with excellent color reproducibility.

  On the other hand, the images obtained with the two-component developers 27, 28 and 29 for comparison were dull in both images and were inferior in color reproducibility.

<Example 24 and Comparative Example 5>
In this example, a color laser beam printer LBP-2040 (manufactured by Canon Inc.) was remodeled and reset for use. This image forming apparatus is equipped with a fixing roller having no oil application mechanism, and the developing method is a non-magnetic one-component jumping developing method.

As a charging roller, a rubber roller having a diameter of 12 mm in which conductive carbon coated with nylon resin is dispersed is used, and the electrostatic latent image carrier is exposed to laser by dark portion potential V _D = −600 V, bright portion potential V _L = −200 V. Formed. A developing sleeve having a surface roughness Ra of 1.1 coated with a resin in which carbon black is dispersed on the surface as a toner carrier is set to 1.1 times the moving speed of the photosensitive drum surface, The distance between the photosensitive drum and the developing sleeve (SD) was 300 μm, and a phosphor bronze blade was used as a toner regulating member. As a developing bias, an AC bias component is superimposed on a DC bias component.

The cyan developing device is filled with the cyan toner 1 of the present invention, the magenta developing device is filled with the magenta toner 23 of the present invention, and the yellow developing device is filled with the yellow toner 24 of the present invention, and the normal temperature and humidity (25 ° C., 60% RH) are filled. ) In the environment, print out 3000 sheets of character images with an image area ratio of 5% at a process speed of 160 mm / s, using cardboard for printer (105 g / m ² , plain paper for printer, manufactured by Canon Inc.) as a transfer material. did. Then, a halftone image was printed out in the magenta single color mode. Thereafter, the photosensitive drum is removed from the printer and replaced with a new photosensitive drum, and then a cyan toner 27 for comparison in the cyan developer unit, a magenta toner 28 for comparison in the magenta developer unit, and a comparison toner in the yellow developer unit. Each of yellow toner 29 was filled and printed out in the same manner.

  When the obtained halftone images were evaluated, the halftone images obtained with the toners 1, 23 and 24 of the present invention were good images free from image defects such as white spots and image streaks. Further, when the photosensitive drum used for printing out the toner of the present invention was removed from the image forming apparatus and observed with a microscope, filming of inorganic fine powder (silica fine powder) was not observed. On the other hand, the halftone images obtained with the comparative toners 27, 28 and 29 had two oval white spots with a minor axis of about 0.5 mm and a major axis of about 1 mm. Further, when the photosensitive drum used for the printout of the comparative toner was observed in the same manner, filming of the inorganic fine powder occurred at a portion corresponding to the oval white spot in the image.

FIG. 2 is a schematic explanatory diagram of an image forming apparatus for a two-component developer used in an example of the present invention. FIG. 2 is an enlarged cross-sectional view of a main part of a developing device for a two-component developer used in an example of the present invention. 1 is a schematic explanatory diagram of an image forming apparatus for a non-magnetic one-component developer used in an embodiment of the present invention. It is a schematic diagram which shows the state of the hollow of the character image for evaluating the hollow after the end of an Example.

Explanation of symbols

1 Photosensitive drum (electrostatic latent image carrier)
2 Charging roller 3 Exposure means 4 4 color developing device (4-1, 4-2, 4-3, 4-4)
5 Intermediate transfer body 6 Transfer material 7 Transfer roller 12 Developer carrier 13 Photosensitive drum (electrostatic latent image carrier)
DESCRIPTION OF SYMBOLS 14 Magnet 15 Screw 16 Developer conveyance roller 17 Developer 18 Magnetic blade 21 Toner container 22 Supply member 23 Restriction member (elastic blade)
24 Toner carrier (developing sleeve)
25 Photosensitive drum (electrostatic image carrier)

Claims (10)

In a toner containing at least a binder resin, a colorant, and a reaction composition of an α-olefin and a carboxylic acid ,
Before SL reaction composition, the double methylene group hydrogens adjacent to the coupling is pulled alpha-olefin and the carboxylic acids include compounds obtained by adding a reaction at the site where the hydrogen of the alpha-olefin is withdrawn (except, alpha- A reaction composition containing at least a olefin (co) polymer) , wherein a carboxyl group derived from the carboxylic acid remains in the molecule,
A toner wherein the reaction composition has a weight average molecular weight (Mw) in terms of polyethylene as measured by gel permeation chromatography (GPC) in the range of 200 to 2800.   The toner according to claim 1, wherein the reaction composition contains 1 to 10 parts by mass with respect to 100 parts by mass of the binder resin.   The toner according to claim 1, wherein a weight average molecular weight (Mw) of the reaction composition is in a range of 300 to 1,000.   4. The toner according to claim 1, wherein 50% by mass or more of the reaction composition is an addition product having a molar ratio of α-olefin to carboxylic acid of 1: 1.   The toner according to claim 1, wherein the carboxylic acid is an aliphatic carboxylic acid having 3 to 30 carbon atoms.   The toner according to claim 1, wherein the carboxylic acid is an aliphatic carboxylic acid having 3 to 30 carbon atoms that does not contain an unsaturated group.   The toner according to claim 1, wherein the peak temperature of the maximum endothermic peak of the reaction composition is in the range of 55 to 99 ° C.   The toner according to any one of claims 1 to 7, wherein a low temperature-side onset temperature when the reaction composition absorbs heat by a differential scanning calorimeter (DSC) is in a range of 50 to 90 ° C.   The toner according to any one of claims 1 to 8, wherein a penetration of the reaction composition at 25 ° C is in a range of 1 to 9.   The toner according to claim 1, wherein the toner has an average circularity of 0.925 to 0.985 of particles having an equivalent circle diameter of 2 μm or more.

Images