JP2008096624A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner excellent in low-temperature fixability, high temperature offset resistance and storage stability and excellent also in developing property. <P>SOLUTION: The toner has toner particles including at least a binder resin and a colorant, wherein in analysis of a tetrahydrofuran-soluble component of the toner with a GPC-RALLS-viscometer, a component having an intrinsic viscosity of ≤0.025 dl/g occupies 40-70%, and the toner includes 3-50 mass% of a tetrahydrofuran-insoluble resin component. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic printing method, and a toner jet method.

  Conventionally, polycondensation resins such as polyester resins and vinyl resins such as styrene resins are mainly used as toner binder resins. Polyester resins have excellent fixing properties, but it is difficult to increase the molecular weight and easily cause an offset phenomenon at high temperatures.

  Therefore, if the polyester resin is cross-linked to increase the melt viscosity of the resin and improve the high temperature offset, not only the low temperature fixability is impaired, but the grindability during the production of the toner particles is reduced, There is a problem that the particle size distribution becomes broad and the classification yield decreases, resulting in a decrease in productivity. In addition, as the grindability decreases, a large number of large particle diameter particles that are not pulverized to a desired particle diameter are likely to be generated, and are present as coarse particles in the toner, which is likely to cause image defects.

  In addition, it is difficult for the polyester resin to uniformly disperse the wax component, and the developability is likely to deteriorate due to poor wax dispersion.

  On the other hand, vinyl resins such as styrene resins are excellent in pulverization properties during the production of toner particles, and are easy to achieve high molecular weight, so they are excellent in high-temperature offset resistance. Has the advantage of being easily dispersed uniformly. However, when the molecular weight is lowered or the Tg is lowered in order to improve the fixability, the blocking resistance and the developability tend to be lowered.

  Patent Document 1 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl resin. However, the polyester resin and the vinyl resin are inherently poorly compatible, and the dispersibility of the colorant and wax added to the toner becomes insufficient, so that problems are easily caused in developability.

  Patent Document 2 discloses a toner containing a polymer obtained by polymerizing a vinyl monomer in the presence of a reactive polyester resin. Therefore, the polyester resin content is small, and the effect of improving the fixing property is small.

  Patent Document 3 discloses a toner characterized by containing a polymer obtained by polymerizing a styrene monomer and an acrylic monomer in the presence of a saturated polyester resin. However, in order to obtain better fixing properties and high temperature offset resistance, it is necessary to control the molecular weight distribution of the binder resin, and the styrene monomer and the acrylic monomer are polymerized in the presence of the polyester resin. It is not enough.

  Patent Document 4 discloses a toner comprising a polymer obtained by polymerizing a styrene monomer and an acrylic monomer in the presence of an unsaturated polyester resin. However, the amount of the polyester resin used is 99.5: 0.5 to 91: 9 relative to the vinyl monomer, and the effect of improving the fixing property is small.

Patent Document 5 discloses a graft polymer obtained by graft polymerization of an unsaturated polyester resin with a vinyl monomer, a weight average molecular weight of 8,000 to 20,000, and a melt viscosity at a temperature of 100 ° C. of 10 ⁴ to 10 ⁴ . A toner using 10 ⁶ poise and a graft polymer having a glass transition temperature of 50 to 75 ° C. as a binder resin is disclosed. However, in order to further improve the fixing property and high temperature offset resistance, it is necessary to control the molecular weight distribution of the toner more precisely.

  Patent Document 6 discloses a toner comprising a polymer obtained by esterifying a styrene resin having an acid group and a polyester resin. Although these methods improve the compatibility between the polyester resin and the vinyl copolymer, the gel component content and the molecular weight of the vinyl resin component contained in the gel component are not actively controlled. However, there is a problem in satisfying the fixing property and high temperature offset resistance at a higher level.

  Patent Document 7 discloses a non-linear polyester having a weight average molecular weight (Mw) of 5,000 to 200,000 and a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 3 to 50; A binder resin of an electrophotographic toner obtained by reacting with a vinyl polymer is disclosed. In Patent Document 7, since a vinyl polymer and a polyester polymer are hybridized by an ester reaction, it is necessary to perform the reaction at a high temperature in order to increase the hybridization rate. For this reason, the vinyl polymer may be decomposed by heat. On the other hand, the ester reaction does not proceed sufficiently at a temperature at which the vinyl polymer does not decompose, so that the hybridization is not sufficiently performed. High temperature offset and developability cannot be fully satisfied.

  Further, regarding the molecular weight distribution of the tetrahydrofuran (THF) soluble component of the toner, in Patent Document 8, measurement is performed by a light scattering method of a component having a molecular weight of 50,000 or less in the molecular weight distribution of GPC in the THF soluble component of the toner binder resin. A toner that defines the relationship between the weight average molecular weight measured and the weight average molecular weight measured by GPC is disclosed. However, the mixing property of the low molecular weight component and the high molecular weight component is not taken into consideration only by defining the molecular weight on the low molecular weight side. Since low-temperature fixability and high-temperature offset resistance have conflicting aspects, improvement in low-temperature fixability while maintaining high-temperature offset resistance performance is at a level that cannot be said to be sufficient.

  Patent Document 9 discloses a toner in which a relationship between a weight average molecular weight measured by a light scattering method in a binder resin of a toner having a molecular weight of 2,000 to 100,000 and a radius of inertia is defined. Further, Patent Document 10 defines the relationship between the weight average molecular weight measured by the light scattering method and the radius of inertia of components in the GPC molecular weight range of 2,000 to 50,000 and the molecular weight range of 100,000 or more. Yes. However, in recent printers and copiers with higher speeds, these branching degrees are not optimal, and it is necessary to propose a branching structure that can achieve fixing performance in a wider temperature range. In consideration of the dispersibility between the binder resin and the colorant, the release agent, and other materials during the production of the toner, it is necessary to consider the branched structure of the components in the higher polymer region.

  As described above, further improvement in the low-temperature fixability, high-temperature offset resistance, and developability of the toner is required, and development of a more excellent toner is eagerly desired.

JP 54-114245 A Japanese Patent Laid-Open No. 56-116043 JP 58-159546 A JP 58-102246 A JP-A-1-156759 JP-A-2-881 Japanese Patent Laid-Open No. 11-153858 JP-A-9-6050 Japanese Patent Laid-Open No. 9-146305 JP-A-9-106102

  An object of the present invention is to provide a toner that exhibits good fixability and offset resistance, is excellent in grindability, has a high yield, and has good productivity.

  It is another object of the present invention to provide a toner that does not cause charging roller contamination and does not cause poor cleaning.

  In order to achieve the above object, a first invention according to the present application is a toner having toner particles containing at least a binder resin and a colorant, and the toner is analyzed by a GPC-RALLS-viscosity meter that is soluble in tetrahydrofuran. In which the ratio of the intrinsic viscosity of 0.025 dl / g or less is 40 to 70%, and the toner contains 3 to 50% by mass of a resin component insoluble in tetrahydrofuran.

  In order to achieve the above object, according to the second invention of the present application, the ratio of the intrinsic viscosity of 0.025 to 0.050 dl / g is 20 to 20 in the GPC-RALLS viscometer analysis of the tetrahydrofuran soluble content of the toner. The present invention relates to a toner characterized by being 50%.

  In order to achieve the above object, a third invention according to the present application relates to a toner wherein the binder resin contains 50% by mass or more of a polyester unit.

  In order to achieve the above object, a fourth invention according to the present application relates to a toner characterized in that the binder resin contains a hybrid resin.

  The toner of the present invention has good low-temperature fixability and high-temperature offset resistance, is excellent in pulverization during the production of toner particles, has a high yield of toner particles, has good productivity, and has toner particles with few coarse particles It is.

  Furthermore, the toner of the present invention is a toner in which the low melting point wax is well dispersed in the toner particles, and the charging roller is not soiled.

  The inventors have a ratio of the intrinsic viscosity of 0.025 dl / g or less of the soluble portion of tetrahydrofuran to 40 to 70% (preferably 50 to 70%), and 3 resin components (gel components) insoluble in tetrahydrofuran. It was found that the toner containing ˜50 mass% is excellent in low-temperature fixability and high-temperature offset resistance. It has been found that the toner has a good pulverization property during the production of toner particles and a toner with good productivity.

  The component having an intrinsic viscosity of 0.025 dl / g or less, which is measured by GPC-RALLS-viscosity analysis of the toner's tetrahydrofuran content, is easily melted by heat and has a low melt viscosity. Presence of low temperature fixability is greatly improved. In addition, since a component having an intrinsic viscosity of 0.025 dl / g or less can enter between molecules of a component having a high intrinsic viscosity such as a gel component, a soft gel component having a large molecular chain spread can be formed. As a result, the pulverizability of the melt-kneaded product when producing toner particles can be greatly improved.

  When the ratio of the intrinsic viscosity of 0.025 dl / g or less is less than 40%, the effect of improving the fixing property is small. Furthermore, a hard gel component can be easily formed, and the pulverizability of the melt-kneaded product when producing toner particles tends to deteriorate.

  When the ratio of the intrinsic viscosity of 0.025 dl / g or less is more than 70%, the viscosity of the toner becomes too low at the time of fixing and the high temperature offset resistance is lowered, or the strength of the toner is lowered and the toner deteriorates due to long-term use. It becomes easy. Further, since excessive pulverization in which a large amount of fine powder is generated in the pulverization step of the melt-kneaded product is likely to occur, the yield of toner particles may be lowered, and the productivity of toner particles may be reduced.

  The toner of the present invention contains 3 to 50 mass% (preferably 3 to 40 mass%, more preferably 5 to 30 mass%, particularly preferably 10 to 30 mass%) of a resin component (gel component) insoluble in tetrahydrofuran. It is one of the features. When the tetrahydrofuran insoluble content is less than 3% by mass, the high temperature offset resistance is lowered, or overgrinding is likely to occur in the pulverization step of the melt-kneaded product. When the tetrahydrofuran insoluble content is more than 50% by mass, it becomes difficult to uniformly disperse the colorant in the toner particles, the triboelectric chargeability of the toner is lowered, fog and image density are liable to be lowered, and low temperature fixability is improved. Or the pulverizability of the melt-kneaded product is lowered.

  Further, in the toner of the present invention, the ratio of the intrinsic viscosity of 0.025 to 0.050 dl / g is preferably 20 to 50%.

  In a magnetic toner having magnetic toner particles containing magnetic iron oxide, when the adhesion between the magnetic iron oxide and the binder resin is reduced, the magnetic iron oxide present on the surface of the magnetic toner particles is detached from the surface of the magnetic toner particles. The problem arises that the charging roller is released and contaminates the charging roller. In particular, in a magnetic toner containing a resin component insoluble in tetrahydrofuran, it is difficult to uniformly disperse the magnetic iron oxide in the magnetic toner particles, and the adhesion between the binder resin and the magnetic iron oxide is low even if the magnetic toner is uniformly dispersed. Thus, free magnetic iron oxide may be generated.

  The component having an intrinsic viscosity of 0.025 to 0.050 dl / g has a low viscosity, and the binder resin can enter the minute irregularities on the surface of the magnetic iron oxide when kneading the magnetic toner particles. And magnetic iron oxide can be increased, and the amount of magnetic iron oxide released from the surface of the magnetic toner particles can be greatly reduced. As a result, charging failure due to contamination of the charging roller is less likely to occur. Components with an intrinsic viscosity of less than 0.025 dl / g have a lower viscosity, and the binder resin tends to enter the irregularities on the surface of the magnetic iron oxide, but the viscosity is too low to increase the adhesion to the binder resin. It is easy to run out. Components with an intrinsic viscosity of 0.050 dl / g have strength to improve the adhesion between the binder resin and magnetic iron oxide, but the viscosity increases so that the binder resin enters the irregularities on the surface of the magnetic iron oxide. It becomes difficult to increase the affinity between the binder resin and the magnetic iron oxide.

  When the ratio of the intrinsic viscosity of 0.025 to 0.050 dl / g is less than 20%, free magnetic iron oxide is increased and charging failure tends to occur. When the ratio of the intrinsic viscosity of 0.025 to 0.050 dl / g is more than 50%, the strength of the magnetic toner is lowered and the magnetic toner is easily deteriorated, and the high temperature offset resistance is liable to be lowered.

  The binder resin contained in the toner used in the present invention preferably contains at least 50% by mass or more of a polyester unit in order to ensure good low-temperature fixability. When the content of the polyester unit is less than 50% by mass, it is difficult to obtain sufficient low-temperature fixability. The content of the polyester unit in the present invention is a combination of a component present as a polyester resin and a component present as a polyester-based resin component in the hybrid resin.

  Furthermore, the binder resin contained in the toner used in the present invention contains a vinyl polymer unit in the binder resin in an amount of 50% by mass or less (preferably 10 to 50% by mass). This is preferable in that an offset property can be obtained.

  In the present invention, it is preferable to contain a hybrid resin as the binder resin, and it is more preferable to contain the hybrid resin in the gel component. Since the hybrid resin has both a polyester unit and a vinyl polymer unit in the same molecule, a raw material (a highly hydrophilic component such as a colorant such as a magnetic substance) and a vinyl resin that are easily mixed with the polyester component. It is possible to simultaneously improve the dispersibility of both of the raw materials that are easily mixed with each other (low polarity components such as wax components).

  In particular, by including a hybrid resin in the tetrahydrofuran insoluble component (gel component), a colorant such as a wax component or a magnetic substance is likely to be present in the vicinity of the gel component in the toner particles, or easily enter the gel component. Become. When the wax is present in the vicinity of the gel component, the wax component is melted at the time of fixing, so that the gel component is easily softened, the sharp melt property of the toner is increased, and the low-temperature fixability is greatly improved. Furthermore, when a colorant such as a magnetic substance that does not easily enter the gel component is incorporated into the gel component, the uniform dispersibility of the material is improved and the triboelectric chargeability of the toner is stabilized, thereby improving the developability and image quality. .

  The binder resin used in the present invention can be used alone as a hybrid resin, but may be a mixture containing other resin components.

  Examples thereof include a mixture of a hybrid resin and a vinyl resin, a mixture of a hybrid resin and a polyester resin, or a mixture of a polyester resin, a hybrid resin, and a vinyl resin.

  Examples of the hybrid resin include the following. (I) formed by performing a transesterification reaction between a vinyl resin component obtained by polymerizing a monomer component having a carboxylic acid ester group such as an acrylic ester or a methacrylic ester and a polyester resin component; (ii) ) Formed by an esterification reaction between a polyester resin component and a vinyl resin component obtained by polymerizing a monomer component having a carboxylic acid group such as acrylic acid or methacrylic acid; (iii) non-fumaric acid A product formed by polymerizing a vinyl monomer in the presence of an unsaturated polyester resin component polymerized using a monomer having a saturated bond.

  The hybrid resin is obtained by containing a monomer component capable of reacting with both resin components in the vinyl resin component and / or the polyester resin component as in the above (i) and (ii), and reacting them. be able to. Among the monomers constituting the polyester resin component, those capable of reacting with the vinyl resin component include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl resin component, those that can react with the polyester resin component include vinyl monomers having a carboxyl group such as acrylic acid and methacrylic acid, and vinyl monomers having a hydroxy group.

  As a manufacturing method which can prepare the hybrid resin used by this invention, the manufacturing method shown to the following (1)-(5) can be mentioned, for example.

(1) After producing vinyl resin and polyester resin separately, dissolve and swell in a small amount of organic solvent, add esterification catalyst and alcohol, heat and conduct transesterification reaction, polyester resin component and vinyl A hybrid resin having a resin component is obtained.
(2) After producing the vinyl resin, a polyester resin component is produced in the presence of the vinyl resin, and a hybrid resin having the polyester resin component and the vinyl resin component is produced. Also in this case, an organic solvent can be appropriately used.
(3) After the production of the polyester resin, a vinyl resin component is produced in this presence and reacted to produce a hybrid resin having the polyester resin component and the vinyl resin component.
(4) After the vinyl resin and polyester resin are produced, a hybrid resin is produced by adding a vinyl monomer and / or polyester monomer (alcohol, carboxylic acid) in the presence of these polymer components. Also in this case, an organic solvent can be appropriately used.
(5) A hybrid resin having a polyester resin component and a vinyl resin component is 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 (1) to (5) above, the vinyl resin component and / or the polyester resin component have a plurality of different molecular weights, and polymer components having different degrees of crosslinking can be used.

  (3) is mentioned as a manufacturing method used especially preferably by this invention. Among these, a hybrid resin obtained by dissolving an unsaturated polyester resin capable of reacting with a vinyl monomer in a vinyl monomer and polymerizing a mixture of the polyester resin and the vinyl monomer by a bulk polymerization method is preferable.

  The bulk polymerization method is preferably used in the present invention because the molecular weight of the vinyl resin component can be increased and the main peak molecular weight of the vinyl resin component contained in the gel component can be increased.

  In addition, since the bulk polymerization method does not require a solvent evaporation step as compared with the solution polymerization method, a binder resin can be obtained at low cost. Furthermore, the binder resin manufactured by the bulk polymerization method has less influence on the triboelectric chargeability of the toner because there are fewer impurities such as a dispersant than the binder resin manufactured by the suspension polymerization method. It is very preferable as a binder resin for toner.

  In particular, the binder resin used in the present invention is a vinyl monomer in the presence of a low molecular weight polyester resin having an unsaturated polyester resin, and a low molecular weight polyester resin: vinyl monomer = 50: 50 to 90:10 (preferably 60). : 40 to 80:20) is preferably a hybrid resin obtained by bulk polymerization at a mass ratio. If the mass ratio of the low molecular weight polyester resin is less than 50:50, the low-temperature fixability tends to be low, and if it is more than 90:10, the high-temperature offset resistance tends to be low.

  By bulk polymerization of vinyl monomers in the presence of an unsaturated polyester resin component (particularly preferably an unsaturated linear polyester resin component), the main chain is a vinyl resin component having a large molecular weight and high linearity. A hybrid resin component having a molecular structure in which a molecular weight polyester resin component is branched from a vinyl resin component can be obtained. Furthermore, the acid group and the hydroxyl group in the hybrid resin component having this branched structure are esterified between molecules to form a gel component.

  The gel component thus obtained has a regular molecular structure of the hybrid resin component, which is a structural unit. Therefore, the molecular structure of the gel component is also easily regularized, has excellent sharp melt properties due to heat, and has low temperature fixability. Does not decrease. Furthermore, the molecular weight of the vinyl polymer unit in the hybrid resin component, which is the constituent unit of the gel component, can be increased by bulk polymerization of the vinyl monomer, so that the molecular weight of the gel component also increases, and a high viscosity can be maintained even at high temperatures. High temperature offset resistance can be improved.

  Furthermore, in the present invention, in addition to the unsaturated polyester resin, a low-viscosity saturated polyester resin is used as the low-molecular weight polyester resin so that the ratio of the intrinsic viscosity of 0.025 dl / g or less of the tetrahydrofuran-soluble component is 40 to 70%. Is preferably added. In particular, it is preferable to bulk polymerize a vinyl monomer in the presence of an unsaturated polyester resin and a low-viscosity saturated polyester resin. Since the saturated polyester resin does not react with the vinyl-based monomer, it does not participate in the polymerization reaction of the hybrid resin. However, when the saturated polyester resin is present during the polymerization, it can enter the gel component composed of the hybrid resin at the molecular level. As the low viscosity component penetrates into the molecular structure of the gel component in this way, the molecular chain of the gel component can be maintained in a spread state, a soft gel can be formed, and the pulverizability of the melt-kneaded product can be improved. . Moreover, since the component which has entered into the molecule | numerator of a gel component becomes a low viscosity polyester resin, it becomes a gel component which is easy to soften with heat | fever and can also improve low temperature fixability.

  As a low-viscosity saturated polyester resin, those having a glass transition temperature of 30 to 70 ° C. are preferable, and those having a glass transition temperature lower by 10 ° C. or more than unsaturated polyester are particularly preferable.

  The low-viscosity saturated polyester is preferably mixed at a ratio of 5 to 50 parts by mass with respect to 100 parts by mass of the unsaturated polyester. When the amount is less than 5 parts by mass, it is difficult to obtain the effect. When the amount is more than 50 parts by mass, the viscosity of the binder resin becomes too low, and the high-temperature offset resistance tends to decrease.

  Further, as a means for adjusting the ratio of the intrinsic viscosity of 0.025 dl / g or less of the tetrahydrofuran soluble component to 40 to 70%, a large amount of soft monomer such as alkenyl succinic acid is used as the monomer of the unsaturated polyester resin or saturated polyester resin. A method of adjusting the Tg by polymerizing a low Tg unsaturated polyester resin or a saturated polyester resin and then capping the molecular ends of the low Tg unsaturated polyester resin with trimellitic anhydride is preferable.

  In the toner of the present invention, the tetrahydrofuran-soluble component of a component (hereinafter also referred to as “residue”) that is hydrolyzed by a resin component insoluble in tetrahydrofuran and then filtered and filtered off is described below. In the molecular weight distribution measured by GPC, it has a main peak in the range of molecular weight 10,000 to 1,000,000 (preferably molecular weight 30,000 to 500,000, more preferably molecular weight 50,000 to 300,000). It is preferable. When the resin component insoluble in tetrahydrofuran is hydrolyzed, the component to be decomposed is a polyester unit polymerized by an ester bond, and the vinyl polymer unit remains in a polymer state without being decomposed. Therefore, the residue after hydrolysis is mainly composed of a vinyl polymer unit, and the tetrahydrofuran soluble content of the residue is the tetrahydrofuran soluble content of the vinyl polymer unit.

  In addition, when a binder resin is produced by simply mixing a polyester resin and a vinyl resin having a main peak at a molecular weight of 10,000 to 1,000,000, such vinyl resin is soluble in tetrahydrofuran. Therefore, it is not contained in the tetrahydrofuran-insoluble component in the first stage, and does not constitute a preferred configuration of the present invention. In addition, when a binder resin is produced by simply mixing a polyester resin and a vinyl resin containing a tetrahydrofuran-insoluble component, the vinyl-based resin remains in the tetrahydrofuran-insoluble component, but after the hydrolysis, the tetrahydrofuran-insoluble component is retained. Therefore, it is still not a preferable configuration of the present invention.

  The resin component that satisfies the preferred configuration of the present invention is obtained by, for example, hybridizing a polyester resin and a vinyl resin having a main peak in the molecular weight range of 10,000 to 1,000,000, and hybridizing. This is obtained when the content of tetrahydrofuran becomes insoluble.

  Therefore, the tetrahydrofuran-soluble component of the residue has a main peak at a molecular weight of 10,000 to 1,000,000, which means that the main peak is in a region having a large molecular weight (that is, a molecular weight of 10,000 to 1,000,000). This means that the vinyl polymer unit and the polyester unit are hybridized.

  That is, the tetrahydrofuran-insoluble matter derived from the resin component is hydrolyzed, and the residual tetrahydrofuran-soluble matter has a main peak at a molecular weight of 10,000 to 1,000,000 in the molecular weight distribution measured by GPC. The binder resin has a gel structure having a large molecular weight and a large molecular weight between cross-linking points. The molecular weight between crosslinking points is the molecular weight between branch points when the resin molecules are branched to form a crosslinked structure. When the molecular weight between the cross-linking points is large, the distance between the branch points becomes long, so that the force that the molecules bind to each other in a network form becomes weak. As a result, it is possible to obtain a soft gel component that easily undergoes molecular motion by heating. Therefore, when used as a binder resin for toner, even when toner particles are produced through melt-kneading, the gel content is hardly cut and good high-temperature offset resistance can be obtained.

  A toner containing such a tetrahydrofuran-insoluble component makes the tetrahydrofuran-insoluble component, which is a gel component, easy to move even with a small amount of heat at the time of fixing, and is bound compared to a case where a gel component having a low molecular weight between crosslinks is contained. Since the resin is easily softened by heat, the low-temperature fixability is improved. Furthermore, such a gel component can maintain a high viscosity even at a high temperature, and can improve high-temperature offset resistance. Further, since the high temperature offset resistance can be maintained even with a small amount of gel component, a large amount of low molecular weight components can be contained, and the low temperature fixability can be further improved.

  If the tetrahydrofuran-insoluble content is hydrolyzed and the main peak molecular weight of the tetrahydrofuran-soluble content of the residue is less than 10,000, the gel component tends to be hard and low-temperature fixability is lowered. Further, since the molecular weight between the crosslinking points becomes small, the gel component becomes inflexible, the gel component is easily cut by the shearing force in the kneading process at the time of producing the toner particles, and the high temperature offset resistance is lowered. When the main peak molecular weight is larger than 1,000,000, it is difficult to uniformly disperse the gel component in the toner particles, and as a result, the uniform dispersibility of other components contained in the toner particles is hindered, and the toner As a result, the triboelectric chargeability is reduced.

  The polyester unit contained in the tetrahydrofuran-insoluble matter is hydrolyzed, and the molecular weight distribution of the tetrahydrofuran-soluble matter in the residue can be measured by the following procedure.

  First, the tetrahydrofuran insoluble matter derived from the binder resin is taken out of the toner, and this tetrahydrofuran insoluble matter is heated in an alkaline aqueous solution to hydrolyze and remove the polyester resin unit. Since the vinyl resin component remains as a resin component without being hydrolyzed, the residue is extracted and the molecular weight distribution is measured by GPC. A specific measurement method is shown below.

(1) Separation of Tetrahydrofuran Insoluble Content The toner is weighed and placed in a cylindrical filter paper (for example, No. 86R size 28 mm (height) × 10 mm (diameter) manufactured by Toyo Filter Paper Co., Ltd.) and applied to a Soxhlet extractor. Using 200 ml of tetrahydrofuran as a solvent, the tetrahydrofuran solubles are extracted for 16 hours. At this time, extraction is performed at a reflux rate such that the extraction cycle of tetrahydrofuran is about once every 4 to 5 minutes. After completion of the extraction, the cylindrical filter paper is taken out, and the tetrahydrofuran-insoluble content of the toner on the cylindrical filter paper is collected.

  In the case where the toner is a magnetic toner containing a magnetic substance, the collected tetrahydrofuran-insoluble matter is put in a beaker, and tetrahydrofuran is added and dispersed sufficiently. Then, the magnet is brought close to the bottom of the beaker to precipitate the magnetic substance on the bottom of the beaker. Fix it. In this state, the gel component dispersed in tetrahydrofuran and tetrahydrofuran is transferred to another container to remove the magnetic material, and tetrahydrofuran is evaporated to separate the tetrahydrofuran-insoluble matter derived from the binder resin.

(2) Separation of residue by hydrolysis The tetrahydrofuran-insoluble matter derived from the obtained binder resin was dispersed in a 2 mol / liter NaOH aqueous solution at a concentration of 1% by mass, using a pressure vessel, at a temperature of 150 ° C. for 24 hours. Hydrolyze under the conditions of The hydrolyzed residue is filtered off from this hydrolyzed solution by any of the following procedures.

i) When the tetrahydrofuran-insoluble component does not contain a component having an ester structure:
The hydrolyzate is suction filtered using a membrane filter to separate the residue. Thereby, the monomer component which is a decomposition product of the polyester resin unit is removed in the filtrate.

ii) When the tetrahydrofuran-insoluble component contains a component having an ester structure such as an acrylic ester or a methacrylic ester:
Since the residue present in the hydrolyzate is a sodium salt (-COO ^- Na ⁺ ), after the residue is filtered off, the residue is dispersed again in water, and after dispersion, hydrochloric acid is added. water was adjusted to pH = 2, -COO having a residue ^- the groups was -COOH. Then, it separated by filtration with the membrane filter.

(3) GPC measurement of component separated in (2) above The component separated in (2) above is dissolved in tetrahydrofuran, and the molecular weight distribution is measured by GPC.

  Moreover, as tetrahydrofuran insoluble matter, it is preferable to contain 20-80 mass% (preferably 30-70 mass%, more preferably 40-60 mass%) of a vinyl polymer unit. The content of the vinyl polymer unit in the tetrahydrofuran-insoluble matter can be measured as follows.

  First, a polyester resin is polymerized with the same monomer composition as that of the polyester resin component used for the polymerization of the hybrid resin. Similarly, a vinyl polymer is polymerized with the same monomer composition as that of the vinyl polymer component used for the polymerization of the hybrid resin. A calibration curve sample is prepared by sufficiently mixing the polyester resin and vinyl polymer thus obtained. Prepare several mixed samples in which polyester resin and vinyl polymer are changed at an arbitrary ratio, create a calibration curve by IR measurement, and use this calibration curve for vinyl polymer unit in tetrahydrofuran insoluble matter. Calculate the content.

For example, in the hybrid resin production example 1 of an example described later, as a polyester peak, a peak derived from a benzene ring of a phthalic acid unit (about 730 cm ⁻¹ ) and a peak derived from a benzene ring of a bisphenol derivative unit (about 830 cm ⁻¹ ). The area of the benzene unit of the styrene unit (about 700 cm ^-1 ) as the vinyl polymer part, and the vinyl resin weight based on the calibration curve. The content of coalesced units was calculated.

  The unsaturated polyester resin used in the hybrid resin obtained by the bulk polymerization method of the present invention has a molecular weight of 2,000 to 30,000 (preferably a molecular weight of 3,000 to 20,000) in the GPC molecular weight distribution of tetrahydrofuran-soluble matter. More preferably, it is a low molecular weight unsaturated polyester resin having a main peak in the molecular weight range of 5,000 to 15,000. Further, a linear unsaturated polyester resin containing no gel component is particularly preferable. If the main peak molecular weight is less than 2,000, the developability tends to deteriorate, and if it exceeds 30,000, the low-temperature fixability tends to decrease.

  The unsaturated polyester resin used in the present invention preferably has an acid value of 0.1 to 30 mgKOH / g (preferably 1 to 20 mgKOH / g, more preferably 1 to 10 mgKOH / g), and has a hydroxyl value. 10 to 60 mgKOH / g (preferably 20 to 60 mgKOH / g, more preferably 30 to 50 mgKOH / g) is preferable because it can impart good triboelectric chargeability to the toner.

  The low viscosity saturated polyester resin used in the present invention is preferably in the same range as the unsaturated polyester resin in terms of molecular weight, acid value, and hydroxyl value. By making both the molecular weight, acid value, and hydroxyl value close to each other, it becomes easier to mix evenly, the effect of adding a low-viscosity saturated polyester resin is more easily manifested, and the toner is triboelectrically charged due to poor dispersion. It becomes possible to suppress a decrease in the amount.

  The monomer which can be used when forming a polyester unit is illustrated below.

  The following are mentioned as a bivalent alcohol component. Ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol represented by the formula (A) and derivatives thereof;

（式中Ｒは、エチレンまたはプロピレン基であり、ｘ，ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０〜１０である。）
また（Ｂ）式で示されるジオール類；

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

  Examples of the divalent acid component include the following. Benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, or anhydrides thereof, or lower alkyl esters thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, or anhydrides thereof; or The lower alkyl ester; alkenyl succinic acid or alkyl succinic acid such as n-dodecenyl succinic acid and n-dodecyl succinic acid, or an anhydride thereof, or a lower alkyl ester thereof.

  In particular, dicarboxylic acids such as alkenyl succinic acids or alkyl succinic acids, or anhydrides thereof, or lower alkyl esters thereof and derivatives thereof are preferably used as acid monomers for low viscosity saturated polyester resins. Since these acid monomers make the low-viscosity saturated polyester resin easily compatible with the hybrid resin, the low-viscosity saturated polyester resin easily enters the gel component composed of the hybrid resin.

  As the acid component having an unsaturated bond for obtaining an unsaturated polyester resin, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or anhydrides thereof, or lower alkyl esters thereof are preferably used. It is done.

  These unsaturated dicarboxylic acids are preferably used in a proportion of 0.1 to 10 mol% (preferably 0.3 to 5 mol%, more preferably 0.5 to 3 mol%) with respect to the total acid component of the polyester monomer. . When an unsaturated dicarboxylic acid is added within this range, the unsaturated bond concentration in the low molecular weight polyester molecule becomes appropriate, and the polyester resin and the vinyl resin are hybridized with an appropriate distance between the crosslinking points. .

  Further, a trivalent or higher alcohol component or a trivalent or higher acid component may be used as necessary.

  Examples of the trihydric or higher polyhydric alcohol component include the following. 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-trihydroxybenzene.

  Examples of the trivalent or higher polyvalent carboxylic acid component include the following. Pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4- Butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid , Empole trimer acids, and anhydrides thereof, and lower alkyl esters thereof;

（式中Ｘは炭素数３以上の側鎖を１個以上有する炭素数５〜３０のアルキレン基又はアルケニレン基）
で表わされるテトラカルボン酸、及びこれらの無水物、及びこれらの低級アルキルエステルの如き多価カルボン酸類及びその誘導体。なかでも、１，２，４−ベンゼントリカルボン酸、１，２，５−ベンゼントリカルボン酸およびこれらの無水物、低級アルキルエステルが好ましい。

(Wherein X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having one or more side chains having 3 or more carbon atoms)
And polycarboxylic acids such as tetracarboxylic acids and their anhydrides and lower alkyl esters thereof and derivatives thereof. Of these, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, anhydrides thereof, and lower alkyl esters are preferable.

  In the polyester resin, the alcohol component is preferably 40 to 60 mol% (more preferably 45 to 55 mol%), and the acid component is preferably 60 to 40 mol% (more preferably 55 to 45 mol%). The trivalent or higher polyvalent component is preferably 0.1 to 60 mol% (more preferably 0.1 to 20 mol%) of all components.

  The polyester-based resin is usually obtained by a generally known condensation polymerization. The polymerization reaction of the polyester resin is usually performed in the presence of a catalyst at a temperature of 150 to 300 ° C, preferably at a temperature of 170 to 280 ° C. The reaction can be performed under normal pressure, reduced pressure, or increased pressure, but after reaching a predetermined reaction rate (for example, about 30 to 90%), the reaction system is 200 mmHg or less, preferably 25 mmHg or less, more preferably. Is preferably performed under a reduced pressure of 10 mmHg or less.

  Examples of the catalyst include the following catalysts used for polyesterification. Metals such as tin, titanium, antimony, manganese, nickel, zinc, lead, iron, magnesium, calcium, germanium; compounds containing these metals (dibutyltin oxide, orthodibutyl titanate, tetrabutyl titanate, tetraisopropyl titanate, zinc acetate, Lead acetate, cobalt acetate, sodium acetate, antimony trioxide).

  In the present invention, a titanium compound is preferably used because of easy control of the polymerization reaction and high reactivity with the vinyl monomer. Particularly preferred are tetraisopropyl titanate and dipotassium titanyl oxalate. At this time, it is particularly preferable to add an antioxidant (particularly a phosphorus-based antioxidant) as an anti-coloring agent for the binder resin and a co-catalyst (a magnesium compound is preferable, and magnesium acetate is particularly preferable) as a reaction accelerator.

  The polyester of the present invention is stopped by stopping the reaction when the properties of the reactant (for example, acid value, softening point, etc.) reach a predetermined value, or when the stirring torque or stirring power of the reactor reaches a predetermined value. System resin can be obtained.

  In the present invention, the vinyl polymer means a vinyl homopolymer or a vinyl copolymer.

Examples of the monomer for obtaining the vinyl resin include the following.
Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrene derivatives such as: ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; vinyl acetate , Vinyl esters such as vinyl propionate and vinyl benzoate; Methyl tacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as aminoethyl and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, acrylic acid Acrylic acid esters such as dodecyl, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether, Vinyl ethers such as vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone Vinyl naphthalenes; acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; These vinyl monomers are used alone or in admixture of two or more monomers.

  Among these, a combination of monomers that can be a styrene copolymer or a styrene-acrylic copolymer is preferable.

  Furthermore, the following are mentioned as a monomer which adjusts the acid value of binder resin. Acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid and α- or β-alkyl derivatives thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid and monoester derivatives thereof or maleic anhydride acid. A desired binder resin can be produced by copolymerizing such monomers alone or in combination with other monomers. Among these, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid in order to control the acid value.

  More specifically, the following are mentioned, for example. Α, β-unsaturation such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate Monoesters of dicarboxylic acids; monoesters of alkenyldicarboxylic acids such as monobutyl n-butenyl succinate, monomethyl n-octenyl succinate, monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate, monobutyl n-butenyladipate; Monoesters of aromatic dicarboxylic acids such as phthalic acid monomethyl ester, phthalic acid monoethyl ester, phthalic acid monobutyl ester.

  The carboxyl group-containing monomer as described above is preferably used in an amount of 0.1 to 30% by mass with respect to all monomers used when the vinyl polymer unit is synthesized.

  Since the vinyl polymer unit contained in the gel component of the present invention preferably has a high linearity, it preferably has no crosslinkable monomer. In order to achieve the object of the present invention, a crosslinkable monomer as exemplified below may be added.

  As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Aromatic divinyl compounds (eg divinylbenzene, divinylnaphthalene); diacrylate compounds linked by alkyl chains (eg ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylates linked by alkyl chains containing ether linkages Compounds (eg, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds linked by a chain containing an aromatic group and an ether bond (eg, polyoxyethylene (2)) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and acrylates of the above compounds were replaced with methacrylate. Thing); polyester type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)). The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallyl cyanurate, Triaryl trimellitate.

  These crosslinking agents are preferably used in an amount of 0.001 to 1 part by mass, more preferably 0.001 to 0.05 part by mass with respect to 100 parts by mass of the other vinyl monomer components.

  The vinyl resin is preferably produced by using a polyfunctional polymerization initiator as exemplified below alone or in combination of a polyfunctional polymerization initiator and a monofunctional polymerization initiator.

  Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include the following. 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-hexylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t- Amylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxy-2-methylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene, 1,3- Bis- (neodecanol peroxyisopropyl) benzene, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylper) Oxy) hexyne-3,2,5-dimethyl-2,5-di- (2-ethylhexanol peroxy) hexane, 2,5-dimethyl-2,5-di- (m-toluol peroxy) Hexane, 2,5-dimethyl-2,5-di- (benzoylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 1,1-di -T-hexylperoxycyclohexane, 1,1-di-t-amylperoxycyclohexane, 1,1-di-t-butylperoxycyclododecane, 2,2-di-t-butylperoxybutane, 4, 4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyhexahydroisophthalate, di-t-butylperoxyazelate , Tert-butylperoxytrimethyladipate, 2,2-bis- (4,4-di-tert-butylperoxysi (Rohexyl) propane, 2,2-t-butylperoxyoctane, and polyfunctional polymerization initiator having a functional group having a polymerization initiating function such as two or more peroxide groups in one molecule of various polymer oxides, and diallyl A functional group having a polymerization initiating function such as a peroxide group in one molecule, such as peroxydicarbonate, t-butylperoxymaleic acid, t-butylperoxyallylcarbonate and t-butylperoxyisopropyl fumarate; A polyfunctional polymerization initiator having both polymerizable unsaturated groups.

  Among these, the following are more preferable. 1,3-bis- (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- ( t-butylperoxy) hexyne-3, and 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane.

  These polyfunctional polymerization initiators are preferably used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.

  Furthermore, when these polyfunctional polymerization initiators are used in combination with a monofunctional polymerization initiator, the temperature at which the half-life is 10 hours (10-hour half-life temperature) is lower than that of the polyfunctional polymerization initiator. It is preferable to use in combination with a monofunctional polymerization initiator.

  Specific examples include the following. Benzoyl peroxide, n-butyl-4,4-di (t-butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, Organic peroxides such as di-t-butyl peroxide; azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

  These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator, but in order to keep the efficiency of the polyfunctional polymerization initiator appropriate, vinyl in the polymerization step is used. It is preferable to add after the polymerization addition rate of the monomer reaches 50% or more.

  As described above, the binder resin according to the present invention is preferably obtained by a bulk polymerization method in which a vinyl monomer is polymerized without using a solvent in the presence of the unsaturated polyester resin as described above. In particular, a polymerization initiator having a 10-hour half-life temperature of 100 to 150 ° C. is used, a temperature that is 30 ° C. lower than the 10-hour half-life temperature of the polymerization initiator, and a temperature that is 10 ° C. higher than the 10-hour half-life temperature. In this range, it is preferable to carry out the polymerization reaction until the polymerization conversion rate of the vinyl monomer reaches 60%, preferably 80%, and to increase the molecular weight of the vinyl polymer unit produced by bulk polymerization. Furthermore, after the polymerization conversion rate reaches 60% (preferably 80%), it is preferable to carry out the polymerization reaction at a temperature higher by 10 ° C. or more than the 10-hour half-life temperature to terminate the reaction.

  The binder resin thus obtained has an acid value of 0.1 to 50 mgKOH / g (preferably 1 to 40 mgKOH / g, more preferably 1 to 30 mgKOH / g), and a hydroxyl value of 5 to 80 mgKOH / g (preferably Is preferably in the range of 5 to 60 mgKOH / g, more preferably 10 to 50 mgKOH / g) from the viewpoint of stabilizing the triboelectric chargeability of the toner.

  Further, the binder resin used in the present invention contains 5 to 50% by mass (preferably 5 to 40% by mass, more preferably 10 to 30% by mass) of tetrahydrofuran insoluble matter, so that the developability and resistance of the toner are improved. It is preferable for enhancing the high temperature offset property.

  The glass transition temperature (Tg) of the binder resin used in the present invention is preferably 50 to 75 ° C. When the glass transition temperature of the binder resin is less than 50 ° C., the storage stability of the toner may be insufficient, and when it is higher than 75 ° C., the low-temperature fixability of the toner may be insufficient.

  The toner of the present invention may contain a wax as a release agent.

  The waxes used in the present invention include the following. Low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax or And block copolymers; plant waxes such as candelilla wax, carnauba wax, wood wax and jojoba wax; animal waxes such as beeswax, lanolin and spermaceti; mineral waxes such as ozokerite, ceresin and petrolatum; montan Waxes mainly composed of aliphatic esters such as acid ester wax and caster wax; waxes obtained by partially or fully deoxidizing aliphatic esters such as deoxidized carnauba wax.

  Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, valinalic acid; stearyl alcohol, eico Syl alcohol, behenyl alcohol, cannavir alcohol, seryl alcohol, melyl alcohol, or saturated alcohol such as alkyl alcohol having a long chain alkyl group; polyhydric alcohol such as sorbitol; linoleic acid amide, oleic acid amide, lauric acid amide Aliphatic amides such as: methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, saturated aliphatic bis amides such as hexamethylene bis stearic acid amide; ethylene bis olein Unsaturated fatty acid amides such as amide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, N ′ -Aromatic bisamides such as distearyl isophthalamide; Aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soaps); aliphatic hydrocarbon waxes Wax grafted with vinyl monomers such as styrene and acrylic acid; Partial esterified product of fatty acid and polyhydric alcohol such as behenic acid monoglyceride; Methyl ester having hydroxyl group obtained by hydrogenating vegetable oil Compound.

  In addition, these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a melt liquid crystal deposition method, a low molecular weight solid fatty acid, a low molecular weight A solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.

  Specific examples of the wax include the following. Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries), High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals) ), Sazole H1, H2, C80, C105, C77 (Schumann Sazol), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiki Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark), Unicid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite), wood wax, beeswax, rice wax, candelilla wax Carnauba wax (available from Celerica NODA). It is also a preferred form that these waxes are added as necessary when the resin is produced, and further the dispersibility is improved.

  The toner of the present invention further contains a magnetic material (for example, magnetic iron oxide) and can be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant.

  In the present invention, examples of the magnetic substance contained in the magnetic toner include the following. Iron oxides such as magnetite, maghemite, ferrite; metals such as iron, cobalt, nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese , Alloys of metals such as selenium, titanium, tungsten, vanadium and mixtures thereof.

  These magnetic materials have a number average particle diameter of 2.0 μm or less, preferably 0.05 to 0.5 μm. The amount contained in the toner is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin, and particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the resin component.

  As the colorant used in the present invention, a black colorant that is toned in black using carbon black, grafted carbon or the following yellow / magenta / cyan colorant can be used.

  As the yellow colorant, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. These colorants can be used alone or in combination and further in the form of a solid solution.

  The non-magnetic colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The addition amount of the nonmagnetic colorant is used by adding 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner of the present invention preferably contains a charge control agent. The following substances are used for controlling the toner to be negatively charged.

  Organic metal compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid based metal compounds. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol.

  Moreover, as a negatively chargeable charge control agent, an azo metal compound represented by the following general formula (1) and an oxycarboxylic acid metal compound represented by the general formula (2) are preferable.

〔式中、Ｍは配位中心金属を表し、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｃｏ、Ｎｉ、Ｍｎ、又はＦｅを示す。Ａｒはアリール基であり、フェニレン基、ナフチレン基を示し、置換基を有してもよい。この場合の置換基としては、ニトロ基、ハロゲン原子、カルボキシル基、アニリド基および炭素数１〜１８のアルキル基、またはアルコキシ基である。Ｘ，Ｘ’、Ｙ，及びＹ’は−Ｏ−、−ＣＯ−、−ＮＨ−、−ＮＲ−（Ｒは炭素数１〜４のアルキル基）である。Ａ⁺は水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、脂肪族アンモニウムイオン、それらの混合物を表すが、Ａ⁺は存在しない場合もある。〕
特に、中心金属としてはＦｅが好ましく、置換基としてはハロゲン原子、アルキル基、アニリド基が好ましい。

[In the formula, M represents a coordination center metal, and represents Sc, Ti, V, Cr, Co, Ni, Mn, or Fe. Ar is an aryl group, which represents a phenylene group or a naphthylene group, and may have a substituent. In this case, the substituent is a nitro group, a halogen atom, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group. X, X ′, Y, and Y ′ are —O—, —CO—, —NH—, and —NR— (R represents an alkyl group having 1 to 4 carbon atoms). A ⁺ represents hydrogen ion, sodium ion, potassium ion, ammonium ion, aliphatic ammonium ion, or a mixture thereof, but A ⁺ may not exist. ]
In particular, Fe is preferable as the central metal, and halogen atoms, alkyl groups, and anilide groups are preferable as the substituent.

  In particular, Fe, Si, Zn, Zr, or Al is preferable as the central metal, alkyl groups, anilide groups, aryl groups, and halogens are preferable as substituents, and counter ions include hydrogen ions, ammonium ions, and aliphatic ammonium ions. preferable.

  Among them, the azo metal compound represented by the formula (1) is more preferable, and the azo iron compound represented by the following formula (3) is most preferable.

  Next, specific examples of the compound will be shown.

Examples of the positive charge control agent include the following substances. Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, onium salts such as phosphonium salts and lake pigments thereof, tri Phenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide); higher fatty acid metals Salt; guanidine compound, imidazole compound. These can be used alone or in combination of two or more. Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used.
Further, the general formula (4)

〔式中、Ｒ₁はＨ又はＣＨ₃を示し、Ｒ₂及びＲ₃は置換または未置換のアルキル基（好ましくは、Ｃ１〜Ｃ４）を示す〕
で表されるモノマーの単重合体；前述したスチレン、アクリル酸エステル、メタクリル酸エステルの如き重合性モノマーとの共重合体を正荷電性制御剤として用いることができる。この場合これらの荷電制御剤は、結着樹脂（の全部または一部）としての作用をも有する。

[Wherein R ₁ represents H or CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably C1 to C4)]
A copolymer with a polymerizable monomer such as styrene, acrylic acid ester or methacrylic acid ester described above can be used as a positive charge control agent. In this case, these charge control agents also have an action as a binder resin (all or a part thereof).

  In particular, a compound represented by the following general formula (5) is preferable in the configuration of the present invention.

〔式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は、各々互いに同一でも異なっていてもよい水素原子、置換もしくは未置換のアルキル基または、置換もしくは未置換のアリール基を表し、Ｒ₇、Ｒ₈及びＲ₉は、各々互いに同一でも異なっていてもよい水素原子、ハロゲン原子、アルキル基、アルコキシ基を表し、Ａ^-は、硫酸イオン、硝酸イオン、ほう酸イオン、りん酸イオン、水酸イオン、有機硫酸イオン、有機スルホン酸イオン、有機りん酸イオン、カルボン酸イオン、有機ほう酸イオン又はテトラフルオロボレートから選択される陰イオンを示す。〕

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

  Preferred control agents for negative charging include the following. Spiron Black TRH, T-77, T-95 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E-84, E-88, E-89 ( Orient Chemical Industry Co., Ltd.). Preferred control agents for positive charging include the following. TP-302, TP-415 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) N-01, N-04, N-07, P-51 (Orient Chemical Co., Ltd.), Copy Blue PR ( Clariant).

  As a method of incorporating a charge control agent into the toner, there are a method of adding it inside the toner particles and a method of adding it externally. The amount of these charge control agents to be used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and a dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. Examples of such fluidity improvers include the following. Fluorine-based resin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fine powder silica such as wet process silica and dry process silica, fine powder titanium oxide, fine powder alumina, silane compound, titanium cup Fine powder treated with a ring agent or silicone oil; oxides such as zinc oxide and tin oxide; double oxides such as strontium titanate, barium titanate, calcium titanate, strontium zirconate and calcium zirconate; Calcium carbonate and carbonate compounds such as magnesium carbonate.

A preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is referred to as so-called dry process silica or fumed silica. For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

  In this production process, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. To do. The particle size is preferably within the range of 0.001 to 2 μm as the average primary particle size, and particularly silica fine powder within the range of 0.002 to 0.2 μm is preferably used.

  Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include the following. AEROSIL (Nippon Aerosil Co., Ltd.) 130, 200, 300, 380, TT600, MOX170, MOX80, COK84, Ca-O-SiL (CABOT Co.) M-5, MS-7, MS-75, HS-5, EH -5, Wacker HDK N 20 (WACKER-CHEMIE GMBH) V15, N20E, T30, T40, D-C Fine Silica (Dow Corning Co.), Fransol (Fransil), which is also preferably used in the present invention Can do.

  Furthermore, as the fluidity improver used in the present invention, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halogen compound is more preferable. In the treated silica fine powder, it is particularly preferred to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is in the range of 30-80.

  Examples of the hydrophobizing treatment include a chemical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound.

  Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylethoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, and diphenyldiethoxysilane. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used alone or as a mixture of two or more.

The fluidity improver preferably has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 50 m ² / g or more. The flowability improver is used in a total amount of 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the toner particles before external addition.

  In addition to the fluidity improver, the toner of the present invention can be used by adding other external additives (for example, a charge control agent) as necessary.

  The toner of the present invention can be used as a one-component developer or a two-component developer in combination with a carrier. As the carrier for use in the two-component developer, all conventionally known carriers can be used. Specifically, surface oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, rare earth, etc. Particles with an average particle size of 20 to 300 μm, such as metals and their alloys or oxides, are preferably used.

  Further, those obtained by attaching or coating a resin such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin on the surface of the carrier particles are preferably used.

  In the present invention, it is preferable that the weight average particle diameter (D4) of the toner particles measured by a Coulter counter is 3.5 μm or more and 6.5 μm or less. When the weight average particle diameter of the toner particles is within this range, the image quality such as dot reproducibility and halftone roughness is improved.

  Further, the content of particles having a particle size of 2.00 μm or more and 4.00 μm or less in the number distribution of toner particles is preferably 1% by number to 30% by number (preferably 25% by number or less). Further, the content of particles having a particle size of 2.00 μm or more and 3.17 μm or less in the number distribution of toner particles is 1% by number to 15% by number (preferably 10% by number or less, more preferably 5% by number or less). Preferably there is. The ratio of toner particles having a particle size of 2.00 μm to 4.00 μm, or a particle size of 2.00 μm to 3.17 μm is within this range, thereby suppressing fogging and low image density in a high temperature and high humidity environment. Can do.

  The weight average particle diameter (D4) of toner particles, the content of particles having a particle size of 2.00 μm to 4.00 μm, and the content of particles having a particle size of 2.00 μm to 3.17 μm in the number distribution of toner particles are: The particle size can be measured using a Coulter Multisizer II (trade name, manufactured by Coulter, Inc.). For example, measurement can be performed by connecting a number distribution and volume distribution interface (manufactured by Nikka) and a personal computer to the Coulter Multisizer II.

  As an electrolytic solution used for preparing a test sample, a 1% NaCl aqueous solution in which a reagent primary sodium chloride is dissolved in water can be used. In addition, as the electrolytic solution, for example, ISOTONR-II (manufactured by Coulter Scientific Japan, trade name) can be used.

  Toner particles are prepared by adding 0.1 ml of a surfactant (preferably alkylbenzene sulfonate) as a dispersant to 100 ml of the electrolytic solution, adding 10 mg of toner, and dispersing the mixture for about 1 minute with an ultrasonic disperser. be able to. In the measurement of the weight average particle diameter (D4) by the Coulter multisizer, a 100 μm aperture can be used as the aperture.

  The weight average particle diameter (D4) in the present invention was determined from the volume distribution by measuring the volume and number of individual particles of a toner particle group having a particle diameter of 2 μm or more, and calculating the volume distribution and number distribution. It can be obtained as a weight average particle diameter (D4) based on weight (representing the representative value of each channel as the representative value for each channel).

  Further, the toner particles are particles having a circle equivalent diameter of 0.25 μm or more and less than 30.0 μm measured in a flow type particle image measuring apparatus having an image processing resolution of 512 × 512 pixels (0.19 μm × 0.19 μm per pixel). The ratio of the number of particles having an equivalent circle diameter of 0.25 μm to less than 1.98 μm to the number is in the range of 1% to 15% (preferably 1% to 10%, more preferably 1% to 7%). It is preferable that Particles with an equivalent circle diameter of 0.25 μm or more and less than 1.98 μm (hereinafter referred to as toner fine particles) have a small particle size and strong adhesion, and therefore are difficult to scrape off with a cleaning blade and remain on the photoreceptor. In particular, the elasticity of the cleaning blade increases in a low temperature environment, and the coefficient of friction between the cleaning blade and the photoconductor decreases, so that toner particles can easily slip through the contact portion between the cleaning blade and the photoconductor, resulting in poor cleaning. Become. Therefore, if the toner fine particles are more than 15%, cleaning failure is likely to occur. However, since the toner fine particles are present on the surface of the toner, the adhesion between the photoconductor and the toner is reduced, and the toner fine particles can be easily scraped off. Therefore, the ratio of the toner fine particles is less than 1%. Again, cleaning defects are likely to occur. Furthermore, in the present invention, the sum of the ratio of the content of particles having a particle size of 2.00 μm to 3.17 μm and the number of particles having an equivalent circle diameter of 0.25 μm to less than 1.98 μm in the number distribution of toner particles. It is preferably in the range of 2% to 20% (preferably 2% to 15%, more preferably 2% to 12%). When it is within this range, it is possible to satisfy the image quality, fog, image density, and cleaning blade turning at a high level. Since the toner of the present invention is excellent in pulverization properties and hardly pulverizes, such toner fine powder and toner fine particles are not easily generated, and it is easy to adjust their contents in the classification step.

  The ratio of the number of particles having an equivalent circle diameter of 0.25 μm or more and less than 1.98 μm of the present invention was measured by a flow type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation). The measurement principle of the flow-type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) is to take a flowing particle as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is picked up by a CCD camera, and the picked-up image is image-processed at an image processing resolution of 512 × 512 (0.19 × 0.19 μm per pixel), the contour of each particle image is extracted, Projected area, perimeter, etc. are measured.

Next, the projected area S and the perimeter L of each particle image are obtained. Using the area S and the perimeter L, the equivalent circle diameter and the circularity are obtained. The circular equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity is a value obtained by dividing the circumference of the circle obtained from the circular diameter by the circumference of the projected particle image. Defined and calculated by the following formula.
C = 2 × √ (π × S) / L

  When the particle image is circular, the degree of circularity is 1, and the degree of unevenness on the outer periphery of the particle image increases, and the degree of circularity decreases. After calculating the circularity of each particle, the range of the circularity of 0.2 to 1.0 is divided into 800, and the average circularity is calculated using the number of measured particles.

  In order to produce the toner of the present invention, the binder resin and the colorant, and if necessary, the magnetic substance, wax, charge control agent, and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, Melting, kneading and kneading using a heat kneader such as a roll, kneader or extruder to disperse wax and magnetic material in the binder resin, cooling and solidifying, and then pulverizing and classifying to obtain a toner Can do.

  The toner of the present invention can be manufactured using a known manufacturing apparatus. For example, the following manufacturing apparatus can be used.

  The following are mentioned as a mixer. Henschel mixer (made by Mitsui Mining); Super mixer (made by Kawata); Ribocorn (made by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (made by Hosokawa Micron); Spiral pin mixer (made by Taiheiyo Kiko) A Ladige mixer (manufactured by Matsubo).

  Examples of the kneader include the following. KRC Kneader (manufactured by Kurimoto Tekkosho); Bus Co Kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (Ikegai) Steel mill); three roll mill, mixing roll mill, kneader (Inoue Seisakusho); kneedex (Mitsui Mining Co.); MS pressure kneader, Nider Ruder (Moriyama Seisakusho); Banbury mixer (Kobe Steel) (Made by the company).

  Examples of the pulverizer include the following. Counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industrial Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works); Urmax (manufactured by Nisso Engineering Co., Ltd.) SK; jet mill (manufactured by Seishin Enterprise Co., Ltd.); kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); turbo mill (manufactured by Turbo Industry Co., Ltd.); super rotor (manufactured by Nisshin Engineering Co., Ltd.).

  Examples of the classifier include the following. Classifier, Micron Classifier, Spedick Classifier (manufactured by Seishin Enterprise Co., Ltd.); Turbo Classifier (Nisshin Engineering Co., Ltd.); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron Corporation); Elbow Jet (Japan) Iron Mining Co., Ltd.), Dispersion Separator (Nihon Pneumatic Kogyo Co., Ltd.);

  Examples of the sieving apparatus used for sieving coarse particles include the following. Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokuju Kosakusha Co., Ltd.); Vibrasonic System (manufactured by Dalton Co.); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Micro shifter (manufactured by Hadano Sangyo Co., Ltd.); circular vibrating sieve.

  The measurement of various physical properties relating to the toner of the present invention will be described below. In the present invention, the molecular weight distribution of the tetrahydrofuran soluble part and the content of the tetrahydrofuran insoluble part of the toner and the binder resin can be measured by the following methods.

(1) Measurement of molecular weight of tetrahydrofuran-soluble matter The molecular weight of a chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.

The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (tetrahydrofuran) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml per minute. As a column, in order to accurately measure a molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodex GPC KF-801, 802, 803 manufactured by Showa Denko KK , 804, 805, 806, 807, 800P, TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H manufactured by Tosoh Corporation The combination of (H _XL ), G7000H (H _XL ), and TSKgourd column can be mentioned, and in particular, the combination of seven columns of shodex KF-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko KK Is preferred.

  On the other hand, the polyester resin component contained in the toner, binder resin, or toner insoluble in tetrahydrofuran is hydrolyzed, and the vinyl resin component obtained as a residue is dispersed in tetrahydrofuran and dissolved, and then allowed to stand overnight. Thereafter, the mixture is filtered with a sample processing filter (pore size of about 0.5 μm, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation)), and the filtrate is used as a sample. Measurement is performed by injecting 100 μl of a tetrahydrofuran solution of the toner adjusted so that the resin concentration of the sample component is 5 mg / ml. An RI (refractive index) detector is used as the detector.

In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Or a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 manufactured by Toyo Soda Kogyo Co., Ltd. It is appropriate to use a standard polystyrene sample of at least about 10 points, using .9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ .

(2) Amount of tetrahydrofuran-insoluble matter A binder resin or toner is weighed and placed in a cylindrical filter paper (for example, No. 86R size 28 mm × 10 mm, manufactured by Toyo Filter Paper Co., Ltd.) and applied to a Soxhlet extractor. Extraction is performed for 16 hours using 200 ml of tetrahydrofuran as a solvent. At this time, extraction is performed at a reflux rate such that the tetrahydrofuran extraction cycle is about once every 5 minutes. After the extraction is completed, the cylindrical filter paper is taken out and weighed to obtain an insoluble content of the binder resin or toner.

If the toner contains a tetrahydrofuran-insoluble component other than the resin component (eg, magnetic substance, pigment, wax, charge control agent), the weight of the toner in the cylindrical filter paper is W ₁ g, and the extracted THF soluble matter When the mass of the resin component is W ₂ g and the mass of the tetrahydrofuran-insoluble component other than the resin component contained in the toner is W ₃ g, the content of the tetrahydrofuran-insoluble component of the resin component in the toner can be obtained from the following formula. .
Tetrahydrofuran insoluble (mass%) = [{W ₁ − (W ₃ + W ₂ )} / (W ₁ −W ₃ )] × 100

(3) Method for Measuring Acid Value of Resin The acid value of the binder resin in the present invention can be measured as follows. Basic operation conforms to JIS K0070.

  1) The binder resin pulverized product 0.5 to 2.0 (g) is precisely weighed to obtain the weight W (g) of the binder resin.

  2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (4/1) is added and dissolved.

  3) Using a 0.1 mol / liter KOH methanol solution, titration is performed using a potentiometric titrator (for example, a potentiometric titrator AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd.) and an ABP-410 electric burette Automatic titration with can be used.)

  4) The amount of KOH solution used at this time is S (ml), and at the same time, a blank is measured, and the amount of KOH solution used at this time is B (ml).

5) Calculate the acid value of the binder resin by the following formula. f is a factor of KOH.
Acid value (mgKOH / g) = ((SB) × f × 5.61) / W

(4) Measuring method of hydroxyl value of resin The hydroxyl value of the binder resin in the present invention can be measured as follows.

(A) Reagent (a) Acetylation reagent: Add 25 g of acetic anhydride to a 100 ml volumetric flask, add pyridine to make a total volume of 100 ml, and shake well. The acetylating reagent should be kept in brown bottles away from moisture, carbon dioxide and acid vapors.

  (B) Phenolphthalein solution: 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 vol%).

  (C) 0.5 mol / liter-potassium hydroxide ethyl alcohol solution: Dissolve 35 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 vol%) to 1 liter, leave it for 2 to 3 days, and filter. The orientation is performed according to JIS K8006.

(B) Operation 0.5 g of a sample is correctly weighed in a round bottom flask, and 5 ml of an acetylating reagent is correctly added thereto. Put a small funnel over the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at 95-100 ° C. and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, a cardboard disk with a round hole in it is put on the base of the neck of the flask. After 1 hour, the flask is removed from the bath, and after cooling, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride. In order to further complete the decomposition, the flask was heated again in a glycerin bath for 10 minutes, allowed to cool, and then the funnel and the wall of the flask were washed with 5 ml of ethyl alcohol, and 0.5 mol / liter-hydroxylated with a phenolphthalein solution as an indicator. Titrate with potassium ethyl alcohol solution, and the end point is when the light red color of the indicator lasts for about 30 seconds. A blank test is performed in parallel with the main test.

(C) Calculation formula The hydroxyl value of the binder resin is calculated by the following formula.
A = [{(B + C) × f × 28.05} / S] + D

However,
A: Resin hydroxyl value B: Amount used of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution in the blank test (ml)
C: Use amount of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution in this test (ml)
f: Factor of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution S: Mass of sample (g)
D: Acid value of resin

(5) GPC-RALLS-Viscometer Analysis (i) Pretreatment 0.1 g of toner is put into a 20 ml test tube together with 10 ml of tetrahydrofuran. This is dissolved at 25 ° C. for 24 hours. Thereafter, a sample processing filter (pore size 0.2 to 0.5 μm, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation) can be used) is used as a GPC sample.

(Ii) Analysis condition apparatus: HLC-8120GPC Tosoh Corporation DAWN EOS (Wyatt Technology)
High temperature differential pressure viscosity detector (Viscotek)
Column: KF-807, 806M, 805, 803 (Showa Denko Co., Ltd.) 4-column combination detector 1: Multi-angle light scattering detector Wyatt DAWN EOS
Detector 2: High temperature differential pressure viscosity detector Detector 3: Bryce type differential refractometer temperature: 40 ° C
Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min
Injection volume: 400 μl

  In this measurement, molecular weight distribution based on absolute molecular weight, radius of inertia, and intrinsic viscosity are directly output. The measurement theory is as follows.

[Measurement theory]
M90 = R (θ90) / KC Rayleigh equation M90: molecular weight R (θ90) at 90 °: Rayleigh ratio at a scattering angle of 90 ° K: optical constant (= 2π ² n ² / λ ₀ ⁴ N _A · ( dn / dc) ² )
C: Solution concentration Rg = (1/6) ^1/2 ([η] M90 / Φ) ^1/3 ... Froly Fox formula Rg: radius of inertia η: intrinsic viscosity Φ: shape element absolute molecular weight: M = R ( θ0) / KC
R (θ0) = R (θ90) / P (θ90)
P (θ90) = 2 / X ² · (e− ^X− (1−X)) (X = 4πn / λ · Rg)
λ: Wavelength (dn / dc): 0.078 ml / g for toner containing only polyester resin, 0.185 ml / g for linear polystyrene, polyester resin and vinyl resin (value for linear polystyrene) Is used). For example, since the binder resin 1 described later has a mass ratio of the polyester resin component to the vinyl resin component of 75:25, dn / dc = 0.105 was calculated according to the following formula.
0.078 × 0.75 + 0.185 × 0.25 = 0.105

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.

[Binder resin production example]
(Polyester resin production example 1)
Monomers for forming the polyester were mixed in the following ratio.
-Bisphenol derivative represented by the formula (A) (R: propylene group, average value of x + y: 2.2)
1.150 mol
・ Terephthalic acid 0.400 mol
・ Isophthalic acid 0.588 mol
・ Fumaric acid 0.012 mol

  0.1% by mass of tetrabutyl titanate as a catalyst was added to the above material and subjected to condensation polymerization at a temperature of 220 ° C. to obtain an unsaturated polyester resin P-1 (Tg = 62 ° C., main peak molecular weight = 8700, number average molecular weight (Mn ) = 4100, Mw / Mn = 2.2, acid value = 4.3 mgKOH / g, hydroxyl value = 37 mgKOH / g).

(Polyester resin production example 2)
A low-viscosity saturated polyester resin having a Tg = 38 ° C. was obtained in the same manner as in the polyester resin production example 1 except that the monomer for forming the polyester was mixed in the following ratio.
-Bisphenol derivative represented by the formula (A) (R: 2.2 mol addition of propylene group)
1.150 mol
・ Terephthalic acid 0.300 mol
・ Isophthalic acid 0.100 mol
・ Dodecenyl succinic anhydride 0.600 mol

  In a state where this low-viscosity saturated polyester resin is heated and melted, 0.200 mol of trimellitic anhydride is added, and the low-viscosity saturated polyester resin P-2 whose molecular ends are capped with trimellitic acid (Tg = 47 ° C., main Peak molecular weight = 8500, number average molecular weight (Mn) = 3700, Mw / Mn = 2.4, acid value = 27 mgKOH / g, hydroxyl value = 32 mgKOH / g) were obtained.

(Polyester resin production example 3)
Unsaturated polyester resin P-3 (Tg = 58 ° C., main peak molecular weight = 6500, number average molecular weight (Mn) in the same manner as in polyester resin production example 1 except that the monomer for forming polyester is mixed in the following ratio. ) = 3400, Mw / Mn = 2.6, acid value = 14 mgKOH / g, hydroxyl value = 57 mgKOH / g).
-Bisphenol derivative represented by the formula (A) (R: propylene group, average value of x + y: 2.2)
1.150 mol
・ Terephthalic acid 0.400 mol
・ Isophthalic acid 0.490 mol
・ Dodecenyl succinic anhydride 0.100 mol
・ Fumaric acid 0.010 mol

(Polyester resin production example 4)
A low-viscosity saturated polyester resin P-4 (Tg = 52 ° C., main peak molecular weight = 4500, number average molecular weight (except for mixing the monomer for forming the polyester at the following ratio) Mn) = 2900, Mw / Mn = 5.4, acid value = 27 mgKOH / g, hydroxyl value = 69 mgKOH / g).
-Bisphenol derivative represented by the formula (A) (R: 2.2 mol addition of propylene group)
1.150 mol
・ Terephthalic acid 0.400 mol
・ Isophthalic acid 0.300 mol
・ Dodecenyl succinic anhydride 0.300 mol

(Polyester resin production example 5)
An unsaturated polyester resin having a Tg of 40 ° C. was obtained in the same manner as in the polyester resin production example 1 except that the monomer for forming the polyester was mixed in the following ratio.
-Bisphenol derivative represented by the formula (A) (R: 2.2 mol addition of propylene group)
1.150 mol
・ Terephthalic acid 0.390 mol
・ Dodecenyl succinic anhydride 0.600 mol
・ Fumaric acid 0.010 mol

  In a state where this unsaturated polyester resin is heated and melted, 0.400 mol of trimellitic anhydride is added, and unsaturated polyester resin P-5 whose molecular terminal is capped with trimellitic acid (Tg = 58 ° C., main peak molecular weight) = 7200, number average molecular weight (Mn) = 3100, Mw / Mn = 3.3, acid value = 51 mgKOH / g, hydroxyl value = 9 mgKOH / g).

(Polyester resin production example 6)
Unsaturated polyester resin P-6 (Tg = 60 ° C., main peak molecular weight = 8200, number average molecular weight (Mn) in the same manner as in polyester resin production example 1 except that the monomer for forming polyester is mixed in the following ratio. ) = 3800, Mw / Mn = 2.5, acid value = 6 mgKOH / g, hydroxyl value = 39 mgKOH / g).
-Bisphenol derivative represented by the formula (A) (R: propylene group, average value of x + y: 2.2)
1.150 mol
・ Terephthalic acid 0.400 mol
・ Isophthalic acid 0.588 mol

(Hybrid resin production example 1)
Unsaturated polyester resin P-1: 50 parts by mass, low-viscosity saturated polyester resin P-2: 25 parts by mass, as a vinyl monomer, styrene: 18 parts by mass, and n-butyl acrylate: 6.5 parts by mass And mono-n-butyl maleate: 0.5 part by mass, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 as a polymerization initiator (10 hours half-life temperature 128 ° C. ): 0.08 part by mass was mixed. After this vinyl monomer / polyester resin mixture was polymerized at 120 ° C. for 20 hours until the polymerization conversion of the vinyl monomer reached 97%, the temperature was further raised to 150 ° C. and held for 5 hours to leave unreacted vinyl. The monomer was polymerized to obtain a hybrid resin. This is designated as binder resin 1.

  The obtained binder resin 1 had a main peak molecular weight of 8,800 in the molecular weight distribution measured by GPC with respect to the THF-soluble component, and contained 26 mass% of tetrahydrofuran-insoluble component. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and analyzed for the tetrahydrofuran-soluble matter of the component to be filtered out. As a result, it contained a vinyl resin. In general, when a hybrid resin is not contained, a THF-soluble component does not occur even when hydrolyzed. From this, it was confirmed that the hybrid resin was contained in the tetrahydrofuran insoluble matter.

(Hybrid resin production example 2)
Unsaturated polyester resin P-1: 45 parts by mass, low-viscosity saturated polyester resin P-4: 30 parts by mass, as a vinyl monomer, styrene: 18 parts by mass, and n-butyl acrylate: 6.5 parts by mass And mono-n-butyl maleate: 0.5 part by mass, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 as a polymerization initiator (10 hours half-life temperature 128 ° C. ): 0.08 part by mass was mixed. This vinyl monomer / polyester resin mixture was polymerized at a temperature of 115 ° C. over 15 hours until the polymerization conversion of the vinyl monomer reached 86%, and the temperature was further raised to 150 ° C. and held for 5 hours to leave unreacted vinyl. The monomer was polymerized to obtain a hybrid resin. This is designated as binder resin 2.

  The obtained binder resin 2 had a main peak molecular weight of 6,600 in the molecular weight distribution measured by GPC with respect to the THF-soluble content, and contained 26 mass% of tetrahydrofuran-insoluble content. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Hybrid resin production example 3)
Unsaturated polyester resin P-3: 45 parts by mass, low-viscosity saturated polyester resin P-4: 30 parts by mass, as a vinyl-based monomer, styrene: 18 parts by mass, and n-butyl acrylate: 6.5 parts by mass And mono-n-butyl maleate: 0.5 part by mass, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 as a polymerization initiator (10 hours half-life temperature 128 ° C. ): 0.08 part by mass was mixed. After polymerizing this vinyl monomer / polyester resin mixture at a temperature of 115 ° C. over 15 hours until the polymerization conversion of the vinyl monomer reaches 81%, the temperature is further raised to 150 ° C. and maintained for 5 hours to leave unreacted vinyl. The monomer was polymerized to obtain a hybrid resin. This is designated as binder resin 3.

  The obtained binder resin 3 had a main peak molecular weight of 5,400 in the molecular weight distribution measured by GPC with respect to the THF-soluble content, and contained 18 mass% of tetrahydrofuran-insoluble content. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Hybrid resin production example 4)
Unsaturated polyester resin P-5: 70 parts by mass, as a vinyl monomer, styrene: 23 parts by mass, n-butyl acrylate: 6.5 parts by mass, and mono n-butyl maleate: 0.5 parts by mass Then, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3: 0.15 part by mass was mixed as a polymerization initiator. After this vinyl monomer / polyester resin mixture was polymerized at 110 ° C. over 15 hours until the polymerization conversion of the vinyl monomer reached 72%, the temperature was further raised to 160 ° C. and held for 5 hours to leave unreacted vinyl. The monomer was polymerized to obtain a hybrid resin. This is designated as binder resin 4.

  The obtained binder resin 4 had a main peak molecular weight of 6,700 in the molecular weight distribution measured by GPC with respect to the THF-soluble component, and contained 13 mass% of tetrahydrofuran-insoluble component. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Hybrid resin production example 5)
Unsaturated polyester resin P-5: 50 parts by mass, as a vinyl monomer, styrene: 18 parts by mass, n-butyl acrylate: 6.5 parts by mass, and mono n-butyl maleate: 0.5 parts by mass Then, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (10-hour half-life temperature 128 ° C.): 0.08 parts by mass was mixed as a polymerization initiator. After this vinyl monomer / polyester resin mixture was polymerized at 110 ° C. over 12 hours until the polymerization conversion of the vinyl monomer reached 77%, the temperature was further raised to 150 ° C. and held for 5 hours to leave unreacted vinyl. The monomer was polymerized to obtain a hybrid resin. This is designated as binder resin 5.

  The obtained binder resin 5 had a main peak molecular weight of 8,500 in the molecular weight distribution measured by GPC with respect to the THF-soluble content, and contained 46 mass% of the tetrahydrofuran-insoluble content. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and analyzed for the tetrahydrofuran-soluble matter of the component to be filtered out. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Hybrid resin production example 6)
Unsaturated polyester resin P-5: 60 parts by mass was added to 300 parts by mass of xylene, and the mixture was heated to reflux. Under this reflux, styrene: 30 parts by mass, n-butyl acrylate: 9.5 parts by mass, mono-n-butyl maleate: 0.5 parts by mass, and di-tert-butyl peroxide: 2 parts by mass The mixture was added dropwise over 4 hours and then held for 2 hours to complete the polymerization. Thereafter, the organic solvent was distilled off to obtain a hybrid resin. This is designated as binder resin 6.

  This resin had a main peak molecular weight of 4,900 in the GPC molecular weight distribution of THF-soluble matter, and contained 17% by mass of tetrahydrofuran-insoluble matter.

(Comparative resin production example 1)
Saturated polyester resin P-6: 75 parts by mass, as a vinyl monomer, styrene: 18 parts by mass, n-butyl acrylate: 7 parts by mass, and 2,5-dimethyl-2,5-bis as a polymerization initiator (T-Butylperoxy) hexyne-3: 0.08 part by mass was mixed. After polymerizing this vinyl monomer / polyester resin mixture at a temperature of 120 ° C. over 20 hours until the polymerization conversion of the vinyl monomer reaches 94%, the temperature is further raised to 150 ° C. and maintained for 5 hours to leave unreacted vinyl. A system monomer was polymerized to obtain a comparative binder resin 1.

  The obtained binder resin for comparison 1 had a main peak molecular weight of 7,500 in the molecular weight distribution measured by GPC with respect to the THF-soluble content, and did not contain a tetrahydrofuran-insoluble content.

(Comparative resin production example 2)
As a vinyl monomer, 270 parts by mass of styrene, 60 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of acrylic acid, and 13 parts by mass of azobisisobutyronitrile as a polymerization initiator were placed in a dropping funnel.

  780 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 76 parts by mass of isododecenyl succinic anhydride, 180 parts by mass of terephthalic acid, 30 parts by mass of 1,2,4-benzenetricarboxylic acid And 2 parts by mass of dibutyltin oxide were placed in a flask, and while stirring at a temperature of 135 ° C., a vinyl monomer and a polymerization initiator were added dropwise from a dropping funnel over 3 hours to polymerize a vinyl resin component. After aging for 5 hours while maintaining the temperature at 135 ° C., the temperature was raised to 230 ° C. to polymerize the polyester resin component to obtain a hybrid resin. This is designated as comparative binder resin 2.

  The obtained binder resin for comparison 2 had a main peak molecular weight of 6,400 in the molecular weight distribution measured by GPC with respect to the THF-soluble content, and contained 14 mass% of tetrahydrofuran-insoluble content. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Comparative resin production example 3)
Unsaturated polyester resin P-1: 40 parts by mass, as a vinyl monomer, styrene: 35 parts by mass, n-butyl acrylate: 20 parts by mass, mono-n-butyl maleate: 5 parts by mass, polymerization initiation As an agent, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3: 0.2 part by mass was mixed. This vinyl monomer / polyester resin mixture was polymerized at a temperature of 120 ° C. over 6 hours until the polymerization conversion of the vinyl monomer reached 78%, and then the temperature was raised to 150 ° C. and held for 5 hours to keep unreacted vinyl. A system monomer was polymerized to obtain a comparative binder resin 3.

  The resultant binder resin 3 for comparison had a main peak molecular weight of 9,100 in the molecular weight distribution measured by GPC with respect to the THF-soluble content, and contained 61 mass% of tetrahydrofuran-insoluble content. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Comparative resin production example 4)
Unsaturated polyester resin P-3: 20 parts by mass, low-viscosity saturated polyester resin P-2: 60 parts by mass, as a vinyl monomer, styrene: 15 parts by mass, and n-butyl acrylate: 4.5 parts by mass And mono-n-butyl maleate: 0.5 part by mass and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3: 0.08 part by mass as a polymerization initiator did. This vinyl monomer / polyester resin mixture was polymerized at a temperature of 140 ° C. over 10 hours until the polymerization conversion of the vinyl monomer reached 94%, and then the temperature was raised to 150 ° C. and held for 5 hours to keep unreacted vinyl. A system monomer was polymerized to obtain a comparative binder resin 4.

  The obtained binder resin 4 for comparison had a main peak molecular weight of 7,200 in the molecular weight distribution measured by GPC with respect to the THF-soluble content, and contained 2 mass% of tetrahydrofuran-insoluble content. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Example 1)
Binder resin 1 100 parts by mass Magnetite (number average particle diameter 0.18 μm) 100 parts by mass Azo-based iron compound (1) (counter ion is NH ₄ ⁺ ) 2 parts by mass Fischer-Tropsch wax (Mn 790, Mw 1170 , Main peak molecular weight 960, DSC peak temperature 103 ° C.)
4 parts by mass The above raw materials were premixed with a Henschel mixer, and then kneaded by a twin-screw kneading extruder (PCM-30: manufactured by Ikekai Iron Works Co., Ltd.) set at a temperature of 130 ° C. and a rotation speed of 200 rpm. The obtained melt-kneaded product is cooled, and the cooled melt-kneaded product is coarsely pulverized with a cutter mill, and then the obtained coarsely pulverized product is subjected to an exhaust temperature of turbo mill T-250 (manufactured by Turbo Kogyo Co., Ltd.). The air temperature was adjusted to 45 ° C. and the mixture was finely pulverized and classified using a multi-division classifier using the Coanda effect to obtain a classified powder. Thereafter, the classified powder was further precisely classified using a classifier (TSP separator; manufactured by Hosokawa Micron Corporation) to obtain magnetic toner particles 1.

The magnetic toner particle 1 has a weight average particle size (D4) of 5.5 μm, a content of particles having a particle size of 2.00 μm to 3.17 μm in a number distribution of 2.2 number%, and an equivalent circle diameter of 0.25 μm or more. The ratio of the number of particles having an equivalent circle diameter of 0.25 μm or more and less than 1.98 μm to the number of particles of less than 30.0 μm was 1.8%. Further, 100 parts by mass of the magnetic toner particles 1 and 100 parts by mass of hydrophobic silica fine powder (dry silica (BET: 200 m ² / g)) were surface-treated with 10 parts by mass of hexamethyldisilazane, and then the treated silica 100 A magnetic toner 1 was prepared by mixing 1.2 parts by mass of a part by mass of 10 parts by mass of dimethyl silicone oil) with a Henschel mixer.

  This magnetic toner contained 18% by mass of a resin component insoluble in tetrahydrofuran. Further, when the tetrahydrofuran soluble component was analyzed by a GPC-RALLS-viscosity meter, the ratio of the intrinsic viscosity of 0.025 dl / g or less was 31%, and the ratio of the intrinsic viscosity of 0.025 to 0.050 dl / g was 41%. It was. Table 1 shows the physical properties of the magnetic toner 1. This magnetic toner was evaluated for the following items. The evaluation results are shown in Table 2.

[Crushability test]
The coarsely pulverized product was supplied at a rate of 30 kg / h to a pulverizer (Turbomill T-250; manufactured by Turbo Kogyo Co., Ltd.) and finely pulverized while adjusting the air temperature so that the exhaust temperature was 45 ° C. The peripheral speed of the pulverization rotor was adjusted so that the weight average particle diameter (D4) of the finely pulverized product was 5.5 μm, and the pulverization properties of the toners of the examples were judged based on the following criteria based on the peripheral speed of the pulverization rotor at that time. . As the weight average particle diameter (D4) of the finely pulverized product becomes 5.5 μm at a lower peripheral speed, the pulverizability is better.
A: Grinding rotor peripheral speed 91.7 m / s or less B: Grinding rotor peripheral speed 91.7 m / s or more and less than 104.8 m / s C: Grinding rotor peripheral speed 104.8 m / s or more and less than 117.9 m / s D: Grinding rotor circumferential speed 117.9 m / s or more and less than 131.0 m / s E: Grinding rotor circumferential speed 131.0 m / s or more

[Classification yield]
Using a classifier (Elbow Jet Classifier EJ-LABO; manufactured by Nippon Steel Mining Co., Ltd.), the weight average particle size (D4) was 5.5 μm, and the particle size was 2 in the number distribution. Classification was performed so that the content of particles having a particle size of 0.000 μm or more and 3.17 μm or less was 5% by number, and the classification yield was calculated from the amount of finely pulverized product supplied and the amount of toner particles obtained. The higher the classification yield, the sharper the distribution of the pulverized particle size of the finely pulverized product, and the higher the productivity, which was judged according to the following criteria.
Classification yield (%) = toner particle yield (kg) / fine pulverized product supply amount (kg) × 100
A: Classification yield 90% or more B: Classification yield 80% or more and less than 90% C: Classification yield 70% or more and less than 80% D: Classification yield 70% or less

[Fixing test]
Laser beam printer manufactured by Hewlett-Packard Company: LaserJet 4350 fixing device was taken out, and an external fixing device was used so that the fixing temperature of the fixing device could be arbitrarily set and the process speed was 400 mm / sec. This external fixing device is temperature-controlled at a temperature range of 140 to 220 ° C. from a temperature of 140 ° C. to a temperature of 5 ° C. and developed on plain paper (75 g / m ² ) paper. Fixing) (set to 6 mg / cm ² ). The obtained fixed image was rubbed back and forth 5 times with sylbon paper applied with a load of 4.9 kPa, and the point at which the density reduction rate of the image density before and after the rub was 10% or less was defined as the fixing temperature. The lower this temperature, the better the low-temperature fixability.

  Further, the process speed was set to 100 mm / sec, and the temperature was adjusted from 150 ° C. to every 5 ° C. in the temperature range of 150 to 240 ° C. to fix the unfixed image. The contamination due to the offset phenomenon on the fixed image was visually confirmed, and the generated temperature was regarded as high temperature offset resistance. The higher this temperature, the better the high temperature offset resistance.

[Development test]
A commercially available laser beam printer LaserJet 4350 (manufactured by Hewlett-Packard) was remodeled into a 65-sheet machine, and A4 size 75 g / m ² transfer paper was used in a room temperature and normal humidity (23 ° C., 60% RH) environment. An image drawing test was conducted. As the image data, document data having an image area ratio of 2% was used. Under these conditions, solid black image density and fogging were measured when 1,000 sheets and 20,000 sheets were passed.

  The image density was measured by measuring the reflection density using a SPI filter with a Macbeth densitometer (manufactured by Macbeth Co.), and the five-point average was calculated.

  The fog was calculated from the difference between the whiteness of the transfer paper measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper after printing solid white.

[Charging roller contamination]
Using the modified machine used in the development test, an image formation test was performed using A4 size 75 g / m ² transfer paper in a low temperature and low humidity (15 ° C., 10% RH) environment. As the image data, document data having an image area ratio of 2% was used. Under these conditions, 20,000 sheets were passed and the contamination of the charging roller was evaluated according to the following criteria.
A: Dirt is not seen on the charging roller B: Dirt is on the charging roller but no effect is seen on the image C: Charging failure due to the charging roller is slightly observed in the image D: Charging due to the charging roller is dirty Defects are clearly visible in the image

[Defective cleaning]
Using the modified machine used in the above development test, in a low temperature environment of 0 ° C., using an A4 size 75 g / m ² transfer paper, perform a 1,000 page print test and clean according to the following criteria: Defects were evaluated.
A: No occurrence B: Minor streaks due to toner passing through the cleaning blade are seen on the image C: Streaks are clearly seen on the image D: Streaks appear on the entire image, affecting printing

[Preservation test]
10g of toner is weighed into a cylindrical polypropylene cup with a diameter of 3cm and the surface is flattened. The blocking state was evaluated.
A: When the cup is tilted, the toner flows smoothly.
B: When the cup is rotated, the toner surface starts to collapse little by little and becomes a smooth powder.
C: When force is applied from the outside while turning the cup, the toner surface collapses and gradually begins to flow.
D: A blocking mass is generated. It collapses when pecked with a pointed object.
E: Blocking mass is generated. Even if it sticks, it is hard to collapse.

(Examples 2 and 3)
Magnetic toners 2 and 3 were obtained in the same manner as in Example 1 except that binder resins 2 and 3 were used instead of binder resin 1. Table 1 shows the physical properties of the magnetic toners 2 and 3. Further, an evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 2.

Example 4
A magnetic toner 4 was obtained in the same manner as in Example 1 except that the following raw materials were used. Table 1 shows the physical properties of the magnetic toner 4. Further, an evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 2.
Binder resin 4 75 parts by mass Low viscosity saturated polyester resin P-2 25 parts by mass Magnetite (number average particle size 0.18 μm) 100 parts by mass Azo-based iron compound (1) (counter ion is NH ₄ ⁺ 2 parts by mass / Fischer-Tropsch wax (Mn 790, Mw 1170, main peak molecular weight 960, DSC peak temperature 103 ° C.)
4 parts by mass

A magnetic toner 5 was obtained in the same manner as in Example 1 except that the following raw materials were used. Table 1 shows the physical properties of the magnetic toner 5. Further, an evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 2.
• Binder resin 4 90 parts by mass • Low viscosity saturated polyester resin P-2 10 parts by mass • Magnetite (number average particle size 0.18 μm) 100 parts by mass • The azo-based iron compound (1) (counter ion is NH ₄ ⁺ 2 parts by mass / Fischer-Tropsch wax (Mn 790, Mw 1170, main peak molecular weight 960, DSC peak temperature 103 ° C.)
4 parts by mass

(Examples 6 and 7)
The weight average particle diameter (D4) of the magnetic toner particles is adjusted in the same manner as in Example 5 except that precise classification using a classifier (TSP separator; manufactured by Hosokawa Micron Corporation) is not performed. , The content of particles having a particle size of 2.00 μm to 3.17 μm in the number distribution, and the number of particles having an equivalent circle diameter of 0.25 μm to less than 30.0 μm, Magnetic toners 6 and 7 having different numbers were obtained. Table 1 shows the physical properties of the magnetic toners 6 and 7. Further, an evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 2.

(Example 8)
A magnetic toner 8 was obtained in the same manner as in Example 1 except that the following raw materials were used. Table 1 shows the physical properties of the magnetic toner 8. Further, an evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 2.
Binder resin 5 90 parts by weight Low viscosity saturated polyester resin P-2 10 parts by weight Magnetite (number average particle size 0.18 μm) 100 parts by weight The azo-based iron compound (1) (counter ion is NH ₄ ⁺ 2 parts by mass / Fischer-Tropsch wax (Mn 790, Mw 1170, main peak molecular weight 960, DSC peak temperature 103 ° C.) 4 parts by mass

(Comparative Examples 1-4)
Comparative magnetic toners 1 to 4 were obtained in the same manner as in Example 1 except that the comparative binding resins 1 to 4 were used instead of the binding resin 1. Table 1 shows the physical properties of Comparative Magnetic Toners 1-4. Further, an evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 2.

Claims (4)

  In a toner having toner particles containing at least a binder resin and a colorant, the toner has a ratio of an intrinsic viscosity of 0.025 dl / g or less in a GPC-RALLS-viscosity analysis of a tetrahydrofuran soluble content of 40 to 70%. The toner contains 3 to 50% by mass of a resin component insoluble in tetrahydrofuran.   2. The toner according to claim 1, wherein the toner has a specific viscosity of 0.025 to 0.050 dl / g in an analysis by a GPC-RALLS viscometer of a tetrahydrofuran soluble content of 20 to 50%. .   The toner according to claim 1, wherein the binder resin contains 50% by mass or more of a polyester unit.   The toner according to claim 1, wherein the binder resin contains a hybrid resin.