JP4857009B2 - toner - Google Patents

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 they also have the disadvantages that it is difficult to increase the molecular weight and that an offset phenomenon is likely to occur at high temperatures. In order to make up for this defect, if the polyester resin contains a cross-linking component to increase the melt viscosity of the resin and attempt to improve the high temperature offset, not only the fixability is impaired, but the grindability at the time of toner production also deteriorates. End up.

  On the other hand, vinyl resins such as styrene resins are excellent in pulverization properties during toner production and easy to increase in molecular weight, so that they are excellent in high temperature offset resistance, but low in order to improve fixability. When molecular weight reduction or Tg reduction is performed, blocking resistance and developability tend to deteriorate.

  In order to make effective use of the advantages of these two types of resins and to make up for the drawbacks, several methods of mixing and using these resins have been studied.

  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 or wax added to the toner becomes insufficient.

  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 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 essential to control the molecular weight distribution of the binder resin, and it is not possible to polymerize styrene acrylic monomers in the presence of polyester resin. It is enough.

  Patent Document 4 discloses a toner characterized by containing a polymer obtained by polymerizing a styrene acrylic monomer in the presence of an unsaturated polyester resin. However, the content of the polyester resin with respect to the vinyl monomer is as small as 99.5: 0.5 to 91: 9, and the effect of improving the fixing property is small.

In Patent Document 5, a weight-average molecular weight obtained by graft polymerization of an unsaturated polyester resin with a vinyl monomer is 8000 to 20000, a melt viscosity at 100 ° C. is 10 ⁴ to 10 ⁶ poise, and a glass transition temperature is 50 to 75. A toner using a graft polymer having a temperature of 0 ° C. as a binder resin is disclosed. However, in order to further improve the fixing property and the high temperature offset resistance, it is necessary to control the molecular weight distribution of the toner more precisely.

  Patent Document 6 discloses a toner including a polymer obtained by esterifying an acid value-containing styrene resin and a polyester resin. In these methods, although the compatibility between the polyester resin and the vinyl copolymer is improved, the content of the gel component and the molecular weight of the vinyl resin component contained in the gel component are not controlled. There is a problem in satisfying high temperature offset resistance at a higher level.

  In Patent Document 7, 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 is reacted with a vinyl polymer. The toner binder for electrophotography obtained by making it have disclosed is disclosed. In this method, since the vinyl polymer and the 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, and the vinyl polymer may be decomposed by heat. is there. Since the ester reaction does not proceed sufficiently at a temperature at which the vinyl polymer does not decompose, it is difficult to achieve sufficient hybridization, and the fixing property, high temperature offset resistance, and developability cannot be satisfied.

  As described above, the toner is required to have further improved fixability, high temperature offset resistance, and developability, 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 Japanese Patent Laid-Open No. 1-156759 JP-A-2-881 Japanese Patent Laid-Open No. 11-153858

  An object of the present invention is to provide a toner having excellent fixability, high-temperature offset resistance and blocking resistance, and excellent developability.

(1) The present invention relates to a toner containing at least a binder resin and a colorant.
The binder resin is a polyester unit containing more than 50 wt%, and has contained hybrid resin,
The hybrid resin includes the unsaturated group of a polyester having an unsaturated group at a molecular end formed by a reaction of a hydroxyl group at the molecular end of a saturated polyester with an acid anhydride of a polycarboxylic acid having an unsaturated group , vinyl System unit is chemically bonded to the copolymer unit,
The toner contains 3 to 50% by mass of a resin component insoluble in tetrahydrofuran, the resin component insoluble in tetrahydrofuran contains a hybrid resin, and the polyester unit contained in the resin component insoluble in tetrahydrofuran is hydrolyzed. The present invention relates to a toner which is decomposed and has a main peak in the molecular weight range of 10,000 to 500,000 in the GPC molecular weight distribution of the tetrahydrofuran-soluble content of the residue.

  (2) According to the present invention, in the GPC molecular weight distribution of the tetrahydrofuran-soluble component of the toner, a main peak exists in the molecular weight range of 2,000 to 30,000, and the molecular weight ranges from 40,000 to 1,000,000. The toner according to (1), wherein the component is contained in an amount of 3 to 30 area%.

(3) In the present invention, the hybrid resin has a vinyl monomer in the presence of a polyester having an unsaturated group at the molecular end, and a polyester having an unsaturated group at the molecular end : vinyl monomer = 60: 40 to a toner having the constitution and Turkey obtained by bulk polymerization at 80:20 weight ratio of (1) or (2).

  (4) The present invention relates to the toner according to (3), wherein the vinyl monomer contains an unsaturated dicarboxylic acid and / or a derivative of an unsaturated dicarboxylic acid.

  According to the present invention, a toner having excellent fixability, high-temperature offset resistance and blocking resistance, and excellent developability can be obtained.

  The present inventors control the molecular weight distribution of the residue after hydrolyzing the polyester unit contained in the resin component (gel component) insoluble in tetrahydrofuran (THF) with the toner using the hybrid resin as described above. As a result, the present inventors have found a configuration capable of satisfactorily exhibiting the excellent performances of fixing properties of polyester resins and high temperature offset resistance of vinyl resins. In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl copolymer unit” refers to a portion derived from a vinyl copolymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component. The vinyl monomer constituting the vinyl copolymer unit is a monomer component having a vinyl group.

  In the present invention, “hybrid resin” means a resin in which a vinyl copolymer unit and a polyester unit are chemically bonded. Specifically, for example, a vinyl copolymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester, and a polyester unit formed by a transesterification reaction, an unsaturated polyester, Examples include those formed by addition polymerization of vinyl monomers.

  The binder resin contained in the toner used in the present invention needs to contain at least 50% by mass or more of a polyester unit in order to ensure good fixability. If the content of the polyester unit is less than 50% by mass, sufficient fixability cannot be obtained. The content of the polyester unit in the present invention is a combination of the polyester unit present in the polyester resin or the hybrid unit.

  The toner of the present invention contains 3 to 50% by mass (preferably 5 to 40% by mass, more preferably 5 to 30% by mass) of a resin component (gel component) insoluble in tetrahydrofuran. The component contains a hybrid resin which is a reaction product of a polyester unit and a vinyl copolymer unit. When the gel component is less than 3% by mass, high-temperature offset resistance cannot be satisfied. When the gel component is more than 50% by mass, it is difficult to uniformly disperse a material such as a colorant in the toner, the chargeability of the toner is deteriorated, and the fog and the image density are lowered.

  Since hybrid resin has both polyester resin composition and vinyl resin composition in the same molecule, it is easy to mix with raw materials that are easy to mix with polyester components (for example, coloring agents such as highly hydrophilic magnetic materials) and vinyl resin. It has the function of simultaneously improving the dispersibility of raw materials (for example, wax components having low polarity).

  In particular, the inclusion of a hybrid resin in the gel component makes it easier for the wax to be present in the vicinity of the gel component in the toner, so the wax component melts during fixing, making it easier to soften the gel component and sharpening the toner. The melt property becomes high and the fixability is greatly improved. In addition, the inclusion of a hybrid resin in the gel component facilitates the incorporation of a colorant such as a magnetic substance that is not likely to enter the gel component into the gel component. Developability and image quality are improved.

  Further, it is very important that the polyester unit contained in the binder resin of the present invention contains an unsaturated polyester unit in which a monomer having an unsaturated group is bonded to the molecular terminal. When a polyester unit having an unsaturated group at the molecular terminal is hybridized with a vinyl copolymer unit, the molecular terminal of the polyester unit is chemically bonded to the vinyl copolymer unit, and the polyester unit is branched to a copolymer. A graft copolymer having a vinyl copolymer unit as a backbone polymer is obtained. The molecular end of the polyester unit, which is a branched polymer, is bonded to the vinyl copolymer unit, which is a trunk polymer, so that the molecules of the branch portion are fixed only at the molecular end, so the molecular motion of the polyester unit Becomes difficult to be inhibited, and it becomes possible to generate a flexible gel component that is easily softened by heat. Such a binder resin containing a gel component can exhibit excellent high-temperature offset resistance because the gel component is not easily cut even when a strong shearing force such as melt kneading is applied during toner production. Further, since such a highly flexible gel component does not easily inhibit the fixing, the fixing property does not deteriorate even if a large amount of the gel component is contained in the toner.

  In the present invention, the polyester unit contained in the resin component (gel component) insoluble in tetrahydrofuran in the toner is hydrolyzed, and the THF soluble content of the residue has a molecular weight of 10,000 to 500,000 (preferably 30,000). 000 to 300,000, more preferably 50,000 to 200,000). As described above, the polyester unit is hybridized to the vinyl copolymer unit having a large molecular weight, whereby a flexible gel structure having a large molecular weight and a large molecular weight between cross-linking points can be obtained.

  In the toner containing such a gel component, the gel component is likely to undergo molecular motion even with a small amount of heat at the time of fixing, and the binder resin is softened by heat compared to the case of containing a gel component having a low molecular weight between crosslinking points. Since it becomes easy, fixing property improves. Furthermore, such a gel component can maintain a high viscosity even at a high temperature, and can improve high-temperature offset resistance. Further, since 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 fixability can be further improved.

  If the main peak molecular weight of the tetrahydrofuran-soluble portion of the residue obtained by hydrolyzing the polyester unit contained in the gel component is less than 10,000, the gel component tends to be hard and the fixability is deteriorated. Further, since the molecular weight between the crosslinking points is small, the gel component is not flexible, the gel component is easily cut by the shearing force at the time of kneading into toner, and the high temperature offset resistance is deteriorated. When the main peak molecular weight is larger than 500,000, it is difficult to uniformly disperse the gel component in the toner, and the gel component is easily separated, so that developability is deteriorated.

  The residue obtained by hydrolyzing the polyester unit contained in the gel component is mainly a vinyl copolymer unit, and the molecular weight distribution of the THF soluble matter of the residue is determined based on the vinyl copolymer that is the backbone polymer of the hybrid resin. It means that the molecular weight distribution of the polymer unit is being measured.

  The molecular weight distribution of the THF soluble content of the residue obtained by hydrolyzing the polyester unit contained in the gel component 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 unit. Since the vinyl copolymer unit 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 matter The toner is weighed and placed in a cylindrical filter paper (for example, No. 86R size 28 × 10 mm, 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 vinyl copolymer unit by hydrolysis The tetrahydrofuran-insoluble matter derived from the obtained binder resin was dispersed in a 2 mol / l NaOH aqueous solution at a concentration of 1% by mass, and a pressure vessel, 150 ° C., 24 hours. The polyester unit is hydrolyzed under the following conditions. The vinyl copolymer unit is separated from this hydrolyzed solution by the following procedure.

  i) The hydrolyzed solution was suction filtered using a membrane filter to separate the residual vinyl copolymer unit. Thereby, the monomer component which is the decomposition product of the polyester unit is removed in the filtrate.

ii) Since the vinyl copolymer unit as a residue is a sodium salt due to hydrolysis of the acrylic acid ester component contained in the vinyl copolymer unit, the residue is dispersed in water, Was added to adjust pH = 2, and the COO ⁻ group produced by hydrolysis of the acrylate component contained in the vinyl copolymer unit was protonated, and then filtered and separated with a membrane filter.

(3) GPC measurement of vinyl-based copolymer unit The vinyl-based copolymer unit contained in the tetrahydrofuran-insoluble matter separated by hydrolysis is dissolved in tetrahydrofuran, and the molecular weight distribution is measured by GPC.

  The toner of the present invention has a molecular weight range of 2,000 to 30,000 (preferably 3,000 to 20,000, more preferably 5,000 to 10,000) in the GPC molecular weight distribution of the tetrahydrofuran-soluble component of the toner. It preferably contains 3 to 30 area% (preferably 5 to 25 area%, more preferably 5 to 20 area%) of a component having a main peak at a molecular weight of 40,000 to 1,000,000. .

  In the molecular weight distribution of the tetrahydrofuran solubles of the toner, it has a main peak in the low molecular weight region, contains a certain amount of components in the high molecular weight region, and further has a gel component as described above, thereby fixing at a high level. It is possible to provide stable developability (high durability) over a long period of use while maintaining the properties and high-temperature offset resistance.

  The hybrid resin component having a large molecular weight between crosslinking points, which is a feature of the present invention, easily incorporates a low molecular weight component having a peak molecular weight in the range of 2,000 to 30,000 into the crosslinked structure, so that the gel component is melted by heat. Easier to fix and better fixability. Moreover, since the high molecular weight component in the molecular weight range of 40,000 to 1,000,000 improves the mixing property of the low molecular weight component and the gel component, the high temperature offset resistance is improved. In addition, since the gel component is uniformly mixed in the toner, the pulverization property at the time of toner production is improved, and the fine powder and coarse powder generated during the pulverization are greatly reduced. As a result, the factor that inhibits charging of the toner is reduced, and excellent development durability can be provided.

  When the main peak has a molecular weight of less than 2,000, the storage stability and developability of the toner are likely to deteriorate, and when it exceeds 30,000, the fixability tends to deteriorate.

  When the component in the molecular weight range of 40,000 to 1,000,000 is less than 3% by area, the uniform mixing property of the gel component is liable to be lowered, and fine powder and coarse powder are liable to be generated during pulverization. It is easy to get worse. When the component having a molecular weight in the range of 40,000 to 1,000,000 is more than 30% by area, the toner viscosity becomes too high and the fixability tends to deteriorate.

  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 as long as it contains at least a hybrid resin.

  For example, a mixture of a hybrid resin and a vinyl resin, a mixture of a hybrid resin and a polyester resin, a mixture of a polyester resin, a hybrid resin, and a vinyl resin, or the like can be given.

  The hybrid resin is formed by a transesterification reaction between a polyester component and a vinyl polymer component obtained by polymerizing a monomer component having a carboxylic acid ester group such as (meth) acrylic acid ester, a polyester component and (meth) acrylic acid. Unsaturated polyester resin polymerized using a monomer having an unsaturated group such as fumaric acid formed by esterification with a vinyl polymer component obtained by polymerizing a monomer component having a carboxylic acid group such as There are those formed by polymerizing vinyl monomers in the presence of components.

  The hybrid resin can be obtained by containing a monomer component capable of reacting with both resin components in the vinyl copolymer unit and / or the polyester resin component and reacting them. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer unit include, for example, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl copolymer unit, those capable of reacting with the polyester component include those having a carboxyl group or a hydroxy group, and (meth) acrylic acid or (meth) acrylic acid esters.

  As a manufacturing method which can prepare the hybrid resin used by this invention, the manufacturing method shown to the following (1)-(6) can be mentioned, for example.

  (1) The hybrid resin component is manufactured separately from the vinyl copolymer unit and the polyester unit, dissolved and swollen in a small amount of an organic solvent, added with an esterification catalyst and alcohol, and heated to effect transesterification. In this way, a hybrid resin having a polyester unit and a vinyl copolymer unit can be obtained.

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

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

  (4) After producing the vinyl copolymer unit and the polyester unit, a hybrid resin is produced by adding a vinyl monomer and / or a 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 vinyl copolymer unit, a polyester unit, and a polyester unit are mixed with a vinyl monomer by mixing an vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) A hybrid resin having a coalescing unit is produced. Furthermore, an organic solvent can be used as appropriate.

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

  The production method particularly preferably used in the present invention includes (3). Among them, an unsaturated polyester resin in which a monomer having an unsaturated group is bonded to a molecular terminal capable of reacting with a vinyl monomer is used as a vinyl monomer. Those obtained by dissolving and polymerizing a mixture of this polyester resin and vinyl monomer by a bulk polymerization method are preferred.

  Bulk polymerization is preferable in the present invention because the molecular weight of the vinyl copolymer unit can be increased, so that the main peak molecular weight of the vinyl copolymer unit contained in the gel component can be increased. Used.

  The bulk polymerization method does not require a step such as evaporation of the solvent as compared with the solution polymerization method, so that a binder resin can be obtained at a low cost. Also, compared with the suspension polymerization method, a dispersant or the like can be obtained. Since it does not contain impurities, it has a great merit as a binder resin for toners, such as being able to obtain excellent developability with little influence on the chargeability of the toner, etc., which is preferable.

  In particular, the binder resin used in the present invention is a vinyl monomer in the presence of an unsaturated polyester resin, unsaturated polyester resin: vinyl monomer = 50: 50 to 90:10 (preferably 60:40 to 80:20). It is preferable to contain a hybrid resin component obtained by bulk polymerization at a mass ratio of When the mass ratio of the unsaturated polyester resin is less than 50:50, the fixability tends to be deteriorated, and when it is more than 90:10, the high temperature offset resistance tends to be deteriorated.

  The unsaturated polyester resin component 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 3,000 to 20,000) in the GPC molecular weight distribution of THF soluble matter. More preferably, a low molecular weight unsaturated polyester resin component having a main peak in the range of 5,000 to 10,000) is preferably used, and further, a linear low molecular weight unsaturated polyester resin component containing no gel component is used. Particularly preferred. When the main peak molecular weight is less than 2,000, the developability tends to deteriorate, and when it exceeds 30,000, the fixability tends to deteriorate.

  Further, the unsaturated polyester resin component used in the present invention has a number average molecular weight (Mn) of 2,000 to 20,000, preferably 3,000 to 10,000. When the number average molecular weight (Mn) is less than 2,000, a gel component is hardly generated in the hybrid resin, and high temperature offset resistance and development durability are likely to deteriorate. If the number average molecular weight (Mn) is larger than 20,000, the solubility of the unsaturated polyester resin component in the vinyl monomer is lowered, and it becomes difficult to obtain a hybrid resin by bulk polymerization. The polymer unit may be separated or the chargeability of the toner may be deteriorated.

  The polyester resin component having an unsaturated group at the molecular end particularly preferably used in the present invention includes a monocarboxylic acid having an unsaturated group or a monoalcohol having an unsaturated group as a monomer, or a low molecular weight polyester. Examples include those obtained by capping the hydroxyl group at the molecular end of the resin component with an anhydride of a polyvalent carboxylic acid having an unsaturated group.

  In particular, those with molecular ends capped with polyhydric carboxylic acid anhydrides easily react with the hydroxyl groups present at the molecular ends of the polyester resin component even under conditions where esterification and transesterification reactions are unlikely to occur. A linear polyester having an unsaturated group is easily obtained, and is preferably used in the present invention.

  Specifically, after polymerizing a linear saturated polyester having a desired molecular weight, the temperature of the reaction vessel and the degree of pressure reduction are reduced to conditions where the esterification reaction or transesterification reaction is unlikely to occur. By adding and stirring an acid anhydride of a polyvalent carboxylic acid, the hydroxyl group and acid anhydride at the end of the saturated polyester molecule undergo a ring-opening reaction, and an unsaturated linear polyester resin having an unsaturated group at the molecule end can be obtained. .

  The unsaturated polyester resin component used in the present invention is a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), Mw / Mn is 1.0 to 5.0, preferably 1.0 to 3.0. Is preferable from the viewpoint of a sharp melt property at the time of fixing, since the molecular weight distribution is small. If Mw / Mn is greater than 5.0, the fixability tends to deteriorate.

  The unsaturated polyester resin component used in the present invention has an acid value of 0.1 to 50 mgKOH / g (preferably 1 to 30 mgKOH / g, more preferably 1 to 20 mgKOH / g, and still more preferably 1 to 10 mgKOH / g. ), A hydroxyl value of 10 to 60 mgKOH / g (preferably 20 to 60 mgKOH / g, more preferably 30 to 50 mgKOH / g) is preferable because the toner exhibits excellent chargeability. If the acid value or the hydroxyl value is smaller than this range, the chargeability of the toner becomes insufficient and the developability tends to deteriorate, and if it is larger than this range, the water adsorption property of the binder resin increases, As the charging is likely to be unstable, fog is deteriorated.

  By bulk polymerization of vinyl monomers in the presence of such unsaturated linear polyester resin components, a low molecular weight polyester unit is a vinyl with a high molecular weight and high linearity vinyl copolymer unit as the main chain. A hybrid resin component having a molecular structure branched from the system copolymer unit can be obtained. Furthermore, an acid group or a hydroxyl group in the hybrid resin having this branched structure forms an ester bond between molecules, thereby forming a gel component having a larger molecular structure.

  The gel component formed by the hybrid resin thus obtained has a large molecular weight between cross-linking points and is easily softened by heat. Further, since the molecular structure contains a large amount of polyester units, a low molecular weight polyester unit that is not hybridized can be incorporated in a large amount into the gel structure. As a result, even when a large amount of a low molecular weight polyester unit having a low softening point is added, the mechanical strength of the toner can be maintained, and both excellent fixing properties and development durability can be achieved. Further, the gel component thus obtained has a high linearity and a flexible molecular structure, so that it has a high shearing force, and it is difficult for the gel component to be cleaved in the kneading step of the toner. Therefore, it is possible to make the toner contain a constant gel component regardless of the kneading conditions, and it is possible to stably impart excellent high temperature offset resistance to the toner.

  The composition of the polyester resin used in the present invention is as follows.

  Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 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。）

(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 benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride or anhydrides thereof, lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. Dicarboxylic acids and derivatives thereof such as acids or anhydrides thereof, lower alkyl esters; alkenyl succinic acids or alkyl succinic acids such as n-dodecenyl succinic acid and n-dodecyl succinic acid, or anhydrides, lower alkyl esters thereof, and the like.

  In addition, as an acid component having an unsaturated group for obtaining an unsaturated polyester resin, monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Products, lower alkyl esters and the like, and unsaturated dicarboxylic anhydrides are particularly preferably used.

  These unsaturated carboxylic acids may be added at a ratio 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. preferable.

  When the unsaturated carboxylic acid is added in this range, the unsaturated group concentration in the low molecular weight polyester molecule is optimal. When the unsaturated carboxylic acid is less than 0.1 mol%, the polyester unit and the vinyl copolymer unit are hardly hybridized, and the effect of improving the fixing property and the developing property is hardly obtained. When the unsaturated carboxylic acid is more than 10 mol%, the number of unsaturated groups contained in one molecule of the polyester unit increases, so the vinyl resin that hybridizes with one molecule of the polyester unit increases, and the molecular weight between crosslinking points decreases. Gel component tends to be hard. As a result, the fixing property is deteriorated, or the gel component is sheared by kneading at the time of toner formation, and the high temperature offset resistance is deteriorated.

  Since the polyester used in the present invention is preferably a linear low molecular weight unsaturated polyester, it is preferable not to use a trivalent or higher alcohol component or a trivalent or higher acid component, but use a small amount as necessary. It is also possible to do.

  Examples of the trihydric or higher polyhydric alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butane. Triol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, etc. Is mentioned.

  Examples of the trivalent or higher polyvalent carboxylic acid component include 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, empol trimer acid, and their anhydrides, lower alkyl esters;

（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等、及びこれらの無水物、低級アルキルエステル等の多価カルボン酸類及びその誘導体が挙げられる。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 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.

  The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%, and the acid component is 60 to 40 mol%, preferably 55 to 45 mol%. The trivalent or higher polyvalent component is preferably 30 mol% or less of the total components.

  The polyester resin is usually obtained by a generally known condensation polymerization. The polymerization reaction of the polyester resin is usually carried out in the presence of a catalyst at a temperature of about 150 to 300 ° C., preferably about 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 10 mmHg. It is desirable to carry out the reaction under reduced pressure below.

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

  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, and tetraisopropyl titanate, dipotassium oxalate titanate, terephthalic acid titanate are particularly preferable. Potassium. 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 copolymer unit means a vinyl homopolymer or a vinyl copolymer.

  Examples of the monomer for obtaining the vinyl copolymer unit include the following.

  For example, 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 derivatives such as styrene; Ethylene 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; Acetic acid Vinyl esthetics such as vinyl, vinyl propionate and vinyl benzoate Class: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, Acrylic esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether Ter, vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N- such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone. Vinyl compounds; vinyl naphthalenes; acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. These vinyl monomers are used alone or in admixture of two or more monomers.

  Among these, a combination of monomers that becomes a styrene copolymer or a styrene acrylic copolymer is preferable.

  Furthermore, as a monomer for adjusting the acid value of the binder resin, for example, acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, and α- or β-alkyl derivatives thereof, fumaric acid, maleic acid, There are unsaturated dicarboxylic acids such as citraconic acid and their monoester derivatives or maleic anhydride, and such monomers are used alone or mixed to copolymerize with other monomers to produce the desired binder resin. Can do. 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, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate Monoesters of α, β-unsaturated dicarboxylic acids such as: monobutyl n-butenyl succinate, monomethyl n-octenyl succinate, monoethyl n-butenylmalonate, monomethyl n-dodecenyl glutarate, monobutyl n-butenyl adipate Monoesters of alkenyl dicarboxylic acids such as, and the like; monoesters of aromatic dicarboxylic acids such as phthalic acid monomethyl ester, phthalic acid monoethyl ester, phthalic acid monobutyl ester, and the like.

  What is necessary is just to add 0.1-30 mass% of the above carboxyl group containing monomers with respect to all the monomers which comprise the vinyl-type copolymer unit.

  Since the vinyl copolymer unit contained in the gel component of the present invention preferably has a high linearity, it preferably has no crosslinkable monomer, but in order to achieve the object of the present invention, It is also possible to add a crosslinkable monomer as exemplified in the above.

  As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); 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); di-linked by an alkyl chain containing an ether bond Acrylate 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 are replaced with methacrylate. Polyester type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)). Polyfunctional crosslinkers include pentaerythritol acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate. Alternatives: triallyl cyanurate, triallyl trimellitate and the like.

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

  In order to achieve the object of the present invention, the vinyl copolymer unit used for the preparation of the binder resin may be a polyfunctional polymerization initiator alone or a monofunctional polymerization initiator as exemplified below. It is preferable to produce.

  Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 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- (neodecanolperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di- (2-ethylhexanolperoxy) hexane, 2, 5-dimethyl-2,5-di- (m-toluolperoxy) 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-butylperoxycyclohexane Cyclododecane, 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-t-butylperoxycyclohexyl) propane, 2,2-t-butylperoxyoctane and various polymer oxides, and two or more peroxide groups in one molecule A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as diallyl peroxydicarbonate, t-butylperoxymaleic acid, t-butylperoxyallylcarbonate, t-butylperoxyisopropyl fumarate, etc. The polyfunctional polymerization initiator which has both the functional group which has polymerization initiation functions, such as a peroxide group, and a polymerizable unsaturated group in 1 molecule of these is mentioned.

  Of these, more preferred are 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 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, these polyfunctional polymerization initiators can be used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder for toner. In particular, it is preferable to use in combination with a polymerization initiator having a half-life of 10 hours lower than the decomposition temperature for obtaining a half-life of 10 hours of the polyfunctional polymerization initiator.

  Specifically, benzoyl peroxide, n-butyl-4,4-di (t-butylperoxy) valerate, dicumyl peroxide, α, α′-bis (t-butylperoxydiisopropyl) benzene, t- Examples thereof include organic peroxides such as butyl peroxycumene and di-t-butyl peroxide, and 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.

  The binder resin of the present invention is preferably obtained by a bulk polymerization method in which a vinyl monomer is polymerized without using a solvent or the like in the presence of the unsaturated polyester resin component 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% or more, and to increase the molecular weight of the vinyl copolymer unit produced by bulk polymerization. Furthermore, after the polymerization conversion rate reaches 60% (preferably 80%) or more, the polymerization reaction is preferably carried out 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 chargeability of the toner.

  Furthermore, the tetrahydrofuran insoluble content is preferably 3 to 50% by mass in order to improve the developability and high temperature offset resistance of the toner.

  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 toner fixability may be insufficient.

  The toner of the present invention may contain a wax.

  The waxes used in the present invention include the following. For example, 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 block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wax wax, jojoba wax; animal waxes such as beeswax, lanolin, spermaceti; mineral waxes such as ozokerite, ceresin, petrolatum; Waxes based on aliphatic esters such as montanic acid ester wax and caster wax; those obtained by partially or fully deoxidizing aliphatic esters such as deoxidized carnauba waxFurther, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinal acid; stearyl alcohol Saturated alcohol such as eicosyl alcohol, behenyl alcohol, cannavir alcohol, seryl alcohol, melyl alcohol, or alkyl alcohol having a long chain alkyl group; polyhydric alcohol such as sorbitol; linoleic acid amide, oleic acid amide, lauric acid Aliphatic amides such as acid amides; saturated aliphatic bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amides, ethylene bislauric acid amides, hexamethylene bisstearic acid amides; Unsaturated fatty acid amides such as inamide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, Aromatic bisamides such as N'-distearylisophthalamide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soap); aliphatic hydrocarbons Wax grafted with a vinyl monomer such as styrene or acrylic acid; Partial esterified product of fatty acid and polyhydric alcohol such as behenic acid monoglyceride; Hydroxyl group obtained by hydrogenating vegetable oil Methyl ester compounds It is.

  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 that can be used as a release agent include 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), Sazol 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) ), Wax, beeswax, rice wax, candelilla wax, carnauba wax (Serari Co., Ltd.) Available), and the like at the 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 may further contain a magnetic material and be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant.

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

  These magnetic materials have an average particle diameter of 2 μm or less, preferably 0.05 to 0.5 μm. The amount to be contained in the toner is about 20 to 200 parts by mass, 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 represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds, and the like are used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds, and the like 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 colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the 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.

  For example, an organic metal compound and a chelate compound are effective, and there are a monoazo metal compound, an acetylacetone metal compound, an aromatic hydroxycarboxylic acid, and an aromatic dicarboxylic acid metal compound. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol.

  Moreover, the azo metal compound represented by the following general formula (1) is preferable.

〔式中、Ｍは配位中心金属を表わし、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ等があげられる。Ａｒはアリール基であり、フェニル基、ナフチル基などがあげられ、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、ハロゲン基、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、アルコキシ基などがある。Ｘ，Ｘ’、Ｙ，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、それらの混合物或いはなしを示す。〕

[Wherein M represents a coordination center metal, and examples thereof include Sc, Ti, V, Cr, Co, Ni, Mn, and Fe. Ar is an aryl group, and examples thereof include a phenyl group and a naphthyl group, which may have a substituent. Examples of the substituent in this case include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and 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, a mixture thereof, or none. ]

  In particular, the central metal is preferably Fe or Cr, the substituent is preferably a halogen, an alkyl group, or an anilide group, and the counter ion is preferably a hydrogen ion, an alkali metal ammonium ion, or an aliphatic ammonium ion. A mixture of compounds having different counter ions is also preferably used.

  Alternatively, the basic organic acid metal compound represented by the following general formula (2) also gives negative chargeability and can be used in the present invention.

  In particular, the central metal is preferably Fe, Cr, Si, Zn, Zr, or Al, the substituent is preferably an alkyl group, anilide group, aryl group, or halogen, and the counter ion is preferably hydrogen, ammonium, or aliphatic ammonium.

  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.

  The following substances are used for controlling the toner to be positively charged. Modified products with nigrosine and fatty acid metal salts, etc .; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs such as oniums such as phosphonium salts Salts and their lake pigments, triphenylmethane dyes and their lake pigments (the rake agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, Russian compounds, metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyl Diorgano tin borate such as Suzuboreto; guanidine compounds, imidazole compounds. 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〕
で表わ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 homopolymer of a monomer represented by the following: 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 constitution 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 for negative charging are, for example, Spiron Black TRH, T-77, T-95 (Hodogaya Chemical), BONTRON (registered trademark) S-34, S-44, S-54, E-84, E- 88, E-89 (Orient Chemical Co., Ltd.), and preferable examples for positive charging include TP-302, TP-415 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) N-01, N- 04, N-07, P-51 (Orient Chemical), and 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 and a method of adding it externally. The amount of these charge control agents used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. 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 fluorine resin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fine powder silica such as wet process silica and dry process silica, and fine powder titanium oxide. , Fine powder alumina, fine powder treated with silane compound, titanium coupling agent, silicone oil; oxides such as zinc oxide and tin oxide; strontium titanate, barium titanate, calcium titanate, zircon Examples thereof include double oxides such as strontium acid 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 AEROSIL (Nippon Aerosil Co., Ltd.) 130, 200, 300, 380, TT600, MOX170, MOX80, COK84, Ca—O—SiL (CABOT CoL). Company) M-5, MS-7, MS-75, HS-5, EH-5, Wacker HDK N 20 (WACKER-CHEMIE GMBH) V15, N20E, T30, T40, DC Fine Silica (Dow Corning) Co.) and Fransol (Fransil) are commercially available, and these can also be used favorably in the present invention.

  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.

  As a hydrophobizing method, it is applied by 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, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethridimethylchlorosilane, α- Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyl Disiloxane, 1,3-divinyltetramethyldisiloxane, 1 , 3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used alone or as a mixture of two or more.

As the fluidity improver, those having a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more by nitrogen adsorption measured by the BET method, give good results. The total amount of the fluidity improver is 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the toner.

  The toner of the present invention can be used as a one-component developer by mixing with the fluidity improver and, if necessary, further mixing with other external additives (for example, a charge control agent). And can be used as a two-component developer. As the carrier for use in the two-component development method, 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 adhering or coating substances such as styrene resin, acrylic resin, silicone resin, fluorine resin, polyester resin on the surface of the carrier particles are preferably used.

  In order to produce the toner of the present invention, a mixture containing at least a binder resin and a colorant is used as a material, and a magnetic material, wax, a charge control agent, other additives, and the like are used as necessary. These materials are thoroughly mixed by a mixer such as a Henschel mixer or a ball mill, and then melted, kneaded and kneaded using a heat kneader such as a roll, a kneader and an extruder so that the resins are mutually compatible. In addition, a toner can be obtained by dispersing wax and magnetic material, cooling and solidifying, and then pulverizing and classifying.

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

  As a toner production apparatus, for example, as a mixer, Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); Super mixer (manufactured by Kawata Corporation); Ribocorn (manufactured by Okawara Seisakusho Co., Ltd.); A spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); a radige mixer (manufactured by Matsubo).

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

  Examples of the pulverizer include counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet pulverizer (manufactured by Nippon Pneumatic Industrial Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); (Nisso Engineering Co., Ltd.); SK Jet Oh Mill (Seishin Enterprise Co., Ltd.); Kryptron (Kawasaki Heavy Industries Co., Ltd.); Turbo Mill (Turbo Industry Co., Ltd.); Super Rotor (Nisshin Engineering Co., Ltd.) It is done.

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

  Examples of sieving devices used to screen coarse particles include Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokuju Kosakusha Co., Ltd.); Vibrasonic System (Dalton Co., Ltd.); Examples include a turbo screener (manufactured by Turbo Industry Co., Ltd.), a micro shifter (manufactured by Kanno Sangyo Co., Ltd.), and a 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 soluble in tetrahydrofuran (THF) The molecular weight of the 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 (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min. 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 , combination or 804,805,806,807,800P, Tosoh Corp. of _{TSKgel G1000H (H XL), G2000H} (H XL), G3000H (H XL), G4000H (H XL), G5000H (H XL), G6000H The combination of (H _XL ), G7000H (H _XL ), and TSKgourd column can be mentioned. Is preferred.

  On the other hand, the polyester unit contained in the tetrahydrofuran, insoluble matter of the toner, resin, or toner is hydrolyzed, and the vinyl copolymer unit obtained as a residue is dispersed and dissolved in tetrahydrofuran. The solution is filtered with a treatment filter (pore size 0.2 to 0.5 μm, such as Mysholy disk H-25-2 (manufactured by Tosoh Corporation)), and the filtrate is used as a sample. Measurement is performed by injecting 50 to 200 μl of a THF solution of the toner adjusted so that the resin component is 0.5 to 5 mg / ml as a sample concentration. 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) Tetrahydrofuran (THF) insoluble content A binder resin or toner is weighed and placed in a cylindrical filter paper (for example, No. 86R size 28 × 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 (THF) as a solvent. At this time, extraction is performed at a reflux rate such that the extraction cycle of THF is about once every 4 to 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.

When the toner contains a THF-insoluble component such as a magnetic substance or pigment other than the resin component, the mass of the toner put in the cylindrical filter paper is W ₁ g, and the mass of the extracted THF-soluble resin component is W ₂ When the weight of the THF-insoluble component other than the resin component contained in the toner is W ₃ g, the content of the THF-insoluble component of the resin component in the toner can be obtained from the following formula.
THF insoluble matter (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 0.1N 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 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 0.5-2.0 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 again heated in a glycerin bath for 10 minutes, allowed to cool, and then the funnel and the flask wall were washed with 5 ml of ethyl alcohol, and 0.5 mol / liter-water with a phenolphthalein solution as an indicator. Titrate with potassium oxide ethyl alcohol solution. 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: Hydroxyl value of resin B: Amount used of 0.5 mol / liter of potassium hydroxide ethyl alcohol solution in blank test (ml)
C: Amount used 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

  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)
The polyester monomer is mixed in the following ratio.
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.150 mol
・ Terephthalic acid 0.400 mol
・ Isophthalic acid 0.400 mol
・ Dodecenyl succinic anhydride 0.200 mol
After adding 0.1% by mass of tetrabutyl titanate as a catalyst to this and performing condensation polymerization at 220 ° C. to obtain a saturated linear polyester, the temperature was lowered to 180 ° C. and 0.03 mol of maleic anhydride was added. The hydroxyl group at the molecular end of the polyester was reacted with maleic anhydride.

  The unsaturated linear polyester resin P-1 having an unsaturated group at the molecular end obtained has a peak molecular weight = 7600, a number average molecular weight = 4600, Mw / Mn = 2.1, an acid value = 5 mgKOH / g, and a hydroxyl value. = 37 mg KOH / g.

(Hybrid resin production example 1)
Unsaturated linear polyester resin P-1: 75 parts by mass, vinyl monomer as styrene: 17 parts by mass, butyl acrylate: 6 parts by mass, monobutyl maleate: 2 parts by mass, 2,5-dimethyl as initiator -2,5-di (t-butylperoxy) hexyne-3 (10 hour half-life temperature 128 ° C): 0.08 parts by mass were mixed. This vinyl monomer / polyester resin mixture was bulk polymerized at 125 ° C. over 20 hours until the polymerization conversion of the vinyl monomer reached 96%, and then the temperature was raised to 150 ° C. and held for 5 hours to keep unreacted vinyl. The monomer was polymerized to obtain a hybrid resin. This is designated as binder resin 1. This resin had a main peak molecular weight of 7900, an acid value = 11 mgKOH / g, a hydroxyl value = 28 mgKOH / g, and 19% by mass of THF-insoluble matter in the GPC molecular weight distribution of THF-soluble matter.

(Hybrid resin production example 2)
Unsaturated linear polyester resin P-1: 75 parts by mass, vinyl monomer as styrene: 17 parts by mass, butyl acrylate: 6 parts by mass, monobutyl maleate: 2 parts by mass, 2,5-dimethyl as initiator -2,5-bis (t-butylperoxy) hexane (10 hour half-life temperature 118 ° C.): 0.08 part by mass was mixed. After bulk polymerization of this vinyl monomer / polyester resin mixture at 115 ° C. over 10 hours until the polymerization conversion of the vinyl monomer reaches 68%, the temperature is raised to 150 ° C. and held for 5 hours to leave unreacted vinyl Monomers were polymerized to obtain a hybrid resin. This is designated as binder resin 2. This resin had a main peak molecular weight of 7800, an acid value of 12 mgKOH / g, a hydroxyl value of 29 mgKOH / g, and 11% by mass of a THF-insoluble component in the GPC molecular weight distribution of the THF-soluble component.

(Hybrid resin production example 3)
Unsaturated linear polyester resin P-1: 70 parts by mass, as vinyl monomers, styrene: 21 parts by mass, butyl acrylate: 7.5 parts by mass, monobutyl maleate: 1.5 parts by mass, 2 as an initiator , 5-dimethyl-2,5-bis (t-butylperoxy) hexane (10 hour half-life temperature 118 ° C.): 0.10 parts by mass were mixed. After bulk polymerization of this vinyl monomer / polyester resin mixture at 115 ° C. over 10 hours until the polymerization conversion of the vinyl monomer reaches 74%, the temperature is raised to 125 ° C. and held for 10 hours to leave unreacted vinyl Monomers were polymerized to obtain a hybrid resin. This is designated as binder resin 3. This resin had a main peak molecular weight of 7900, an acid value = 16 mgKOH / g, a hydroxyl value = 24 mgKOH / g, and a THF-insoluble content of 27% by mass in the GPC molecular weight distribution of THF-soluble matter.

(Polyester resin production example 2)
The polyester monomer is mixed in the following ratio.
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.100 mol
・ Terephthalic acid 0.450 mol
・ Isophthalic acid 0.400 mol
・ Dodecenyl succinic anhydride 0.200 mol
After adding 0.1% by mass of tetrabutyl titanate as a catalyst and performing condensation polymerization at 220 ° C. to obtain a saturated linear polyester, the temperature was lowered to 180 ° C. and 0.05 mol of maleic anhydride was added. The hydroxyl group at the molecular end of the polyester was reacted with maleic anhydride.
The unsaturated linear polyester resin P-2 having an unsaturated group at the molecular end obtained has a peak molecular weight = 5400, a number average molecular weight = 2800, Mw / Mn = 3.4, an acid value = 14 mgKOH / g, and a hydroxyl value. = 46 mg KOH / g.

(Hybrid resin production example 4)
Unsaturated linear polyester resin P-2: 80 parts by mass, as vinyl monomer, styrene: 13 parts by mass, butyl acrylate: 6 parts by mass, monobutyl maleate: 1 part by mass, 2,5-dimethyl as an initiator -2,5-bis (t-butylperoxy) hexane (10 hour half-life temperature 118 ° C.): 0.08 part by mass was mixed. After bulk polymerization of this vinyl monomer / polyester resin mixture at 100 ° C. over 10 hours until the polymerization conversion of the vinyl monomer reaches 65%, the temperature is raised to 120 ° C. and held for 10 hours to leave unreacted vinyl Monomers were polymerized to obtain a hybrid resin. This is designated as binder resin 4. This resin had a main peak molecular weight of 5600, an acid value of 15 mgKOH / g, a hydroxyl value of 37 mgKOH / g, and a THF-insoluble content of 7% by mass in the GPC molecular weight distribution of THF-soluble matter.

(Polyester resin production example 3)
The polyester monomer is mixed in the following ratio.
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.050 mol
・ Terephthalic acid 0.400 mol
・ Isophthalic acid 0.395 mol
・ Dodecenyl succinic anhydride 0.200 mol
・ Fumaric acid 0.005 mol
After adding 0.1% by mass of tetrabutyl titanate as a catalyst to this and conducting condensation polymerization at 220 ° C. to obtain an unsaturated linear polyester, the temperature was lowered to 180 ° C. and 0.01 mol of maleic anhydride was added. Then, the hydroxyl group at the molecular end of the polyester was reacted with maleic anhydride.

  The unsaturated linear polyester resin P-3 having an unsaturated group at the molecular end obtained has a peak molecular weight = 13800, a number average molecular weight = 6400, Mw / Mn = 3.4, an acid value = 2 mgKOH / g, and a hydroxyl value. = 17 mg KOH / g.

(Hybrid resin production example 5)
Unsaturated linear polyester resin P-3: 85 parts by mass, vinyl monomer as styrene: 10 parts by mass, butyl acrylate: 4 parts by mass, monobutyl maleate: 1 part by mass, 2,5-dimethyl as initiator -2,5-bis (t-butylperoxy) hexane (10 hour half-life temperature 118 ° C): 0.02 parts by mass were mixed. After bulk polymerization of this vinyl monomer / polyester resin mixture at 100 ° C. over 10 hours until the polymerization conversion of the vinyl monomer reaches 55%, the temperature is raised to 120 ° C. and held for 20 hours to keep unreacted vinyl Monomers were polymerized to obtain a hybrid resin. This is designated as binder resin 5. This resin had a main peak molecular weight of 14200, an acid value of 3 mgKOH / g, a hydroxyl value of 13 mgKOH / g, and a THF insoluble content of 14% by mass in the GPC molecular weight distribution of THF-soluble matter.

(Polyester resin production example 4)
The polyester monomer is mixed in the following ratio.
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.150 mol
・ Terephthalic acid 0.400 mol
・ Isophthalic acid 0.395 mol
・ Dodecenyl succinic anhydride 0.200 mol
・ Acrylic acid 0.005mol
To these, 0.1% by mass of tetrabutyl titanate was added as a catalyst and subjected to condensation polymerization at 220 ° C. to obtain unsaturated linear polyester P-4 having an unsaturated group at the molecular end.

  The unsaturated linear polyester resin P-4 having an unsaturated group at the molecular end obtained has a peak molecular weight = 4400, a number average molecular weight = 2200, Mw / Mn = 3.4, an acid value = 25 mgKOH / g, and a hydroxyl value. = 68 mg KOH / g.

(Hybrid resin production example 6)
Unsaturated linear polyester resin P-4: 55 parts by mass, vinyl monomer as styrene: 29 parts by mass, butyl acrylate: 16 parts by mass, initiator as 2,5-dimethyl-2,5-bis (t -Butylperoxy) hexane (10-hour half-life temperature 118 degreeC): 0.05 mass part was mixed. After bulk polymerization of this vinyl monomer / polyester resin mixture at 100 ° C. over 10 hours until the polymerization conversion of the vinyl monomer reaches 55%, the temperature is raised to 120 ° C. and held for 20 hours to keep unreacted vinyl Monomers were polymerized to obtain a hybrid resin. This is designated as binder resin 6. This resin had a main peak molecular weight of 4500, an acid value of 13 mgKOH / g, a hydroxyl value of 36 mgKOH / g, and a THF-insoluble content of 16% by mass in the GPC molecular weight distribution of THF-soluble matter.

(Polyester resin production example 5)
The polyester monomer is mixed in the following ratio.
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.100 mol
・ Terephthalic acid 0.400 mol
・ Isophthalic acid 0.400 mol
・ Dodecenyl succinic anhydride 0.200 mol
To these, 0.1% by mass of tetrabutyl titanate was added as a catalyst and subjected to condensation polymerization at 220 ° C. to obtain a saturated linear polyester.

  The obtained saturated linear polyester resin P-5 had a peak molecular weight = 4100, a number average molecular weight = 1800, Mw / Mn = 1.8, an acid value = 15 mgKOH / g, and a hydroxyl value = 54 mgKOH / g.

(Comparative hybrid resin production example 1)
Saturated polyester resin P-5: 45 parts by weight, vinyl monomer as styrene: 39 parts by weight, butyl acrylate: 21 parts by weight, initiator as 2,5-dimethyl-2,5-bis (t-butyl par Oxy) hexyne-3: 0.15 parts by mass were mixed. After bulk polymerization of this vinyl monomer / polyester resin mixture at 120 ° C. over 15 hours until the polymerization conversion of the vinyl monomer reaches 77%, the temperature is further raised to 150 ° C. and held for 5 hours to leave unreacted vinyl. The system monomer was polymerized to obtain a comparative binder resin 1.

  This resin had a main peak molecular weight of 4100 in the GPC molecular weight distribution of THF-soluble matter, acid value = 7 mgKOH / g, hydroxyl value = 22 mgKOH / g, and did not contain THF-insoluble matter.

(Comparative hybrid resin production example 2)
As a vinyl monomer, 270 g of styrene, 60 g of 2-ethylhexyl acrylate, 20 g of acrylic acid, and 14 g of azobisisobutyronitrile as a polymerization initiator are placed in a dropping funnel.

  780 g (2.23 mol) of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 76 g (0.28 mol) of isododecenyl succinic anhydride, 180 g (1.09 mol) of terephthalic acid, 1, While putting 30 g (0.16 mol) of 2,4-benzenetricarboxylic acid and 2 g (8.0 mmol) of dibutyltin oxide into a flask and stirring at a temperature of 130 ° C., a vinyl monomer and a polymerization initiator were added from a dropping funnel for 3 hours. And the vinyl copolymer unit was polymerized. After aging for 5 hours while maintaining at 130 ° C., the temperature was raised to 220 ° C. to polymerize the polyester unit to obtain a hybrid resin. This is referred to as comparative binder resin 2. This resin had a main peak molecular weight of 5400 in the GPC molecular weight distribution of THF-soluble matter, acid value = 29 mgKOH / g, hydroxyl value = 72 mgKOH / g, and contained 24 mass% of THF-insoluble matter.

<Example 1>
Binder resin 1 100 parts by mass Magnetite (average particle size 0.18 μm) 100 parts by mass Illustrated monoazo iron compound (1) 2 parts by mass Fischer-Tropsch wax (DSC peak temperature 103 ° C.) 4 parts by mass After premixing with a Henschel mixer, the mixture was kneaded by a twin-screw kneading extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) set at 130 ° C. and 200 rpm. The obtained kneaded product is cooled and coarsely pulverized with a cutter mill, then finely pulverized using a pulverizer using a jet stream, classified using a multi-division classifier utilizing the Coanda effect, and the weight average diameter (D4 ) A negatively chargeable magnetic toner of 6.7 μm was obtained. Toner 1 was obtained by adding 1.2 parts by mass of negatively chargeable hydrophobic silica to 100 parts by mass of this toner with a Henschel mixer. Table 1 shows the physical properties of Toner 1. This toner was evaluated for the following items. The evaluation results are shown in Table 2.

[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 390 mm / sec. This external fixing device is temperature-controlled at a temperature of 140 to 220 ° C. every 5 ° C. and developed on plain paper (75 g / m ² ) paper (solid toner development amount on paper set to 0.6 mg / cm ² ) The fixed image is fixed, and the obtained image is rubbed and reciprocated 5 times with sylbon paper with a load of 4.9 kPa. The fixing temperature is the point at which the density reduction rate of the image density before and after the rubbing is 10% or less. did. The lower this temperature, the better the low-temperature fixability.

  For high-temperature offset resistance, the process speed is set to 120 mm / sec, the temperature is adjusted every 5 ° C. within the range of 200 to 240 ° C., the unfixed image is fixed, and the stain due to the offset phenomenon on the image is visually confirmed. The generated temperature was defined 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 60-sheet machine, and in a normal temperature and normal humidity (23 ° C., 60% RH) environment, an A4 size image area ratio was 2%. An image formation test was performed using A4 size 75 g / m ² transfer paper, and solid black image density and fog 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 by comparing 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.

[Preservation test]
10 g of toner was weighed into a polypropylene cup and the surface was flattened. Then, a medicine-wrapping paper was applied, 10 g of an iron powder carrier was placed on the paper, and left at 50 ° C. for 5 days to evaluate the toner blocking state.
A: When the cup is tilted, the toner flows more smoothly. B: When the cup is rotated, the toner surface gradually collapses and becomes a smooth powder.
C: When a force is applied from the outside while turning the cup, the toner surface collapses and gradually flows out.
D: A blocking sphere is generated. It collapses when pecked with a pointed object.
E: Blocking spheres are generated. Even if it sticks, it is hard to collapse.

<Examples 2 to 4, Reference Examples 1 to 2 and Comparative Examples 1 to 2>
Toners 2 to 8 were obtained in the same manner as in Example 1 except that binder resins 2 to 6 and comparative binder resins 1 and 2 were used instead of binder resin 1. Table 1 shows the physical properties of Toners 2-8. The test results are shown in Table 2.

Claims (4)

In a toner containing at least a binder resin and a colorant,
The binder resin is a polyester unit containing more than 50 wt%, and has contained hybrid resin,
The hybrid resin includes the unsaturated group of a polyester having an unsaturated group at a molecular end formed by a reaction of a hydroxyl group at the molecular end of a saturated polyester with an acid anhydride of a polycarboxylic acid having an unsaturated group , vinyl System unit is chemically bonded to the copolymer unit,
The toner contains 3 to 50% by mass of a resin component insoluble in tetrahydrofuran, the resin component insoluble in tetrahydrofuran contains a hybrid resin, and the polyester unit contained in the resin component insoluble in tetrahydrofuran is hydrolyzed. A toner which is decomposed and has a main peak in a molecular weight range of 10,000 to 500,000 in a GPC molecular weight distribution of a tetrahydrofuran soluble part of the residue.   In the GPC molecular weight distribution of the tetrahydrofuran-soluble content of the toner, a main peak exists in the molecular weight range of 2,000 to 30,000, and components in the molecular weight range of 40,000 to 1,000,000 are 3 to 30 area%. The toner according to claim 1, wherein the toner is contained. The hybrid resin contains a vinyl monomer in the presence of a polyester having an unsaturated group at the molecular end, and a polyester : vinyl monomer having an unsaturated group at the molecular end = 60: 40 to 80:20 in a mass ratio. the toner according to claim 1 or 2, characterized in the Turkey obtained by bulk polymerization.   The toner according to claim 3, wherein the vinyl monomer contains an unsaturated dicarboxylic acid and / or a derivative of an unsaturated dicarboxylic acid.