JP4773862B2 - 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, and thus excellent in high-temperature offset properties, but have low molecular weight in order to improve fixability. When the temperature is lowered or the glass transition temperature is lowered, the blocking property and the developing property 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 properties, it is essential to control the molecular weight distribution of the binder resin, and it is not sufficient to polymerize styrene acrylic monomers in the presence of polyester resin. It is.

  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.

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

  Patent Document 7 discloses a non-linear polyester having a weight average molecular weight (Mw) of 5,000 to 200,000 and a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 3 to 50; An electrophotographic toner binder obtained by reacting with a polymer 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. Thus, the binder resin is required to further improve developability, fixability and high temperature offset property, and development of a better binder resin is eagerly desired.

On the other hand, in order to further improve the fixability and releasability of toner, it has been proposed that the toner contains two types of wax components (for example, see Patent Documents 8 to 10).
However, although the range of low-temperature fixability and high-temperature offset resistance certainly increases with toners using these release agents, it is difficult to uniformly disperse each wax component in the toner. If the dispersibility of the wax is insufficient, the charge amount of the toner particles tends to be non-uniform, and tailing may be deteriorated.
From the viewpoint of improving the dispersibility of the wax, Patent Documents 11 and 12 disclose a toner using a polyester resin having a specific hydroxyl value and a release agent in a specific ratio. In addition, it has been proposed to improve the low-temperature fixability, fixing strength, and compatibility with the binder resin by providing a Fischer-Tropsch wax with a polar group or containing a predetermined alcohol wax (for example, Patent Document 13). To 15).
Although it is true that these toners are excellent in low-temperature fixability and offset resistance, there is a problem that the dispersibility of the wax is not sufficient particularly in toners that are becoming finer in recent years.
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 JP-A-8-278657 JP-A-8-334919 JP-A-8-334920 JP 2003-167377 A Japanese Patent Laid-Open No. 2003-162087 Japanese Patent Laid-Open No. 9-179342 JP 2000-338707 A JP 2004-029160 A

  An object of the present invention is to provide a toner that is excellent in fixing property, high temperature offset property and blocking property, is excellent in developability, and does not cause tailing.

  The present invention is a toner containing at least a binder resin, a wax, and a colorant, wherein the binder resin contains 50 to 95% by mass of a polyester-based resin component with respect to the total amount of the binder resin. The resin contains a hybrid resin in which a vinyl resin component and a vinyl resin component are chemically bonded, and the toner contains 3 to 50% by mass of tetrahydrofuran (THF) insoluble matter derived from a binder resin, And a wax having a hydroxyl value (WHv) of 5 to 150 mgKOH / g, the THF-insoluble matter contains a hybrid resin, and the vinyl-based resin contained in the residue when the THF-insoluble matter is hydrolyzed The present invention relates to a toner wherein the component has a main peak in the molecular weight range of 50,000 to 500,000.

  According to the present invention, it is possible to obtain a toner that is excellent in fixing property, high-temperature offset property and blocking property, is excellent in developability, and does not cause tailing.

  The present inventors use a hybrid resin in which a polyester resin component and a vinyl resin component as described above are combined, and the molecular weight of the vinyl resin component contained in the residue when hydrolyzing tetrahydrofuran-insoluble matter (gel component). By controlling the distribution, the present inventors have found a configuration capable of satisfactorily exhibiting the excellent performance of both the fixing property of the polyester resin component and the high temperature offset resistance of the vinyl resin component.

  The binder resin contained in the toner used in the present invention needs to contain at least a polyester-based resin component in an amount of 50 to 95% by mass with respect to the total amount of the binder resin in order to ensure good fixability. When the content of the polyester-based resin component is less than 50% by mass with respect to the total amount of the binder resin, sufficient fixability cannot be obtained. When the content of the polyester resin component is more than 95% by mass with respect to the total amount of the binder resin, the high temperature offset property cannot be satisfied. The content of the polyester-based resin component in the present invention is a combination of the polyester-based resin component present in the polyester resin or the hybrid resin.

  In addition, 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 tetrahydrofuran-insoluble component (gel component) derived from the binder resin. The gel component contains a hybrid resin which is a reaction product of a polyester resin component and a vinyl resin component. If the tetrahydrofuran insoluble content is less than 3% by mass, the high temperature offset cannot be satisfied. When the tetrahydrofuran insoluble content is more than 50% by mass, it becomes difficult to uniformly disperse a material such as a colorant in the toner, the chargeability of the toner deteriorates, and fogging and image density decrease occur.

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

  In particular, the inclusion of a hybrid resin in the tetrahydrofuran-insoluble component (gel component) makes it easier for the wax to be present in the vicinity of the gel component in the toner. The sharp melt property of the toner is increased, and the fixing property 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. Stability is improved, and developability and image quality are improved.

  Further, the polyester resin component contained in the tetrahydrofuran insoluble component derived from the binder resin is hydrolyzed, and the THF soluble component of the vinyl resin component obtained as a residue has a molecular weight of 50,000 to 500,000 (preferably 50,000). To 300,000, more preferably 50,000 to 200,000), the polyester resin component is hybridized to the vinyl resin component having a high molecular weight, resulting in a large molecular weight and a molecular weight between cross-linking points. It is possible to obtain a large gel structure.

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

  When the polyester resin component contained in the tetrahydrofuran-insoluble component derived from the binder resin is hydrolyzed and the main peak molecular weight of the THF-soluble component of the vinyl resin component obtained as a residue is less than 50,000, the gel component is It tends to become hard and the fixability deteriorates. 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 to toner, and the high temperature offset property is deteriorated. When the main peak molecular weight is larger than 500,000, it becomes difficult to uniformly disperse the gel component in the toner, and developability deteriorates.

  The molecular weight distribution of the THF-soluble component of the vinyl resin component obtained by hydrolyzing the polyester resin component contained in the tetrahydrofuran-insoluble component derived from the binder resin can be measured by the following procedure.

  First, the tetrahydrofuran-insoluble matter derived from the binder resin is taken out from the toner, and the tetrahydrofuran-insoluble matter is heated in an alkaline aqueous solution to hydrolyze and remove the polyester resin component. Since the vinyl resin component remains as a resin component without being hydrolyzed, the residue is extracted with THF 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.
When the toner is a magnetic toner containing a magnetic material, 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 and the magnetic material is precipitated and fixed on the bottom of the beaker. Let 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-based resin component by hydrolysis The tetrahydrofuran-insoluble matter derived from the resulting binder resin was dispersed in a 2 mol NaOH aqueous solution at a concentration of 1% by mass, and the polyester was obtained under the conditions of a pressure vessel, 150 ° C. and 24 hours. Hydrolyzes the resin component. The vinyl resin component is separated from this hydrolyzed solution by the following procedure.
i) The hydrolyzate was suction filtered using a membrane filter to separate the vinyl resin component as a residue. Thereby, the monomer component which is a decomposition product of the polyester resin component is removed in the filtrate.
ii) Since the vinyl resin component as a residue is a sodium salt due to hydrolysis of the acrylic acid ester component contained in the vinyl resin component, the residue is dispersed in water, and hydrochloric acid is added to adjust the pH. The COO group produced by hydrolysis of the acrylic ester component contained in the vinyl resin component was protonated, and then filtered and separated with a membrane filter.
(3) GPC measurement of vinyl resin component The vinyl resin component 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 main peak in the molecular weight distribution 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 THF soluble content of the toner. And containing 3 to 30 area% (preferably 5 to 25 area%, more preferably 5 to 20 area%) of a component having a molecular weight in the range of 40,000 to 1,000,000. In the molecular weight distribution of the THF soluble matter 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 property and the high temperature offset property.

  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 of 2,000 to 30,000 into the crosslinked structure, so that the gel component is melted by heat. It becomes easy and fixing property improves. Moreover, since the high molecular weight component having a molecular weight in the 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 property 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 ultrafine 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 storability and developability of the toner tend to deteriorate, and when it exceeds 30,000, the fixability tends to deteriorate.

  When the component having a molecular weight in the 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 ultrafine powder and coarse powder are liable to be generated during pulverization, and the development durability is liable to deteriorate. . If 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 resin component and a vinyl polymer component obtained by polymerizing a monomer component having a carboxylic acid ester group such as (meth) acrylic acid ester, and a polyester resin component and (meth). Unsaturation produced by esterification reaction with a vinyl polymer component obtained by polymerizing a monomer component having a carboxylic acid group such as acrylic acid, or a monomer having an unsaturated group such as fumaric acid There are those formed by polymerizing vinyl monomers in the presence of a polyester resin component.

  The hybrid resin can be obtained by containing a monomer component capable of reacting with both resin components in a vinyl resin component and / or a polyester resin component and reacting them. Among the monomers constituting the polyester resin component, those capable of reacting with the vinyl resin component include, for example, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl resin component, those capable of reacting with the polyester resin 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)-(5) can be mentioned, for example.

(1) The hybrid resin component is manufactured separately from the vinyl resin component and the polyester resin component, dissolved and swollen in a small amount of an organic solvent, added with an esterification catalyst and alcohol, and heated to perform a transesterification reaction. Thus, a hybrid resin having a polyester resin component and a vinyl resin component can be obtained.
(2) A method of producing a hybrid resin having a polyester resin component and a vinyl resin component by reacting the polyester resin component in the presence of the vinyl resin component after the production. The hybrid resin is produced by a reaction between a vinyl resin component (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, carboxylic acid) and / or a polyester resin component. Also in this case, an organic solvent can be appropriately used.
(3) A method of producing a hybrid resin by producing a vinyl resin component in the presence of the polyester resin component after production and reacting the polyester resin component with the vinyl resin component. The hybrid resin is produced by a reaction between a polyester resin component (a polyester monomer can be added if necessary) and a vinyl monomer and / or a vinyl resin component.
(4) After the vinyl resin component and the polyester resin component are produced, 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) Vinyl resin component, polyester resin component, polyester resin component and vinyl resin component by mixing vinyl monomer and polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction Is produced. Furthermore, an organic solvent can be used as appropriate.

  In the production methods (1) to (5) above, a vinyl resin component and / or a polyester resin component can use polymer components having a plurality of 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 capable of reacting with a vinyl monomer is dissolved in the vinyl monomer, and a mixture of the polyester resin and the vinyl monomer is prepared. Those obtained by polymerization by a bulk polymerization method are preferred.

  In the bulk polymerization method, since the molecular weight of the vinyl resin component can be increased, the main peak molecular weight of the vinyl resin component contained in the gel component can be increased. Therefore, it is preferably used in the present invention. .

In the bulk polymerization method, a binder resin can be obtained at a low cost because steps such as evaporation of the solvent are not required as compared with the solution polymerization method. Also, compared with the suspension polymerization method, the bulk polymerization method is used. The produced toner does not contain impurities such as a dispersant, and has an excellent developability with little influence on the chargeability of the toner, so that it has a great merit as a method for producing a binder resin for toner and 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 95: 5 (preferably 60:40 to 80:20). It is preferable to contain a hybrid resin component obtained by bulk polymerization at a mass ratio of If the mass ratio of the unsaturated polyester resin is less than 50:50, the fixability tends to deteriorate, and if it exceeds 95: 5, the high temperature offset property tends to deteriorate.

  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, more preferably, in the GPC molecular weight distribution of THF soluble matter). 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 a linear unsaturated polyester resin component containing no gel component is particularly preferable. 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 property and development durability are likely to deteriorate. If the number average molecular weight (Mn) is greater than 20,000, the solubility of the unsaturated polyester resin component in the vinyl monomer is lowered, making it difficult to obtain a hybrid resin by bulk polymerization, and the polyester resin component and the vinyl resin The resin component may be separated or the chargeability of the toner may be deteriorated.

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 30 mgKOH / g (preferably 1 to 20 mgKOH / g, more preferably 1 to 10 mgKOH / g), and a hydroxyl value of 10 to 60 mgKOH / g. g
In the case of (preferably 20 to 60 mg KOH / g, more preferably 30 to 50 mg KOH / g), it 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, low molecular weight polyester resin components are vinyl-based with a vinyl resin component having a large molecular weight and high linearity as the main chain. A hybrid resin component having a molecular structure branched from the resin component can be obtained. Furthermore, the acid group and the hydroxyl group in the hybrid resin having this branched structure form an ester bond between molecules to form a gel component.

Since the gel component formed by the hybrid resin thus obtained has a large molecular weight between cross-linking points, it is easily softened by heat. Further, since the molecular structure contains a large amount of the polyester resin component, a low molecular weight polyester resin component that is not hybridized can be incorporated in a large amount into the gel structure. As a result, even if a large amount of a low molecular weight polyester resin component having a low softening point is added, the mechanical strength of the toner can be maintained, and both excellent fixability and development durability can be achieved. Become. Furthermore, a gel component having a large molecular weight between cross-linking points and a high linearity has a high molecular structure and is strong in shearing force, so that the gel component is less likely to be cut in the kneading step of toner formation. Therefore, it is possible to contain a constant gel component in the toner regardless of the kneading conditions, and excellent high temperature offset property can be stably given 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, Examples include 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol represented by the following formula (A) and derivatives thereof.

(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.)

  Moreover, the diol shown by the following (B) formula is mentioned.

  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.

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

These unsaturated dicarboxylic 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 dicarboxylic acid is added in this range, the unsaturated group concentration in the low molecular weight polyester molecule is optimal. When the amount of unsaturated dicarboxylic acid is less than 0.1 mol%, the polyester resin component and the vinyl resin component are not easily hybridized, and the effect of improving the fixability and developability is hardly obtained. When the amount of unsaturated dicarboxylic acid is more than 10 mol%, the number of unsaturated groups contained in one molecule of the polyester resin increases, so the vinyl resin that hybridizes with one molecule of the polyester resin increases, and the molecular weight between crosslinking points decreases. Gel component tends to be hard. As a result, the fixability is deteriorated, or the gel component is sheared by kneading at the time of toner formation and the high temperature offset property is deteriorated.

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

  Examples of the trihydric or higher polyhydric alcohol component include 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, emporic trimer acid, and anhydrides thereof, and lower alkyl esters, for example, tetracarboxylic acid represented by the following formula and the like, and anhydrides thereof: Examples thereof include polyvalent carboxylic acids such as lower alkyl esters and derivatives thereof. Of these, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, anhydrides thereof, and lower alkyl esters are preferable.

(In the formula, 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.)

  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%. Moreover, it is preferable that the polyvalent component more than trivalence is 0.1-60 mol% in all the components.

  The polyester resin is usually obtained by commonly 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 tetrabutylisopropyl titanate, dipotassium oxalate titanate, titanium terephthalate are particularly preferable. Examples include potassium acid. 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 resin component means a vinyl homopolymer or a vinyl copolymer.

Examples of the monomer for obtaining the vinyl resin component 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.

  The carboxyl group-containing monomer as described above is preferably added in an amount of 0.1 to 30% by mass (more preferably 0.5 to 10% by mass) with respect to all monomers constituting the vinyl resin component. By adding a monomer having an acid value, the molecular structure of the gel component in the toner can have an appropriate acid value. If the gel component does not have a polar group, it becomes difficult to control the dispersion state of the wax, and the chargeability of the toner is deteriorated, and problems such as developability are likely to occur. In this way, by adding an acid value to the molecular structure of the gel component, it becomes easier to finely disperse the wax component in the toner, which is difficult to control the dispersion state, in the vicinity of the gel component, and the toner has a stable chargeability. Can be provided.

  Since the vinyl resin component contained in the gel component of the present invention preferably has a high linearity, it preferably contains no crosslinkable monomer, but in order to achieve the object of the present invention, the following examples are given. It is also possible to add such a crosslinkable monomer.

  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.

  The crosslinking agent is 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 resin component used in the preparation of the binder resin may be a polyfunctional polymerization initiator as exemplified below alone or in combination with a monofunctional polymerization initiator. It is preferable to produce them.

  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 the polyfunctional polymerization initiators, 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 polymerization initiators are preferably used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer in terms 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 resin for toner.

  In particular, the polyfunctional polymerization initiator is preferably used in combination with a polymerization initiator having a decomposition temperature for obtaining a half-life of 10 hours, which is lower than the decomposition temperature for obtaining a half-life of 10 hours.

  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 monofunctional polymerization initiators such as azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

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

  As the binder resin of the present invention, it is preferable to obtain a hybrid resin by a bulk polymerization method in which a vinyl monomer is polymerized without using a solvent in the presence of the unsaturated polyester resin component as described above. Furthermore, it is preferable to add waxes in this step from the viewpoint of improving the dispersibility of the waxes. 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 resin component 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 preferably has a tetrahydrofuran (THF) insoluble content of 3 to 50% by mass based on the total amount of the toner in order to improve the developing property and high temperature offset property of the toner.
The content of insoluble content of tetrahydrofuran (THF) derived from the binder resin is the number of unsaturated groups of the unsaturated polyester resin, the polymerization initiator of the vinyl resin, the monomer having an acid value, the addition amount of the crosslinkable monomer, the hybrid resin It can be adjusted by the polymerization temperature at the time of polymerization.
In the present invention, the main peak molecular weight of the THF-soluble component of the vinyl resin component obtained as a residue by hydrolyzing the polyester resin component contained in the tetrahydrofuran-insoluble component derived from the binder resin is the above-mentioned mass In the polymerization method, the polymerization can be adjusted by the polymerization initiator of the vinyl resin, the monomer having an acid value, the addition amount of the crosslinkable monomer, the polymerization temperature during the hybrid resin polymerization, and the like.

  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 binder resin used in the present invention 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 The range of 5 to 60 mgKOH / g, more preferably 10 to 50 mgKOH / g) is preferable from the viewpoint of stabilizing the chargeability of the toner. In the toner of the present invention, by using the binder resin and the wax used in the present invention, it becomes possible to improve the dispersibility of the resin and the wax, and to adjust the speed of the wax exudation during fixing, Excellent low-temperature fixing and offset resistance. In order to achieve both the dispersibility and the adjustment of the wax exuding speed, the ranges of the acid value and the hydroxyl value of the binder resin and the wax are defined.

  The wax used in the present invention has a hydroxyl value of 5 to 150 mgKOH / g. The wax is not particularly limited as long as it is such a wax.

The wax used in the present invention preferably contains a hydrocarbon wax.
From the viewpoint that the hydrocarbon wax has a desired range in the relationship between the acid value and the hydroxyl value with the binder resin, and further has a desired range in the relationship between the hydroxyl value and the ester value of the hydrocarbon wax, the following It preferably includes a hydrocarbon molecular chain having a structure.

That is, the hydrocarbon wax can be represented by at least the following partial structural formula A or E.
It has a molecular chain having a structure of a secondary alcohol having a hydroxyl group on the secondary carbon, or a molecular chain having a structure of a primary alcohol having a hydroxyl group on the primary carbon. Alternatively, the hydrocarbon wax has a molecular chain having a carboxyl group on primary or secondary carbon, which can be represented by the following partial structural formula C or D.

  The following partial structural formulas A or E, or C or D may each have both in one hydrocarbon chain. Further, the hydrocarbon wax may have a molecular chain having an ester structure having an ester bond, which can be represented by the following partial structural formula B. More preferably, it is a hydrocarbon chain having a molecular chain having an alcohol structure represented by the following partial structural formulas A to E, C to D, and B, a carboxyl group, and an ester bond.

  The hydrocarbon wax may have a structure of any of the following partial structural formulas A, C, D, and E in one hydrocarbon chain. Furthermore, you may have the structure of the following partial structural formula B.

  The hydrocarbon wax used in the present invention is preferably an aliphatic hydrocarbon wax because of its influence on the dispersibility in the toner particles and the chargeability of the toner. In particular, a hydrocarbon wax having a hydroxyl group is preferred.

  A series of steps for producing a hydrocarbon wax having a hydroxyl group from an aliphatic hydrocarbon wax is referred to as alcohol conversion. The alcohol conversion can include various process groups. For example, a boric acid ester of the hydrocarbon wax is produced from a hydrocarbon wax, and the boric acid ester of the hydrocarbon wax is hydrolyzed. And a method of producing a hydrocarbon wax having a hydroxyl group. It is preferable to obtain a hydrocarbon wax having desired characteristics by utilizing an alcohol conversion step because the conversion of acid groups, hydroxyl groups and ester groups of the hydrocarbon wax can be easily controlled.

As an example of production of a hydrocarbon wax having a hydroxyl group from an aliphatic hydrocarbon wax, a hydrocarbon wax is subjected to liquid phase oxidation with a molecular oxygen-containing gas in the presence of boric acid and boric anhydride. The method obtained is mentioned. A mixture of boric acid and boric anhydride can be used as the catalyst. The mixing ratio of boric acid and boric anhydride (boric acid / boric anhydride) is mo
The ratio is 1.0 to 2.0, preferably 1.2 to 1.7. When the proportion of boric anhydride is less than the above range, an excess of boric acid is not preferable because it causes an aggregation phenomenon. On the other hand, if the proportion of boric anhydride is more than the above range, the powder substance derived from boric anhydride is recovered after the reaction, and excess boric anhydride does not contribute to the reaction, which is not preferable from an economical viewpoint.

  The addition amount of boric acid and boric anhydride used is preferably 0.001 to 10 mol, particularly preferably 0.1 to 1.0 mol with respect to 1 mol of the aliphatic hydrocarbon as a raw material when the mixture is converted to boric acid. .

  As the molecular oxygen-containing gas blown into the reaction system, oxygen, air, or a wide range of those diluted with an inert gas can be used, but the oxygen concentration is preferably 1 to 30% by volume, more preferably. Is 3-20% by volume.

  The liquid phase oxidation reaction is usually carried out in the molten state of the starting aliphatic hydrocarbon without using a solvent. The reaction temperature is 120 to 280 ° C, preferably 150 to 250 ° C. The reaction time is preferably 1 to 15 hours. It is preferable that boric acid and boric anhydride are mixed in advance and added to the reaction system. If only boric acid is added alone, a dehydration reaction of boric acid or the like occurs, which is not preferable. Further, the addition temperature of the mixed solvent of boric acid and boric anhydride is preferably 100 ° C. to 180 ° C., preferably 110 ° C. to 160 ° C. When the temperature is lower than 100 ° C., it is caused by moisture remaining in the system. This is not preferable because the catalytic function of boric anhydride is lowered.

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

  The hydroxyl value (WOHv) of the hydrocarbon wax used in the present invention is 5 to 150 mgKOH / g (preferably 10 to 100 mgKOH / g, more preferably 30 to 80 mgKOH / g).

  By having an appropriate hydroxyl group in the molecule of the hydrocarbon-based wax, the hydrocarbon-based wax can be dispersed in fine particles in the binder resin, so that an appropriate plastic effect is obtained and fixing properties are improved. When the hydroxyl value of the hydrocarbon wax is less than 5 mgKOH / g, the hydrocarbon wax is not sufficiently finely dispersed, and the toner fixability may be lowered. On the other hand, if the hydroxyl value of the hydrocarbon wax is larger than 150 mgKOH / g, the plasticizing effect of the hydrocarbon wax becomes too large, and the toner blocking resistance may be lowered.

The ester value (WEv) of the hydrocarbon wax used in the present invention is preferably 1 to 50 mgKOH / g, and more preferably 5 to 20 mgKOH / g. The hydrocarbon wax preferably further satisfies the following formula (1) in terms of the relationship between the hydroxyl value and the ester value.
[Equation 1]
WHv> WEv (1)

  If the ester value of the hydrocarbon wax is less than 1 mg KOH / g, the effect of the hydrocarbon wax on the toner fixability may be reduced. If the ester value of the hydrocarbon wax is larger than 50 mgKOH / g, the affinity of the hydrocarbon wax to the binder resin becomes too high, and the binder resin is likely to deteriorate. It may become inferior.

If the ester value of the hydrocarbon wax is greater than the hydroxyl value, the affinity between the hydrocarbon wax and the binder resin is increased, making it difficult for the hydrocarbon wax to permeate the surface of the toner particles. The offset resistance may be affected.

  The acid value (WAv) of the wax used in the present invention is preferably 1 to 30 mgKOH / g (preferably 1 to 15 mgKOH / g, more preferably 1 to 10 mgKOH / g).

Since the hydrocarbon wax has an acid group, the interfacial adhesive force with other components constituting the toner particles is increased, and the effect of the hydrocarbon wax in plasticizing the toner is increased, so that the toner is fixed. Improves. If the acid value of the hydrocarbon wax is less than 1 mg KOH / g, the interfacial adhesive force with other components constituting the toner particles becomes small, the hydrocarbon wax is easily released, and the action of the hydrocarbon wax is sufficient. May not be obtained. On the other hand, if the acid value of the hydrocarbon wax is greater than 30 mgKOH / g, the interfacial adhesive force is excessively increased, and the toner is plasticized so that sufficient release properties may not be maintained. In the hydrocarbon wax, it is preferable that the relationship between the acid value (WAv) and the hydroxyl value (WHv) satisfies the following formula (2).
[Equation 2]
WHv> WAv (2)

  If the acid value of the hydrocarbon wax is higher than the hydroxyl value, the affinity between the hydrocarbon wax and the binder resin will be high, the compatibility between the hydrocarbon wax and the toner particles will be too high, and the release property of the wax will be high. It will be damaged.

  The acid value, hydroxyl value, and ester value of the hydrocarbon wax can be measured by the methods described later. The acid value, hydroxyl value, and ester value of the hydrocarbon wax are, for example, a step of producing a boric acid ester of a hydrocarbon wax from an aliphatic hydrocarbon wax and hydrolyzing the boric acid ester of the hydrocarbon wax. In addition, it is possible to adjust by the addition amount or addition ratio of the boric acid and boric anhydride added as a catalyst, reaction temperature, and reaction time. In particular, the ratio between the hydroxyl value and the ester value can be adjusted by adjusting the conversion rate according to the reaction temperature and the reaction time in each reaction step of the esterification reaction and the hydrolysis reaction.

  As the hydrocarbon wax, the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 100 to 3,000, more preferably 200 to 2,000, still more preferably 250 to 1, in terms of polyethylene. Saturated or unsaturated aliphatic hydrocarbons in the range of 1,000 are preferably used.

  If the number average molecular weight of the hydrocarbon wax is less than 100, it is likely to be excessively affected by heat, resulting in poor blocking resistance and developability. If the number average molecular weight of the hydrocarbon wax is greater than 3,000, heat from the outside cannot be used effectively, and excellent fixability may not be obtained. The number average molecular weight of the hydrocarbon wax can be measured by the method described later.

  The number average molecular weight of the hydrocarbon wax is adjusted, for example, by adjusting the type of the aliphatic hydrocarbon wax used as a raw material for the hydrocarbon wax and the number average molecular weight associated with the production process such as synthesis, pyrolysis, and petroleum extraction. It is possible. Further, as a method for adjusting the acid value, the hydroxyl value, and the ester value, a boric acid ester of a hydrocarbon wax is generated from the aliphatic hydrocarbon wax described above, and the boric acid ester of the hydrocarbon wax is hydrolyzed. In the process, the number average molecular weight also changes due to thermal decomposition. Therefore, the number average molecular weight can be adjusted by combining different types of hydrocarbon waxes.

  The melting point of the hydrocarbon wax is preferably 50 to 130 ° C, more preferably 50 ° C to 100 ° C, and still more preferably 60 ° C to 80 ° C.

  When the melting point of the hydrocarbon wax is less than 50 ° C., the blocking resistance and offset resistance of the toner are lowered, and the developer carrying member is likely to be contaminated. When the melting point is 130 ° C. or more, the toner fixing performance is adversely affected. May give.

  The melting point of the hydrocarbon wax can be measured by the method described later. In addition, the melting point of the hydrocarbon wax can be adjusted by, for example, reforming by the type of hydrocarbon wax or alcohol conversion.

  The penetration of the hydrocarbon wax at 25 ° C. is preferably 5 or more and 15 or less from the viewpoint of improving the charging performance of the toner and providing a stable image against environmental changes. From such a viewpoint, the penetration of the hydrocarbon wax is more preferably 5 or more and 9 or less.

  If the penetration of the hydrocarbon wax at 25 ° C. is less than 5, the compatibility with the binder resin is deteriorated, the dispersion of the wax in the toner particles is deteriorated, the chargeability is uneven, and the developability is improved. make worse. On the other hand, if the penetration is greater than 15, the storage stability (blocking resistance) of the toner at high temperatures may be reduced. In the present invention, the penetration of the hydrocarbon wax is determined according to “5.4 Penetration test method” of JIS K2235.

  The penetration can be adjusted, for example, by reforming by the type of hydrocarbon wax or alcohol conversion. Furthermore, in the manufacturing process of hydrocarbon wax, it is possible to adjust by adjusting the molecular weight, molecular weight distribution, and branching state of the hydrocarbon wax.

  The hydrocarbon wax has a heat absorption peak of the DSC curve of the toner measured by a differential scanning calorimeter (DSC), and the ΔH (J / g) corresponding to the heat of fusion of the hydrocarbon wax is 35 ° C. or more and 85 The ratio of the heat of fusion ΔHb of 35 ° C. or higher and 60 ° C. or lower to the heat of fusion ΔHa of 0 ° C. or lower is preferably 1% or higher and 20% or lower from the viewpoint of stability at high temperature and high humidity. From such a viewpoint, the ratio of ΔHb to ΔHa of the heat of fusion of the hydrocarbon wax is more preferably 5% or more and 20% or less.

  Of the heat of fusion of the hydrocarbon wax, the heat of fusion ΔHa between 35 ° C. and 85 ° C. corresponds to the heat of fusion of the entire hydrocarbon wax. Further, it is considered that the heat of fusion ΔHb of 35 ° C. or more and 60 ° C. or less corresponds to the heat of fusion of the low molecular weight low melting point component. Since the hydrocarbon wax used in the present invention has an appropriate hydroxyl group in the molecule, the hydrocarbon wax can be dispersed in fine particles in the binder resin, so that an appropriate plastic effect is obtained, Fixability is improved.

  However, if the ratio of ΔHb to ΔHa is less than 1%, the hydrocarbon wax may not be sufficiently finely dispersed in the toner, and the effect of improving the toner fixability may not be sufficiently obtained. On the other hand, if the ratio of ΔHb to ΔHa is greater than 20%, that is, if the amount of the low melting point component having a low molecular weight is too large, the plastic effect tends to be too large, and the blocking resistance of the toner tends to decrease.

The ratio of ΔHb to the heat of fusion ΔHa of the toner can be adjusted by adjusting the molecular weight distribution, for example, by removing low molecular weight components of the aliphatic hydrocarbon wax used as the raw material for the hydrocarbon wax. It can also be adjusted by adjusting the molecular weight distribution after an alcohol conversion step for producing a hydrocarbon wax having a hydroxyl group from an aliphatic hydrocarbon wax.

  The toner particles used in the present invention preferably contain one or more waxes selected from the following group in addition to the hydrocarbon wax. By including one or more waxes in the toner particles, it is possible to obtain a toner that is more excellent in the balance between low-temperature fixability and offset resistance.

Examples of the second type of wax used in the present invention include the following.
For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, paraffin wax, microcrystalline wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax, oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax, And alcohols obtained by hydrolyzing these oxides, or block copolymers of these oxides; plant waxes such as candelilla wax, carnauba wax, wood wax, rice wax, jojoba wax; beeswax, lanolin, whale wax Animal waxes such as mineral waxes such as ozokerite, ceresin and petrolatum; waxes based on fatty acid esters such as montanic acid esters and castor waxes; deacidified carnauba waxes Those deoxidizing a part or the whole of fatty acid esters. Furthermore, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, parinaric acid; stearyl alcohol Saturated alcohols such as eicosyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol, or long chain alkyl alcohols having a long chain alkyl group; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid Fatty acid amides such as amides and lauric acid amides; saturated fatty acid bisamides such as methylene bisstearic acid amides, ethylene biscapric acid amides, ethylene bislauric acid amides and hexamethylene bisstearic acid amides; Unsaturated fatty acid amides such as lenbis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; Aromatic bisamides such as N, N'-distearylisophthalamide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soap); aliphatic hydrocarbons Wax grafted with vinyl monomers such as styrene and acrylic acid; partially esterified products of aliphatic and polyhydric alcohols such as behenic acid monoglyceride; hydroxyl groups obtained by hydrogenating vegetable oils and fats Methyl esterification with Objects; and the like.

  The wax of the second type used in the present invention is preferably a hydrocarbon wax because of its influence on the dispersibility of the material of the toner particles in the toner particles and the chargeability of the toner. For example, low molecular weight polyolefin obtained by polymerizing paraffin wax, Fischer-Tropsch wax, olefin with radical polymerization under high pressure or Ziegler catalyst, metallocene catalyst under low pressure (for example, high molecular weight polyolefin with molecular weight of 5 to 500,000 is Heat-degraded polyolefin obtained by thermal decomposition (thermal degradation) at high temperature), polyolefin obtained by thermal decomposition (thermal degradation) of high-molecular-weight polyolefin at high temperature, synthesis gas composed of carbon monoxide and hydrogen A Fischer-Tropsch wax such as a synthetic hydrocarbon obtained from a distilled component of a hydrocarbon obtained by the age method or by hydrogenating these components can be used. An antioxidant may be added to the hydrocarbon wax.

Further, as the hydrocarbon wax used as the second type of wax, a product obtained by fractionating the hydrocarbon wax by using a press sweating method, a solvent method, vacuum distillation or a fractional crystallization method is preferably used. Hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) (even if the raw material is coal, it is natural gas) For example, the Jintole method, Hydrocol method (using a fluidized catalyst bed), or the Age method (using a fixed catalyst bed) in which a large amount of waxy hydrocarbons can be obtained up to about several hundred carbon atoms And hydrocarbons obtained by polymerizing olefins such as ethylene with a Ziegler catalyst or a metallocene catalyst, and are preferred because they are straight-chain hydrocarbons with little branching and long saturation.

  As the hydrocarbon wax used as the second type of wax, Fischer-Tropsch wax is particularly preferably used from the viewpoint of dispersibility in the toner particles and releasability.

  The addition amount of the wax in the present invention is preferably 1 to 15 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Even when two or more kinds of wax are included, any mixing ratio may be used as long as the total amount of the wax is within the above range, but the toner may contain a large amount of the hydrocarbon wax having a hydroxyl value of the present invention. preferable. Furthermore, it is more preferable from the viewpoint of the dispersibility of the wax to add two types of waxes during the binder resin polymerization. Regarding the amount of wax added at the time of polymerizing the binder resin, when adding the second type wax, the total amount of the second type wax is added, and the addition amount of the hydrocarbon wax having a hydroxyl value is the second type. It is even more preferable that the amount is less than that of the wax. When the addition amount of the hydrocarbon wax having a hydroxyl value is larger than the addition amount of the second type wax during the binder resin polymerization, the Tg of the binder resin is lowered and the developability is likely to be lowered. Become.

  When the amount of the wax added to 100 parts by mass of the binder resin is less than 1 part by mass, the fixability as a toner tends to be lowered, and when it exceeds 15 parts by mass, the offset resistance tends to be lowered.

The present invention includes an acid value (RAv) of the binder resin, an acid value (WAv) of the hydrocarbon wax, a hydroxyl value (WHv) of the hydrocarbon wax, and a hydroxyl value (RHv) of the binder resin. Are characterized by satisfying the following relationships.
[Equation 3]
0 <| RAv-WAv | ≦ 35 (3-1)
0 <| WHv-RHv | <90 (3-2)

  Since the acid value and hydroxyl value of the binder resin and the hydrocarbon wax are in the above relationship, the compatibility and the binding property of both are improved, and the hydrocarbon wax dispersed in the binder resin is improved. The dispersion diameter becomes an appropriate size, and the function can be sufficiently exhibited.

  If the relationship between the acid value and the hydroxyl value of the binder resin and the hydrocarbon wax is out of the above range, the dispersion diameter of the hydrocarbon wax in the binder resin is too small or too large. The function cannot be fully exerted, and the low-temperature fixability and offset resistance are affected.

  It is preferable that the acid values of the binder resin and the hydrocarbon wax have the above relationship from the viewpoint of appropriately adjusting the plasticization of the toner and exhibiting excellent low-temperature fixability and offset resistance. If the relationship between the acid values of the binder resin and the hydrocarbon wax deviates from the above relationship, the plasticization of the toner may be greatly advanced, and sufficient releasability may not be maintained.

Further, the hydroxyl value (RHv) of the binder resin and the hydroxyl value (WH) of the hydrocarbon-based wax.
The relationship with v) preferably satisfies the following formula.
[Equation 4]
RHv <WHv (4)

Furthermore, the relationship between the hydroxyl value (RHv) of the binder resin and the hydroxyl value (WHv) of the hydrocarbon wax preferably satisfies the following formula (5).
[Equation 5]
21 <(WHv−RHv) <80 (5)

  The hydroxyl value of the binder resin and the hydrocarbon wax satisfying the above relational expression means that the dispersion diameter of the hydrocarbon wax in the toner particles is adjusted to an appropriate size to obtain an appropriate plastic effect, and low temperature fixing. From the viewpoint of improving the property. Further, since the wax dispersion state can be improved, the above-described effects can be obtained without impairing the charging characteristics of the toner. If the relationship between the hydroxyl values deviates from the above relationship, the dispersion diameter of the hydrocarbon wax becomes too large, and the offset resistance may be deteriorated, and the charging characteristics of the toner may be significantly impaired. Sexuality may also deteriorate.

  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.

[Wherein M represents a coordination center metal, and examples thereof include Sc, Ti, V, Cr, Co, Ni, Mn, and Fe. Ar is an arylene group such as a phenylene group or a naphthylene 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.

  Next, specific examples of the above compounds are 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 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, a homopolymer of a monomer represented by the following general formula (4); 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).

[Wherein R ₁ represents H or CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably C _{1 to} C ₄ )]

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

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom which may be the same as or different from each other, 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 Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-5.
4, E-84, E-88, E-89 (Orient Chemical Co., Ltd.), and those preferable for positive charging are, for example, TP-302, TP-415 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark). Examples thereof include N-01, N-04, N-07, P-51 (Orient Chemical Co.), 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 use of these charge control agents 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 vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; wet powder silica, fine powder silica such as dry process silica, fine powder titanium oxide, fine powder Powdered alumina, fine powder with surface treatment with silane compound, titanium coupling agent, silicone oil; oxides such as zinc oxide and tin oxide; strontium titanate, barium titanate, calcium titanate, strontium zirconate, Examples thereof include double oxides such as 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.

  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 halide compound is more preferable. In the above treated silica fine powder, it is particularly preferable 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, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, 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.

The above fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 50 m ² / g or more, giving 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 above fluidity improver and further mixing with other external additives (for example, a charge control agent) if necessary. 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, a wax and a colorant is used as a material, and a magnetic substance, 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 physical properties of the wax and binder resin in the present invention can be measured by the following method.

(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 manufactured by Showa Denko KK
A combination of 802, 803, 804, 805, 806, 807, 800P, or TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (HXL), G5000H (HXL), G6000H (HXL) manufactured by Tosoh Corporation G7000H (HXL) and TSKgullcolumn can be mentioned, and a combination of seven columns of shodex KF-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko is particularly preferable.
The sample is prepared as follows. First, a sample is put in tetrahydrofuran and left for several hours, and then shaken sufficiently, mixed well with tetrahydrofuran (until the sample is no longer united), and further left to stand for 12 hours or more. At that time, the standing time in tetrahydrofuran is set to 24 hours or more. Thereafter, a sample processing filter (pore size 0.2 to 0.5 μm, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation) can be used) is passed. This is a GPC sample. Measurement is performed by injecting 50 to 200 μl of a tetrahydrofuran solution of the toner adjusted so that the resin concentration of the sample component is 0.5 to 5 mg / ml. An RI (refractive index) detector is used as the detector.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical
Co. Or the molecular weight of Toyo Soda Industry Co., Ltd. is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 It is suitable to use a standard polystyrene sample of at least about 10 points using 9.9 × 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 as a solvent. 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 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 tetrahydrofuran-insoluble component such as a magnetic substance or pigment other than the resin component, the weight of the toner put in the cylindrical filter paper is W1 g, and the extracted THF-soluble resin component is W2 g. When the mass of the tetrahydrofuran-insoluble component other than the resin component contained in the toner is W3 g, the content of the tetrahydrofuran-insoluble component of the resin component in the toner can be obtained from the following formula.
[Equation 6]
Tetrahydrofuran insoluble matter (mass%) = [{W1- (W3 + W2)} / (W1-W3)] × 100 (6)

(3) Measuring method of hydroxyl value of wax The measurement of the hydroxyl value of the wax in the present invention can be carried out as follows.
(Devices and instruments)
Measuring cylinder (100ml)
Full pipette (5ml)
Flat bottom flask (200ml)
Glycerin bath (reagent)
Acetylation reagent (25 g of acetic anhydride is taken into a 100-ml volumetric flask and pyridine is added to make a total volume of 100 ml, and shaken well.)
Phenolphthalein solution 0.5 kmol / m ³ Potassium hydroxide ethanol solution (Measurement method)
(A) A hydrocarbon wax is precisely weighed into a 0.5 to 6.0 g flat bottom flask, and 5 ml of an acetylating reagent is added to the flask using a pipette.
(B) Place a small funnel on the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at a temperature of 95-100 ° C. and heat. In order to prevent the temperature of the neck of the flask from rising due to the heat of the glycerin bath, a cardboard disc with a round hole in it is put on the base of the neck of the flask.
(C) After 1 hour, the flask is removed from the glycerin bath, allowed to cool, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride.
(D) Further, in order to complete the decomposition, the flask is heated again in a glycerin bath for 10 minutes, and after cooling, the funnel and the wall of the flask are washed with 5 ml of ethanol (95 vol%).
(E) A few drops of phenolphthalein solution is added as an indicator, and titrated with 0.5 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the indicator is light red for about 30 seconds.
(F) In the blank test, (a) to (e) are performed without adding the hydrocarbon wax (a).
(G) If the sample is difficult to dissolve, add a small amount of pyridine, or add xylene or toluene to dissolve.
(Calculation)
From the obtained results, the hydroxyl value of the hydrocarbon wax is determined by the following formula.
[Equation 7]
A = [{(BC) × 28.05 × f} / S] + D (7)
However,
A: Hydroxyl value of hydrocarbon wax (mgKOH / g)
B: Amount (ml) of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for the blank test
C: Amount of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml)
f: Factor of 0.5 kmol / m ³ potassium hydroxide ethanol solution S: Mass of hydrocarbon wax (g)
D: Acid value of hydrocarbon wax (mgKOH / g)
28.05: Formula weight of potassium hydroxide 56.11 × 1/2

(4) Measuring method of ester value of wax The ester value of the wax in the present invention can be calculated by the following formula using the saponification value as follows.
[Equation 8]
(Ester value of wax) = (Saponification value of wax) − (Acid value of wax) (8)
Measurement of saponification value (apparatus and instruments)
Erlenmeyer flask (200-300ml)
Air cooler (outer diameter 6-8mm, length 100cm glass tube or recirculating cooler, all of which can be connected to the mouth of the Erlenmeyer flask)
Water bath, sand bath or hot plate (can be adjusted to a temperature of about 80 ° C)
Burette (50ml)
Full pipette (25ml)
(reagent)
0.5 kmol / m ³ hydrochloric acid 0.5 kmol / m ³ potassium hydroxide ethanol solution phenolphthalein solution (measurement method)
(A) Hydrocarbon wax (a) 1.5-3.0 g is accurately weighed to an order of 1 mg in an Erlenmeyer flask.
(B) Add 25 ml of 0.5 kmol / m ³ potassium hydroxide ethanol solution using a pipette.
(C) Attach an air cooler to the Erlenmeyer flask and allow it to react by gently heating on a water bath, sand bath or hot plate for 30 minutes with occasional shaking. When heating, the heating temperature is adjusted so that the circulating ethanol ring does not reach the top of the air cooler.
(D) Immediately after the reaction is completed, the inner wall is washed by spraying a small amount of water or a mixed solution of xylene: ethanol = 1: 3 from the top of the air cooler before the contents are hardened into agar. After that, remove the air cooler.
(E) Add 1 ml of phenolphthalein solution as an indicator, titrate with 0.5 kmol / m ³ hydrochloric acid, and when the light red color of the indicator does not appear for about 1 minute, the end point is set.
(F) In the blank test, (a) to (e) are performed without adding the hydrocarbon wax (a).
(G) If the sample is difficult to dissolve, dissolve it in advance using xylene or a xylene-ethanol mixed solvent.
(Calculation)
The saponification value of the wax is calculated from the obtained result by the following formula.
[Equation 9]
A = {(BC) × 28.05 × f} / S (9)
However,
A: Saponification value of hydrocarbon wax (mgKOH / g)
B: Amount of 0.5 kmol / m ³ hydrochloric acid used for the blank test (ml)
C: Amount of 0.5 kmol / m ³ hydrochloric acid used for titration (ml)
f: Factor of 0.5 kmol / m ³ hydrochloric acid S: Mass (g) of hydrocarbon wax (a)
28.05: Formula weight of potassium hydroxide 56.11 × 1/2

(5) Method for Measuring Acid Value of Wax The acid value of the wax in the present invention can be measured as follows.
(Devices and instruments)
Erlenmeyer flask (300 ml)
Burette (25ml)
Water bath or hot plate (reagent)
0.1 kmol / m ³ hydrochloric acid 0.1 kmol / m ³ potassium hydroxide ethanol solution (standardization: 25 ml of 0.1 kmol / m ³ hydrochloric acid is taken into an Erlenmeyer flask using a total pipette, and a phenolphthalein solution is added. Titrate with 1 kmol / m ³ potassium hydroxide ethanol solution, and determine the factor from the amount required for neutralization.)
Phenolphthalein solution solvent (diethyl ether and ethanol (99.5 vol%) mixed at a volume ratio of 1: 1 or 2: 1. These were added several drops of phenolphthalein solution as an indicator just before use. Neutralize with 1 kmol / m ³ potassium hydroxide ethanol solution.)
(Measurement method)
(A) Weigh accurately 1 to 20 g of wax into an Erlenmeyer flask.
(B) Add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the wax is completely dissolved in a water bath.
(C) Titrate with a 0.1 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the light red color of the indicator lasts for 30 seconds.
(Calculation)
The acid value of the wax is calculated from the obtained result by the following formula.
[Equation 10]
A = 5.611 × B × f / S (10)
However,
A: Acid value of wax (mgKOH / g)
B: Amount of 0.1 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml)
f: Factor of 0.1 kmol / m ³ potassium hydroxide ethanol solution S: Mass of wax (g)
5.611: Formula weight of potassium hydroxide 56.11 × 1/10

(6) 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) Titrate with a potentiometric titrator using a 0.1N methanol solution of KOH (for example, potentiometric titrator AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd. and ABP-410 electric burette Automatic titration using can be used.)
4) The amount of KOH solution used at this time is set to S (ml), and a blank is measured at the same time, and the amount of KOH solution used at this time is set to B (ml).
5) Calculate the acid value of the binder resin by the following formula. f is a factor of KOH.
[Equation 11]
Acid value (mgKOH / g) = ((SB) × f × 5.61) / W (11)

(7) 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 into a round bottom flask, and 5 ml of an acetylating reagent is correctly added thereto. Put a small funnel over the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at 95-100 ° C. and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, a cardboard disk with a round hole in it is put on the base of the neck of the flask. After 1 hour, the flask is removed from the bath, and after cooling, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride. In order to further complete the decomposition, the flask was heated again in a glycerin bath for 10 minutes, allowed to cool, and then the funnel and the wall of the flask were washed with 5 ml of ethyl alcohol, and 0.5 mol / liter-hydroxylated with a phenolphthalein solution as an indicator. Titrate with potassium ethyl alcohol solution. 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.
[Equation 12]
A = [{(B + C) × f × 28.05} / S] + D (12)
However,
A: Hydroxyl value of resin B: Amount used of 0.5 mol / liter-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

(8) Method for Measuring Melting Point of Wax, Heat of Melting of Toner, Glass Transition Temperature of Binder Resin Melting point of wax and glass transition temperature of binder resin in the present invention are the differential scanning calorimeter (DSC measuring device), Q -1000 (TA Instruments Japan) can be used according to the following conditions. The melting point of the wax and the glass transition temperature of the binder resin are
The temperature at which an endothermic peak measured at temperature increase II of the following temperature curve is detected is used.
Sample: 5-20 mg, preferably 10 mg
Measurement method: Place the sample in an aluminum pan, and use an empty aluminum pan as a reference.
Temperature curve: Temperature increase I (20 ° C. → 180 ° C., temperature increase rate 10 ° C./min.)
Temperature drop I (180 ° C. → 10 ° C., temperature drop rate 10 ° C./min.)
Temperature increase II (10 ° C. → 180 ° C., temperature increase rate 10 ° C./min.)
The heat of fusion ΔHa of 35 ° C. or more and 85 ° C. or less in the DSC curve of the toner is the heat of fusion in the range of 35 ° C. or more and 85 ° C. or less where the endothermic peak attributed to the wax component in the toner is exhibited. The heat of fusion ΔHb of 35 ° C. or more and 60 ° C. or less in the DSC curve is calculated (calculation of the heat of fusion in the region of 35 ° C. or more and 60 ° C. or less of the heat of fusion exhibited by the endothermic peak attributed to the wax component in the toner). Sought by.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.
[Example of wax synthesis]
(Wax synthesis example A)
1,000 g of Fischer-Tropsch wax (number average molecular weight 711) as a raw material was put into a glass cylindrical reactor, and the temperature was raised to 140 ° C. while blowing a small amount of nitrogen gas (3 liters / minute). After adding 48.24 g (0.33 mol) of a mixed catalyst of boric acid / boric anhydride = 1.4 (molar ratio), while blowing air (21 liter / min) and nitrogen (18 liter / min), 180 The reaction was performed at ° C for 2.5 hours. After completion of the reaction, an equal amount of warm water (95 ° C.) was added to the reaction mixture, and the reaction mixture was hydrolyzed to obtain wax A. The hydroxyl value of wax A is 65.0 mgKOH / g, the ester value is 13.0 mgKOH / g, the acid value is 7 mgKOH / g, the melting point is 75 ° C., the penetration is 6, the viscosity is 12.1 mPa · s, and the softening point is It was 87 ° C. Table 1 shows the physical properties of Wax A.
(Wax synthesis example B)
Wax B was obtained in the same manner as in Wax Synthesis Example A except that 1,000 g of Fischer-Tropsch wax (number average molecular weight 720) was used as a raw material and the synthesis conditions were changed. Table 1 shows the physical properties of Wax B.
(Wax synthesis example C)
A wax C was obtained in the same manner as in the wax synthesis example A except that 1,000 g of α-olefin wax (number average molecular weight 1,633) was used as a raw material and the synthesis conditions were changed. Table 1 shows the physical properties of Wax C.
(Wax synthesis example D)
Wax D was obtained in the same manner as in Wax Synthesis Example A except that 1,000 g of microcrystalline wax (number average molecular weight 362) was used as a raw material and the synthesis conditions were changed. Table 1 shows the physical properties of the wax D.
(Wax synthesis examples E to G)
The physical properties of wax as shown in Table 1 were used as waxes EG.

[Binder resin production example]
(Polyester resin production example 1)
The polyester monomer is mixed in the following ratio.
-Bisphenol derivative represented by the above formula (A) (R: 2.2 mol addition of propylene group)
1.150 mol
・ Terephthalic acid 0.430 mol
・ Isophthalic acid 0.370 mol
・ Fumaric acid 0.040 mol
・ Dodecenyl succinic anhydride 0.160 mol
To these, 0.1% by mass of tetrabutyl titanate as a catalyst was added and subjected to condensation polymerization at 220 ° C. to obtain unsaturated polyester resin P-1 (Tg = 59 ° C., peak molecular weight = 6,400, number average molecular weight = 3, 900, Mw / Mn = 2.8, acid value = 11 mgKOH / g, hydroxyl value = 56 mgKOH / g).

(Polyester resin production example 2)
The unsaturated polyester resin P-2 (Tg = 55 ° C., peak molecular weight = 5,000, number average molecular weight = 3,200, Mw) in the same manner as in the polyester resin production example 1 except that the polyester monomer is mixed in the following ratio. /Mn=2.1, acid value = 38 mgKOH / g, hydroxyl value = 33 mgKOH / g).
-Bisphenol derivative represented by the above formula (A) (R: 2.2 mol addition of propylene group)
1.110 mol
・ Terephthalic acid 0.420 mol
・ Isophthalic acid 0.380 mol
・ Fumaric acid 0.040 mol
・ Dodecenyl succinic anhydride 0.160 mol

(Polyester resin production example 3)
Saturated polyester resin P-3 (Tg = 56 ° C., peak molecular weight = 5,000, number average molecular weight = 3,200, Mw / M) is the same as polyester resin production example 1 except that the polyester monomer is mixed in the following ratio. Mn = 2.1, acid value = 38 mgKOH / g, hydroxyl value = 33 mgKOH / g).
-Bisphenol derivative represented by the above formula (A) (R: 2.2 mol addition of propylene group)
1.110 mol
・ Terephthalic acid 0.420 mol
・ Isophthalic acid 0.380 mol
・ Fumaric acid 0.040 mol
・ Dodecenyl succinic anhydride 0.160 mol

(Hybrid resin production example 1)
Unsaturated polyester resin P-1: 75 parts by mass, vinyl monomer: styrene: 18 parts by mass, butyl acrylate: 6.5 parts by mass, monobutyl maleate: 0.5 parts by mass, polymerization initiator: 2, 5-Dimethyl-2,5-bis (t-butylperoxy) hexyne-3: 0.15 parts by mass, and two kinds of waxes were mixed. After this vinyl monomer / polyester resin mixture was polymerized at 110 ° C. over 15 hours until the polymerization conversion of the vinyl monomer reached 73%, the temperature was further raised to 160 ° C. and held for 5 hours to leave unreacted vinyl Monomers were polymerized to obtain a hybrid resin composition in which a wax was dispersed in the hybrid resin 1. Table 2 shows the physical properties of this hybrid resin 1.
In addition, when calculating | requiring the physical property of the hybrid resin 1 contained in a hybrid resin composition, it measured after removing the wax contained previously. When it was difficult to remove the wax, the physical properties of the contained wax were separately examined, and the influence of the wax was removed from the physical property values measured as the hybrid resin composition in the calculation. The physical properties of the hybrid resin produced by the hybrid resin production example described below were also measured by the same operation as described above.

(Hybrid resin production example 2)
Unsaturated polyester resin P-1: 70 parts by mass, vinyl monomer, styrene: 23 parts by mass, butyl acrylate: 6.0 parts by mass, monobutyl maleate: 1.0 part by mass, 2, 2, 5-Dimethyl-2,5-bis (t-butylperoxy) hexyne-3: 0.08 part by mass, and two kinds of waxes were mixed. After this vinyl monomer / polyester resin mixture was polymerized at 120 ° C. over 20 hours until the polymerization conversion of the vinyl monomer reached 97%, the temperature was further raised to 150 ° C. and held for 5 hours to leave unreacted vinyl Monomers were polymerized to obtain a hybrid resin composition in which a wax was dispersed in the hybrid resin 2. Table 2 shows the physical properties of this hybrid resin 2.

(Hybrid resin production example 3)
Unsaturated polyester resin P-2: 80 parts by mass, vinyl monomer, styrene: 14 parts by mass, butyl acrylate: 5.0 parts by mass, monobutyl maleate: 1.0 part by mass, 2, 2, 5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3: 0.05 part by mass A first type of wax and, if necessary, a second type of wax were mixed. After this vinyl monomer / polyester resin mixture was polymerized at 115 ° C. over 20 hours until the polymerization conversion of the vinyl monomer reached 84%, the temperature was further raised to 150 ° C. and held for 5 hours to leave unreacted vinyl Monomers were polymerized to obtain a hybrid resin composition in which wax was dispersed in the hybrid resin 3. Table 2 shows the physical properties of this hybrid resin 3.

(Hybrid resin production example 4)
Unsaturated polyester resin P-2: 55 parts by mass, vinyl monomer as styrene: 30 parts by mass, butyl acrylate: 15.0 parts by mass, polymerization initiator as 2,5-dimethyl-2,5-bis ( (t-Butylperoxy) hexyne-3: 0.15 parts by mass A first wax and, if necessary, a second wax were mixed. After this vinyl monomer / polyester resin mixture was polymerized at 110 ° C. over 10 hours until the polymerization conversion of the vinyl monomer reached 63%, the temperature was further raised to 150 ° C. and held for 10 hours to leave unreacted vinyl Monomers were polymerized to obtain a hybrid resin composition in which a wax was dispersed in the hybrid resin 4. Table 2 shows the physical properties of this hybrid resin 4.

(Hybrid resin production example 5)
Saturated polyester resin P-3: 70 parts by mass and, as a vinyl monomer, styrene: 2
3 parts by mass, butyl acrylate: 5 parts by mass, monobutyl maleate: 2 parts by mass, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 as a polymerization initiator: 0.08 mass 2 types of waxes were mixed. After polymerization until the polymerization conversion rate of this vinyl monomer reached 94%, the temperature was further raised to 150 ° C. and held for 5 hours to polymerize the unreacted vinyl monomer, and the wax was dispersed in the hybrid resin 5. A hybrid resin composition was obtained. Table 2 shows the physical properties of this hybrid resin 5.

<Example 1>
Hybrid resin composition described in Production Example 1 of hybrid resin 100 parts by mass Magnetite (average particle size 0.18 μm) 100 parts by mass Illustrative monoazo iron compound (1) 2 parts by mass Wax A 3 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, coarsely pulverized by a cutter mill, finely pulverized using a pulverizer using a jet stream, classified using a multi-division classifier utilizing the Coanda effect, and the weight average particle diameter (D4) A 6.0 μm negatively chargeable magnetic toner was obtained. Toner 1 was obtained by adding 1.0 part by mass of negatively chargeable hydrophobic silica to 100 parts by mass of the toner particles with a Henschel mixer. Table 3 shows the types and amounts of the waxes used for the toner 1. Table 4 shows the physical properties of the binder resin (hybrid resin 1) and the wax (first type) added internally during the production of the hybrid resin.

<Examples 2-7 and Comparative Examples 1-3>
Toners 2 to 5 are used in the same manner as in Example 1 except that hybrid resins 2 to 5 are used in place of hybrid resin 1 and that different types of hybrid resin compositions are used by changing the type and amount of wax to be added. 10 were obtained. Table 3 shows the type of hybrid resin used for toners 2 to 10 and the type and amount of wax used. In addition, Table 4 shows the physical properties of the hybrid resin used for the toners 2 to 10 and the physical properties of the wax (first type) added internally during the production of the hybrid resin. The obtained toners 1 to 10 were evaluated as follows. The evaluation results are shown in Table 5.

[Fixing test]
Laser beam printer manufactured by Hewlett-Packard Company: LaserJet 4350 fixing device was taken out, and an external fixing device was used so that the fixing temperature of the fixing device could be arbitrarily set and the process speed was 400 mm / sec. This external fixing device is temperature-controlled every 5 ° C. within a range of 140 to 220 ° C., and is 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 toner at low temperature fixability (Evaluation 1).

  For the high temperature offset property, the process speed is set to 100 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 a high temperature offset property. The higher this temperature is, the more excellent the high temperature offset property (Evaluation 2).

[Development test]
A commercially available laser beam printer LaserJet 4350 (manufactured by Hewlett Packard) was remodeled into a 65-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 fogging were measured when 30,000 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 higher this density is, the better the toner is in image density stability (Evaluation 3).
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. The smaller this value, the better the durability and stability of the toner (Evaluation 4).

[Preservation test]
10 g of toner was weighed into a polypropylene cup and the surface was flattened, and then a medicine-wrapping paper was placed on it, and 10 g of iron powder carrier was placed on it and left at 50 ° C. for 5 days to evaluate the blocking state of the toner (Evaluation 5). .
A: When the cup is tilted, the toner flows smoothly.
B: When the cup is rotated, the toner surface gradually collapses and becomes a smooth powder.
C: When a force is applied from the outside while turning the cup, the toner surface collapses and gradually flows out. This is a level where there is no practical problem.
D: A blocking sphere is generated. It collapses when you prick it with a pointed object. Slightly problematic level.
E: Blocking spheres are generated. Even if it sticks, it is hard to collapse. There is a problem level.

[Tailing]
The external fixing device used in the low-temperature fixing property and cold offset resistance test was set at a fixing temperature of 210 ° C., and 75 g / m ² paper was left in a 32.5 ° C., 80% RH environment for one day.
The evaluation method for tailing is to print out a pattern of 4 dots horizontal lines printed in 20-dot space on the high-humidity environment paper, and pass it through the external fixing device set as above. The number subtracted was counted (evaluation 6).
A: No occurrence B: Less than 3 C: 3 to less than 7 D: Less than 7 to 10 A level at which there is no practical problem.
E: Less than 10-15 A slightly problematic level.
F: 15 or more Levels in question.

Claims (5)

A toner containing at least a binder resin, a wax, and a colorant, wherein the binder resin contains 50 to 95% by mass of a polyester resin component with respect to the total amount of the binder resin, and a polyester resin component The toner contains a hybrid resin in which a vinyl resin component is chemically bonded, and the toner contains 3 to 50% by mass of a tetrahydrofuran (THF) insoluble component derived from a binder resin, and has a hydroxyl value (WHv) as the wax. ) Is a wax having a molecular weight of 5 to 150 mgKOH / g, the THF-insoluble matter contains a hybrid resin, and the vinyl-based resin component contained in the residue when hydrolyzing the THF-insoluble matter has a molecular weight range of from 50,000 to 500,000 in Chi lifting the main peak,
The hybrid resin is a resin obtained by bulk polymerization of a vinyl monomer at a mass ratio of unsaturated polyester resin: vinyl monomer = 50: 50 to 95: 5 in the presence of an unsaturated polyester resin. Toner.   The toner according to claim 1, wherein an ester value (WEv) of the wax having a hydroxyl value is 1 to 50 mgKOH / g.   The toner according to claim 1, wherein an acid value (WAv) of the wax having a hydroxyl value is 1 to 30 mg KOH / g.   The toner according to any one of claims 1 to 3, wherein the wax having a hydroxyl value has a melting point of 50 to 130 ° C.   The toner according to claim 1, wherein the wax having a hydroxyl value is a wax obtained by alcohol conversion of an aliphatic hydrocarbon wax.