JP2007310108A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner excellent in fixing property, high temperature offset resistance and developing property as well as wax dispersibility and having no melt sticking of the toner on a photoreceptor. <P>SOLUTION: The toner comprises at least a binder resin, a colorant and wax, and is characterized in that the binder resin contains a hybrid resin and the hybrid resin is prepared by polymerization in the presence of paraffin wax modified with vinyl monomers. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  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. In addition, it is difficult for the polyester resin to uniformly disperse the wax component, and problems such as deterioration of developability due to poor dispersion of the wax are likely to occur.

  On the other hand, vinyl-based resins such as styrene-based resins are excellent in pulverization properties at the time of toner production, and are easy to increase in molecular weight, so that they are excellent in high-temperature offset resistance. In comparison, it has the advantage of being easily dispersed uniformly. When the molecular weight is lowered or the Tg is lowered in order to improve the fixability, the blocking resistance and developability tend to be deteriorated.

  Attempts have also been made to add a low melting point paraffin wax in order to improve toner fixability. In particular, a combination of a low melting point paraffin wax and a polyester resin with excellent fixability can be expected to greatly improve the fixability. However, this combination makes it difficult to uniformly disperse the wax in the toner and affects the developability. Therefore, it was difficult to improve the fixing property.

  Patent Document 1 discloses a toner in which a hybrid resin having a polyester unit and a vinyl copolymer unit and a modified paraffin wax modified with a styrene monomer are combined.

  Patent Document 2 discloses a hydrocarbon wax treated with a styrene monomer having a specific molecular weight distribution.

  Patent Document 3 discloses a toner in which two types of inorganic fine powders having different BET specific surface areas are combined with a treated wax having a styrenic unit treated with a styrenic monomer.

  According to these proposals, the fixing performance and high-temperature offset resistance are improved, but the fixing performance required due to the speedup of the main body and the downsizing of the fixing device has not been fully satisfied. Improvement of the toner is desired.

JP 2003-84483 A JP 2004-21112 A JP-A-2005-84580

  It is an object of the present invention to provide a toner that is excellent in fixing property, high-temperature offset resistance, developability, and excellent wax dispersibility, and that does not cause toner fusion to a photoreceptor.

  In order to achieve the above object, a first invention according to the present application provides a toner containing at least a binder resin, a colorant, and a wax, wherein the binder resin contains a hybrid resin, and the hybrid resin is a vinyl resin. The present invention relates to a toner which is polymerized in the presence of a paraffin wax modified with a monomer.

  In order to achieve the above object, the second invention according to the present application is characterized in that the hybrid resin is obtained by polymerizing a vinyl monomer in the presence of an unsaturated polyester resin capable of reacting with the vinyl monomer. It relates to toner.

  In order to achieve the above object, a third invention according to the present application relates to a toner characterized in that the binder resin contains at least 50% by mass of a polyester unit.

  It is an object of the present invention to provide a toner that is excellent in fixing property, high-temperature offset resistance, developability, and excellent wax dispersibility, and that does not cause toner fusion to a photoreceptor.

  By using a hybrid resin polymerized in the presence of paraffin wax modified with a vinyl-based monomer as described above, the present inventors have excellent performance in both polyester resin fixability and vinyl resin high-temperature offset resistance. It has been found that a toner having excellent developability and excellent wax dispersibility and no toner fusion to the photoreceptor can be obtained. Although the mechanism of this effect has not yet been clarified, it is presumed as follows.

  When a hybrid resin is polymerized in the presence of paraffin wax modified with vinyl monomer (hereinafter referred to as modified paraffin wax), the vinyl unit in the hybrid resin and the vinyl unit in the modified paraffin wax are very close to each other at the molecular level. The modified paraffin wax can be uniformly dispersed in the hybrid resin and partially compatible. As a result, the affinity between the hybrid resin and the wax is increased, and the wax is uniformly dispersed in the toner, so that the wax is not unevenly distributed on the surface of the toner particles, the factor that inhibits the charging of the toner is reduced, and the high charging is performed. A toner having properties can be obtained. In addition, the presence of the modified paraffin wax in the vicinity of the vinyl unit at the molecular level makes it possible for the vinyl unit to melt even with a small amount of heat during fixing, improving the sharp melt property of the toner and improving the fixability. Significant improvements can be made. As a result, the fixability can be improved without lowering the molecular weight or Tg of the resin component, so that the high temperature offset property can be maintained. Furthermore, the hybrid resin and the modified paraffin wax are partially compatible so that the surface of the toner particles can have a uniform wax releasability, so that the toner is pressed against the photoconductor in the cleaning section and the contact charging section. In this case, the toner is less likely to adhere to the photoreceptor, and toner fusion to the photoreceptor can be prevented.

  On the other hand, when the modified paraffin wax is added after polymerizing the hybrid resin without the presence of the modified paraffin wax, the molecular weight of the hybrid resin is fixed and the degree of freedom of molecular motion is low. It is difficult for the vinyl units in the unit and the modified paraffin wax to approach each other at the molecular level, and it becomes difficult to increase the affinity between the hybrid resin and the wax. As a result, it becomes difficult to uniformly disperse the wax in the toner, and the charge amount of the toner tends to decrease due to the uneven distribution of the wax, resulting in a decrease in developability. Further, since the wax is less likely to be present in the vicinity of the vinyl unit, it is difficult to promote melting of the vinyl unit during fixing, and the effect of improving the fixing property cannot be obtained. Further, since the hybrid resin and the modified paraffin wax cannot be compatible with each other, the surface of the toner particles cannot be given releasability, and toner fusion to the photosensitive member is likely to occur.

  These phenomena become more prominent particularly when a hybrid resin containing a gel component is used, because the molecular motion of the resin molecules is limited by the crosslinked structure.

  The binder resin used in the present invention can be used alone as a hybrid resin, but if it contains at least a hybrid resin polymerized in the presence of a modified paraffin wax, it is a mixture containing other resin components. There may be.

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

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

  The hybrid resin can be obtained by containing a monomer component capable of reacting with both resin components in 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 that can react with the polyester component include those having a carboxyl group or a hydroxy group, and (meth) acrylic acid or (meth) acrylic acid esters.

As a manufacturing method which can prepare the hybrid resin used by this invention, the manufacturing method shown to the following (1)-(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 having a polyester resin component and a vinyl resin component by producing and reacting a vinyl resin component in the presence of the polyester resin component after production. 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.

  (3) is mentioned as a manufacturing method used especially preferably by this invention, It is preferable that the polyester resin component used is an unsaturated polyester resin especially.

  By polymerizing vinyl monomers in the presence of an unsaturated polyester resin, a hybrid unit with a structure in which a polyester unit derived from an unsaturated polyester resin having a vinyl unit as a main chain and reacting with the vinyl unit exists as a branched chain is obtained. I can get it. When this hybrid unit is polymerized in the presence of a modified paraffin wax, the polymerization of the vinyl monomer starts from a state where the vinyl monomer and the modified paraffin wax are uniformly dispersed at the molecular level. Hybrid units can be produced in the presence of paraffin wax, and hybrid units having high affinity with wax can be polymerized. Therefore, when the binder resin containing this hybrid unit is made into a toner, it becomes possible to dramatically improve the wax dispersion and to uniformly release the toner particle surface. The effect of preventing toner fusing is also obtained.

  As a method for polymerizing the hybrid resin used in the present invention, the method described in the above (3) is preferably used. Specifically, a polyester resin component and a modified paraffin wax are dissolved in an organic solvent, a solution polymerization method in which a vinyl monomer and a polymerization initiator are added to perform polymerization, and a polyester resin component that is heated and melted without using an organic solvent. , Bulk polymerization method in which modified paraffin wax and vinyl monomer are added and mixed, polymerization is performed by adding polymerization initiator, polyester resin component and modified paraffin wax are dissolved in vinyl monomer, and organic solvent is added if necessary In addition, a suspension polymerization method in which a polymerization initiator is added and dispersed in water for polymerization is exemplified, and in particular, in the present invention, a bulk polymerization method is preferably used.

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

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

  The unsaturated polyester resin component used in the hybrid resin of the present invention has a molecular weight distribution of 2,000 to 30,000 (preferably 3,000 to 20,000, more preferably 5, A low molecular weight unsaturated polyester resin component having a main peak in the range of 000 to 15,000) 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. Also, if the unsaturated polyester resin component is a non-linear molecule or contains a gel component, the number of cross-linking points increases when a hybrid unit is formed, and a hard gel component with no flexibility is generated in the hybrid resin. As a result, the fixability is likely to deteriorate, which is not preferable.

  Further, the unsaturated polyester resin component used in the present invention has a number average molecular weight (Mn) of 2,000 to 20,000, preferably 3,000 to 10,000. When the number average molecular weight (Mn) is less than 2,000, a gel component is hardly generated in the hybrid resin, and high temperature offset resistance and development durability are likely to deteriorate. If the number average molecular weight (Mn) is 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 vinyl. 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 sharp melt property at the time of fixing. 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 (preferably 20 to 60 mg KOH / g, more preferably 30 to 50 mg KOH / g), since the toner exhibits excellent chargeability, it is preferable. 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 polymerizing a vinyl monomer in the presence of such an unsaturated linear polyester resin component, the main chain is a vinyl resin component having a large molecular weight and high linearity, and the low molecular weight polyester resin component is a vinyl resin. A hybrid unit having a molecular structure branched from the components can be obtained. Furthermore, an acid group or a hydroxyl group in the hybrid unit having this branched structure forms an ester bond between the hybrid units to form a gel component.

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

  The toner of the present invention contains 1 to 50% by mass (preferably 1 to 40% by mass, more preferably 3 to 30% by mass) of a tetrahydrofuran-insoluble component (gel component) derived from a binder resin. The component preferably 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 1% by mass, the high temperature offset may deteriorate. When the tetrahydrofuran insoluble content is more than 50% by mass, it is difficult to uniformly disperse a material such as a colorant in the toner, the toner chargeability is deteriorated, and fogging and a decrease in image density may occur.

  Further, the polyester-based resin component contained in the tetrahydrofuran-insoluble component is hydrolyzed, and the THF-soluble component of the component obtained as a residue has a molecular weight of 50,000 to 500,000 (preferably 50,000 to 300,000, More preferably, it has a main peak in the range of 50,000 to 200,000). Such a structure indicates that a polyester unit is hybridized to a vinyl unit having a large molecular weight, and a gel structure having a large molecular weight between the crosslinking points is obtained.

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

  If the main peak molecular weight of the THF-soluble component of the vinyl resin component obtained by hydrolyzing the polyester resin component contained in the tetrahydrofuran-insoluble component is less than 50,000, the gel component tends to be hard, Fixability may deteriorate. In addition, since the molecular weight between cross-linking points is small, the gel component becomes inflexible, the gel component is easily cut by the shearing force at the time of kneading into toner, and the high temperature offset resistance may be 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 the developability tends to deteriorate. The molecular weight distribution of the THF-soluble component of the component obtained by hydrolyzing the polyester-based resin component contained in the tetrahydrofuran-insoluble component 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 and the molecular weight distribution is measured by GPC. A specific measurement method is shown below.

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

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

(2) Separation of vinyl-based resin component by hydrolysis The tetrahydrofuran-insoluble matter derived from the obtained binder resin is dispersed in a 2 mol / l NaOH aqueous solution at a concentration of 1% by mass, and the pressure vessel is at 150 ° C. for 24 hours. To hydrolyze the polyester 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 generated by hydrolysis of the acrylic ester component contained in the vinyl resin component was protonated and then separated by filtration 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 molecular weight of 2,000 to 30,000 (preferably 3,000 to 20,000, more preferably 5,000 to 15,000) in the GPC molecular weight distribution of the THF soluble content of the toner. Containing 3 to 30 area% (preferably 5 to 25 area%, more preferably 5 to 20 area%) of a component having a main peak in the range of 40 to 1,000,000. Is preferred.

  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 properties and high-temperature offset resistance.

  The hybrid resin component having a large molecular weight between cross-linking points easily incorporates a low molecular weight component having a peak molecular weight in the range of 2,000 to 30,000 into the cross-linked structure, so that the gel component is easily melted by heat and has a fixing property. Will improve. Moreover, since the high molecular weight component in the molecular weight range of 40,000 to 1,000,000 improves the mixing property of the low molecular weight component and the gel component, the high temperature offset resistance is improved. In addition, since the gel component is uniformly mixed in the toner, the pulverization property at the time of toner production is improved, and the 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 storage stability and developability of the toner are likely to deteriorate, and when it exceeds 30,000, the fixability tends to deteriorate. When the component 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 easily generated during pulverization. Tends to get worse. When the component having a molecular weight in the range of 40,000 to 1,000,000 is more than 30% by area, the toner viscosity becomes too high and the fixability tends to deteriorate.

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

  Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol represented by the formula (A) and derivatives thereof;

（式中Ｒはエチレンまたはプロピレン基であり、ｘ，ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０〜１０である。）

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

  And diols represented by the formula (B);

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

  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 fixing property is deteriorated, or the gel component is sheared by kneading at the time of toner formation, and the high temperature offset resistance is deteriorated.

  The polyester resin used in the present invention is preferably linear, but a trivalent or higher alcohol component or a trivalent or higher acid component can 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, empol trimer acid, and their anhydrides, lower alkyl esters;

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

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

  The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%, and the acid component is 60 to 40 mol%, preferably 55 to 45 mol%. 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 a generally known condensation polymerization. The polymerization reaction of the polyester resin is usually performed in the presence of a catalyst at a temperature of about 150 to 300 ° C., preferably about 170 to 280 ° C. The reaction can be performed under normal pressure, reduced pressure, or increased pressure, but after reaching a predetermined reaction rate (for example, about 30 to 90%), the reaction system is 200 mmHg or less, preferably 25 mmHg or less, more preferably 10 mmHg. It is desirable to carry out the reaction under reduced pressure below.

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

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

  The polyester of the present invention is stopped by stopping the reaction when the properties of the reactant (for example, acid value, softening point, etc.) reach a predetermined value, or when the stirring torque or stirring power of the reactor reaches a predetermined value. System resin can be obtained. In the present invention, the vinyl 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, N-vinyl pyrrolidone. Vinyl compounds; vinyl naphthalenes; and acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. These vinyl monomers are used alone or in admixture of two or more monomers.

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

  Furthermore, as a monomer for adjusting the acid value of the binder resin, for example, acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, and α- or β-alkyl derivatives thereof, fumaric acid, maleic acid, There are unsaturated dicarboxylic acids such as citraconic acid and their monoester derivatives or maleic anhydride, and such monomers are used alone or mixed to copolymerize with other monomers to produce the desired binder resin. Can do. Among these, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid in order to control the acid value.

  More specifically, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate Monoesters of α, β-unsaturated dicarboxylic acids such as: monobutyl n-butenyl succinate, monomethyl n-octenyl succinate, monoethyl n-butenylmalonate, monomethyl n-dodecenyl glutarate, monobutyl n-butenyl adipate Monoesters of alkenyl dicarboxylic acids such as, and the like; monoesters of aromatic dicarboxylic acids such as phthalic acid monomethyl ester, phthalic acid monoethyl ester, phthalic acid monobutyl ester, and the like.

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

  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.

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

  In order to achieve the object of the present invention, the vinyl resin component used for the preparation of the binder resin is produced by using a polyfunctional polymerization initiator alone or in combination with a monofunctional polymerization initiator as exemplified below. It is preferable.

  Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-hexylperoxy- 3,3,5-trimethylcyclohexane, 1,1-di-t-amylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxy-2-methylcyclohexane, 1,3 -Bis- (t-butylperoxyisopropyl) benzene, 1,3-bis- (neodecanolperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di- (2-ethylhexanolperoxy) hexane, 2, 5-dimethyl-2,5-di- (m-toluolperoxy) hexane, 2,5-dimethyl-2,5-di- (benzoylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 1,1-di-t-hexylperoxycyclohexane, 1,1-di-t-amylperoxycyclohexane, 1,1-di-t-butylperoxycyclohexane Cyclododecane, 2,2-di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t -Butylperoxyhexahydroisophthalate, di-t-butylperoxyazelate, tert-butylperoxytrimethyladipate , 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-t-butylperoxyoctane and various polymer oxides, and two or more peroxide groups in one molecule A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as diallyl peroxydicarbonate, t-butylperoxymaleic acid, t-butylperoxyallylcarbonate, t-butylperoxyisopropyl fumarate, etc. The polyfunctional polymerization initiator which has both the functional group which has polymerization initiation functions, such as a peroxide group, and a polymerizable unsaturated group in 1 molecule of these is mentioned.

  Of these, more preferred are 1,3-bis- (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5- Dimethyl-2,5-di- (t-butylperoxy) hexyne-3 and 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane.

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

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

  Specifically, benzoyl peroxide, n-butyl-4,4-di (t-butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t- Examples thereof include organic peroxides such as butyl peroxycumene and di-t-butyl peroxide, and azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

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

  The binder resin of the present invention is preferably obtained by a bulk polymerization method in which a vinyl monomer is polymerized without using a solvent or the like in the presence of the unsaturated polyester resin component as described above. In particular, a polymerization initiator having a 10-hour half-life temperature of 100 to 150 ° C. is used, a temperature that is 30 ° C. lower than the 10-hour half-life temperature of the polymerization initiator, and a temperature that is 10 ° C. higher than the 10-hour half-life temperature. In this range, it is preferable to carry out the polymerization reaction until the polymerization conversion rate of the vinyl monomer reaches 60%, preferably 80% or more, and to increase the molecular weight of the vinyl 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 has an acid value of 0.1 to 50 mgKOH / g (preferably 1 to 40 mgKOH / g, more preferably 1 to 30 mgKOH / g), and a hydroxyl value of 5 to 80 mgKOH / g (preferably Is preferably in the range of 5 to 60 mgKOH / g, more preferably 10 to 50 mgKOH / g) from the viewpoint of stabilizing the chargeability of the toner.

  Furthermore, the binder resin used in the present invention preferably has a tetrahydrofuran insoluble content of 1 to 50% by mass in order to improve the developability and high temperature offset resistance of the toner.

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

  The binder resin used in the present invention is characterized in that it is a hybrid resin polymerized in the presence of paraffin wax modified with a vinyl monomer, and this modified paraffin wax has an important role in the present invention. .

  As a method of modifying paraffin wax with a vinyl monomer, a method of polymerizing a vinyl monomer in the presence of wax under a relatively high temperature condition as a radical polymerization reaction using a polymerization initiator having a high hydrogen abstraction ability can be mentioned. .

  Specifically, the vinyl monomer mixed with the polymerization initiator is stirred for 1 to 10 hours while stirring the paraffin wax in a molten state at a high temperature of 130 ° C. or higher (preferably 150 ° C. or higher, more preferably 180 ° C. or higher). After completion of the dropwise addition, stirring is continued for several hours to complete the monomer polymerization and the wax modification reaction. It is preferable to perform the reaction at a high temperature of 130 ° C. or higher because the reaction between the paraffin wax and the vinyl monomer is efficiently performed and the modification rate is increased.

  In particular, the reaction at a high temperature of 180 ° C. or higher is preferable because the dispersibility of the modified paraffin wax in the hybrid resin is dramatically improved.

  The reason for this is not clear yet, but it is expected that an unsaturated bond is generated at the molecular terminal of the vinyl polymer present in the modified paraffin wax due to the high temperature polymerization of the vinyl monomer. When the hybrid resin is polymerized in the presence of the modified paraffin wax having an unsaturated group, the unsaturated group reacts with the vinyl monomer, and the modified paraffin wax is incorporated into the molecular structure of the hybrid unit, so that the wax dispersion is improved. It is thought that. Further, since the hybrid resin thus obtained contains a wax component in the molecular structure, the surface of the toner particles can have excellent releasability, and also has an effect of preventing toner fusion to the photoreceptor. It seems to improve dramatically.

  The paraffin wax obtained from petroleum wax is used as a raw material for the modified paraffin wax in the present invention, and the peak top temperature of the maximum endothermic peak is particularly 60 to 100 ° C. (preferably 65 ° C.) in the endothermic curve measured by DSC. It is preferable that the temperature is ˜90 ° C., more preferably 70 to 85 ° C., because the effect of improving fixability is large. When the peak top temperature is less than 60 ° C., the storage stability tends to be lowered, and when it exceeds 100 ° C., a great effect of improving fixability cannot be expected.

  In particular, in the present invention, the end point onset temperature at the endothermic peak measured by DSC is preferably 50 ° C. or higher and the end point onset temperature is 110 ° C. or lower in order to improve the sharp melt property of the wax. When the start point onset temperature is less than 50 ° C., the storage stability is poor, and when the end point onset temperature exceeds 110 ° C., the effect of improving the fixability is reduced.

  In the present invention, the molecular weight distribution is sharpened by performing purification and fractionation with high precision using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, a fused liquid crystal deposition method, and the like. It can be paraffin wax. Among these, a method using a solvent method in which purification is performed using a poor solvent for wax is preferable. For example, solvents such as benzene or toluene and ketone (acetone or methyl ethyl ketone); methyl isobutyl ketone; liquefied propane; trichloroethylene and benzene; dichloroethane and dichloromethane are used.

  For example, the following method can be applied. A solvent is added to the raw material wax and heated to completely dissolve the wax component, and then cooled with a cooler to crystallize the wax. Depending on the peak top temperature of the DSC maximum thermal peak of the target wax, the wax is cooled to a predetermined temperature and filtered. Further, the wax cake is washed with a solvent to separate oil, isoparaffin, naphthene, aromatics and the like. This process can be repeated to sharpen the molecular weight distribution. Finally, the solvent is separated by a solvent recovery device to obtain a wax. Thereafter, hydrogen purification, activated clay treatment, and deodorization treatment are performed as necessary.

  As the vinyl monomer used in the modification of the paraffin wax in the present invention, those exemplified as the monomer for obtaining the above-mentioned vinyl resin component can be used, and in particular, styrene homopolymer or styrene acrylic Combinations of monomers that are copolymers are preferred. Further, in order to bring the polarity of the modified paraffin wax closer to the binder resin, for example, unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid and the monoester derivative thereof or monomers such as maleic anhydride are mixed alone or mixed. It is also possible to copolymerize with other monomers. These vinyl monomers used for the modification of paraffin wax are used in a proportion of 5 to 200 parts by mass (preferably 10 to 150 parts by mass, more preferably 20 to 100 parts by mass) with respect to 100 parts by mass of paraffin wax.

  As the polymerization initiator used for the modification of paraffin wax in the present invention, those having a one-minute half-life temperature of 130 ° C. or higher (preferably 150 ° C. or higher, more preferably 180 ° C. or higher) are preferably used. Specifically, among those exemplified as polymerization initiators used when polymerizing the vinyl-based resin component, those having a 1-minute half-life temperature of 130 ° C. or higher are preferable, and in particular, di-t-butyl peroxide. (1 minute half-life temperature = 186 ° C.) is preferably used. These 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 vinyl monomer.

  The modified paraffin wax used in the present invention is preferably used at a ratio of 0.1 to 20 parts by mass with respect to 100 parts by mass of the hybrid resin.

  The toner of the present invention may contain a wax in addition to the modified paraffin wax.

  Examples of the wax other than the modified paraffin wax used in the present invention include the following. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax Or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wax wax, jojoba wax; animal waxes such as beeswax, lanolin, spermaceti; mineral waxes such as ozokerite, ceresin, petrolatum Waxes based on aliphatic esters such as montanic acid ester wax and caster wax; those obtained by partially or fully deoxidizing aliphatic esters such as deoxidized carnauba waxFurther, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinal acid; stearyl alcohol Saturated alcohol such as eicosyl alcohol, behenyl alcohol, cannavir alcohol, seryl alcohol, melyl alcohol, or alkyl alcohol having a long chain alkyl group; polyhydric alcohol such as sorbitol; linoleic acid amide, oleic acid amide, lauric acid Aliphatic amides such as acid amides; saturated aliphatic bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amides, ethylene bislauric acid amides, hexamethylene bisstearic acid amides; Unsaturated fatty acid amides such as inamide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, Aromatic bisamides such as N'-distearylisophthalamide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soap); such as behenic acid monoglyceride Examples include partially esterified products of fatty acids and polyhydric alcohols; methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.

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

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

  The toner of the present invention may further contain a magnetic material and be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant.

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

  These magnetic materials have an average particle diameter of 2 μm or less, preferably 0.05 to 0.5 μm. The amount to be contained in the toner is about 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the resin component.

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

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

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

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

  The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin.

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

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

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

〔式中、Ｍは配位中心金属を表わし、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ等があげられる。Ａｒはアリール基であり、フェニル基、ナフチル基などがあげられ、置換基を有してもよい。この場合の置換基としては、ニトロ基、ハロゲン基、カルボキシル基、アニリド基および炭素数１〜１８のアルキル基、アルコキシ基などがある。Ｘ，Ｘ’、Ｙ，Ｙ’は−Ｏ−、−ＣＯ−、−ＮＨ−、−ＮＲ−（Ｒは炭素数１〜４のアルキル基）である。Ａ⁺は水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、脂肪族アンモニウムイオン、それらの混合物或いはなしを示す。〕

[Wherein M represents a coordination center metal, and examples thereof include Sc, Ti, V, Cr, Co, Ni, Mn, and Fe. Ar is an aryl group, and examples thereof include a phenyl group and a naphthyl group, which may have a substituent. Examples of the substituent in this case include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group. X, X ′, Y, and Y ′ are —O—, —CO—, —NH—, and —NR— (R represents an alkyl group having 1 to 4 carbon atoms). A ⁺ represents hydrogen ion, sodium ion, potassium ion, ammonium ion, aliphatic ammonium ion, a mixture thereof, or none. ]

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

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

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

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

  Next, specific examples of the compound will be shown.

  The following substances are used for controlling the toner to be positively charged. Modified products of 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 (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, Russian compounds, metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyl Diorgano tin borate such as Suzuboreto; guanidine compounds, imidazole compounds. These can be used alone or in combination of two or more. Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used.

  Further, the general formula (4)

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

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

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

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

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

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

  As a method of incorporating a charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally. The amount of 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 fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fine powder silica such as wet process silica and dry process silica, and fine powder titanium oxide. , Fine powder alumina, fine powder treated with silane compound, titanium coupling agent, silicone oil; oxides such as zinc oxide and tin oxide; strontium titanate, barium titanate, calcium titanate, zircon Examples thereof include double oxides such as strontium acid and calcium zirconate; calcium carbonate and carbonate compounds such as magnesium carbonate.

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

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

  Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include AEROSIL (Nippon Aerosil Co., Ltd.) 130, 200, 300, 380, TT600, MOX170, MOX80, COK84, Ca—O—SiL (CABOT CoL). Company) M-5, MS-7, MS-75, HS-5, EH-5, Wacker HDK N 20 (WACKER-CHEMIE GMBH) V15, N20E, T30, T40, DC Fine Silica (Dow Corning) Co.) and Fransol (Fransil) are commercially available, and these can also be used favorably in the present invention.

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

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

  Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethridimethylchlorosilane, α- Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, 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.

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

  The toner of the present invention can be used as a one-component developer by mixing with the fluidity improver and, if necessary, further mixing with other external additives (for example, a charge control agent). And can be used as a two-component developer. As the carrier for use in the two-component development method, all conventionally known carriers can be used. Specifically, surface oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, rare earth, etc. Particles with an average particle size of 20 to 300 μm, such as metals and their alloys or oxides, are preferably used.

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

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

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

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

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

  Examples of the pulverizer include counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet pulverizer (manufactured by Nippon Pneumatic Industry); cross jet mill (manufactured by Kurimoto Iron Works); (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.)

  Examples of sieving devices used to screen coarse particles include Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokuju Kosakusha Co., Ltd.); Vibrasonic System (Dalton Co., Ltd.); Examples include a turbo screener (manufactured by Turbo Industry Co., Ltd.), a micro shifter (manufactured by Kanno Sangyo Co., Ltd.), and a circular vibrating sieve.

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

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

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

  On the other hand, the polyester resin component contained in the toner, resin or toner insoluble content of the toner is hydrolyzed, the vinyl resin component obtained as a residue is dispersed in tetrahydrofuran and dissolved, and then allowed to stand overnight. The mixture is filtered with a treatment filter (pore size 0.2 to 0.5 μm, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation)), and the filtrate is used as a sample. Measurement is performed by injecting 50 to 200 μl of a THF solution of the toner adjusted so that the resin component is 0.5 to 5 mg / ml as a sample concentration. An RI (refractive index) detector is used as the detector.

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

Tetrahydrofuran insoluble content Weigh out the binder resin or toner, put it in a cylindrical filter paper (for example, No. 86R size 28 × 10 mm, manufactured by Toyo Filter Paper Co., Ltd.), and apply it 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 mass of the toner placed in the cylindrical filter paper is W ₁ g, and the extracted THF-soluble resin component is the mass of W ₂ When the weight of g of the tetrahydrofuran-insoluble component other than the resin component contained in the toner is W ₃ g, the content of the tetrahydrofuran-insoluble component of the resin component in the toner can be obtained from the following formula.
Tetrahydrofuran insoluble matter (mass%) = [{W ₁ − (W ₃ + W ₂ )} / (W ₁ −W ₃ )] × 100

Method for Measuring Acid Value of Resin The acid value of the binder resin in the present invention can be measured as follows. Basic operation conforms to JIS K0070.
1) The binder resin pulverized product 0.5 to 2.0 (g) is precisely weighed to obtain the weight W (g) of the binder resin.
2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (4/1) is added and dissolved.
3) Using a 0.1N KOH methanol solution, titration is performed using a potentiometric titrator (for example, a potentiometric titrator AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd.) and an ABP-410 electric burette. Automatic titration can be used.)
4) The amount of KOH solution used at this time is S (ml), and at the same time, a blank is measured, and the amount of KOH solution used at this time is B (ml).
5) Calculate the acid value of the binder resin by the following formula. f is a factor of KOH.
Acid value (mgKOH / g) = ((SB) × f × 5.61) / W

Measuring Method of Hydroxyl Value of Resin The measurement of the hydroxyl value of the binder resin in the present invention can be carried out as follows.
(A) Reagent (a) Acetylation reagent: Add 25 g of acetic anhydride to a 100 ml volumetric flask, add pyridine to make a total volume of 100 ml, and shake well. The acetylating reagent should be kept in brown bottles away from moisture, carbon dioxide and acid vapors.
(B) Phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 vol%).
(C) 0.5 mol / liter-potassium hydroxide-ethyl alcohol solution Dissolve 35 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 vol%) to 1 liter, leave it for 2 to 3 days, and filter. . The orientation is performed according to JIS K8006.
(B) Operation 0.5-2.0 g of a sample is correctly weighed in a round bottom flask, and 5 ml of an acetylating reagent is correctly added thereto. Put a small funnel over the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at 95-100 ° C. and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, a cardboard disk with a round hole in it is put on the base of the neck of the flask. After 1 hour, the flask is removed from the bath, and after cooling, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride. In order to further complete the decomposition, the flask was again heated in a glycerin bath for 10 minutes, allowed to cool, and then the funnel and the flask wall were washed with 5 ml of ethyl alcohol, and 0.5 mol / liter-water with a phenolphthalein solution as an indicator. Titrate with potassium oxide ethyl alcohol solution. In parallel with this test, a blank test is performed. (C) Calculation formula The hydroxyl value of the binder resin is calculated by the following formula.
A = [{(B + C) × f × 28.05} / S] + D
However,
A: Hydroxyl value of resin B: Amount used of 0.5 mol / liter of potassium hydroxide ethyl alcohol solution in blank test (ml)
C: Amount used of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution in this test (ml)
f: Factor of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution S: Mass of sample (g)
D: Acid value of resin

(5) DSC measurement method of wax For the DSC measurement in the present invention, for example, Q-1000 manufactured by TA Instruments can be used. The measurement method is performed according to ASTM D3418-82. The DSC curve used in the present invention is a DSC curve that is measured when the temperature is lowered once and the temperature is raised at a temperature rate of 10 ° C./min after raising the temperature once and taking a previous history. Each temperature is defined as follows.
• Peak top temperature of maximum endothermic peak The peak top temperature of the peak with the highest height from the baseline.
・ End-point onset temperature of endothermic peak Temperature at the intersection of the tangent of the curve and the base line at the point where the differential value of the rising temperature curve is maximum ・ End-point onset temperature of the endothermic peak The differential value of the rising temperature curve is the minimum Temperature at the intersection of the tangent of the curve and the baseline at a point

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

[Modified Paraffin Wax Production Example 1]
100 parts by mass of paraffin wax having a peak end temperature of the maximum endothermic peak = 76 ° C., an onset temperature of the endothermic peak = 62 ° C., and an onset temperature of the endothermic peak = 84 ° C. was melted at 190 ° C. and stirred. Here, 100 parts by mass of styrene and 4 parts by mass of di-t-butyl peroxide as an initiator were added dropwise over 10 hours. Stirring was continued for 5 hours while maintaining the temperature at 190 ° C., and then the polymerization was terminated to obtain a modified paraffin wax-1.

[Modified Paraffin Wax Production Example 2]
100 parts by mass of paraffin wax having a maximum endothermic peak peak top temperature = 76 ° C., an endothermic peak starting onset temperature = 62 ° C., and an endothermic peak end onset temperature = 84 ° C. was melted at 160 ° C. and stirred. Here, 50 parts by mass of styrene and 2 parts by mass of di-t-butyl peroxide as an initiator were added dropwise over 5 hours. Stirring was continued for 5 hours while maintaining the temperature at 160 ° C., and then the polymerization was terminated to obtain modified paraffin wax-2.

[Modified Paraffin Wax Production Example 3]
100 parts by mass of paraffin wax having a peak end temperature at the maximum endothermic peak = 66 ° C., an onset temperature at the end point of the endothermic peak = 46 ° C., and an onset temperature at the end point of the endothermic peak = 75 ° C. was melted at 120 ° C. and stirred. A mixture of 50 parts by mass of styrene and 2 parts by mass of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane as an initiator was added dropwise over 5 hours. Stirring was continued for 5 hours while maintaining at 120 ° C., and then the polymerization was terminated to obtain modified paraffin wax-3.

[Binder resin production example]
(Polyester resin production example 1)
The polyester monomer is mixed in the following ratio.
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.150 mol
・ Terephthalic acid 0.420 mol
・ Isophthalic acid 0.400 mol
・ Fumaric acid 0.010 mol
・ Dodecenyl succinic anhydride 0.170 mol
Tetrabutyl titanate 0.1% by mass was added to these as a catalyst and subjected to condensation polymerization at 220 ° C., and unsaturated polyester resin P-1 (Tg = 60 ° C., peak molecular weight = 8500, number average molecular weight = 4600, Mw / Mn = 2.2, acid value = 7 mgKOH / g, hydroxyl value = 32 mgKOH / g).

(Polyester resin production example 2)
Unsaturated polyester resin P-2 (Tg = 55 ° C., peak molecular weight = 4700, number average molecular weight = 1800, Mw / Mn = 3) in the same manner as in polyester resin production example 1 except that the polyester monomer is mixed in the following ratio. 0.7, acid value = 14 mgKOH / g, hydroxyl value = 57 mgKOH / g).
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.100 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 = 55 ° C., peak molecular weight = 7700, number average molecular weight = 5100, Mw / Mn = 2.M) is the same as polyester resin production example 1 except that the polyester monomer is mixed in the following ratio. 6, acid value = 4 mgKOH / g, hydroxyl value = 38 mgKOH / g).
-Bisphenol derivative represented by formula (A) (R: propylene group 2.2 mol addition)
1.150 mol
・ Terephthalic acid 0.420 mol
・ Isophthalic acid 0.410 mol
・ Dodecenyl succinic anhydride 0.170 mol

(Hybrid resin production example 1)
Unsaturated polyester resin P-1: 75 parts by mass and, as a vinyl monomer, styrene: 18 parts by mass, butyl acrylate: 6.5 parts by mass, monobutyl maleate: 0.5 parts by mass, modified paraffin wax-1: 5 parts by mass and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (10 hour half-life temperature 128 ° C.): 0.08 parts by mass were mixed as an initiator. After this vinyl monomer / polyester resin mixture was polymerized at 120 ° C. over 20 hours until the polymerization conversion of the vinyl monomer reached 98%, 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. This is designated as binder resin 1. This resin had a main peak molecular weight of 8600 in the GPC molecular weight distribution of THF-soluble matter, contained 11 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained 24 mass% of tetrahydrofuran-insoluble matter. .

(Hybrid resin production example 2)
A hybrid resin was obtained in the same manner as in Hybrid resin production example 1 except that the modified paraffin wax-1 was changed to the modified paraffin wax-2. This is designated as binder resin 2. This resin had a main peak molecular weight of 8500 in the GPC molecular weight distribution of THF-soluble matter, contained 9 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained 21 mass% of tetrahydrofuran-insoluble matter. .

(Hybrid resin production example 3)
Unsaturated polyester resin P-2: 75 parts by mass, modified paraffin wax-2: 5 parts by mass in methyl ethyl ketone: 75 parts by mass, and after cooling, styrene: 16 parts by mass, butyl acrylate: 7.5 parts by mass Then, 1.5 parts by mass of monobutyl maleate and 0.5 parts by mass of 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane as an initiator were mixed.

  The monomer mixed polyester solution was added to 150 parts by mass of a 0.2% by mass aqueous polyvinyl alcohol solution prepared in advance with stirring, and dispersed in water to obtain a suspension.

  This suspension was heated under a nitrogen stream and heated while distilling methyl ethyl ketone. Polymerization was carried out for 20 hours while keeping the flask internal temperature at 85 ° C. and distilling off methyl ethyl ketone. Thereafter, 0.05 part by mass of benzoyl peroxide was further added as an initiator, polymerization was performed for 5 hours, the polymerization rate was sufficiently increased, and then cooled. The obtained suspension slurry was dehydrated and dried to obtain a hybrid resin. This is designated as binder resin 3. This resin had a main peak molecular weight of 4800 in a GPC molecular weight distribution of THF-soluble matter, contained 4 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained 16 mass% of tetrahydrofuran-insoluble matter. .

(Hybrid resin production example 4)
A hybrid resin was obtained in the same manner as in Hybrid resin production example 3 except that the modified paraffin wax-2 was changed to the modified paraffin wax-3. This is designated as binder resin 4. This resin had a main peak molecular weight of 4600 in the GPC molecular weight distribution of THF-soluble matter, contained 2 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained 11 mass% of tetrahydrofuran-insoluble matter. .

(Hybrid resin production example 5)
45 parts by weight of unsaturated polyester resin P-2 and 5 parts by weight of modified paraffin wax-3 were added to 300 parts by weight of xylene, and the mixture was heated to reflux. Under this reflux, a mixture of styrene: 37 parts by mass, acrylic acid-n-butyl: 10 parts by mass, monobutyl maleate: 8 parts by mass, and di-tert-butyl peroxide: 2 parts by mass over 4 hours. After the dropping, the polymerization was completed by maintaining for 2 hours. Thereafter, the organic solvent was distilled off to obtain a hybrid resin. This is designated as binder resin 5. This resin had a main peak molecular weight of 4900 in the GPC molecular weight distribution of THF-soluble matter, contained 42 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained 17 mass% of tetrahydrofuran-insoluble matter. .

(Hybrid resin production example 6)
As a vinyl monomer, 270 g of styrene, 60 g of 2-ethylhexyl acrylate, 20 g of acrylic acid, and 13 g of azobisisobutyronitrile as a polymerization initiator are placed in a dropping funnel.

  Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 780 g, isododecenyl succinic anhydride: 76 g, terephthalic acid: 180 g, 1,2,4-benzenetricarboxylic acid: 30 g, modified paraffin Wax-3: 65 g and dibutyltin oxide 2 g were put into a flask, and while stirring at a temperature of 135 ° C., a vinyl monomer and a polymerization initiator were dropped from a dropping funnel over 3 hours to polymerize the vinyl resin component. went. After aging for 5 hours while maintaining the temperature at 135 ° C., the temperature was raised to 220 ° C. to polymerize the polyester resin component to obtain a hybrid resin. This is designated as binder resin 6. This resin had a main peak molecular weight of 5200 in the GPC molecular weight distribution of THF-soluble content, contained 31 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained 26 mass% of tetrahydrofuran-insoluble matter. .

(Comparative resin production example 1)
40 parts by mass of unsaturated polyester resin P-2 was added to 300 parts by weight of xylene, and the mixture was heated to reflux. Under this reflux, a mixture of styrene: 39 parts by mass, acrylic acid-n-butyl: 12 parts by mass, monobutyl maleate: 9 parts by mass, and di-tert-butyl peroxide: 2 parts by mass over 4 hours. After the dropping, the polymerization was completed by maintaining for 2 hours. Thereafter, modified paraffin wax-3: 5 parts by mass was added and stirred for 3 hours to uniformly disperse the modified paraffin wax, and then the organic solvent was distilled off to obtain a hybrid resin. This is designated as comparative binder resin 1. This resin had a main peak molecular weight of 4700 in the GPC molecular weight distribution of THF-soluble matter, contained 46 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained 14 mass% of tetrahydrofuran-insoluble matter. .

(Comparative resin production example 2)
300 parts by weight of xylene, unsaturated polyester resin P-2: 60 parts by mass, peak end temperature of maximum endothermic peak = 66 ° C., end point onset temperature of endothermic peak = 46 ° C., end point onset temperature of endothermic peak = 75 ° C. Paraffin wax: 5 parts by mass was added and heated to reflux. Under this reflux, a mixture of styrene: 27 parts by mass, acrylic acid-n-butyl: 7 parts by mass, monobutyl maleate: 6 parts by mass, and di-tert-butyl peroxide: 1.5 parts by mass was mixed for 4 hours. After the dropwise addition, the polymerization was completed by maintaining for 2 hours. Thereafter, the organic solvent was distilled off to obtain a hybrid resin. This is referred to as comparative binder resin 2. This resin had a main peak molecular weight of 4600 in the GPC molecular weight distribution of THF-soluble matter, contained 28 area% of components having a molecular weight in the range of 40,000 to 1,000,000, and contained 16 mass% of tetrahydrofuran-insoluble matter. .

<Example 1>
-Binder resin 1 105 parts by mass-Magnetite (average particle size 0.18 µm) 100 parts by mass-Illustrative monoazo iron compound (1) 2 parts by mass-Fischer-Tropsch wax (DSC peak temperature 103 ° C) 2 parts by mass After premixing with a Henschel mixer, the mixture was kneaded by a twin-screw kneading extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) set at 130 ° C. and 200 rpm. The obtained kneaded product is cooled and coarsely pulverized with a cutter mill, then finely pulverized using a pulverizer using a jet stream, classified using a multi-division classifier utilizing the Coanda effect, and the weight average diameter (D4 ) A negatively chargeable magnetic toner of 6.9 μm was obtained. Toner 100 was obtained by adding 1.0 part by mass of negatively chargeable hydrophobic silica to 100 parts by mass of this toner with a Henschel mixer. Table 1 shows the physical properties of Toner 1. This toner was evaluated for the following items. The evaluation results are shown in Table 2.

[Fixing test]
Laser beam printer manufactured by Hewlett-Packard Company: LaserJet 4350 fixing device was taken out, and an external fixing device was used so that the fixing temperature of the fixing device could be arbitrarily set and the process speed was 400 mm / sec. This external fixing device is temperature-controlled at a temperature of 140 to 220 ° C. every 5 ° C. and developed on plain paper (75 g / m ² ) paper (solid toner development amount on paper set to 0.6 mg / cm ² ) The fixed image is fixed, and the obtained image is rubbed and reciprocated 5 times with sylbon paper with a load of 4.9 kPa. The fixing temperature is the point at which the density reduction rate of the image density before and after the rubbing is 10% or less. did. The lower this temperature, the better the low-temperature fixability.

  For high-temperature offset resistance, the process speed is set to 100 mm / sec, the temperature is adjusted every 5 ° C. within the range of 200 to 240 ° C., unfixed images are fixed, and stains due to offset phenomenon on the images are visually confirmed The generated temperature was defined as high temperature offset resistance. The higher this temperature, the better the high temperature offset resistance.

[Development test]
A commercially available laser beam printer LaserJet 4350 (manufactured by Hewlett Packard) was remodeled into a 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 fog were measured when 1,000 sheets and 20,000 sheets were passed.

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

[Toner fusion test to photoreceptor]
Using the test machine used in the development test, 10,000 sheets of 2-dot vertical line patterns were continuously passed in a high temperature and high humidity (32.5 ° C., 80% RH) environment, and the toner on the photoconductor Fusion was evaluated according to the following criteria.
A: No toner fusion B: Slight toner fusion on the photoreceptor (less than 5 locations)
C: There is toner fusion on the photoreceptor (5 or more and less than 20)
D: There is toner fusion on the entire surface of the photoconductor. E: There is intense toner fusion on the entire surface of the photoconductor.

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

Claims (3)

In a toner containing at least a binder resin, a colorant, and a wax,
The toner, wherein the binder resin contains a hybrid resin, and the hybrid resin is polymerized in the presence of paraffin wax modified with a vinyl monomer.   The toner according to claim 1, wherein the hybrid resin is obtained by polymerizing a vinyl monomer in the presence of an unsaturated polyester resin capable of reacting with the vinyl monomer.   The toner according to claim 1, wherein the binder resin contains at least 50% by mass of a polyester unit.