JP2008145492A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner whose consumption amount small and which can keep satisfactory developing property even in long-term use. <P>SOLUTION: The toner comprises toner particles containing at least a binder resin, a colorant, wax and petroleum resin. The binder resin is a hybrid resin obtained by chemically bonding a polyester resin component and a vinyl resin component. The petroleum resin has the weight average mol. wt. Mw of 600 to 4,000 and a bromine value of 10 to 60 g/100 g, and the petroleum resin is included by 0.5 to 15.0 pts.mass with respect to 100 parts by mass of the binder resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner used in an image forming method for visualizing an electrostatic charge image.

  In recent years, devices using electrophotography have begun to be used in printers for output of computers, facsimiles, etc., in addition to copying machines for copying original documents. As a result, smaller, lighter, faster, and more reliable are being sought, and machines are becoming simpler in various ways. As a result, the performance required for the toner becomes higher, and if the improvement in the performance of the toner cannot be achieved, a better machine cannot be realized.

  It is known that the wax dispersibility of toner particles affects various electrophotographic characteristics such as toner chargeability and developability.

  Patent Document 1 discloses a method of using a petroleum resin in a system using a polyester resin. However, there was room for further improvement in the fusion to the sleeve. Polyester resin also has high charging performance, but when it contains wax, it is difficult to uniformly disperse the wax, and the original high chargeability can be drawn sufficiently because the wax is localized on the surface. There was no possibility.

  Patent Document 2 discloses a method for improving the dispersibility of wax by using a petroleum resin in a system using a vinyl resin. Although the dispersibility of the wax is easier to disperse uniformly than the polyester resin, there is still room for reduction in consumption.

  Patent Document 3 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl resin. However, the polyester resin and the vinyl resin are inherently poorly compatible, and the dispersibility of the colorant and wax added to the toner becomes insufficient, so that problems are easily caused in developability.

  Patent Document 4 discloses a toner containing a polymer obtained by polymerizing a vinyl monomer in the presence of a reactive polyester resin. Therefore, the polyester resin content is small, and the chargeability tends to be insufficient.

JP 2005-17593 A JP 2003-195 566 A JP 54-114245 A Japanese Patent Laid-Open No. 56-116043

  An object of the present invention is to provide a toner that solves the above-mentioned problems of the prior art.

  An object of the present invention is to provide a toner with low consumption.

  An object of the present invention is to provide a toner that maintains good developability even during long-term use.

  An object of the present invention is to provide a toner that does not cause sleeve fusion.

The present invention is a toner having toner particles containing at least a binder resin, a colorant, a wax and a petroleum resin,
The binder resin is a hybrid resin in which a polyester resin component and a vinyl resin component are chemically bonded.
The petroleum resin has a weight average molecular weight Mw of 600 to 4000, a bromine number of 10 to 60 g / 100 g, and 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the binder resin. It relates to toner.

  According to the present invention, it is possible to provide a toner that consumes little amount and can maintain good developability even in long-term use.

  When the hybrid resin in which the polyester resin component and the vinyl resin component are chemically bonded is used as the binder resin, the inventors of the present invention contain a wax in the binder resin and further have a weight average molecular weight Mw. Is contained in 0.5 to 20.0 parts by mass with respect to 100 parts by mass of the binder resin by adding a petroleum resin having a bromine value of 10 to 60 g / 100 g to 100 parts by mass of the binder resin. A configuration that can achieve both the excellent performance of wax dispersibility at a higher level, further reduce consumption, maintain good developability even in long-term use, and prevent sleeve fusion from occurring I found. Although the mechanism of this effect has not yet been clarified, it is presumed as follows.

  Polyester resin has high charging performance, but when it contains wax, it is difficult to uniformly disperse the wax, and the original high chargeability is sufficiently extracted because the wax is localized on the surface. There was no possibility. On the other hand, the vinyl-based resin has an advantage that it can be uniformly dispersed as compared with the polyester resin with respect to the dispersibility of the wax, but it is necessary to further finely disperse the resin.

  In order to further improve the dispersibility of the wax of the vinyl resin and maximize the charging performance of the polyester resin, a hybrid resin in which the polyester resin component and the vinyl resin component are chemically bonded is bound. Used as resin. It is considered that by adding a petroleum resin to the binder resin, the dispersibility of the wax is further increased and finely dispersed, and the surface composition is made uniform, so that higher chargeability can be obtained.

If a binder resin is produced simply by mixing without creating a chemical bond between the polyester resin and the vinyl resin, the fine dispersion of the binder resin or wax at the molecular level cannot be achieved. The configuration of the present invention is not satisfied.

  Petroleum resin and wax have the property of being compatible with each other. Further, the hybrid resin inherently has a vinyl resin component that is excellent in wax dispersibility. For this reason, it is considered that the petroleum resin penetrates into the molecular structure of the hybrid resin, and at the same time, the wax is also drawn by the petroleum resin and penetrates uniformly into the molecular structure of the hybrid resin. As a result, it is considered that the wax can be finely dispersed more than before. For this reason, the wax can be finely dispersed uniformly including the inside of the toner and the toner surface, and a large wax domain is hardly formed. As a result, a uniform surface composition can be obtained, the chargeability of the toner can be further increased, the consumption can be reduced, and good developability can be maintained even during long-term use. Furthermore, since the wax is uniformly finely dispersed, it is possible to suppress the generation of free wax and free binder resin that does not contain wax. Occurrence is improved.

  In the toner of the present invention, the petroleum resin used for the toner resin is not particularly limited, and any one of various conventionally known resins can be selected and used.

  Petroleum resin is a resin obtained by heat polymerization using a unsaturated hydrocarbon produced as a by-product when synthesizing ethylene, propylene or the like by naphtha cracking.

  Petroleum resins include C5-based petroleum resins made mainly of at least one selected from aliphatic hydrocarbons such as isoprene, piperylene, 2-methylbutene, α- and β-methylstyrene, vinyltoluene, indene, naphthalene, etc. C9 petroleum resin mainly containing at least one selected from aromatic hydrocarbons of the above, alicyclic petroleum resins mainly containing at least one selected from alicyclic hydrocarbons such as cyclopentadiene, or the like Examples include petroleum resins obtained by polymerizing two or more raw material monomers of aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons, for example, C5 / C9 copolymer petroleum resins.

  In the present invention, it is preferable to use a product obtained by adding hydrogen to an unsaturated bond contained in a petroleum resin and reducing it. When hydrogen is added to the petroleum resin, the transparency is improved and the heat resistance is also improved, so that excellent blocking resistance can be obtained. The method for adding hydrogen to the petroleum resin is not particularly limited as long as it is a general method, but a catalytic reduction method using a heavy metal catalyst such as palladium or platinum is preferably used. The hydrogenation rate is evaluated by measuring bromine number by bromine addition. When bromine is added to the petroleum resin, the more unsaturated bonds in the petroleum resin, the more bromine to be added and the higher the bromine number. The measuring method was performed based on JIS K-2605. The bromine number of the petroleum resin is preferably 10 to 60 g / 100 g (preferably 25 to 60 g / 100 g, more preferably 35 to 60 g / 100 g).

  When the weight average molecular weight Mw is 600 to 4000 (preferably 1000 to 4000, more preferably 2000 to 4000) in the molecular weight distribution measured by GPC by dissolving petroleum resin in tetrahydrofuran, the compatibility with the wax is improved. In addition, the effect of fine dispersion of wax is easily obtained. When the weight average molecular weight is less than 600, the petroleum resin tends to exude to the toner surface, the wax may be localized on the surface, and uniform chargeability cannot be obtained, and the blocking resistance tends to be lowered. On the other hand, when it is larger than 4000, the petroleum resin is less likely to penetrate into the molecular structure of the hybrid resin, and the dispersibility of the wax is lowered.

  When the glass transition temperature Tg of the petroleum resin is 50.0 ° C. to 90.0 ° C. (preferably 54.0 ° C. to 80.0 ° C.), an effect is easily obtained with respect to fine dispersion of the wax. When the glass transition temperature Tg is less than 50.0 ° C., the petroleum resin tends to exude to the toner surface, the wax may be localized on the surface, and uniform chargeability cannot be obtained, and the anti-blocking property is also obtained. It tends to decline. On the other hand, when the temperature is higher than 90.0 ° C., the dispersibility of the petroleum resin is lowered and the dispersion of the wax may be lowered.

  The amount of petroleum resin added is preferably 0.5 to 15.0% (preferably 0.5 to 8.0%) in the binder resin. When the addition amount is less than 0.5%, the dispersibility of the wax in the toner decreases, so that sufficient chargeability cannot be obtained, and the consumption increases and the developability tends to decrease. Further, since loose substances of the wax and the binder resin are likely to be generated, sleeve fusion is likely to occur, which may cause an image defect. When it is more than 15.0%, the blocking resistance tends to decrease, and the developability tends to decrease.

As a method of incorporating a wax and petroleum resin into the binder resin,
1) A method of adding at any timing before the polymerization of the binder resin 2) A method of adding the binder resin to the molten binder resin after polymerization 3) After drying the binder resin, A method of mixing with a binder resin and melt-kneading can be mentioned, and it may be added at any one of timings 1) to 3). A preferred method of adding a wax and a petroleum resin to appropriately control the polymerization of the binder resin and create a finely dispersed state by uniformly dispersing the wax at the molecular level and exhibit the effects of the present invention is 2). The order is>1)> 3). The timing of adding the wax and petroleum resin may be different.

  When only the wax is added to the binder resin without adding the petroleum resin, the wax does not easily penetrate into the molecular structure of the hybrid resin. Therefore, it becomes easy for the wax to form a large domain locally in the binder resin, and it becomes difficult to finely disperse it uniformly throughout.

  The toner of the present invention contains a wax. The waxes used in the present invention include the following.

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

  Further, those waxes having a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a melt liquid crystal deposition method are also preferably used. Also, low molecular weight solid fatty acids, low molecular weight solid alcohols, low molecular weight solid compounds, 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.

  In the toner of the present invention, the total content of these waxes is 0.1 to 15 parts by mass, preferably 0.5 to 12 parts by mass with respect to 100 parts by mass of the binder resin. It is.

  These waxes have a melting point of 65 ° C. or higher and lower than 130 ° C., preferably 70 ° C. or higher and lower than 120 ° C., more preferably 70 ° C. or higher and lower than 110 ° C., measured using a differential thermal analyzer (DSC). The wax having such a melting point has good compatibility with the petroleum resin, and the wax easily forms a finely dispersed state in the toner.

  When the melting point of the wax is less than 65 ° C., the wax tends to ooze out from the molecular structure of the hybrid resin, and the finely dispersed state cannot be maintained, and the blocking resistance and developability are likely to deteriorate. When the melting point of the wax exceeds 120 ° C., the compatibility with the petroleum resin is insufficient and it is difficult to form a finely dispersed state.

The weight average molecular weight Mw of the wax used in the present invention is 200 to 3000 (preferably 200 to 1000),
Weight average molecular weight Mw of petroleum resin> Weight average molecular weight Mw of wax
It is preferable to satisfy the relationship. When the weight average molecular weight Mw of the wax is less than 200, the blocking resistance tends to decrease. When it exceeds 3000, the compatibility with the petroleum resin decreases, and it may be difficult to penetrate into the molecular structure of the binder resin together with the petroleum resin. If the weight average molecular weight Mw of the petroleum resin is greater than the weight average molecular weight Mw of the wax, the compatibility between the petroleum resin and the wax and the fine dispersion of the wax are further improved. When the weight average molecular weight Mw of the petroleum resin is smaller than the weight average molecular weight Mw of the wax, the function of the petroleum resin as a carrier is lowered, and the fine dispersibility of the wax tends to be lowered.

  The wax dispersion diameter in the toner is preferably 2.0 μm or less (preferably 0.6 μm or less) in order to obtain uniform surface properties. When the wax dispersion diameter is larger than 2.0 μm, the wax domains are localized on the toner surface and uniform chargeability cannot be obtained, and free wax is easily generated, which is likely to cause sleeve fusion.

In the present invention, the content of each of the vinyl resin component and the petroleum resin with respect to 100% by mass of the binder resin is
25 <mass% of vinyl resin component × mass% of petroleum resin <200
(Preferably 50 <mass% of vinyl resin component × mass% of petroleum resin <150)
Satisfying this relationship is more preferable for achieving the effects of the present invention. Since the vinyl resin has the property of easily dispersing the wax, when the proportion of the vinyl resin component in the binder resin is increased, the amount of the petroleum resin can be suppressed with respect to the wax dispersion. When the proportion of the vinyl resin component is reduced, it becomes difficult to disperse the wax in the binder resin, and therefore it is necessary to add a petroleum resin accordingly.

  When the mass% of the vinyl-based resin component × the mass% of the petroleum resin ≧ 200, the chargeability and blocking resistance may be lowered. When the mass% of the vinyl-based resin component × the mass% of the petroleum resin ≦ 25, it becomes difficult to finely disperse the wax, the consumption increases, and the developability tends to decrease.

  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). A hybrid resin obtained by bulk polymerization at a mass ratio is preferred. When the mass ratio of the unsaturated polyester resin is less than 50:50, the charging performance becomes insufficient, and it becomes difficult to reduce the consumption. Furthermore, the toner fixing property is likely to be lowered. When the ratio is more than 90:10, the dispersion of the wax in the binder resin is likely to be biased, the consumption is increased, and the developability tends to be lowered. Furthermore, adverse effects such as a decrease in the high temperature offset resistance of the toner are likely to occur.

  In the toner of the present invention, the tetrahydrofuran-insoluble content (gel component) derived from the binder resin is 3 to 50% by mass (preferably 5 to 40% by mass, more preferably 5 to 30% by mass, particularly preferably 10 to 30%). (Mass%) is preferable. Petroleum resins are highly compatible with gel components. If the gel component is present, it is considered that the dispersed state of the petroleum resin can be maintained. When the tetrahydrofuran insoluble content is less than 3% by mass, the petroleum resin in the binder resin becomes easy to move, the fine dispersion property of the wax is lowered, and good high temperature offset resistance is difficult to obtain. When the tetrahydrofuran insoluble content is more than 50% by mass, it becomes difficult to uniformly disperse materials such as petroleum resins and colorants in the toner, the chargeability of the toner deteriorates, the consumption increases, and the developability decreases. And sleeve fusion is likely to occur.

  The toner of the present invention hydrolyzes tetrahydrofuran-insoluble components derived from the resin component, and then filters the components that are filtered and filtered (hereinafter sometimes referred to as “residue”). However, the molecular weight distribution measured by GPC has a main peak in the molecular weight range of 10,000 to 1,000,000 (preferably 20,000 to 500,000, more preferably 50,000 to 200,000). When hydrolyzing the tetrahydrofuran-insoluble matter derived from the resin component, the component to be decomposed is a polyester resin component polymerized by an ester bond, and the vinyl resin component remains in a polymer state without being decomposed. . Therefore, the residue after hydrolysis is mainly composed of a vinyl resin component, and the tetrahydrofuran soluble content of the residue is the tetrahydrofuran soluble content of the vinyl resin component.

  Further, when a binder resin is produced by simply mixing a polyester resin and a vinyl resin having a main peak at a molecular weight of 10,000 to 1,000,000, such a vinyl resin becomes soluble in tetrahydrofuran. End up. For this reason, it is not contained in the tetrahydrofuran insoluble matter in the first stage, and does not satisfy the constitution of the present invention.

  In addition, when a binder resin is produced by simply mixing a polyester resin and a vinyl resin containing a tetrahydrofuran-insoluble component, the vinyl-based resin remains in the tetrahydrofuran-insoluble component, but after the hydrolysis, the tetrahydrofuran-insoluble component is retained. It remains. For this reason, it does not satisfy the configuration of the present invention.

  The resin component that satisfies the configuration of the present invention becomes, for example, a tetrahydrofuran-insoluble component by hybridizing a polyester-based resin and a vinyl-based resin having a main peak in the molecular weight range of 50,000 to 500,000. This is what you get.

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

  That is, a binder resin in which tetrahydrofuran-insoluble matter derived from the resin component is hydrolyzed and the residual tetrahydrofuran-soluble matter has a main peak at a molecular weight of 10,000 to 1,000,000 in the molecular weight distribution measured by GPC is The gel structure has a large molecular weight and a large molecular weight between cross-linking points.

  The toner containing such a tetrahydrofuran-insoluble component can further bring out the effects of the present invention. Having a gel structure with a large molecular weight and a large molecular weight between cross-linking points makes it easy to incorporate petroleum resin into the molecular structure and keep it stable, so that the fine dispersion of wax is maintained and uniform charging is achieved. Can have sex. In addition, the tetrahydrofuran insoluble matter that is a gel component is likely to undergo molecular motion even with a small amount of heat at the time of fixing, and the binder resin is easily softened by heat compared to the case of containing a gel component having a low molecular weight between cross-linking points. 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.

  If the tetrahydrofuran-insoluble content is hydrolyzed and the main peak molecular weight of the tetrahydrofuran-soluble content in the residue is less than 10,000, the gel component tends to be hard, the compatibility with petroleum resin is reduced, and the wax fine dispersibility is also reduced. descend. Further, the fixing property is also lowered. 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 high temperature offset resistance is lowered. When the main peak molecular weight is larger than 1,000,000, it is difficult to uniformly disperse the gel component itself in the toner, and as a result, the uniform dispersibility of other components contained in the toner is hindered, and the chargeability as a toner. Decreases.

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

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

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

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

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

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

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

  Moreover, as a tetrahydrofuran insoluble part, it is preferable to contain 30-80% of vinyl resin components. The content of the vinyl resin component in the tetrahydrofuran insoluble matter can be measured as follows.

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

For example, the area of the hybrid resin production example 1 of the embodiment described below, as the peak of the polyester, the benzene ring derived peak of the benzene ring derived peak of phthalic acid (about 730 cm ^-1) bisphenol derivative (approximately 830 cm ^-1) Was the polyester resin part. As the vinyl resin peak, the area of the peak derived from the benzene ring of styrene (about 700 cm ⁻¹ ) was taken as the vinyl resin part, and the content of the vinyl resin component was calculated based on the calibration curve.

  In the toner of the present invention, the tetrahydrofuran soluble content of the toner has a molecular weight distribution of 2,000 to 30,000 (preferably 3,000 to 20,000, more preferably 5,000 to 10,000) in the molecular weight distribution measured by GPC. It is preferable to have a main peak in the range. Moreover, it is preferable to contain 3-50 mass% (preferably 3-30 mass%, more preferably 5-20 mass%) of components having a molecular weight in the range of 40,000 to 1,000,000.

  In this way, it has a main peak in the low molecular weight region, contains a certain amount of components in the high molecular weight region, further has a gel component as described above, and contains a petroleum resin, thereby fixing at a high level. And high temperature offset resistance can be maintained. Along with this, high chargeability can be obtained, consumption is reduced, and stable developability can be provided over a long period of use.

  The hybrid resin having a large molecular weight between cross-linking points, which is a feature of the present invention, easily incorporates a petroleum resin or a low molecular weight component having a peak molecular weight of 2,000 to 30,000 into the crosslinked molecular structure. For this reason, the wax in which the gel component is dispersed in the gel facilitates melting by heat, and the fixability is improved. Moreover, since the high molecular weight component having a molecular weight in the range of 40,000 to 1,000,000 improves the mixing property of the low molecular weight component and the gel component, the dispersibility of the material including the petroleum resin of the entire binder resin can be improved. Furthermore, 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 the effects of the present invention can be exhibited more effectively.

  When the main peak molecular weight of the tetrahydrofuran soluble part of the toner is less than 2,000, the blocking resistance and developability of the toner are liable to be lowered. On the other hand, if it is larger than 30,000, the molecular structure becomes hard and the petroleum resin is difficult to penetrate, the fine dispersion property of the wax is lowered, and the uniform chargeability is lowered.

  If the content of the component having a molecular weight in the range of 40,000 to 1,000,000 is less than 3% by mass in the tetrahydrofuran-soluble component of the toner, the uniform mixing property of the gel component into the toner tends to be lowered, and the uniform charging property is lowered. there's a possibility that. Further, the effect of improving the high-temperature offset resistance is not sufficiently obtained, and ultrafine powder and coarse powder are easily generated during pulverization, so that developability tends to be lowered. When the content of the component having a molecular weight in the range of 40,000 to 1,000,000 is more than 50% by mass, the toner viscosity becomes too high and the petroleum resin hardly penetrates into the molecule, and the fine dispersion property of the wax is lowered and uniform. Chargeability tends to decrease. In addition, the fixability tends to decrease.

  The binder resin used in the present invention can be used alone as a hybrid resin, but may be a mixture containing other resin components as long as it contains at least a hybrid resin. For example, a mixture of a hybrid resin and a vinyl resin, a mixture of a hybrid resin and a polyester resin, a mixture of a polyester resin, a hybrid resin, and a vinyl resin, or the like can be given.

  The hybrid resin is formed by performing a transesterification reaction between a vinyl resin component obtained by polymerizing a monomer component having a carboxylic acid ester group such as acrylic acid ester or methacrylic acid ester and a polyester resin component. (Ii) formed by an esterification reaction between a vinyl resin component obtained by polymerizing a monomer component having a carboxylic acid group such as acrylic acid or methacrylic acid, and a polyester component; And those formed by polymerizing a vinyl monomer in the presence of an unsaturated polyester resin component polymerized using a monomer having an unsaturated bond such as an acid.

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

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

  (1) After producing vinyl resin and polyester resin separately, dissolve and swell in a small amount of organic solvent, add esterification catalyst and alcohol, heat and conduct transesterification reaction, polyester resin component and vinyl A hybrid resin having a resin component is obtained.

  (2) After producing the vinyl resin, a polyester resin component is produced in the presence of the vinyl resin, and a hybrid resin having the polyester resin component and the vinyl resin component is produced. Also in this case, an organic solvent can be appropriately used.

  (3) After the production of the polyester resin, a vinyl resin component is produced in this presence and reacted to produce a hybrid resin having the polyester resin component and the vinyl resin component.

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

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

  In the production methods (1) to (5) above, 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. Among these, a hybrid resin obtained by dissolving an unsaturated polyester resin capable of reacting with a vinyl monomer in a vinyl monomer and polymerizing a mixture of the polyester resin and the vinyl monomer by a bulk polymerization method is preferable.

  In the bulk polymerization method, a binder resin can be obtained at a low cost because steps such as evaporation of the solvent are not required as compared with the solution polymerization method. Furthermore, the binder resin produced by the bulk polymerization method has fewer impurities such as a dispersant than the binder resin produced by the suspension polymerization method. For this reason, since the influence on the fine dispersibility of the material in the toner is extremely small, the influence on the chargeability of the toner is small, and the effect of the present invention can be easily obtained, it is very preferable as a binder resin for toner. Furthermore, since the molecular weight of the hybrid resin can be increased in the bulk polymerization method, the petroleum resin can be taken into the large molecular structure and the wax can be finely dispersed more effectively. Therefore, it is possible to maintain a stable wax fine dispersion state even under the influence of heat, which is effective in developability and blocking resistance.

  As the unsaturated polyester resin used in the hybrid resin of the present invention, the tetrahydrofuran soluble component has a molecular weight of 2,000 to 30,000 (preferably 3,000 to 20,000, more preferably 5,000) in the molecular weight distribution measured by GPC. It is preferably an unsaturated polyester resin having a low molecular weight that has a main peak in the range of ˜10,000. Further, a linear unsaturated polyester resin containing no gel component is particularly preferable. If the main peak molecular weight is less than 2,000, the developability tends to decrease. When the molecular weight is larger than 30,000, the molecular structure becomes hard, so that it becomes difficult for the petroleum resin to penetrate the inside of the molecular structure of the hybrid resin, the dispersibility of the wax is lowered, and the effects of the present invention are hardly obtained. In addition, if the unsaturated polyester resin component is a non-linear molecule or contains a gel component, the number of crosslinking points increases when the hybrid component is formed, and a hard gel component with no flexibility is generated in the hybrid resin. Resulting in. For this reason, since it may interfere with disperse | distributing a petroleum resin and wax to a hybrid resin uniformly, it is unpreferable.

  Further, as the unsaturated polyester resin used in the present invention, those having a number average molecular weight (Mn) of tetrahydrofuran-soluble content of 2,000 to 20,000 (more preferably 3,000 to 10,000) are preferable. When the number average molecular weight (Mn) is less than 2,000, a gel component is hardly generated in the hybrid resin, and the developability tends to be lowered. Also, the high temperature offset resistance of the toner may be reduced. If the number average molecular weight (Mn) is larger than 20,000, the gel component of the hybrid resin tends to become hard, and a structure that allows the petroleum resin and wax to penetrate into the hybrid resin cannot be made. , Developability may decrease and consumption may increase.

  The unsaturated polyester resin used in the present invention has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of 1.0 to 5.0 from the viewpoint of sharp melt properties at the time of fixing. What is (more preferably 1.0-3.0) is preferable.

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

  The monomer which can be used when forming a polyester-type resin component is illustrated below.

  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。）
また（Ｂ）式で示されるジオール類；

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

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

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

  Examples of the trihydric or higher polyhydric alcohol component include 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.

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

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

  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 means a vinyl homopolymer or a vinyl copolymer.

  Examples of the monomer for obtaining the vinyl resin 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. A desired binder resin can be produced by copolymerizing such monomers alone or in combination with other monomers. Among these, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid in order to control the acid value.

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

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

  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)). As polyfunctional crosslinking agents, pentaerythritol acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced with methacrylate. Triallyl cyanurate, triallyl trimellitate and the like.

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

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

  Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 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 polymerization initiators are preferably used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.

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

  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.

  As described above, 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%, 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%), it is preferable to carry out the polymerization reaction at a temperature higher by 10 ° C. or more than the 10-hour half-life temperature to terminate the reaction. The binder resin thus obtained has an acid value of 0.1 to 50 mgKOH / g (preferably 1 to 40 mgKOH / g, more preferably 1 to 30 mgKOH / g), and a hydroxyl value of 5 to 80 mgKOH / g (preferably Is preferably in the range of 5 to 60 mgKOH / g, more preferably 10 to 50 mgKOH / g) from the viewpoint of stabilizing the chargeability of the toner.

  Further, the binder resin used in the present invention preferably contains 10 to 30% by mass of tetrahydrofuran-insoluble matter from the viewpoint of improving toner consumption, developability, and high-temperature offset property.

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

  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 black-toned 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. In addition, a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group may be used. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol.

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

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

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

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

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

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

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

  Next, specific examples of the compound will be shown.

  The following substances are used for controlling the toner to be positively charged. Modified products with nigrosine and fatty acid metal salts, etc .; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs such as oniums such as phosphonium salts Salts and their lake pigments, triphenylmethane dyes and their lake pigments (the rake agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, Russian compounds, metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyl Diorgano tin borate such as Suzuboreto; guanidine compounds, imidazole compounds. These can be used alone or in combination of two or more. Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used.

  Further, the general formula (4)

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

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

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

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

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

  It is also possible to use a polymer or copolymer having a quaternary ammonium base.

  Preferred for negative charging are, for example, Spiron Black TRH, T-77, T-95 (Hodogaya Chemical Co.), BONTRON (registered trademark) S-34, S-44, S-54, E-84, E- 88, E-89 (Orient Chemical). Preferred 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 Co., Ltd.), An example is 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). ) M-5, MS-7, MS-75, HS-5, EH-5, Wacker HDK N 20 (WACKER-CHEMIE GMBH) V15, N20E, T30, T40, DC Fine Silica (Dow Corning) Co.) and Fransol (Fransil) are commercially available, and these can also be used favorably in the present invention.

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

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

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

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

  The toner of the present invention can be used as a one-component developer by mixing with the fluidity improver and, if necessary, further mixing with other external additives (for example, a charge control agent). And can be used as a two-component developer. As the carrier for use in the two-component development method, any conventionally known carrier can be used. Specifically, particles having an average particle diameter of 20 to 300 μm, such as metal such as surface oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, rare earth, and alloys or oxides thereof, 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 mixed thoroughly 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 to make the resins compatible with each other. 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, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); a super mixer (manufactured by Kawata Corporation); a ribocorn (manufactured by Okawara Seisakusho Co., Ltd.); a nauter mixer, a turbulizer, and a cyclomix (Hosokawa Micron Corporation) 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); PCM kneading machine (Ikegai Iron Works); Three roll mill, mixing roll mill, kneader (Inoue Seisakusho); Needex (Mitsui Mining); MS pressure kneader, Nider Ruder (Moriyama Seisakusho) A Banbury mixer (manufactured by Kobe Steel).

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

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

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

  The toner of the present invention preferably has a charge distribution suitable for obtaining the effects of the present invention when the weight average particle diameter is preferably 2.5 to 10.0 μm, preferably 5.0 to 8.0 μm.

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

(1) Measurement of Wax Dispersion Diameter The method for measuring the wax dispersion diameter is to randomly select 30 toners and observe the transmission electron microscope to observe the dispersion diameter of the wax dispersed in the toner (the value with the longest particle diameter). Was measured and the average value was calculated.

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

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

  On the other hand, the polyester resin component contained in the tetrahydrofuran insoluble matter of toner, binder resin, petroleum resin or toner is hydrolyzed, and the vinyl resin component obtained as a residue is dispersed and dissolved in tetrahydrofuran. After being placed, the solution is filtered with a sample processing filter (pore size of about 0.5 μm, for example, Mysori Disk H-25-2 (manufactured by Tosoh Corporation)), and the filtrate is used as a sample. About 100 μl of a tetrahydrofuran solution of the toner adjusted so that the resin concentration of the sample component is about 5 mg / ml is injected and measured. 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 .

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

When the toner contains a tetrahydrofuran-insoluble component such as a magnetic substance or a pigment other than the resin component, the mass of the toner put in the cylindrical filter paper is W ₁ g, and the mass of the extracted tetrahydrofuran-soluble resin component is 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

(4) 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

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

(C) Calculation formula The hydroxyl value of the binder resin is calculated by the following formula.
A = [{(B + C) × f × 28.05} / S] + D
However,
A: Resin hydroxyl value B: Amount of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution used in the 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

(6) DSC measurement method of wax In 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

(7) Apparatus for measuring molecular weight of wax: GPC-150C (manufactured by Waters)
Column: Duplex temperature of GMH-HT (manufactured by Tosoh Corporation): 135 ° C
Solvent: O-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml injection of 0.15% by weight sample A molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used to calculate the molecular weight of the sample. Furthermore, it is calculated by converting to polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

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

[Binder resin production example]
(Polyester resin production example 1)
The polyester monomer is mixed in the following ratio.
-Bisphenol derivative represented by the formula (A) (R: propylene group, average value of x + y: 2.2)
1.150 mol
・ Terephthalic acid 0.430 mol
・ Isophthalic acid 0.385 mol
・ Fumaric acid 0.015 mol
・ Dodecenyl succinic anhydride 0.170 mol
Tetrabutyl titanate 0.1% by mass was added to these as a catalyst, and condensation polymerization was carried out at 220 ° C. to obtain unsaturated polyester resin P-1 (Tg = 58.0 ° C., main peak molecular weight = 7700, number average molecular weight (Mn ) = 4400, Mw / Mn = 2.3, acid value = 8 mgKOH / g, hydroxyl value = 32 mgKOH / g).

(Polyester resin production example 2)
Unsaturated polyester resin P-2 (Tg = 56.0 ° C., main peak molecular weight = 7200, number average molecular weight (Mn) = 4500 in the same manner as in polyester resin production example 1 except that the polyester monomer is mixed in the following ratio. Mw / Mn = 2.9, acid value = 14 mgKOH / g, hydroxyl value = 44 mgKOH / g).
-Bisphenol derivative represented by the formula (A) (R: 2.2 mol addition of propylene group)
1.150 mol
・ Terephthalic acid 0.430 mol
・ Isophthalic acid 0.380 mol
・ Fumaric acid 0.020 mol
・ Dodecenyl succinic anhydride 0.170 mol

(Polyester resin production example 3)
The unsaturated polyester resin P-3 (Tg = 53.0 ° C., main peak molecular weight = 9800, number average molecular weight (Mn) = 6900) in the same manner as in the polyester resin production example 1 except that the polyester monomer is mixed in the following ratio. Mw / Mn = 2.9, acid value = 14 mgKOH / g, hydroxyl value = 44 mgKOH / g).
-Bisphenol derivative represented by the formula (A) (R: 2.2 mol addition of propylene group)
1.250 mol
・ Terephthalic acid 0.480 mol
・ Isophthalic acid 0.230 mol
・ Fumaric acid 0.020 mol
・ Dodecenyl succinic anhydride 0.170 mol

(Polyester resin production example 4)
Saturated polyester resin P-4 (Tg = 59.0 ° C., main peak molecular weight = 12300, number average molecular weight (Mn) = 8700, in the same manner as in polyester resin production example 1 except that the polyester monomer is mixed in the following ratio: Mw / Mn = 1.5, acid value = 11 mgKOH / g, hydroxyl value = 24 mgKOH / g).
-Bisphenol derivative represented by the formula (A) (R: 2.2 mol addition of propylene group)
1.250 mol
・ Terephthalic acid 0.430 mol
・ Isophthalic acid 0.400 mol
・ Dodecenyl succinic anhydride 0.170 mol
・ Trimellitic anhydride 0.300 mol

(Binder resin production example 1)
Unsaturated polyester resin P-1: 75 parts by mass and, as a vinyl monomer, styrene: 18 parts by mass, n-butyl acrylate: 6.2 parts by mass, mono n-butyl maleate: 0.8 parts by mass, start 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (10-hour half-life temperature 128 ° C.): 0.08 parts by mass was mixed as an agent. 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 The monomer was polymerized to obtain a hybrid resin 1.

  Furthermore, petroleum resin 1 (C5 / C9 copolymerization system, Mw: 3700, Tg: 55.0 ° C., bromine number: 50 g / 100 g) 5 parts by mass, paraffin wax (100 parts by mass of hybrid resin in molten state) DSC peak temperature 103 ° C., Mw: 500) 6 parts by mass were added to obtain a uniform binder resin 1.

  The obtained binder resin 1 has a main peak molecular weight of 6900 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran soluble content, and contains 8% by mass of a component having a molecular weight in the range of 40,000 to 1,000,000. It contained 30% by mass of insoluble matter. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and analyzed for the tetrahydrofuran-soluble matter of the component to be filtered out. As a result, it contained a vinyl resin. Generally, when a hybrid resin is not contained, a tetrahydrofuran-soluble component does not occur even when hydrolyzed. From this, it was confirmed that the hybrid resin was contained in the tetrahydrofuran insoluble matter.

(Binder resin production example 2)
Petroleum resin 2 (cyclopentadiene polymerization system, Mw: 2800, Tg: 78.0 ° C., bromine number: 46 g / 100 g) 5 parts by mass, paraffin wax (DSC peak temperature) with respect to 100 parts by mass of hybrid resin in the molten state (103 ° C., Mw: 500) 6 parts by mass was added to obtain a uniform binder resin 2.

  The obtained binder resin 2 has a main peak molecular weight of 7000 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran soluble content, and contains 10% by mass of a component having a molecular weight in the range of 40,000 to 1,000,000. It contained 29% by mass of insoluble matter. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and analyzed for the tetrahydrofuran-soluble matter of the component to be filtered out. As a result, it contained a vinyl resin. Generally, when a hybrid resin is not contained, a tetrahydrofuran-soluble component does not occur even when hydrolyzed. From this, it was confirmed that the hybrid resin was contained in the tetrahydrofuran insoluble matter.

(Binder resin production example 3)
Unsaturated polyester resin P-2: 70 parts by mass, and vinyl monomer, styrene: 22 parts by mass, n-butyl acrylate: 7.0 parts by mass, mono n-butyl maleate: 1.0 parts by mass, start 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (10-hour half-life temperature 128 ° C.): 0.08 parts by mass was mixed as an agent. After this vinyl monomer / polyester resin mixture was polymerized at 120 ° C. over 20 hours until the polymerization conversion of the vinyl monomer reached 97%, the temperature was further raised to 150 ° C. and held for 5 hours to leave unreacted vinyl The monomer was polymerized to obtain a hybrid resin 3.

  Furthermore, petroleum resin 2 (cyclopentadiene polymerization system, Mw: 2800, Tg: 78.0 ° C., bromine number: 46 g / 100 g) 5 parts by mass, paraffin wax (DSC peak) with respect to 100 parts by mass of hybrid resin 3 in the molten state 6 parts by mass of a temperature 103 ° C. and Mw: 500) was added to obtain a uniform binder resin 3.

  The obtained binder resin 3 has a main peak molecular weight of 7000 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran soluble content, and contains 13% by mass of a component having a molecular weight in the range of 40,000 to 1,000,000. It contained 38% by mass of insoluble matter. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and analyzed for the tetrahydrofuran-soluble matter of the component to be filtered out. As a result, it contained a vinyl resin. Generally, when a hybrid resin is not contained, a tetrahydrofuran-soluble component does not occur even when hydrolyzed. From this, it was confirmed that the hybrid resin was contained in the tetrahydrofuran insoluble matter.

(Binder resin production example 4)
Unsaturated polyester resin P-3: 70 parts by mass, and as a vinyl monomer, styrene: 22 parts by mass, n-butyl acrylate: 7.0 parts by mass, mono n-butyl maleate: 1.0 parts by mass, start As an agent, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3: 0.05 part by mass was mixed. After this vinyl monomer / polyester resin mixture was polymerized at 110 ° C. over 10 hours until the polymerization conversion of the vinyl monomer reached 94%, the temperature was further raised to 150 ° C. and held for 5 hours to leave unreacted vinyl The monomer was polymerized to obtain a hybrid resin 4.

  Further, petroleum resin 3 (C5 / C9 copolymer system, Mw: 1300, Tg: 56.2 ° C., bromine number: 45 g / 100 g) 5 parts by mass, Fischer-Tropsch wax with respect to 100 parts by mass of hybrid resin 4: 100 in molten state (DSC peak temperature 103 ° C., Mw: 1100) 6 parts by mass was added to obtain a uniform binder resin 4.

  The obtained binder resin 4 has a main peak molecular weight of 12500 in a molecular weight distribution measured by GPC with respect to tetrahydrofuran-soluble content, and contains 12% by mass of a component having a molecular weight in the range of 40,000 to 1,000,000. It contained 39% by mass of insoluble matter. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Binder resin production example 5)
Petroleum resin 4 (C5 / C9 copolymerization system, Mw: 1900, Tg: 54.8 ° C., bromine number: 30 g / 100 g) 6 parts by mass, Fischer-Tropsch wax (100 parts by mass of molten hybrid resin 4: 100 parts by mass) DSC peak temperature 103 ° C., Mw: 1100) 6 parts by mass were added to obtain a uniform binder resin 5.

  The obtained binder resin 5 has a main peak molecular weight of 7000 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran soluble content, and contains 10% by mass of a component having a molecular weight in the range of 40,000 to 1,000,000. It contained 29% by mass of insoluble matter. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and analyzed for the tetrahydrofuran-soluble matter of the component to be filtered out. As a result, it contained a vinyl resin. Generally, when a hybrid resin is not contained, a tetrahydrofuran-soluble component does not occur even when hydrolyzed. From this, it was confirmed that the hybrid resin was contained in the tetrahydrofuran insoluble matter.

(Binder resin production example 6)
Unsaturated polyester resin P-3: 75 parts by mass of methyl ethyl ketone: 75 parts by mass with heating, and after cooling, as a vinyl monomer, styrene: 18 parts by mass, n-butyl acrylate: 5.8 parts by mass, maleic acid Mono n-butyl: 1.2 parts by mass, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3: 0.08 parts by mass as an initiator, and petroleum resin 5 (both C9) Polymerization system, Mw: 1400, Tg: 53.8 ° C., bromine number: 22 g / 100 g) 7 parts by mass, Fischer-Tropsch wax (DSC peak temperature 103 ° C., Mw: 1100) 6 parts by mass were mixed. The monomer, petroleum resin, and wax-mixed polyester solution was added to 150 parts by mass of a previously prepared 0.2% by mass aqueous polyvinyl alcohol solution 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. The temperature inside the flask was kept at 85 ° C., and polymerization was carried out for 20 hours while distilling off methyl ethyl ketone, followed by cooling. The obtained suspension slurry was dehydrated and dried to obtain a binder resin 6.

  The obtained binder resin 6 has a main peak molecular weight of 13400 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble content, and contains 18% by mass of a component having a molecular weight in the range of 40,000 to 1,000,000. It contained 40% by mass of insoluble matter. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Binder resin production example 7)
As the vinyl monomer, 33 parts by mass of styrene, 9.0 parts by mass of 2-ethylhexyl acrylate, 3.0 parts by mass of acrylic acid, and 0.12 parts by mass of azobisisobutyronitrile as a polymerization initiator are added to the dropping funnel. Put in.

  Bisphenol derivative represented by the formula (A) (R: propylene group 2.2 mol addition): 37 parts by mass, terephthalic acid: 6 parts by mass, isophthalic acid: 5.5 parts by mass, dodecenyl succinic anhydride: 4 parts by mass Part, trimellitic acid: 2.5 parts by mass and 0.07 parts by mass of dibutyltin oxide are placed in a flask, and a vinyl monomer and a polymerization initiator are added dropwise from a dropping funnel over 3 hours while stirring at a temperature of 125 ° C. Then, the vinyl resin component was polymerized. After aging for 5 hours while maintaining the temperature at 135 ° C., the temperature was raised to 230 ° C. to polymerize the polyester resin component to obtain a hybrid resin 7.

  Furthermore, hybrid resin 7: 100 parts by mass, petroleum resin 6 (C9 copolymerization system, Mw: 800, Tg: 49.2 ° C., bromine number: 24 g / 100 g) 9 parts by mass, Fischer-Tropsch wax (DSC peak temperature 103 ° C., (Mw: 1100) 6 parts by mass were dry blended and then kneaded by a biaxial kneading extruder (PCM-30: manufactured by Ikegai Ironworks Co., Ltd.) to obtain a uniform binder resin 7.

  The obtained binder resin 7 has a main peak molecular weight of 5700 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble content, and contains 25% by mass of a component having a molecular weight in the range of 40,000 to 1,000,000. It contained 37% by mass of insoluble matter. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Binder resin production example 8)
As a vinyl monomer, 33 parts by mass of styrene, 16 parts by mass of 2-ethylhexyl acrylate, 6 parts by mass of acrylic acid, and 0.12 parts by mass of azobisisobutyronitrile as a polymerization initiator are placed in a dropping funnel.

  Bisphenol derivative represented by the formula (A) (R: propylene group 2.2 mol addition): 27 parts by mass, terephthalic acid: 7 parts by mass, isophthalic acid: 4.5 parts by mass, dodecenyl succinic anhydride: 4 parts by mass Part, trimellitic acid: 2.5 parts by mass and 0.07 parts by mass of dibutyltin oxide are placed in a flask, and a vinyl monomer and a polymerization initiator are added dropwise from a dropping funnel over 3 hours while stirring at a temperature of 125 ° C. Then, the vinyl resin component was polymerized. After aging for 5 hours while maintaining at 135 ° C., the temperature was raised to 230 ° C. to polymerize the polyester-based resin component to obtain hybrid resin 8.

  Furthermore, hybrid resin 8: 100 parts by mass, petroleum resin 6 (C9 copolymerization system, Mw: 800, Tg: 49.2 ° C., bromine number: 24 g / 100 g) 9 parts by mass, Fischer-Tropsch wax (DSC peak temperature 103 ° C., Mw: 1100) 6 parts by mass were dry blended and then kneaded by a biaxial kneading extruder (PCM-30: manufactured by Ikegai Iron Works Co., Ltd.) to obtain a uniform binder resin 8.

  The obtained binder resin 8 has a main peak molecular weight of 5200 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran soluble content, and contains 33% by mass of a component having a molecular weight in the range of 40,000 to 1,000,000. It contained 43% by mass of insoluble matter. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Binder resin production example 9)
As a vinyl monomer, 33 parts by mass of styrene, 16 parts by mass of 2-ethylhexyl acrylate, 6 parts by mass of acrylic acid, and 0.12 parts by mass of azobisisobutyronitrile as a polymerization initiator are placed in a dropping funnel.

  Bisphenol derivative represented by the formula (A) (R: propylene group 2.2 mol addition): 27 parts by mass, terephthalic acid: 7 parts by mass, isophthalic acid: 4.5 parts by mass, dodecenyl succinic anhydride: 4 parts by mass Part, trimellitic acid: 2.5 parts by mass and 0.07 parts by mass of dibutyltin oxide are placed in a flask, and a vinyl monomer and a polymerization initiator are added dropwise from a dropping funnel over 3 hours while stirring at a temperature of 125 ° C. Then, the vinyl resin component was polymerized. After aging for 5 hours while maintaining the temperature at 135 ° C., the temperature was raised to 230 ° C. to polymerize the polyester resin component, and a hybrid resin 9 was obtained.

  Furthermore, hybrid resin 9: 100 parts by mass, petroleum resin 7 (C5 / C9 copolymer system, Mw: 900, Tg: 49.0 ° C., bromine number: 6 g / 100 g) 9 parts by mass, polyethylene wax (DSC peak temperature 120 ° C.) , Mw: 4000) 6 parts by mass were dry blended and then kneaded by a biaxial kneading extruder (PCM-30: manufactured by Ikegai Iron Works Co., Ltd.) to obtain a uniform binder resin 9.

  The resulting binder resin 9 has a main peak molecular weight of 5100 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran soluble content, and contains 35% by mass of a component having a molecular weight in the range of 40,000 to 1,000,000. It contained 41% by mass of insoluble matter. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and the components separated by filtration were analyzed. As a result, it contained a vinyl resin. Thereby, it was confirmed that the hybrid resin was contained in tetrahydrofuran insoluble matter.

(Binder resin production example 10)
Polyester resin P-4: 100 parts by mass, petroleum resin 4 (C5 / C9 copolymerization system, Mw: 1900, Tg: 54.8 ° C., bromine number: 30 g / 100 g), polyethylene wax (DSC peak temperature 120) C., Mw: 4000) 6 parts by mass were dry blended and then kneaded by a biaxial kneading extruder (PCM-30: manufactured by Ikegai Iron Works Co., Ltd.) to obtain a uniform binder resin 10.

  The obtained binder resin 10 has a main peak molecular weight of 13400 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran soluble content, and contains 10% by mass of a component having a molecular weight in the range of 40,000 to 1,000,000. It contained 27% by mass of insoluble matter.

(Toner 1)
・ Binder resin 1 111 parts by mass ・ Magnetite (number average particle size 0.18 μm) 95 parts by mass ・ Azo-based iron complex compound (1) (counter ion is NH ₄ ⁺ ) 2 parts by mass After mixing, the mixture was kneaded with a biaxial kneading extruder (PCM-30: manufactured by Ikegai Iron Works Co., Ltd.) set at 150 ° C. and 200 rpm. The obtained kneaded material was cooled and coarsely pulverized with a cutter mill, and then a mechanical pulverizer turbo mill (manufactured by Turbo Kogyo Co., Ltd .; coated with chromium alloy plating containing chromium carbide on the rotor and stator surfaces (plating thickness 150 μm, Using surface hardness HV1050)), the air temperature at the inlet and outlet is adjusted, mechanically pulverized, finely pulverized using a pulverizer, and classified using a multi-division classifier utilizing the Coanda effect. As a result, negatively chargeable magnetic substance-containing resin particles having a weight average particle diameter (D4) of 6.2 μm were obtained. To 100 parts by mass of the resin particles, 1.0 part by mass of negatively chargeable hydrophobic silica (BET specific surface area 120 m ^{2 /} g) treated with hexamethyldisilazane was externally added and mixed with a Henschel mixer to obtain toner 1. Table 1 shows the physical properties of Toner 1.

(Toner 2 to 10)
Toners 2 to 10 were obtained in the same manner as toner 1 except that binder resins 2 to 10 were used instead of binder resin 1. Table 1 shows the physical properties of Toners 2 to 10.

(Toner 11)
A toner 11 was obtained in the same manner as the toner 1 except that the raw materials were mixed in the following ratio. Table 1 shows the physical properties of Toner 11.
Polyester resin P-4 100 parts by mass Magnetite (number average particle size 0.18 μm) 95 parts by mass Azo-based iron complex compound (1) (counter ion is NH ₄ ⁺ ) 2 parts by mass Polyethylene wax (DSC peak Temperature 120 ° C., Mw: 4000) 6 parts by mass Petroleum resin 7 (C5 / C9 copolymerization system, Mw: 900, Tg: 49.0 ° C., bromine number: 6 g / 100 g) 15 parts by mass

(Toner 12)
A toner 12 was obtained in the same manner as the toner 1 except that the raw materials were mixed in the following ratio. Table 1 shows the physical properties of Toner 12.
Polyester resin P-4 100 parts by mass Magnetite (number average particle size 0.18 μm) 95 parts by mass Azo-based iron complex compound (1) (counter ion is NH ₄ ⁺ ) 2 parts by mass Polyethylene wax (DSC peak Temperature 120 ° C., Mw: 4000) 6 parts by mass

[Examples 1-8, Comparative Examples 1-4]
Next, the prepared toner was used for evaluation by the following method.

  A laser beam printer Laser Jet4350n manufactured by Hewlett-Packard Co. was modified to obtain an A4 size of 67 sheets / minute, and the following evaluation was performed. Table 2 shows the toner used and the evaluation results.

(1) Image density Plain paper for copiers in a high temperature and high humidity environment (35.0 ° C, 80% RH) with a printing speed of 2 sheets / 10 seconds and a printing ratio of 4% (A4 size: 75 g / m ² ) In addition, an image printing test was performed at 9,000 sheets / day, and a total of 18000 sheet image forming tests were performed, and the image density at the initial stage and at 18,000 sheets was measured.

  For the image density, a “Macbeth reflection densitometer” (manufactured by Macbeth) was used to measure a relative density with respect to a printout image of a white background portion having an original density of 0.00.

(2) Toner consumption Image printing test of 5000 sheets on plain paper for copying machines (A4 size: 75 g / m ² ) with an image with a printing ratio of 4% in a normal temperature and humidity environment (23 ° C, 60% RH). Before and after the process, the amount of toner in the toner container was measured, and the amount of toner consumed per image was measured.

(3) Sleeve fusion The sleeve surface after endurance in a high-temperature and high-humidity environment (35.0 ° C., 80% RH) was visually observed, and the degree of toner contamination was evaluated according to the following criteria.
A: Contamination is not observed.
B: Minor contamination is observed.
C: Contamination is partially observed.
D: Significant contamination is observed.

(4) Blocking test 10 g of toner was put into a 100 cc polycup and the degree of aggregation when left at 50 ° C. for 3 days was judged visually.
A No aggregate is seen.
B Agglomerates are seen but break up easily.
C Agglomerates are seen, but they collapse if shaken.
D Agglomerates can be grasped and do not collapse easily.

Claims (4)

A toner having toner particles containing at least a binder resin, a colorant, a wax and a petroleum resin,
The binder resin is a hybrid resin in which a polyester resin component and a vinyl resin component are chemically bonded.
The petroleum resin has a weight average molecular weight Mw of 600 to 4000, a bromine number of 10 to 60 g / 100 g, and 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the binder resin. Toner. The weight average molecular weight Mw of the wax is 200 to 3000,
Weight average molecular weight Mw of petroleum resin> Weight average molecular weight Mw of wax
The toner according to claim 1, wherein the following relationship is satisfied. The content (% by mass) of each of the vinyl resin component and petroleum resin with respect to 100% by mass of the binder resin is as follows:
25 <mass% of vinyl resin component × mass% of petroleum resin <200
The toner according to claim 1, wherein the toner satisfies the following relationship.   4. The toner according to claim 1, wherein the binder resin is contained in a mass ratio of polyester resin component: vinyl resin component = 50: 50 to 90:10.